Sample records for complex carbon substrates
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Polymer-assisted deposition of films and preparation of carbon nanotube arrays using the films
Luo, Hongmei; Li, Qingwen; Bauer, Eve; Burrell, Anthony Keiran; McCleskey, Thomas Mark; Jia, Quanxi
2013-07-16
Carbon nanotubes were prepared by coating a substrate with a coating solution including a suitable solvent, a soluble polymer, a metal precursor having a first metal selected from iron, nickel, cobalt, and molybdenum, and optionally a second metal selected from aluminum and magnesium, and also a binding agent that forms a complex with the first metal and a complex with the second metal. The coated substrate was exposed to a reducing atmosphere at elevated temperature, and then to a hydrocarbon in the reducing atmosphere. The result was decomposition of the polymer and formation of carbon nanotubes on the substrate. The carbon nanotubes were often in the form of an array on the substrate.
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Energetic Limitations on Microbial Respiration of Organic Compounds using Aqueous Fe(III) Complexes
NASA Astrophysics Data System (ADS)
Naughton, H.; Fendorf, S. E.
2015-12-01
Soil organic matter constitutes up to 75% of the terrestrial carbon stock. Microorganisms mediate the breakdown of organic compounds and the return of carbon to the atmosphere, predominantly through respiration. Microbial respiration requires an electron acceptor and an electron donor such as small fatty acids, organic acids, alcohols, sugars, and other molecules that differ in oxidation state of carbon. Carbon redox state affects how much energy is required to oxidize a molecule through respiration. Therefore, different organic compounds should offer a spectrum of energies to respiring microorganisms. However, microbial respiration has traditionally focused on the availability and reduction potential of electron acceptors, ignoring the organic electron donor. We found through incubation experiments that the organic compound serving as electron donor determined how rapidly Shewanella putrefaciens CN32 respires organic substrate and the extent of reduction of the electron acceptor. We simulated a range of energetically favorable to unfavorable electron acceptors using organic chelators bound to Fe(III) with equilibrium stability constants ranging from log(K) of 11.5 to 25.0 for the 1:1 complex, where more stable complexes are less favorable for microbial respiration. Organic substrates varied in nominal oxidation state of carbon from +2 to -2. The most energetically favorable substrate, lactate, promoted up to 30x more rapid increase in percent Fe(II) compared to less favorable substrates such as formate. This increased respiration on lactate was more substantial with less stable Fe(III)-chelate complexes. Intriguingly, this pattern contradicts respiration rate predicted by nominal oxidation state of carbon. Our results suggest that organic substrates will be consumed so long as the energetic toll corresponding to the electron donor half reaction is counterbalanced by the energy available from the electron accepting half reaction. We propose using the chemical structure of organic matter, elucidated with techniques such as FT-ICR MS, to improve microbial decomposition and carbon cycling models by incorporating energetic limitations due to carbon oxidation.
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Substrate quality alters the microbial mineralization of added substrate and soil organic carbon
NASA Astrophysics Data System (ADS)
Jagadamma, S.; Mayes, M. A.; Steinweg, J. M.; Schaeffer, S. M.
2014-09-01
The rate and extent of decomposition of soil organic carbon (SOC) is dependent, among other factors, on substrate chemistry and microbial dynamics. Our objectives were to understand the influence of substrate chemistry on microbial decomposition of carbon (C), and to use model fitting to quantify differences in pool sizes and mineralization rates. We conducted an incubation experiment for 270 days using four uniformly labeled 14C substrates (glucose, starch, cinnamic acid and stearic acid) on four different soils (a temperate Mollisol, a tropical Ultisol, a sub-arctic Andisol, and an arctic Gelisol). The 14C labeling enabled us to separate CO2 respired from added substrates and from native SOC. Microbial gene copy numbers were quantified at days 4, 30 and 270 using quantitative polymerase chain reaction (qPCR). Substrate C respiration was always higher for glucose than other substrates. Soils with cinnamic and stearic acid lost more native SOC than glucose- and starch-amended soils. Cinnamic and stearic acid amendments also exhibited higher fungal gene copy numbers at the end of incubation compared to unamended soils. We found that 270 days were sufficient to model the decomposition of simple substrates (glucose and starch) with three pools, but were insufficient for more complex substrates (cinnamic and stearic acid) and native SOC. This study reveals that substrate quality exerts considerable control on the microbial decomposition of newly added and native SOC, and demonstrates the need for multi-year incubation experiments to constrain decomposition parameters for the most recalcitrant fractions of SOC and complex substrates.
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NASA Astrophysics Data System (ADS)
Lee, Jonghoon; Varshney, Vikas; Park, Jeongho; Farmer, Barry L.; Roy, Ajit K.
2016-05-01
Against the presumption that hexagonal boron-nitride (h-BN) should provide an ideal substrate for van der Waals (vdW) epitaxy to grow high quality graphene films, carbon molecular beam epitaxy (CMBE) techniques using solid carbon sublimation have reported relatively poor quality of the graphene. In this article, the CMBE growth of graphene on the h-BN substrate is numerically studied in order to identify the effect of the carbon source on the quality of the graphene film. The carbon molecular beam generated by the sublimation of solid carbon source materials such as graphite and glassy carbon is mostly composed of atomic carbon, carbon dimers and carbon trimers. Therefore, the graphene film growth becomes a complex process involving various deposition characteristics of a multitude of carbon entities. Based on the study of surface adsorption and film growth characteristics of these three major carbon entities comprising graphite vapour, we report that carbon trimers convey strong traits of vdW epitaxy prone to high quality graphene growth, while atomic carbon deposition is a surface-reaction limited process accompanied by strong chemisorption. The vdW epitaxial behaviour of carbon trimers is found to be substantial enough to nucleate and develop into graphene like planar films within a nanosecond of high flux growth simulation, while reactive atomic carbons tend to impair the structural integrity of the crystalline h-BN substrate upon deposition to form an amorphous interface between the substrate and the growing carbon film. The content of reactive atomic carbons in the molecular beam is suspected to be the primary cause of low quality graphene reported in the literature. A possible optimization of the molecular beam composition towards the synthesis of better quality graphene films is suggested.Against the presumption that hexagonal boron-nitride (h-BN) should provide an ideal substrate for van der Waals (vdW) epitaxy to grow high quality graphene films, carbon molecular beam epitaxy (CMBE) techniques using solid carbon sublimation have reported relatively poor quality of the graphene. In this article, the CMBE growth of graphene on the h-BN substrate is numerically studied in order to identify the effect of the carbon source on the quality of the graphene film. The carbon molecular beam generated by the sublimation of solid carbon source materials such as graphite and glassy carbon is mostly composed of atomic carbon, carbon dimers and carbon trimers. Therefore, the graphene film growth becomes a complex process involving various deposition characteristics of a multitude of carbon entities. Based on the study of surface adsorption and film growth characteristics of these three major carbon entities comprising graphite vapour, we report that carbon trimers convey strong traits of vdW epitaxy prone to high quality graphene growth, while atomic carbon deposition is a surface-reaction limited process accompanied by strong chemisorption. The vdW epitaxial behaviour of carbon trimers is found to be substantial enough to nucleate and develop into graphene like planar films within a nanosecond of high flux growth simulation, while reactive atomic carbons tend to impair the structural integrity of the crystalline h-BN substrate upon deposition to form an amorphous interface between the substrate and the growing carbon film. The content of reactive atomic carbons in the molecular beam is suspected to be the primary cause of low quality graphene reported in the literature. A possible optimization of the molecular beam composition towards the synthesis of better quality graphene films is suggested. Electronic supplementary information (ESI) available: Three movie files: 3mer-physorption.mpg and 3mer-chemisorption.mpg feature examples of the adsorption state sampling of a carbon trimer on the heated h-BN substrate as mentioned in the ``Single Molecule Adsorption Study'' section. In 3mer-film-growth.mpg, an instance of honey comb formation during the initial phase of graphene growth simulation using a carbon trimer beam is captured. An initially sp hybridized carbon atom (red colored) becomes sp2 hybridized as a result of additional covalent bonding with the impinging carbon trimer. As the bond angle around the red carbon changes from 180 degree (sp) to 120 degree (sp2), nearby carbon atoms enclose to form a hexagon structure composed of 6 carbon atoms. See DOI: 10.1039/c6nr01396a
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Di Costanzo, Luigi; Drury, Jason E.; Penning, Trevor M.
2008-07-15
AKR1D1 (steroid 5{beta}-reductase) reduces all {Delta}{sup 4}-3-ketosteroids to form 5{beta}-dihydrosteroids, a first step in the clearance of steroid hormones and an essential step in the synthesis of all bile acids. The reduction of the carbon-carbon double bond in an {alpha}{beta}-unsaturated ketone by 5{beta}-reductase is a unique reaction in steroid enzymology because hydride transfer from NADPH to the {beta}-face of a {Delta}{sup 4}-3-ketosteroid yields a cis-A/B-ring configuration with an {approx}90{sup o} bend in steroid structure. Here, we report the first x-ray crystal structure of a mammalian steroid hormone carbon-carbon double bond reductase, human {Delta}{sup 4}-3-ketosteroid 5{beta}-reductase (AKR1D1), and its complexes withmore » intact substrates. We have determined the structures of AKR1D1 complexes with NADP{sup +} at 1.79- and 1.35-{angstrom} resolution (HEPES bound in the active site), NADP{sup +} and cortisone at 1.90-{angstrom} resolution, NADP{sup +} and progesterone at 2.03-{angstrom} resolution, and NADP{sup +} and testosterone at 1.62-{angstrom} resolution. Complexes with cortisone and progesterone reveal productive substrate binding orientations based on the proximity of each steroid carbon-carbon double bond to the re-face of the nicotinamide ring of NADP{sup +}. This orientation would permit 4-pro-(R)-hydride transfer from NADPH. Each steroid carbonyl accepts hydrogen bonds from catalytic residues Tyr{sup 58} and Glu{sup 120}. The Y58F and E120A mutants are devoid of activity, supporting a role for this dyad in the catalytic mechanism. Intriguingly, testosterone binds nonproductively, thereby rationalizing the substrate inhibition observed with this particular steroid. The locations of disease-linked mutations thought to be responsible for bile acid deficiency are also revealed.« less
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Di Costanzo,L.; Drury, J.; Penning, T.
2008-01-01
AKR1D1 (steroid 5{beta}-reductase) reduces all 4-3-ketosteroids to form 5{beta}-dihydrosteroids, a first step in the clearance of steroid hormones and an essential step in the synthesis of all bile acids. The reduction of the carbon-carbon double bond in an a,{beta}-unsaturated ketone by 5{beta}-reductase is a unique reaction in steroid enzymology because hydride transfer from NADPH to the {beta}-face of a 4-3-ketosteroid yields a cis-A/B-ring configuration with an {approx}90 bend in steroid structure. Here, we report the first x-ray crystal structure of a mammalian steroid hormone carbon-carbon double bond reductase, human 4-3-ketosteroid 5{beta}-reductase (AKR1D1), and its complexes with intact substrates. We havemore » determined the structures of AKR1D1 complexes with NADP+ at 1.79- and 1.35- Angstroms resolution (HEPES bound in the active site), NADP+ and cortisone at 1.90- Angstroms resolution, NADP+ and progesterone at 2.03- Angstroms resolution, and NADP+ and testosterone at 1.62- Angstroms resolution. Complexes with cortisone and progesterone reveal productive substrate binding orientations based on the proximity of each steroid carbon-carbon double bond to the re-face of the nicotinamide ring of NADP+. This orientation would permit 4-pro-(R)-hydride transfer from NADPH. Each steroid carbonyl accepts hydrogen bonds from catalytic residues Tyr58 and Glu120. The Y58F and E120A mutants are devoid of activity, supporting a role for this dyad in the catalytic mechanism. Intriguingly, testosterone binds nonproductively, thereby rationalizing the substrate inhibition observed with this particular steroid. The locations of disease-linked mutations thought to be responsible for bile acid deficiency are also revealed.« less
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Beccalli, Egle M; Broggini, Gianluigi; Gazzola, Silvia; Mazza, Alberto
2014-09-21
The double functionalization of carbon-carbon multiple bonds in one-pot processes has emerged in recent years as a fruitful tool for the rapid synthesis of complex molecular scaffolds. This review covers the advances in domino reactions promoted by the couple palladium(ii)/copper(ii), which was proven to be an excellent catalytic system for the functionalization of substrates.
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Tahara, Keishiro; Pan, Ling; Yamaguchi, Ryoko; Shimakoshi, Hisashi; Abe, Masaaki; Hisaeda, Yoshio
2017-10-01
Among the coenzyme B 12 -dependent enzymes, methylmalonyl-CoA mutase (MMCM) catalyzes the carbon-skeleton rearrangement reaction between R-methylmalonyl-CoA and succinyl-CoA. Diethyl 2-bromomethyl-2-phenylmalonate, an alkyl bromide substrate having two different migrating groups (phenyl and carboxylic ester groups) on the β-carbon, was applied to the electrolysis mediated by a hydrophobic vitamin B 12 model complex, heptamethyl cobyrinate perchlorate in this study. The electrolysis of the substrate at -1.0V vs. Ag-AgCl by light irradiation afforded the simple reduced product (diethyl 2-methyl-2-phenylmalonate) and the phenyl migrated product (diethyl 2-benzyl-2-phenylmalonate), as well as the electrolysis of the substrate at -1.5V vs. Ag-AgCl in the dark. The electrolysis of the substrate at -2.0V vs. Ag-AgCl afforded the carboxylic ester migrated product (diethyl phenylsuccinate) as the major product. The selectivity for the migrating group was successfully tuned by controlling the electrolysis potential. We clarified that the cathodic chemistry of the Co(III) alkylated heptamethyl cobyrinate is critical for the selectivity of the migrating group through mechanistic investigations and comparisons to the simple vitamin B 12 model complex, an imine/oxime-type cobalt complex. Copyright © 2017 Elsevier Inc. All rights reserved.
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NASA Astrophysics Data System (ADS)
Mallela, Jennie
2018-03-01
The continued health and function of tropical coral reefs is highly dependent on the ability of reef-building organisms to build large, complex, three-dimensional structures that continue to accrete and evolve over time. The recent deterioration of reef health globally, including loss of coral cover, has resulted in significant declines in architectural complexity at a large, reef-scape scale. Interestingly, the fine-scale role of micro-structure in initiating and facilitating future reef development and calcium carbonate production has largely been overlooked. In this study, experimental substrates with and without micro-ridges were deployed in the lagoon at One Tree Island for 34 months. This study assessed how the presence or absence of micro-ridges promoted recruitment by key reef-building sclerobionts (corals and encrusters) and their subsequent development at micro (mm) and macro (cm) scales. Experimental plates were examined after 11 and 34 months to assess whether long-term successional and calcification processes on different micro-topographies led to convergent or divergent communities over time. Sclerobionts were most prevalent in micro-grooves when they were available. Interestingly, in shallow lagoon reef sites characterised by shoals of small parrotfish and low urchin abundance, flat substrates were also successfully recruited to. Mean rates of carbonate production were 374 ± 154 (SD) g CaCO3 m-2 yr-1 within the lagoon. Substrates with micro-ridges were characterised by significantly greater rates of carbonate production than smooth substrates. The orientation of the substrate and period of immersion also significantly impacted rates of carbonate production, with CaCO3 on cryptic tiles increasing by 28% between 11 and 34 months. In contrast, rates on exposed tiles declined by 35% over the same time. In conclusion, even at sites characterised by small-sized parrotfish and low urchin density, micro-topography is an important settlement niche clearly favouring sclerobiont early life-history processes and subsequent carbonate production.
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SELECTIVE OXIDATION IN SUPERCRITICAL CARBON DIOXIDE USING CLEAN OXIDANTS
We have systematically investigated heterogeneous catalytic oxidation of different substrates in supercritical carbon dioxide (SC-CO2). Three types of catagysts: a metal complex, 0.5% platinum g-alumina and 0.5% palladium g-alumina were used at a pressure of 200 bar, temperatures...
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Goblirsch, Brandon R.; Jensen, Matthew R.; Mohamed, Fatuma A.; Wackett, Lawrence P.; Wilmot, Carrie M.
2016-01-01
Phylogenetically diverse microbes that produce long chain, olefinic hydrocarbons have received much attention as possible sources of renewable energy biocatalysts. One enzyme that is critical for this process is OleA, a thiolase superfamily enzyme that condenses two fatty acyl-CoA substrates to produce a β-ketoacid product and initiates the biosynthesis of long chain olefins in bacteria. Thiolases typically utilize a ping-pong mechanism centered on an active site cysteine residue. Reaction with the first substrate produces a covalent cysteine-thioester tethered acyl group that is transferred to the second substrate through formation of a carbon-carbon bond. Although the basics of thiolase chemistry are precedented, the mechanism by which OleA accommodates two substrates with extended carbon chains and a coenzyme moiety—unusual for a thiolase—are unknown. Gaining insights into this process could enable manipulation of the system for large scale olefin production with hydrocarbon chains lengths equivalent to those of fossil fuels. In this study, mutagenesis of the active site cysteine in Xanthomonas campestris OleA (Cys143) enabled trapping of two catalytically relevant species in crystals. In the resulting structures, long chain alkyl groups (C12 and C14) and phosphopantetheinate define three substrate channels in a T-shaped configuration, explaining how OleA coordinates its two substrates and product. The C143A OleA co-crystal structure possesses a single bound acyl-CoA representing the Michaelis complex with the first substrate, whereas the C143S co-crystal structure contains both acyl-CoA and fatty acid, defining how a second substrate binds to the acyl-enzyme intermediate. An active site glutamate (Gluβ117) is positioned to deprotonate bound acyl-CoA and initiate carbon-carbon bond formation. PMID:27815501
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Goblirsch, Brandon R.; Jensen, Matthew R.; Mohamed, Fatuma A.
Phylogenetically diverse microbes that produce long chain, olefinic hydrocarbons have received much attention as possible sources of renewable energy biocatalysts. One enzyme that is critical for this process is OleA, a thiolase superfamily enzyme that condenses two fatty acyl-CoA substrates to produce a β-ketoacid product and initiates the biosynthesis of long chain olefins in bacteria. Thiolases typically utilize a ping-pong mechanism centered on an active site cysteine residue. Reaction with the first substrate produces a covalent cysteine-thioester tethered acyl group that is transferred to the second substrate through formation of a carbon-carbon bond. Although the basics of thiolase chemistry aremore » precedented, the mechanism by which OleA accommodates two substrates with extended carbon chains and a coenzyme moiety—unusual for a thiolase—are unknown. Gaining insights into this process could enable manipulation of the system for large scale olefin production with hydrocarbon chains lengths equivalent to those of fossil fuels. In this study, mutagenesis of the active site cysteine in Xanthomonas campestris OleA (Cys143) enabled trapping of two catalytically relevant species in crystals. In the resulting structures, long chain alkyl groups (C12 and C14) and phosphopantetheinate define three substrate channels in a T-shaped configuration, explaining how OleA coordinates its two substrates and product. The C143A OleA co-crystal structure possesses a single bound acyl-CoA representing the Michaelis complex with the first substrate, whereas the C143S co-crystal structure contains both acyl-CoA and fatty acid, defining how a second substrate binds to the acyl-enzyme intermediate. An active site glutamate (Gluβ117) is positioned to deprotonate bound acyl-CoA and initiate carbon-carbon bond formation.« less
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NASA Astrophysics Data System (ADS)
Kuwahara, Masashi; Kim, Yeji; Azumi, Reiko
2015-07-01
We have measured the complex refractive indices of a transparent, conductive carbon nanotube film by spectroscopic ellipsometry at wavelengths of 300-1700 nm (this includes the visible range). The film was produced on a quartz substrate by the doctor-blade method using single-walled carbon nanotube-polymer ink. The imaginary part of the complex refractive index of the film was found to be lower than 0.09 over the entire wavelength range. This film has a large advantage as a transparent, flexible, and conductive material.
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Nitrogenase Reduction of Carbon-Containing Compounds
Seefeldt, Lance C.; Yang, Zhi-Yong; Duval, Simon; Dean, Dennis R.
2013-01-01
Nitrogenase is an enzyme found in many bacteria and archaea that catalyzes biological dinitrogen fixation, the reduction of N2 to NH3, accounting for the major input of fixed nitrogen into the biogeochemical N cycle. In addition to reducing N2 and protons, nitrogenase can reduce a number of small, non-physiological substrates. Among these alternative substrates are included a wide array of carbon containing compounds. These compounds have provided unique insights into aspects of the nitrogenase mechanism. Recently, it was shown that carbon monoxide (CO) and carbon dioxide (CO2) can also be reduced by nitrogenase to yield hydrocarbons, opening new insights into the mechanism of small molecule activation and reduction by this complex enzyme as well as providing clues for the design of novel molecular catalysts. PMID:23597875
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Weilenmann, Hans-Ueli; Engeli, Barbara; Bucheli-Witschel, Margarete; Egli, Thomas
2004-10-01
A Gram-negative, ethylenediaminetetraacetic acid (EDTA)-degrading bacterium (deposited at the German Culture Collection as strain DSM 9103) utilising EDTA as the only source of carbon, energy and nitrogen was isolated from a mixed EDTA-degrading population that was originally enriched in a column system from a mixture of activated sludge and soil. Chemotaxonomic analysis of quinones, polar lipids and fatty acids allowed allocation of the isolate to the alpha-subclass of Proteobacteria. 16S rDNA sequencing and phylogenetic analysis revealed highest similarity to the Mesorhizobium genus followed by the Aminobacter genus. However, the EDTA-degrading strain apparently forms a new branch within the Phyllobacteriaceae/Mesorhizobia family. Growth of the strain was rather slow not only on EDTA (micro(max) = 0.05 h(-1)) but also on other substrates. Classical substrate utilisation testing in batch culture suggested a quite restricted carbon source spectrum with only lactate, glutamate, and complexing agents chemically related to EDTA (nitrilotriacetate, iminodiacetate and ethylenediaminedisuccinate) supporting growth. However, when EDTA-limited continuous cultures of strain DSM 9103 were pulsed with fumarate, succinate, glucose or acetate, these substrates were assimilated immediately. Apparently, the strain can use a broader spectrum than indicated by traditional substrate testing techniques. The EDTA species CaEDTA and MgEDTA served as growth substrates of the strain because in the mineral medium employed EDTA was predicted to be mainly present in the form of these two complexes. The bacterium was not able to degrade Fe3+-complexed EDTA.
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Substrate quality alters microbial mineralization of added substrate and soil organic carbon
NASA Astrophysics Data System (ADS)
Jagadamma, S.; Mayes, M. A.; Steinweg, J. M.; Schaeffer, S. M.
2014-03-01
The rate and extent of decomposition of soil organic carbon (SOC) is dependent on substrate chemistry and microbial dynamics. Our objectives were to understand the influence of substrate chemistry on microbial processing of carbon (C), and to use model fitting to quantify differences in pool sizes and mineralization rates. We conducted an incubation experiment for 270 days using four uniformly-labeled 14C substrates (glucose, starch, cinnamic acid and stearic acid) on four different soils (a temperate Mollisol, a tropical Ultisol, a sub-arctic Andisol, and an arctic Gelisol). The 14C labeling enabled us to separate CO2 respired from added substrates and from native SOC. Microbial gene copy numbers were quantified at days 4, 30 and 270 using quantitative polymerase chain reaction (qPCR). Substrate C respiration was always higher for glucose than other substrates. Soils with cinnamic and stearic acid lost more native SOC than glucose- and starch-amended soils, despite an initial delay in respiration. Cinnamic and stearic acid amendments also exhibited higher fungal gene copy numbers at the end of incubation compared to unamended soils. We found that 270 days was sufficient to model decomposition of simple substrates (glucose and starch) with three pools, but was insufficient for more complex substrates (cinnamic and stearic acid) and native SOC. This study reveals that substrate quality imparts considerable control on microbial decomposition of newly added and native SOC, and demonstrates the need for multi-year incubation experiments to constrain decomposition parameters for the most recalcitrant fractions of SOC and added substrates.
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Goblirsch, Brandon R; Jensen, Matthew R; Mohamed, Fatuma A; Wackett, Lawrence P; Wilmot, Carrie M
2016-12-23
Phylogenetically diverse microbes that produce long chain, olefinic hydrocarbons have received much attention as possible sources of renewable energy biocatalysts. One enzyme that is critical for this process is OleA, a thiolase superfamily enzyme that condenses two fatty acyl-CoA substrates to produce a β-ketoacid product and initiates the biosynthesis of long chain olefins in bacteria. Thiolases typically utilize a ping-pong mechanism centered on an active site cysteine residue. Reaction with the first substrate produces a covalent cysteine-thioester tethered acyl group that is transferred to the second substrate through formation of a carbon-carbon bond. Although the basics of thiolase chemistry are precedented, the mechanism by which OleA accommodates two substrates with extended carbon chains and a coenzyme moiety-unusual for a thiolase-are unknown. Gaining insights into this process could enable manipulation of the system for large scale olefin production with hydrocarbon chains lengths equivalent to those of fossil fuels. In this study, mutagenesis of the active site cysteine in Xanthomonas campestris OleA (Cys 143 ) enabled trapping of two catalytically relevant species in crystals. In the resulting structures, long chain alkyl groups (C 12 and C 14 ) and phosphopantetheinate define three substrate channels in a T-shaped configuration, explaining how OleA coordinates its two substrates and product. The C143A OleA co-crystal structure possesses a single bound acyl-CoA representing the Michaelis complex with the first substrate, whereas the C143S co-crystal structure contains both acyl-CoA and fatty acid, defining how a second substrate binds to the acyl-enzyme intermediate. An active site glutamate (Gluβ 117 ) is positioned to deprotonate bound acyl-CoA and initiate carbon-carbon bond formation. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.
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Xu, Peng; Ji, Xin; Qi, Junlei; Yang, Hongmin; Zheng, Weitao; Abetz, Volker; Jiang, Shimei; Shen, Jiacong
2010-01-01
A convenient approach to synthesize patterned carbon nanotubes (CNTs) of three morphologies on printed substrates by combination of microcontact printing (microCP) and a plasma-enhanced chemical vapor deposition (PECVD) process is presented. Micelles of polystyrene-block-poly-(2-vinylpyridine) (PS-b-P2VP) in toluene were used as nanoreactors to fabricate FeCl3 in the core domains, and the complex solution was used as an ink to print films with polydimethylsiloxane (PDMS) stamps, different morphologies (porous, dots and stripes patterns) of the FeCl3-loaded micellar films were left onto silicon substrates after printed. After removing the polymer by thermal decomposition, the left iron oxide cluster arrays on the substrate were used as catalysts for the growth of CNTs by the process of PECVD, where the CNTs uniformly distributed on the substrates according to the morphologies of patterned catalysts arrays.
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Montpart, Nuria; Rago, Laura; Baeza, Juan A; Guisasola, Albert
2015-01-01
The use of synthetic wastewater containing carbon sources of different complexity (glycerol, milk and starch) was evaluated in single chamber microbial electrolysis cell (MEC) for hydrogen production. The growth of an anodic syntrophic consortium between fermentative and anode respiring bacteria was operationally enhanced and increased the opportunities of these complex substrates to be treated with this technology. During inoculation, current intensities achieved in single chamber microbial fuel cells were 50, 62.5, and 9 A m⁻³ for glycerol, milk and starch respectively. Both current intensities and coulombic efficiencies were higher than other values reported in previous works. The simultaneous degradation of the three complex substrates favored power production and COD removal. After three months in MEC operation, hydrogen production was only sustained with milk as a single substrate and with the simultaneous degradation of the three substrates. The later had the best results in terms of current intensity (150 A m⁻³), hydrogen production (0.94 m³ m⁻³ d⁻¹) and cathodic gas recovery (91%) at an applied voltage of 0.8 V. Glycerol and starch as substrates in MEC could not avoid the complete proliferation of hydrogen scavengers, even under low hydrogen retention time conditions induced by continuous nitrogen sparging.
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Microbial production of rhamnolipids using sugars as carbon sources.
Tan, Yun Nian; Li, Qingxin
2018-06-08
Rhamnolipids are a class of biosurfactants with effective surface-active properties. The high cost of microbial production of rhamnolipids largely affects their commercial applications. To reduce the production post, research has been carried out in screening more powerful strains, engineering microbes with higher biosurfactant yields and exploring cheaper substrates to reduce the production cost. Extensive refining is required for biosurfactant production using oils and oil-containing wastes, necessitating the use of complex and expensive biosurfactant recovery methods such as extraction with solvents or acid precipitation. As raw materials normally can account for 10-30% of the overall production cost, sugars have been proven to be an alternative carbon source for microbial production of rhamnolipids due to its lower costs and straightforward processing techniques. Studies have thus been focused on using tropical agroindustrial crop residues as renewable substrates. Herein, we reviewed studies that are using sugar-containing substrates as carbon sources for producing rhamnolipids. We speculate that sugars derived from agricultural wastes rich in cellulose and sugar-containing wastes are potential carbon sources in fermentation while challenges still remain in large scales.
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NASA Astrophysics Data System (ADS)
McFarlane, K. J.; Keiluweit, M.; Nico, P. S.; Ognibene, T.; Mayali, X.; Nuccio, E.; Weber, P. K.; Pett-Ridge, J.; Guilderson, T. P.
2013-12-01
Globally, more carbon is stored belowground as soil organic matter than in terrestrial vegetation and the atmosphere combined. A critical scientific question is how soils serve as sources and sinks for atmospheric carbon dioxide (CO2) and how these sinks will evolve with expected changes in atmospheric CO2 concentrations, climate, and land-use. Carbon initially enters belowground soil pools as plant detritus, roots, and root exudates. Once in the soil, this organic matter serves as a substrate for decomposer organisms including soil animals, bacteria, and fungi. Most of this carbon is consumed and respired as CO2, but some is converted to microbial biomass and byproducts, which may leave the soil as dissolved organic carbon, be used as a substrate by other microbes, or be stabilized within the soil mineral matrix. Mechanisms that result in the stabilization of soils include: climate stabilization, physical protection within aggregates and organo-mineral complexes, and protection of potential substrates due to physiochemical barriers. These processes, which span broad temporal and spatial scales, are poorly constrained in many dynamic land surface models. At LLNL, we have developed a suite of analytical tools that allow us to follow the movement of carbon at the cell to landscape scale, including: ';Chip-SIP', ';STXM-SIMS', and new sample interfaces for accelerator mass spectrometry (AMS). Experiments, field-based and in vivo, allow us to further the mechanistic understanding of factors that control the fate, transport, and sequestration potential of belowground carbon. The Chip-SIP approach allows us to interrogate which microbial species in a complex community incorporate specific substrates (e.g. cellulose) in order to understand the production of biofuels and better elucidate energy and carbon transfers in wetlands and soils. To disentangle the complex interactions at soil-microbial-film-mineral interfaces with minimal disruption we are using a combination of high-resolution microspectroscopy (STXM-NEXAFS), electron microscopy (SEM), and nano-scale imaging mass spectrometry (nanoSIMS) collectively known as STXM-SIMS. This approach allows us to track labeled litter, exudates and microbial necromass onto microaggregate surfaces and elucidate how organic matter source and environmental conditions influences the physical and molecular fate of soil organic matter. Isotopic characterization (14C, 13C, 2H) of CH4, CO2, dissolved organic carbon (DOC) and physical sources of carbon provide the mechanistic fingerprints of the biogeochemical pathways that cycle carbon through the landscape. Building on our expertise in accelerator mass spectrometry (AMS), we are developing methods for 'direct injection' of CO2 for AMS-14C analyses. Our initial focus has been on a liquid-sample (HPLC) sample interface. The ability to handle liquid samples and continuous flows of liquid will enable more widespread and routine use of AMS in biological and environmental applications. Applied examples of these novel techniques, addressing critical questions in the biogeosciences, will be presented.
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Huang, Liangfang; Wang, Wenmin; Wei, Xiaoqin; Wei, Haiyan
2015-04-23
The hydrosilylation of unsaturated carbon-heteroatom (C═O, C═N) bonds catalyzed by high-valent rhenium(V)-dioxo complex ReO2I(PPh3)2 (1) were studied computationally to determine the underlying mechanism. Our calculations revealed that the ionic outer-sphere pathway in which the organic substrate attacks the Si center in an η(1)-silane rhenium adduct to prompt the heterolytic cleavage of the Si-H bond is the most energetically favorable process for rhenium(V)-dioxo complex 1 catalyzed hydrosilylation of imines. The activation energy of the turnover-limiting step was calculated to be 22.8 kcal/mol with phenylmethanimine. This value is energetically more favorable than the [2 + 2] addition pathway by as much as 10.0 kcal/mol. Moreover, the ionic outer-sphere pathway competes with the [2 + 2] addition mechanism for rhenium(V)-dioxo complex 1 catalyzing the hydrosilylation of carbonyl compounds. Furthermore, the electron-donating group on the organic substrates would induce a better activity favoring the ionic outer-sphere mechanistic pathway. These findings highlight the unique features of high-valent transition-metal complexes as Lewis acids in activating the Si-H bond and catalyzing the reduction reactions.
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Ligand-accelerated enantioselective methylene C(sp3)-H bond activation.
Chen, Gang; Gong, Wei; Zhuang, Zhe; Andrä, Michal S; Chen, Yan-Qiao; Hong, Xin; Yang, Yun-Fang; Liu, Tao; Houk, K N; Yu, Jin-Quan
2016-09-02
Effective differentiation of prochiral carbon-hydrogen (C-H) bonds on a single methylene carbon via asymmetric metal insertion remains a challenge. Here, we report the discovery of chiral acetyl-protected aminoethyl quinoline ligands that enable asymmetric palladium insertion into prochiral C-H bonds on a single methylene carbon center. We apply these palladium complexes to catalytic enantioselective functionalization of β-methylene C-H bonds in aliphatic amides. Using bidentate ligands to accelerate C-H activation of otherwise unreactive monodentate substrates is crucial for outcompeting the background reaction driven by substrate-directed cyclopalladation, thereby avoiding erosion of enantioselectivity. The potential of ligand acceleration in C-H activation is also demonstrated by enantioselective β-C-H arylation of simple carboxylic acids without installing directing groups. Copyright © 2016, American Association for the Advancement of Science.
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2010-01-01
Background The archaeon, Methanosarcina acetivorans strain C2A forms methane, a potent greenhouse gas, from a variety of one-carbon substrates and acetate. Whereas the biochemical pathways leading to methane formation are well understood, little is known about the expression of the many of the genes that encode proteins needed for carbon flow, electron transfer and/or energy conservation. Quantitative transcript analysis was performed on twenty gene clusters encompassing over one hundred genes in M. acetivorans that encode enzymes/proteins with known or potential roles in substrate conversion to methane. Results The expression of many seemingly "redundant" genes/gene clusters establish substrate dependent control of approximately seventy genes for methane production by the pathways for methanol and acetate utilization. These include genes for soluble-type and membrane-type heterodisulfide reductases (hdr), hydrogenases including genes for a vht-type F420 non-reducing hydrogenase, molybdenum-type (fmd) as well as tungsten-type (fwd) formylmethanofuran dehydrogenases, genes for rnf and mrp-type electron transfer complexes, for acetate uptake, plus multiple genes for aha- and atp-type ATP synthesis complexes. Analysis of promoters for seven gene clusters reveal UTR leaders of 51-137 nucleotides in length, raising the possibility of both transcriptional and translational levels of control. Conclusions The above findings establish the differential and coordinated expression of two major gene families in M. acetivorans in response to carbon/energy supply. Furthermore, the quantitative mRNA measurements demonstrate the dynamic range for modulating transcript abundance. Since many of these gene clusters in M. acetivorans are also present in other Methanosarcina species including M. mazei, and in M. barkeri, these findings provide a basis for predicting related control in these environmentally significant methanogens. PMID:20178638
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Aji, A. S., E-mail: aji.ravazes70@gmail.com; Sahdan, M. F.; Hendra, I. B.
In this work, we studied the effect of HF treatment in silicon (111) substrate surface for depositing thin layer carbon. We performed the deposition of carbon by using DC Unbalanced Magnetron Sputtering with carbon pallet (5% Fe) as target. From SEM characterization results it can be concluded that the carbon layer on HF treated substrate is more uniform than on substrate without treated. Carbon deposition rate is higher as confirmed by AFM results if the silicon substrate is treated by HF solution. EDAX characterization results tell that silicon (111) substrate with HF treatment have more carbon fraction than substrate withoutmore » treatment. These results confirmed that HF treatment on silicon Si (111) substrates could enhance the carbon deposition by using DC sputtering. Afterward, the carbon atomic arrangement on silicon (111) surface is studied by performing thermal annealing process to 900 °C. From Raman spectroscopy results, thin film carbon is not changing until 600 °C thermal budged. But, when temperature increase to 900 °C, thin film carbon is starting to diffuse to silicon (111) substrates.« less
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Merging allylic carbon-hydrogen and selective carbon-carbon bond activation.
Masarwa, Ahmad; Didier, Dorian; Zabrodski, Tamar; Schinkel, Marvin; Ackermann, Lutz; Marek, Ilan
2014-01-09
Since the nineteenth century, many synthetic organic chemists have focused on developing new strategies to regio-, diastereo- and enantioselectively build carbon-carbon and carbon-heteroatom bonds in a predictable and efficient manner. Ideal syntheses should use the least number of synthetic steps, with few or no functional group transformations and by-products, and maximum atom efficiency. One potentially attractive method for the synthesis of molecular skeletons that are difficult to prepare would be through the selective activation of C-H and C-C bonds, instead of the conventional construction of new C-C bonds. Here we present an approach that exploits the multifold reactivity of easily accessible substrates with a single organometallic species to furnish complex molecular scaffolds through the merging of otherwise difficult transformations: allylic C-H and selective C-C bond activations. The resulting bifunctional nucleophilic species, all of which have an all-carbon quaternary stereogenic centre, can then be selectively derivatized by the addition of two different electrophiles to obtain more complex molecular architecture from these easily available starting materials.
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Merging allylic carbon-hydrogen and selective carbon-carbon bond activation
NASA Astrophysics Data System (ADS)
Masarwa, Ahmad; Didier, Dorian; Zabrodski, Tamar; Schinkel, Marvin; Ackermann, Lutz; Marek, Ilan
2014-01-01
Since the nineteenth century, many synthetic organic chemists have focused on developing new strategies to regio-, diastereo- and enantioselectively build carbon-carbon and carbon-heteroatom bonds in a predictable and efficient manner. Ideal syntheses should use the least number of synthetic steps, with few or no functional group transformations and by-products, and maximum atom efficiency. One potentially attractive method for the synthesis of molecular skeletons that are difficult to prepare would be through the selective activation of C-H and C-C bonds, instead of the conventional construction of new C-C bonds. Here we present an approach that exploits the multifold reactivity of easily accessible substrates with a single organometallic species to furnish complex molecular scaffolds through the merging of otherwise difficult transformations: allylic C-H and selective C-C bond activations. The resulting bifunctional nucleophilic species, all of which have an all-carbon quaternary stereogenic centre, can then be selectively derivatized by the addition of two different electrophiles to obtain more complex molecular architecture from these easily available starting materials.
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Li, Nan; Zheng, Yun; Jiang, Xuemei; Zhang, Ran; Pei, Kemei; Chen, Wenxing
2017-10-12
Complex wastewater with massive components is now a serious environmental issue facing humanity. Selective removal of low-concentration contaminants in mixed constituents holds great promise for increasing water supplies. Bioenzymes like horseradish peroxidase exhibit oxidizing power and selectivity. Here, we manufactured its mimic through immobilizing non-heme oxamate anionic cobalt(III) complex ([Co III (opba)] - , opba = o-phenylenebis(oxamate)) onto pyridine (Py) modified multiwalled carbon nanotubes ([Co III (opba)] - -Py-MWCNTs, MWCNTs = multiwalled carbon nanotubes), where MWCNTs captured substrates and Py functioned as the fifth ligand. We chose typical azo dye (C.I. Acid Red 1) and antibiotic (ciprofloxacin) as model substrates. Without •OH, this catalyst could detoxify target micropollutants efficiently at pH from 8 to 11. It also remained efficient in repetitive tests, and the final products were non-poisonous OH-containing acids. Combined with radical scavenger tests and electron paramagnetic resonance result, we speculated that high-valent cobalt-oxo active species and oxygen atom transfer reaction dominated in the reaction pathway. According to density functional theory calculations, the electron spin density distribution order showed that electron-withdrawing ligand was beneficial for inward pulling the excess electron and lowering the corresponding energy levels, achieving an electrophilic-attack enhancement of the catalyst. With target removal property and recyclability, this catalyst is prospective in water detoxication.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Wertsching, Alan Kevin; Trantor, Troy Joseph; Ebner, Matthias Anthony
A method and device for producing secure, high-density tritium bonded with carbon. A substrate comprising carbon is provided. A precursor is intercalated between carbon in the substrate. The precursor intercalated in the substrate is irradiated until at least a portion of the precursor, preferably a majority of the precursor, is transmutated into tritium and bonds with carbon of the substrate forming bonded tritium. The resulting bonded tritium, tritium bonded with carbon, produces electrons via beta decay. The substrate is preferably a substrate from the list of substrates consisting of highly-ordered pyrolytic graphite, carbon fibers, carbon nanotunes, buckministerfullerenes, and combinations thereof.more » The precursor is preferably boron-10, more preferably lithium-6. Preferably, thermal neutrons are used to irradiate the precursor. The resulting bonded tritium is preferably used to generate electricity either directly or indirectly.« less
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Fungal Taxa Target Different Carbon Substrates in Harvard Forest Soils
NASA Astrophysics Data System (ADS)
Hanson, C. A.; Allison, S. D.; Wallenstein, M. D.; Mellilo, J. M.; Treseder, K. K.
2006-12-01
The mineralization of soil organic carbon is a major component of the global carbon cycle and is largely controlled by soil microbial communities. However, little is known about the functional roles of soil microbes or whether different microbial taxa target different carbon substrates under natural conditions. To examine this possibility, we assessed the community composition of active fungi by using a novel nucleotide analog technique in soils from the Harvard Forest. We hypothesized that fungal community composition would shift in response to the addition of different substrates and that specific fungal taxa would respond differentially to particular carbon sources. To test this hypothesis, we added a nucleotide analog probe directly to soils in conjunction with one of five carbon compounds of increasing recalcitrance: glycine, sucrose, cellulose, tannin-protein complex, and lignin. During 48 hour incubations, the nucleotide analog was incorporated into newly replicated DNA of soil organisms that proliferated following the addition of the substrates. In this way, we labeled the DNA of microbes that respond to a particular carbon source. Labeled DNA was isolated and fungal Internal Transcribed Spacer (ITS) regions of ribosomal DNA (rDNA) were sequenced and analyzed to identify active fungi to near-species resolution. Diversity analyses at the ≥97% sequence similarity level indicated that taxonomic richness was greater under cellulose (Shannon Index: 3.23 ± 0.11 with ± 95% CI) and lignin (2.87 ± 0.15) additions than the other treatments (2.34 ± 0.16 to 2.64 ± 0.13). In addition, community composition of active fungi shifted under glycine, sucrose, and cellulose additions. Specifically, the community under glycine was significantly different from communities under control, cellulose, and tannin-protein (P<0.05). Additionally, the sucrose and cellulose communities were marginally different from the control community (P = 0.059 and 0.054, respectively) and each other (P = 0.058). Together these results support our hypothesis that fungal communities change in response to different carbon sources. We found 11 fungal operational taxonomic units (OTUs) whose relative abundances differed at least marginally significantly among substrates. One OTU related to Mortierella increased in abundance under cellulose, but was absent or rare under the other substrates. Another OTU related to an unidentified Basidiomycete was only present under lignin addition, while yet another OTU closely related to Mortierella macrocystis greatly increased in abundance under tannin-protein and slightly increased in response to lignin and sucrose. This confirms our hypothesis that particular taxa respond differently to specific carbon substrates and suggests that some fungal taxa may specialize in the break-down of particular carbon sources in soils. Overall, our results imply that microbes have varying roles in the mineralization of soil carbon, and thus microbial community composition may be an important control over ecosystem carbon dynamics and storage, especially in relation to global change.
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Liu, Guozhen; Wang, Shuo; Liu, Jingquan; Song, Dandan
2012-05-01
A glassy carbon substrate was covalently modified with a mixed layer of 4-aminophenyl and phenyl via in situ electrografting of their aryldiazonium salts in acidic solutions. Single-walled carbon nanotubes (SWNTs) were covalently and vertically anchored on the electrode surface via the formation of amide bonds from the reaction between the amines located on the modified substrate and the carboxylic groups at the ends of the nanotubes. Ferrocenedimethylamine (FDMA) was subsequently attached to the ends of SWNTs through amide bonding followed by the attachment of an epitope, i.e., endosulfan hapten to which an antibody would bind. Association or dissociation of the antibody with the sensing interface causes a modulation of the ferrocene electrochemistry. Antibody-complexed electrodes were exposed to samples containing spiked endosulfan (unbound target analyte) in environment water and interrogated using the square wave voltammetry (SWV) technique. The modified sensing surfaces were characterized by atomic force microscopy, XPS, and electrochemistry. The fabricated electrochemical immunosensor can be successfully used for the detection of endosulfan over the range of 0.01-20 ppb by a displacement assay. The lowest detection limit of this immunosensor is 0.01 ppb endosulfan in 50 mM phosphate buffer at pH 7.0.
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Shaffer, Justin P.; U'Ren, Jana M.; Gallery, Rachel E.; Baltrus, David A.; Arnold, A. Elizabeth
2017-01-01
Bacterial endosymbionts occur in diverse fungi, including members of many lineages of Ascomycota that inhabit living plants. These endosymbiotic bacteria (endohyphal bacteria, EHB) often can be removed from living fungi by antibiotic treatment, providing an opportunity to assess their effects on functional traits of their fungal hosts. We examined the effects of an endohyphal bacterium (Chitinophaga sp., Bacteroidetes) on substrate use by its host, a seed-associated strain of the fungus Fusarium keratoplasticum, by comparing growth between naturally infected and cured fungal strains across 95 carbon sources with a Biolog® phenotypic microarray. Across the majority of substrates (62%), the strain harboring the bacterium significantly outperformed the cured strain as measured by respiration and hyphal density. These substrates included many that are important for plant- and seed-fungus interactions, such as D-trehalose, myo-inositol, and sucrose, highlighting the potential influence of EHB on the breadth and efficiency of substrate use by an important Fusarium species. Cases in which the cured strain outperformed the strain harboring the bacterium were observed in only 5% of substrates. We propose that additive or synergistic substrate use by the fungus-bacterium pair enhances fungal growth in this association. More generally, alteration of the breadth or efficiency of substrate use by dispensable EHB may change fungal niches in short timeframes, potentially shaping fungal ecology and the outcomes of fungal-host interactions. PMID:28382021
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Carbon nanotube substrates and catalyzed hot stamp for polishing and patterning the substrates
Wang, Yuhuang [Evanston, IL; Hauge, Robert H [Houston, TX; Schmidt, Howard K [Houston, TX; Kim, Myung Jong [Houston, TX; Kittrell, W Carter [Houston, TX
2009-09-08
The present invention is generally directed to catalyzed hot stamp methods for polishing and/or patterning carbon nanotube-containing substrates. In some embodiments, the substrate, as a carbon nanotube fiber end, is brought into contact with a hot stamp (typically at 200-800.degree. C.), and is kept in contact with the hot stamp until the morphology/patterns on the hot stamp have been transferred to the substrate. In some embodiments, the hot stamp is made of material comprising one or more transition metals (Fe, Ni, Co, Pt, Ag, Au, etc.), which can catalyze the etching reaction of carbon with H.sub.2, CO.sub.2, H.sub.2O, and/or O.sub.2. Such methods can (1) polish the carbon nanotube-containing substrate with a microscopically smooth finish, and/or (2) transfer pre-defined patterns from the hot stamp to the substrate. Such polished or patterned carbon nanotube substrates can find application as carbon nanotube electrodes, field emitters, and field emitter arrays for displays and electron sources.
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Unno, Masaki; Ardèvol, Albert; Rovira, Carme; Ikeda-Saito, Masao
2013-01-01
Heme oxygenase catalyzes the degradation of heme to biliverdin, iron, and carbon monoxide. Here, we present crystal structures of the substrate-free, Fe3+-biliverdin-bound, and biliverdin-bound forms of HmuO, a heme oxygenase from Corynebacterium diphtheriae, refined to 1.80, 1.90, and 1.85 Å resolution, respectively. In the substrate-free structure, the proximal and distal helices, which tightly bracket the substrate heme in the substrate-bound heme complex, move apart, and the proximal helix is partially unwound. These features are supported by the molecular dynamic simulations. The structure implies that the heme binding fixes the enzyme active site structure, including the water hydrogen bond network critical for heme degradation. The biliverdin groups assume the helical conformation and are located in the heme pocket in the crystal structures of the Fe3+-biliverdin-bound and the biliverdin-bound HmuO, prepared by in situ heme oxygenase reaction from the heme complex crystals. The proximal His serves as the Fe3+-biliverdin axial ligand in the former complex and forms a hydrogen bond through a bridging water molecule with the biliverdin pyrrole nitrogen atoms in the latter complex. In both structures, salt bridges between one of the biliverdin propionate groups and the Arg and Lys residues further stabilize biliverdin at the HmuO heme pocket. Additionally, the crystal structure of a mixture of two intermediates between the Fe3+-biliverdin and biliverdin complexes has been determined at 1.70 Å resolution, implying a possible route for iron exit. PMID:24106279
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Peatland Microbial Communities and Decomposition Processes in the James Bay Lowlands, Canada
Preston, Michael D.; Smemo, Kurt A.; McLaughlin, James W.; Basiliko, Nathan
2012-01-01
Northern peatlands are a large repository of atmospheric carbon due to an imbalance between primary production by plants and microbial decomposition. The James Bay Lowlands (JBL) of northern Ontario are a large peatland-complex but remain relatively unstudied. Climate change models predict the region will experience warmer and drier conditions, potentially altering plant community composition, and shifting the region from a long-term carbon sink to a source. We collected a peat core from two geographically separated (ca. 200 km) ombrotrophic peatlands (Victor and Kinoje Bogs) and one minerotrophic peatland (Victor Fen) located near Victor Bog within the JBL. We characterized (i) archaeal, bacterial, and fungal community structure with terminal restriction fragment length polymorphism of ribosomal DNA, (ii) estimated microbial activity using community level physiological profiling and extracellular enzymes activities, and (iii) the aeration and temperature dependence of carbon mineralization at three depths (0–10, 50–60, and 100–110 cm) from each site. Similar dominant microbial taxa were observed at all three peatlands despite differences in nutrient content and substrate quality. In contrast, we observed differences in basal respiration, enzyme activity, and the magnitude of substrate utilization, which were all generally higher at Victor Fen and similar between the two bogs. However, there was no preferential mineralization of carbon substrates between the bogs and fens. Microbial community composition did not correlate with measures of microbial activity but pH was a strong predictor of activity across all sites and depths. Increased peat temperature and aeration stimulated CO2 production but this did not correlate with a change in enzyme activities. Potential microbial activity in the JBL appears to be influenced by the quality of the peat substrate and the presence of microbial inhibitors, which suggests the existing peat substrate will have a large influence on future JBL carbon dynamics. PMID:22393328
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Fonseca, Gustavo Graciano; Fonseca, Gustavo Graciano; de Arruda-Caulkins, Juliana Carvalho; Vasconcellos Antonio, Regina
2008-12-01
Although the biopolymer poly-(3-hydroxybutyrate), P[3HB], presents physicochemical properties that make it an alternative material to conventional plastics, its biotechnological production is quite expensive. As carbon substrates contribute greatly to P[3HB] production cost, the utilization of a cheaper carbon substrate and less demanding micro-organisms should decrease its cost. In the present study a 2(3) factorial experimental design was applied, aiming to evaluate the effects of using hydrolysed corn starch (HCS) and soybean oil (SBO) as carbon substrates, and cheese whey (CW) supplementation in the mineral medium (MM) on the responses, cell dried weigh (DCW), percentage P[3HB] and mass P[3HB] by recombinant Escherichia coli strains JM101 and DH10B, containing the P[3HB] synthase genes from Cupriavidus necator (ex-Ralstonia eutropha). The analysis of effects indicated that the substrates and the supplement and their interactions had positive effect on CDW. Statistically generated equations showed that, at the highest concentrations of HCS, SO and CW, theoretically it should be possible to produce about 2 g L(- 1) DCW, accumulating 50% P[3HB], in both strains. To complement this study, the strain that presented the best results was cultivated in MM added to HCS, SBO and CW (in best composition observed) and complex medium (CM) to compare the obtained P[3HB] in terms of physicochemical parameters. The obtained results showed that the P[3HB] production in MM (1.29 g L( -1)) was approximately 20% lower than in CM (1.63 g L(- 1)); however, this difference can be compensated by the lower cost of the MM achieved by the use of cheap renewable carbon sources. Moreover, using differential scanning calorimetry and thermogravimetry analyses, it was observed that the polymer produced in MM was the one which presented physicochemical properties (Tg and Tf) that were more similar to those found in the literature for P[3HB].
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Bapat, Prashant M; Das, Debasish; Dave, Nishant N; Wangikar, Pramod P
2006-12-15
Antibiotic fermentation processes are raw material cost intensive and the profitability is greatly dependent on the product yield per unit substrate consumed. In order to reduce costs, industrial processes use organic nitrogen substrates (ONS) such as corn steep liquor and yeast extract. Thus, although the stoichiometric analysis is the first logical step in process development, it is often difficult to achieve due to the ill-defined nature of the medium. Here, we present a black-box stoichiometric model for rifamycin B production via Amycolatopsis mediterranei S699 fermentation in complex multi-substrate medium. The stoichiometric coefficients have been experimentally evaluated for nine different media compositions. The ONS was quantified in terms of the amino acid content that it provides. Note that the black box stoichiometric model is an overall result of the metabolic reactions that occur during growth. Hence, the observed stoichiometric coefficients are liable to change during the batch cycle. To capture the shifts in stoichiometry, we carried out the stoichiometric analysis over short intervals of 8-16 h in a batch cycle of 100-200 h. An error analysis shows that there are no systematic errors in the measurements and that there are no unaccounted products in the process. The growth stoichiometry shows a shift from one substrate combination to another during the batch cycle. The shifts were observed to correlate well with the shifts in the trends of pH and exit carbon dioxide profiles. To exemplify, the ammonia uptake and nitrate uptake phases were marked by a decreasing pH trend and an increasing pH trend, respectively. Further, we find the product yield per unit carbon substrate to be greatly dependent on the nature of the nitrogen substrate. The analysis presented here can be readily applied to other fermentation systems that employ multi-substrate complex media.
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Supercapacitors based on carbon nanotube fuzzy fabric structural composites
NASA Astrophysics Data System (ADS)
Alresheedi, Bakheet Awad
Supercapacitors used in conjunction with batteries offer a solution to energy storage and delivery problems in systems where high power output is required, such as in fully electric cars. This project aimed to enhance current supercapacitor technology by fabricating activated carbon on a substrate consisting of carbon nanotubes (CNTs) grown on a carbon fiber fabric (fuzzy fabric). The fuzzy surface of CNTs lowers electrical resistance and increases porosity, resulting in a flexible fabric with high specific capacitance. Experimental results confirm that the capacitance of activated carbon fabricated on the fuzzy fiber composite is significantly higher than when activated carbon is formed simply on a bare carbon fiber substrate, indicating the usefulness of CNTs in supercapacitor technology. The fabrication of the fuzzy fiber based carbon electrode was fairly complex. The processing steps included composite curing, stabilization, carbonization and activation. Ratios of the three basic ingredients for the supercapacitor (fiber, CNT and polymer matrix) were investigated through experimentation and Grey relational analysis. The aim of Grey relational analysis was to examine factors that affect the overall performance of the supercapacitor. It is based on finding relationships in both independent and interrelated data series (parameters). Using this approach, it was determined that the amount of CNTs on the fiber surface plays a major role in the capacitor properties. An increased amount of CNTs increases the surface area and electrical conductivity of the substrate, while also reducing the required time of activation. Technical advances in the field of Materials and Structures are usually focused on attaining superior performance while reducing weight and cost. To achieve such combinations, multi-functionality has become essential; namely, to reduce weight by imparting additional functions simultaneously to a single material. In this study, a structural composite with excellent capacitive energy properties was successfully prepared. Moreover, after carbon nanotube growth the fuzzy fabric gained tangible energy storage properties without any structural degradation to the carbon fiber. These results represent a state-of-the-art advancement for multifunctional structural composites and warrant further development.
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Hairy carbon electrodes studied by cyclic voltammetry and battery discharge testing
NASA Technical Reports Server (NTRS)
Chung, Deborah D. L.; Shui, Xiaoping; Frysz, Christine A.
1993-01-01
Hairy carbon is a new material developed by growing submicron carbon filaments on conventional carbon substrates. Typical substrate materials include carbon black, graphite powder, carbon fibers, and glassy carbon. A catalyst is used to initiate hair growth with carbonaceous gases serving as the carbon source. To study the electrochemical behavior of hairy carbons, cyclic voltammetry (CV) and discharge testing were conducted. In both cases, hairy carbon results surpassed those of the substrate material alone.
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K Jawed, M; Hadjiconstantinou, N G; Parks, D M; Reis, P M
2018-03-14
We develop and perform continuum mechanics simulations of carbon nanotube (CNT) deployment directed by a combination of surface topography and rarefied gas flow. We employ the discrete elastic rods method to model the deposition of CNT as a slender elastic rod that evolves in time under two external forces, namely, van der Waals (vdW) and aerodynamic drag. Our results confirm that this self-assembly process is analogous to a previously studied macroscopic system, the "elastic sewing machine", where an elastic rod deployed onto a moving substrate forms nonlinear patterns. In the case of CNTs, the complex patterns observed on the substrate, such as coils and serpentines, result from an intricate interplay between van der Waals attraction, rarefied aerodynamics, and elastic bending. We systematically sweep through the multidimensional parameter space to quantify the pattern morphology as a function of the relevant material, flow, and geometric parameters. Our findings are in good agreement with available experimental data. Scaling analysis involving the relevant forces helps rationalize our observations.
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Microwave and Millimeter Wave Properties of Vertically-Aligned Single Wall Carbon Nanotubes Films
NASA Astrophysics Data System (ADS)
Haddadi, K.; Tripon-Canseliet, C.; Hivin, Q.; Ducournau, G.; Teo, E.; Coquet, P.; Tay, B. K.; Lepilliet, S.; Avramovic, V.; Chazelas, J.; Decoster, D.
2016-05-01
We present the experimental determination of the complex permittivity of vertically aligned single wall carbon nanotubes (SWCNTs) films grown on quartz substrates in the microwave regime from 10 MHz up to 67 GHz, with the electrical field perpendicular to the main axis of the carbon nanotubes (CNTs), based on coplanar waveguide transmission line approach together with the measurement of the microwave impedance of top metalized vertically—aligned SWCNTs grown on conductive silicon substrates up to 26 GHz. From coplanar waveguide measurements, we obtain a real part of the permittivity almost equal to unity, which is interpreted in terms of low carbon atom density (3 × 1019 at/cm3) associated with a very low imaginary part of permittivity (<10-3) in the frequency range considered due to a very small perpendicular conductivity. The microwave impedance of a vertically aligned CNTs bundle equivalent to a low resistance reveals a good conductivity (3 S/cm) parallel to the CNTs axis. From these two kinds of data, we experimentally demonstrate the tensor nature of the vertically grown CNTs bundles.
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Ye, Baihua; Cramer, Nicolai
2014-07-21
Directed Cp*Rh(III)-catalyzed carbon-hydrogen (C-H) bond functionalizations have evolved as a powerful strategy for the construction of heterocycles. Despite their high value, the development of related asymmetric reactions is largely lagging behind due to a limited availability of robust and tunable chiral cyclopentadienyl ligands. Rhodium complexes comprising a chiral Cp ligand with an atropchiral biaryl backbone enables an asymmetric synthesis of isoindolones from arylhydroxamates and weakly alkyl donor/acceptor diazo derivatives as one-carbon component under mild conditions. The complex guides the substrates with a high double facial selectivity yielding the chiral isoindolones in good yields and excellent enantioselectivities. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Microbial Enzyme Activity and Carbon Cycling in Grassland Soil Fractions
NASA Astrophysics Data System (ADS)
Allison, S. D.; Jastrow, J. D.
2004-12-01
Extracellular enzymes are necessary to degrade complex organic compounds present in soils. Using physical fractionation procedures, we tested whether old soil carbon is spatially isolated from degradative enzymes across a prairie restoration chronosequence in Illinois, USA. We found that carbon-degrading enzymes were abundant in all soil fractions, including macroaggregates, microaggregates, and the clay fraction, which contains carbon with a mean residence time of ~200 years. The activities of two cellulose-degrading enzymes and a chitin-degrading enzyme were 2-10 times greater in organic matter fractions than in bulk soil, consistent with the rapid turnover of these fractions. Polyphenol oxidase activity was 3 times greater in the clay fraction than in the bulk soil, despite very slow carbon turnover in this fraction. Changes in enzyme activity across the restoration chronosequence were small once adjusted for increases in soil carbon concentration, although polyphenol oxidase activity per unit carbon declined by 50% in native prairie versus cultivated soil. These results are consistent with a `two-pool' model of enzyme and carbon turnover in grassland soils. In light organic matter fractions, enzyme production and carbon turnover both occur rapidly. However, in mineral-dominated fractions, both enzymes and their carbon substrates are immobilized on mineral surfaces, leading to slow turnover. Soil carbon accumulation in the clay fraction and across the prairie restoration chronosequence probably reflects increasing physical isolation of enzymes and substrates on the molecular scale, rather than the micron to millimeter scale.
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Horemans, Benjamin; Breugelmans, Philip; Hofkens, Johan; Springael, Dirk
2017-03-01
Organic pollutant degrading biofilms in natural ecosystems and water treatment systems are often exposed to other carbon sources in addition to the pollutant. The availability of auxiliary carbon sources can lead to surplus biomass growth, changes in biofilm structure and carbon catabolite repression (CCR) which together will affect pollutant degradation rate and efficiency of the system. To understand the interplay between these processes, continuous biofilms of the 3,4-dichloroaniline (3,4-DCA) degrading Comamonas testosteroni WDL7-RFP were grown in single- and dual-substrate conditions with 3,4-DCA and/or citrate and reciprocal effects on 3,4-DCA/citrate degradation, biofilm biomass and biofilm structure were examined. The main mechanism affecting 3,4-DCA degradation in biofilms in dual-substrate conditions was citrate-mediated CCR as reflected by a decrease in specific 3,4-DCA degrading activity. Growth on citrate partially compensated for the lowered specific 3,4-DCA degradation activity under dual substrate conditions but not to the extent expected from growth observed under single-substrate conditions with citrate. This was explained by higher residual 3,4-DCA concentrations in the presence of citrate that increased cell dispersal in the biofilms. Our results show hampered pollutant removal in biofilms due to a complex interplay of auxiliary organic C source utilization for growth affecting the specific pollutant degradation rate and changes in cell physiology due to increased exposure to the pollutant as a result of lowered pollutant degradation rates. © FEMS 2017. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.
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Eddy-Current Detection Of Cracks In Reinforced Carbon/Carbon
NASA Technical Reports Server (NTRS)
Christensen, Scott V.; Koshti, Ajay M.
1995-01-01
Investigations of failures of components made of reinforced carbon/carbon show eddy-current flaw-detection techniques applicable to these components. Investigation focused on space shuttle parts, but applicable to other parts made of carbon/carbon materials. Techniques reveal cracks, too small to be detected visually, in carbon/carbon matrix substrates and in silicon carbide coates on substrates. Also reveals delaminations in carbon/carbon matrices. Used to characterize extents and locations of discontinuities in substrates in situations in which ultrasonic techniques and destructive techniques not practical.
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Vertical electric field stimulation of neural cells on porous amorphous carbon electrodes
NASA Astrophysics Data System (ADS)
Jain, Shilpee; Sharma, Ashutosh; Basu, Bikramjit
2014-03-01
We demonstrate the efficacy of amorphous macroporous carbon substrates as electrodes to stimulate neuronal cell proliferation in presence of external electric field. The electric field was applied perpendicular to carbon electrode, while growing mouse neuroblastoma (N2a) cells in vitro. The placement of the second electrode outside of the cell culture medium allows the investigation of cell response to electric field without the concurrent complexities of submerged electrodes such as potentially toxic electrode reactions, electro-kinetic flows and charge transfer (electrical current) in the cell medium. The macroporous carbon electrodes are uniquely characterized by a higher specific charge storage capacity (0.2 mC/cm2) and low impedance (3.3 k Ω at 1 kHz). When a uniform or a gradient electric field was applied perpendicular to the amorphous carbon substrate, it was found that the N2a cell viability and neurite length were higher at low electric field strengths (<= 2.5 V/cm) compared to that measured without an applied field (0 V/cm). Overall, the results of the present study unambiguously establish the uniform/gradient vertical electric field based culture protocol to stimulate neurite outgrowth and viability of nerve cells.
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Microbial Breakdown of Organic Carbon in the Diverse Sediments of Guaymas Basin
NASA Astrophysics Data System (ADS)
Hoarfrost, A.; Snider, R.; Arnosti, C.
2015-12-01
Guaymas Basin is characterized by sediments under conditions ranging from hemipelagic to hydrothermal. This wide range in geochemical contexts results in diverse microbial communities that may have varying abilities to access organic matter. We can address these functional differences by comparing enzyme activities initializing the breakdown of organic matter across these sediment types; however, previous direct measurements of the extracellular hydrolysis of complex organic carbon in sediments are sparse. We measured this first step of heterotrophic processing of organic matter in sediments at 5-10cm and 55-60cm depth from a wide range of environmental settings in Guaymas Basin. Sediment sources included sulfidic seeps on the Sonora Margin, hemipelagic ridge flank sediments, and hydrothermically altered Sonora Margin sediments bordering a methane seep site. Hydrolysis of organic substrates varied by depth and by sediment source, but despite high energy potential and organic carbon load in sulfidic sediments, activity was not highest where hydrothermal influence was highest. These results suggest that heterotrophic breakdown of organic carbon in Guaymas Basin sediments may be sensitive to factors including varying composition of organic carbon available in different sediment types, or differences in microbial community capacities to access specific organic substrates.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Kiick, D.M.; Phillips, R.S.
1988-09-20
The pH dependence of the kinetic parameters and primary deuterium isotope effects have been determined for tyrosine phenol-lyase from both Erwinia herbicola and Citrobacter freundii. The primary deuterium isotope effects indicate that proton abstraction from the 2-position of the substrate is partially rate-limiting for both enzymes. The C. freundii enzyme primary deuterium isotope effects (DV = 3.5 and D(V/Ktyr) = 2.5) are pH independent, indicating that tyrosine is not sticky (i.e., does not dissociate slower than it reacts to give products). Since Vmax for both tyrosine and the alternate substrate S-methyl-L-cysteine is also pH independent, substrate binds only to themore » correctly protonated form of the enzyme. For the E. herbicola enzyme, both Vmax and V/K for tyrosine or S-methyl-L-cysteine are pH dependent, as well as both DV and D(V/Ktyr). Thus, while both the protonated and unprotonated enzyme can bind substrate, and may be interconverted directly, only the unprotonated Michaelis complex is catalytically competent. At pH 9.5, DV = 2.5 and D(V/Ktyr) = 1.5. However, at pH 6.4 the isotope effect on both parameters is equal to 4.1. From these data, the forward commitment factor (cf = 5.2) and catalytic ratio (cvf = 1.1) for tyrosine and S-methyl-L-cysteine (cf = 2.2, cvf = 24) are calculated. Also, the Michaelis complex partition ratio (cf/cvf) for substrate and products is calculated to be 4.7 for tyrosine and 0.1 for S-methyl-L-cysteine.« less
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Method of depositing a high-emissivity layer
Wickersham, Charles E.; Foster, Ellis L.
1983-01-01
A method of depositing a high-emissivity layer on a substrate comprising RF sputter deposition of a carbide-containing target in an atmosphere of a hydrocarbon gas and a noble gas. As the carbide is deposited on the substrate the hydrocarbon gas decomposes to hydrogen and carbon. The carbon deposits on the target and substrate causing a carbide/carbon composition gradient to form on the substrate. At a sufficiently high partial pressure of hydrocarbon gas, a film of high-emissivity pure carbon will eventually form over the substrate.
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Chen, Ming; Zeng, Guangming; Lai, Cui; Zhang, Chang; Xu, Piao; Yan, Min; Xiong, Weiping
2017-10-01
Molecular-level biodegradation processes of bisphenol A (BPA), nonylphenol (NP) and triclosan (TCS) mediated by manganese peroxidase (MnP) were investigated with and without single-walled carbon nanotube (SWCNT) and/or graphene (GRA). Although the incorporation of SWCNT, GRA or their combination (SWCNT+GRA) did not break up the complexes composed of manganese peroxidase (MnP) and these substrates, they had different effects on the native contacts between the substrates and MnP. GRA tended to decrease the overall stability of the binding between MnP and its substrates. SWCNT or SWCNT+GRA generally had a minor impact on the mean binding energy between MnP and its substrates. We detected some sensitive residues from MnP that were dramatically disturbed by the GRA, SWCNT or SWCNT+GRA. Nanomaterials changed the number and behavior of water molecules adjacent to both MnP and its substrates, which was not due to the destruction of H-bond network formed by sensitive regions and water molecules. The present results are useful for understanding the molecular basis of pollutant biodegradation affected by the nanomaterials in the environment, and are also helpful in assessing the risks of these materials to the environment. Copyright © 2017 Elsevier Ltd. All rights reserved.
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Diamond growth on copper rods from polymer composite nanofibres
NASA Astrophysics Data System (ADS)
Varga, M.; Potocky, S.; Tesarek, P.; Babchenko, O.; Davydova, M.; Kromka, A.
2014-09-01
The potential uses of diamond films can be found in a diverse range of industrial applications. However, deposition of diamond films onto some foreign materials is still not a simple task. Here we present the growth of adherent diamond films on copper rods with the focus on substrate pre-treatment by polyvinyl alcohol composite nanofibres. The primary role of the polymer fibres substantially act as a carbon source which enhances the diamond nucleation and accelerates a homogenous CVD growth. Diamond growth was carried out in pulsed linear antenna microwave chemical vapour deposition system, which is characterized by cold plasma due to larger distance of hot plasma region from the substrate, at various gas compositions. The large distance between plasma source and the substrate holder also allows the uniform deposition of diamond on a large number of substrates with complex geometry (3D objects) as well as for the vertically positioned substrates. Moreover, the inhomogeneity in diamond film thickness deposited on vertically positioned substrates was suppressed by using polyvinyl alcohol nanofibre textile. Combination of PVA polymer fibres use together with this unique deposition system leads to a successful overcoating of the copper rods by continuous diamond film without the film cracking or delamination. We propose that the sequence of plasma-chemical reactions enhances the transformation of certain number of carbon atoms into the sp3-bonded form which further are stabilized by atomic hydrogen coming from plasma.
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Poudel, Suresh; Giannone, Richard J.; Basen, Mirko; ...
2018-03-23
Background: Caldicellulosiruptor bescii is a thermophilic cellulolytic bacterium that efficiently deconstructs lignocellulosic biomass into sugars, which subsequently can be fermented into alcohols, such as ethanol, and other products. Deconstruction of complex substrates by C. bescii involves a myriad of highly abundant, substrate-specific extracellular solute binding proteins (ESBPs) and carbohydrate-active enzymes (CAZymes) containing carbohydrate-binding modules (CBMs). Mass spectrometry-based proteomics was employed to investigate how these substrate recognition proteins and enzymes vary as a function of lignocellulosic substrates.Results:Proteomic analysis revealed several key extracellular proteins that respond specifically to either C5 or C6 mono- and polysaccharides. These include proteins of unknown functions (PUFs),more » ESBPs, and CAZymes. ESBPs that were previously shown to interact more efficiently with hemicellulose and pectin were detected in high abundance during growth on complex C5 substrates, such as switchgrass and xylan. Some proteins, such as Athe_0614 and Athe_2368, whose functions are not well defined were predicted to be involved in xylan utilization and ABC transport and were significantly more abundant in complex and C5 substrates, respectively. The proteins encoded by the entire glucan degradation locus (GDL; Athe_1857, 1859, 1860, 1865, 1867, and 1866) were highly abundant under all growth conditions, particularly when C. bescii was grown on cellobiose, switchgrass, or xylan. In contrast, the glycoside hydrolases Athe_0609 (Pullulanase) and 0610, which both possess CBM20 and a starch binding domain, appear preferential to C5/complex substrate deconstruction. Some PUFs, such as Athe_2463 and 2464, were detected as highly abundant when grown on C5 substrates (xylan and xylose), also suggesting C5-substrate specificity. In conclusion, this study reveals the protein membership of the C. bescii secretome and demonstrates its plasticity based on the complexity (mono-/disaccharides vs. polysaccharides) and type of carbon (C5 vs. C6) available to the microorganism. The presence or increased abundance of extracellular proteins as a response to specific substrates helps to further elucidate C. bescii’s utilization and conversion of lignocellulosic biomass to biofuel and other valuable products. This includes improved characterization of extracellular proteins that lack discrete functional roles and are poorly/not annotated.« less
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Poudel, Suresh; Giannone, Richard J.; Basen, Mirko
Background: Caldicellulosiruptor bescii is a thermophilic cellulolytic bacterium that efficiently deconstructs lignocellulosic biomass into sugars, which subsequently can be fermented into alcohols, such as ethanol, and other products. Deconstruction of complex substrates by C. bescii involves a myriad of highly abundant, substrate-specific extracellular solute binding proteins (ESBPs) and carbohydrate-active enzymes (CAZymes) containing carbohydrate-binding modules (CBMs). Mass spectrometry-based proteomics was employed to investigate how these substrate recognition proteins and enzymes vary as a function of lignocellulosic substrates.Results:Proteomic analysis revealed several key extracellular proteins that respond specifically to either C5 or C6 mono- and polysaccharides. These include proteins of unknown functions (PUFs),more » ESBPs, and CAZymes. ESBPs that were previously shown to interact more efficiently with hemicellulose and pectin were detected in high abundance during growth on complex C5 substrates, such as switchgrass and xylan. Some proteins, such as Athe_0614 and Athe_2368, whose functions are not well defined were predicted to be involved in xylan utilization and ABC transport and were significantly more abundant in complex and C5 substrates, respectively. The proteins encoded by the entire glucan degradation locus (GDL; Athe_1857, 1859, 1860, 1865, 1867, and 1866) were highly abundant under all growth conditions, particularly when C. bescii was grown on cellobiose, switchgrass, or xylan. In contrast, the glycoside hydrolases Athe_0609 (Pullulanase) and 0610, which both possess CBM20 and a starch binding domain, appear preferential to C5/complex substrate deconstruction. Some PUFs, such as Athe_2463 and 2464, were detected as highly abundant when grown on C5 substrates (xylan and xylose), also suggesting C5-substrate specificity. In conclusion, this study reveals the protein membership of the C. bescii secretome and demonstrates its plasticity based on the complexity (mono-/disaccharides vs. polysaccharides) and type of carbon (C5 vs. C6) available to the microorganism. The presence or increased abundance of extracellular proteins as a response to specific substrates helps to further elucidate C. bescii’s utilization and conversion of lignocellulosic biomass to biofuel and other valuable products. This includes improved characterization of extracellular proteins that lack discrete functional roles and are poorly/not annotated.« less
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Poudel, Suresh; Giannone, Richard J; Basen, Mirko; Nookaew, Intawat; Poole, Farris L; Kelly, Robert M; Adams, Michael W W; Hettich, Robert L
2018-01-01
Caldicellulosiruptor bescii is a thermophilic cellulolytic bacterium that efficiently deconstructs lignocellulosic biomass into sugars, which subsequently can be fermented into alcohols, such as ethanol, and other products. Deconstruction of complex substrates by C. bescii involves a myriad of highly abundant, substrate-specific extracellular solute binding proteins (ESBPs) and carbohydrate-active enzymes (CAZymes) containing carbohydrate-binding modules (CBMs). Mass spectrometry-based proteomics was employed to investigate how these substrate recognition proteins and enzymes vary as a function of lignocellulosic substrates. Proteomic analysis revealed several key extracellular proteins that respond specifically to either C5 or C6 mono- and polysaccharides. These include proteins of unknown functions (PUFs), ESBPs, and CAZymes. ESBPs that were previously shown to interact more efficiently with hemicellulose and pectin were detected in high abundance during growth on complex C5 substrates, such as switchgrass and xylan. Some proteins, such as Athe_0614 and Athe_2368, whose functions are not well defined were predicted to be involved in xylan utilization and ABC transport and were significantly more abundant in complex and C5 substrates, respectively. The proteins encoded by the entire glucan degradation locus (GDL; Athe_1857, 1859, 1860, 1865, 1867, and 1866) were highly abundant under all growth conditions, particularly when C. bescii was grown on cellobiose, switchgrass, or xylan. In contrast, the glycoside hydrolases Athe_0609 (Pullulanase) and 0610, which both possess CBM20 and a starch binding domain, appear preferential to C5/complex substrate deconstruction. Some PUFs, such as Athe_2463 and 2464, were detected as highly abundant when grown on C5 substrates (xylan and xylose), also suggesting C5-substrate specificity. This study reveals the protein membership of the C. bescii secretome and demonstrates its plasticity based on the complexity (mono-/disaccharides vs. polysaccharides) and type of carbon (C5 vs. C6) available to the microorganism. The presence or increased abundance of extracellular proteins as a response to specific substrates helps to further elucidate C. bescii 's utilization and conversion of lignocellulosic biomass to biofuel and other valuable products. This includes improved characterization of extracellular proteins that lack discrete functional roles and are poorly/not annotated.
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Breaking the regioselectivity rule for acrylate insertion in the Mizoroki-Heck reaction.
Wucher, Philipp; Caporaso, Lucia; Roesle, Philipp; Ragone, Francesco; Cavallo, Luigi; Mecking, Stefan; Göttker-Schnetmann, Inigo
2011-05-31
In modern methods for the preparation of small molecules and polymers, the insertion of substrate carbon-carbon double bonds into metal-carbon bonds is a fundamental step of paramount importance. This issue is illustrated by Mizoroki-Heck coupling as the most prominent example in organic synthesis and also by catalytic insertion polymerization. For unsymmetric substrates H(2)C = CHX the regioselectivity of insertion is decisive for the nature of the product formed. Electron-deficient olefins insert selectively in a 2,1-fashion for electronic reasons. A means for controlling this regioselectivity is lacking to date. In a combined experimental and theoretical study, we now report that, by destabilizing the transition state of 2,1-insertion via steric interactions, the regioselectivity of methyl acrylate insertion into palladium-methyl and phenyl bonds can be inverted entirely to yield the opposite "regioirregular" products in stoichiometric reactions. Insights from these experiments will aid the rational design of complexes which enable a catalytic and regioirregular Mizoroki-Heck reaction of electron-deficient olefins.
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Carbon nanotubes on a substrate
Gao, Yufei [Kennewick, WA; Liu, Jun [West Richland, WA
2002-03-26
The present invention includes carbon nanotubes whose hollow cores are 100% filled with conductive filler. The carbon nanotubes are in uniform arrays on a conductive substrate and are well-aligned and can be densely packed. The uniformity of the carbon nanotube arrays is indicated by the uniform length and diameter of the carbon nanotubes, both which vary from nanotube to nanotube on a given array by no more than about 5%. The alignment of the carbon nanotubes is indicated by the perpendicular growth of the nanotubes from the substrates which is achieved in part by the simultaneous growth of the conductive filler within the hollow core of the nanotube and the densely packed growth of the nanotubes. The present invention provides a densely packed carbon nanotube growth where each nanotube is in contact with at least one nearest-neighbor nanotube. The substrate is a conductive substrate coated with a growth catalyst, and the conductive filler can be single crystals of carbide formed by a solid state reaction between the substrate material and the growth catalyst. The present invention further provides a method for making the filled carbon nanotubes on the conductive substrates. The method includes the steps of depositing a growth catalyst onto the conductive substrate as a prepared substrate, creating a vacuum within a vessel which contains the prepared substrate, flowing H2/inert (e.g. Ar) gas within the vessel to increase and maintain the pressure within the vessel, increasing the temperature of the prepared substrate, and changing the H2/Ar gas to ethylene gas such that the ethylene gas flows within the vessel. Additionally, varying the density and separation of the catalyst particles on the conductive substrate can be used to control the diameter of the nanotubes.
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Method of making carbon nanotubes on a substrate
Gao, Yufei; Liu, Jun
2006-03-14
The present invention includes carbon nanotubes whose hollow cores are 100% filled with conductive filler. The carbon nanotubes are in uniform arrays on a conductive substrate and are well-aligned and can be densely packed. The uniformity of the carbon nanotube arrays is indicated by the uniform length and diameter of the carbon nanotubes, both which vary from nanotube to nanotube on a given array by no more than about 5%. The alignment of the carbon nanotubes is indicated by the perpendicular growth of the nanotubes from the substrates which is achieved in part by the simultaneous growth of the conductive filler within the hollow core of the nanotube and the densely packed growth of the nanotubes. The present invention provides a densely packed carbon nanotube growth where each nanotube is in contact with at least one nearest-neighbor nanotube. The substrate is a conductive substrate coated with a growth catalyst, and the conductive filler can be single crystals of carbide formed by a solid state reaction between the substrate material and the growth catalyst. The present invention further provides a method for making the filled carbon nanotubes on the conductive substrates. The method includes the steps of depositing a growth catalyst onto the conductive substrate as a prepared substrate, creating a vacuum within a vessel which contains the prepared substrate, flowing H2/inert (e.g. Ar) gas within the vessel to increase and maintain the pressure within the vessel, increasing the temperature of the prepared substrate, and changing the H2/Ar gas to ethylene gas such that the ethylene gas flows within the vessel. Additionally, varying the density and separation of the catalyst particles on the conductive substrate can be used to control the diameter of the nanotubes.
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Holder, Jeffrey C; Zou, Lufeng; Marziale, Alexander N; Liu, Peng; Lan, Yu; Gatti, Michele; Kikushima, Kotaro; Houk, K N; Stoltz, Brian M
2013-10-09
Enantioselective conjugate additions of arylboronic acids to β-substituted cyclic enones have been previously reported from our laboratories. Air- and moisture-tolerant conditions were achieved with a catalyst derived in situ from palladium(II) trifluoroacetate and the chiral ligand (S)-t-BuPyOx. We now report a combined experimental and computational investigation on the mechanism, the nature of the active catalyst, the origins of the enantioselectivity, and the stereoelectronic effects of the ligand and the substrates of this transformation. Enantioselectivity is controlled primarily by steric repulsions between the t-Bu group of the chiral ligand and the α-methylene hydrogens of the enone substrate in the enantiodetermining carbopalladation step. Computations indicate that the reaction occurs via formation of a cationic arylpalladium(II) species, and subsequent carbopalladation of the enone olefin forms the key carbon-carbon bond. Studies of nonlinear effects and stoichiometric and catalytic reactions of isolated (PyOx)Pd(Ph)I complexes show that a monomeric arylpalladium-ligand complex is the active species in the selectivity-determining step. The addition of water and ammonium hexafluorophosphate synergistically increases the rate of the reaction, corroborating the hypothesis that a cationic palladium species is involved in the reaction pathway. These additives also allow the reaction to be performed at 40 °C and facilitate an expanded substrate scope.
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Holder, Jeffrey C.; Zou, Lufeng; Marziale, Alexander N.; Liu, Peng; Lan, Yu; Gatti, Michele; Kikushima, Kotaro; Houk, K. N.; Stoltz, Brian M.
2013-01-01
Enantioselective conjugate additions of arylboronic acids to β-substituted cyclic enones have been reported previously from our laboratories. Air and moisture tolerant conditions were achieved with a catalyst derived in situ from palladium(II) trifluoroacetate and the chiral ligand (S)-t-BuPyOx. We now report a combined experimental and computational investigation on the mechanism, the nature of the active catalyst, the origins of the enantioselectivity, and the stereoelectronic effects of the ligand and the substrates of this transformation. Enantioselectivity is controlled primarily by steric repulsions between the t-Bu group of the chiral ligand and the α-methylene hydrogens of the enone substrate in the enantiodetermining carbopalladation step. Computations indicate that the reaction occurs via formation of a cationic arylpalladium(II) species, and subsequent carbopalladation of the enone olefin forms the key carbon-carbon bond. Studies of non-linear effects and stoichiometric and catalytic reactions of isolated (PyOx)Pd(Ph)I complexes show that a monomeric arylpalladium-ligand complex is the active species in the selectivity-determining step. The addition of water and ammonium hexafluorophosphate synergistically increases the rate of the reaction, corroborating the hypothesis that a cationic palladium species is involved in the reaction pathway. These additives also allow the reaction to be performed at 40 °C and facilitate an expanded substrate scope. PMID:24028424
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Systems and Methods for Implementing Robust Carbon Nanotube-Based Field Emitters
NASA Technical Reports Server (NTRS)
Kristof, Valerie (Inventor); Manohara, Harish (Inventor); Toda, Risaku (Inventor)
2015-01-01
Systems and methods in accordance with embodiments of the invention implement carbon nanotube-based field emitters. In one embodiment, a method of fabricating a carbon nanotube field emitter includes: patterning a substrate with a catalyst, where the substrate has thereon disposed a diffusion barrier layer; growing a plurality of carbon nanotubes on at least a portion of the patterned catalyst; and heating the substrate to an extent where it begins to soften such that at least a portion of at least one carbon nanotube becomes enveloped by the softened substrate.
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Refractory Oxidative-Resistant Ceramic Carbon Insulation
NASA Technical Reports Server (NTRS)
Leiser, Daniel B. (Inventor); Hsu, Ming-Ta S. (Inventor); Chen, Timothy S. (Inventor)
2001-01-01
High-temperature, lightweight, ceramic carbon insulation is prepared by coating or impregnating a porous carbon substrate with a siloxane gel derived from the reaction of an organodialkoxy silane and an organotrialkoxy silane in an acid or base medium in the presence of the carbon substrate. The siloxane gel is subsequently dried on the carbon substrate to form a ceramic carbon precursor. The carbon precursor is pyrolyzed, in an inert atmosphere, to form the ceramic insulation containing carbon, silicon, and oxygen. The carbon insulation is characterized as a porous, fibrous, carbon ceramic tile which is particularly useful as lightweight tiles for spacecraft.
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NASA Technical Reports Server (NTRS)
Hung, Ching-Chen (Inventor)
1999-01-01
A process for providing elemental metals or metal oxides distributed on a carbon substrate or self-supported utilizing graphite oxide as a percursor. The graphite oxide is exposed to one or more metal chlorides to form an intermediary product comprising carbon, metal, chloride, and oxygen. This intermediary product can be further processed by direct exposure to carbonate solutions to form a second intermediary product comprising carbon, metal carbonate, and oxygen. Either intermediary product may be further processed: a) in air to produce metal oxide; b) in an inert environment to produce metal oxide on carbon substrate; c) in a reducing environment to produce elemental metal distributed on carbon substrate. The product generally takes the shape of the carbon precursor.
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NASA Technical Reports Server (NTRS)
Hung, Ching-Cheh (Inventor)
1999-01-01
A process for providing elemental metals or metal oxides distributed on a carbon substrate or self-supported utilizing graphite oxide as a precursor. The graphite oxide is exposed to one or more metal chlorides to form an intermediary product comprising carbon, metal, chloride, and oxygen. This intermediary product can be further processed by direct exposure to carbonate-solutions to form a second intermediary product comprising carbon, metal carbonate, and oxygen. Either intermediary product may be further processed: a) in air to produce metal oxide; b) in an inert environment to produce metal oxide on carbon substrate; c) in a reducing environment to produce elemental metal distributed on carbon substrate. The product generally takes the shape of the carbon precursor.
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Contrast of Backscattered Electron SEM Images of Nanoparticles on Substrates with Complex Structure
Müller, Erich; Fritsch-Decker, Susanne; Hettler, Simon; Störmer, Heike; Weiss, Carsten; Gerthsen, Dagmar
2017-01-01
This study is concerned with backscattered electron scanning electron microscopy (BSE SEM) contrast of complex nanoscaled samples which consist of SiO2 nanoparticles (NPs) deposited on indium-tin-oxide covered bulk SiO2 and glassy carbon substrates. BSE SEM contrast of NPs is studied as function of the primary electron energy and working distance. Contrast inversions are observed which prevent intuitive interpretation of NP contrast in terms of material contrast. Experimental data is quantitatively compared with Monte-Carlo- (MC-) simulations. Quantitative agreement between experimental data and MC-simulations is obtained if the transmission characteristics of the annular semiconductor detector are taken into account. MC-simulations facilitate the understanding of NP contrast inversions and are helpful to derive conditions for optimum material and topography contrast. PMID:29109816
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Contrast of Backscattered Electron SEM Images of Nanoparticles on Substrates with Complex Structure.
Kowoll, Thomas; Müller, Erich; Fritsch-Decker, Susanne; Hettler, Simon; Störmer, Heike; Weiss, Carsten; Gerthsen, Dagmar
2017-01-01
This study is concerned with backscattered electron scanning electron microscopy (BSE SEM) contrast of complex nanoscaled samples which consist of SiO 2 nanoparticles (NPs) deposited on indium-tin-oxide covered bulk SiO 2 and glassy carbon substrates. BSE SEM contrast of NPs is studied as function of the primary electron energy and working distance. Contrast inversions are observed which prevent intuitive interpretation of NP contrast in terms of material contrast. Experimental data is quantitatively compared with Monte-Carlo- (MC-) simulations. Quantitative agreement between experimental data and MC-simulations is obtained if the transmission characteristics of the annular semiconductor detector are taken into account. MC-simulations facilitate the understanding of NP contrast inversions and are helpful to derive conditions for optimum material and topography contrast.
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Emerging Carbon and Post-Carbon Nanomaterial Inks for Printed Electronics.
Secor, Ethan B; Hersam, Mark C
2015-02-19
Carbon and post-carbon nanomaterials present desirable electrical, optical, chemical, and mechanical attributes for printed electronics, offering low-cost, large-area functionality on flexible substrates. In this Perspective, recent developments in carbon nanomaterial inks are highlighted. Monodisperse semiconducting single-walled carbon nanotubes compatible with inkjet and aerosol jet printing are ideal channels for thin-film transistors, while inkjet, gravure, and screen-printable graphene-based inks are better-suited for electrodes and interconnects. Despite the high performance achieved in prototype devices, additional effort is required to address materials integration issues encountered in more complex systems. In this regard, post-carbon nanomaterial inks (e.g., electrically insulating boron nitride and optically active transition-metal dichalcogenides) present promising opportunities. Finally, emerging work to extend these nanomaterial inks to three-dimensional printing provides a path toward nonplanar devices. Overall, the superlative properties of these materials, coupled with versatile assembly by printing techniques, offer a powerful platform for next-generation printed electronics.
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Rodriguez-Navarro, Carlos; Jroundi, Fadwa; Schiro, Mara; Ruiz-Agudo, Encarnación; González-Muñoz, María Teresa
2012-06-01
The influence of mineral substrate composition and structure on bacterial calcium carbonate productivity and polymorph selection was studied. Bacterial calcium carbonate precipitation occurred on calcitic (Iceland spar single crystals, marble, and porous limestone) and silicate (glass coverslips, porous sintered glass, and quartz sandstone) substrates following culturing in liquid medium (M-3P) inoculated with different types of bacteria (Myxococcus xanthus, Brevundimonas diminuta, and a carbonatogenic bacterial community isolated from porous calcarenite stone in a historical building) and direct application of sterile M-3P medium to limestone and sandstone with their own bacterial communities. Field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), powder X-ray diffraction (XRD), and 2-dimensional XRD (2D-XRD) analyses revealed that abundant highly oriented calcite crystals formed homoepitaxially on the calcitic substrates, irrespective of the bacterial type. Conversely, scattered spheroidal vaterite entombing bacterial cells formed on the silicate substrates. These results show that carbonate phase selection is not strain specific and that under equal culture conditions, the substrate type is the overruling factor for calcium carbonate polymorph selection. Furthermore, carbonate productivity is strongly dependent on the mineralogy of the substrate. Calcitic substrates offer a higher affinity for bacterial attachment than silicate substrates, thereby fostering bacterial growth and metabolic activity, resulting in higher production of calcium carbonate cement. Bacterial calcite grows coherently over the calcitic substrate and is therefore more chemically and mechanically stable than metastable vaterite, which formed incoherently on the silicate substrates. The implications of these results for technological applications of bacterial carbonatogenesis, including building stone conservation, are discussed.
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Jroundi, Fadwa; Schiro, Mara; Ruiz-Agudo, Encarnación; González-Muñoz, María Teresa
2012-01-01
The influence of mineral substrate composition and structure on bacterial calcium carbonate productivity and polymorph selection was studied. Bacterial calcium carbonate precipitation occurred on calcitic (Iceland spar single crystals, marble, and porous limestone) and silicate (glass coverslips, porous sintered glass, and quartz sandstone) substrates following culturing in liquid medium (M-3P) inoculated with different types of bacteria (Myxococcus xanthus, Brevundimonas diminuta, and a carbonatogenic bacterial community isolated from porous calcarenite stone in a historical building) and direct application of sterile M-3P medium to limestone and sandstone with their own bacterial communities. Field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), powder X-ray diffraction (XRD), and 2-dimensional XRD (2D-XRD) analyses revealed that abundant highly oriented calcite crystals formed homoepitaxially on the calcitic substrates, irrespective of the bacterial type. Conversely, scattered spheroidal vaterite entombing bacterial cells formed on the silicate substrates. These results show that carbonate phase selection is not strain specific and that under equal culture conditions, the substrate type is the overruling factor for calcium carbonate polymorph selection. Furthermore, carbonate productivity is strongly dependent on the mineralogy of the substrate. Calcitic substrates offer a higher affinity for bacterial attachment than silicate substrates, thereby fostering bacterial growth and metabolic activity, resulting in higher production of calcium carbonate cement. Bacterial calcite grows coherently over the calcitic substrate and is therefore more chemically and mechanically stable than metastable vaterite, which formed incoherently on the silicate substrates. The implications of these results for technological applications of bacterial carbonatogenesis, including building stone conservation, are discussed. PMID:22447589
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Lee, Jung-Kul; Pan, Cheol-Ho
2013-01-01
D-Galactose-6-phosphate isomerase from Lactobacillus rhamnosus (LacAB; EC 5.3.1.26), which is encoded by the tagatose-6-phosphate pathway gene cluster (lacABCD), catalyzes the isomerization of D-galactose-6-phosphate to D-tagatose-6-phosphate during lactose catabolism and is used to produce rare sugars as low-calorie natural sweeteners. The crystal structures of LacAB and its complex with D-tagatose-6-phosphate revealed that LacAB is a homotetramer of LacA and LacB subunits, with a structure similar to that of ribose-5-phosphate isomerase (Rpi). Structurally, LacAB belongs to the RpiB/LacAB superfamily, having a Rossmann-like αβα sandwich fold as has been identified in pentose phosphate isomerase and hexose phosphate isomerase. In contrast to other family members, the LacB subunit also has a unique α7 helix in its C-terminus. One active site is distinctly located at the interface between LacA and LacB, whereas two active sites are present in RpiB. In the structure of the product complex, the phosphate group of D-tagatose-6-phosphate is bound to three arginine residues, including Arg-39, producing a different substrate orientation than that in RpiB, where the substrate binds at Asp-43. Due to the proximity of the Arg-134 residue and backbone Cα of the α6 helix in LacA to the last Asp-172 residue of LacB with a hydrogen bond, a six-carbon sugar-phosphate can bind in the larger pocket of LacAB, compared with RpiB. His-96 in the active site is important for ring opening and substrate orientation, and Cys-65 is essential for the isomerization activity of the enzyme. Two rare sugar substrates, D-psicose and D-ribulose, show optimal binding in the LacAB-substrate complex. These findings were supported by the results of LacA activity assays. PMID:24015281
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A study to improve the mechanical properties of silicon carbide ribbon fibers
NASA Technical Reports Server (NTRS)
Debolt, H. E.; Robey, R. J.
1976-01-01
Preliminary deposition studies of SiC ribbon on a carbon ribbon substrate showed that the dominant strength limiting flaws were at the substrate surface. Procedures for making the carbon ribbon substrate from polyimide film were improved, providing lengths up to 450 meters (1,500 ft.) of flat carbon ribbon substrate 1,900 microns (75 mils) wide by 25 microns (1 mil) thick. The flaws on the carbon ribbon were smaller and less frequent than on carbon ribbon used earlier. SiC ribbon made using the improved substrate, including a layer of pyrolytic graphite to reduce further the severity of substrate surface flaws, showed strength levels up to the 2,068 MPa (300 Ksi) target of the program, with average strength levels over 1,700 MPa (250 Ksi) with coefficient of variation as low as 10% for some runs.
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Deng, Yi-Jie; Wang, Shiao Y
2017-03-01
Bacterial competition for resources is common in nature but positive interactions among bacteria are also evident. We speculate that the structural complexity of substrate might play a role in mediating bacterial interactions. We tested the hypothesis that the frequency of antagonistic interactions among lignocellulolytic bacteria is reduced when complex polysaccharide is the main carbon source compared to when a simple sugar such as glucose is available. Results using all possible pairwise interactions among 35 bacteria isolated from salt marsh detritus showed that the frequency of antagonistic interactions was significantly lower on carboxymethyl cellulose (CMC)-xylan medium (7.8%) than on glucose medium (15.5%). The two interaction networks were also different in their structures. Although 75 antagonistic interactions occurred on both media, there were 115 that occurred only on glucose and 20 only on CMC-xylan, indicating that some antagonistic interactions were substrate specific. We also found that the frequency of antagonism differed among phylogenetic groups. Gammaproteobacteria and Bacillus sp. were the most antagonistic and they tended to antagonize Bacteroidetes and Actinobacteria, the most susceptible groups. Results from the study suggest that substrate complexity affects how bacteria interact and that bacterial interactions in a community are dynamic as nutrient conditions change. © FEMS 2017. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.
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Vanengelen, Michael R; Field, Erin K; Gerlach, Robin; Lee, Brady D; Apel, William A; Peyton, Brent M
2010-04-01
In the present study, experiments were performed to investigate how representative cellulosic breakdown products, when serving as growth substrates under aerobic conditions, affect hexavalent uranyl cation (UO(2) (2+)) toxicity and bioaccumulation within a Pseudomonas sp. isolate (designated isolate A). Isolate A taken from the Cold Test Pit South (CTPS) region of the Idaho National Laboratory (INL), Idaho Falls, ID, USA. The INL houses low-level uranium-contaminated cellulosic material and understanding how this material, and specifically its breakdown products, affect U-bacterial interactions is important for understanding UO(2) (2+) fate and mobility. Toxicity was modeled using a generalized Monod expression. Butyrate, dextrose, ethanol, and lactate served as growth substrates. The potential contribution of bicarbonate species present in high concentrations was also investigated and compared with toxicity and bioaccumulation patterns seen in low-bicarbonate conditions. Isolate A was significantly more sensitive to UO(2) (2+) and accumulated significantly more UO(2) (2+) in low-bicarbonate concentrations. In addition, UO(2) (2+) growth inhibition and bioaccumulation varied depending on the growth substrate. In the presence of high bicarbonate concentrations, sensitivity to UO(2) (2+) inhibition was greatly mitigated, and did not vary between the four substrates tested. The extent of UO(2) (2+) accumulation was also diminished. The observed patterns were related to UO(2) (2+) aqueous complexation, as predicted by MINTEQ (ver. 2.52) (Easton, PA, USA). In the low- bicarbonate medium, the presence of positively charged and unstable UO(2) (2+)-hydroxide complexes explained both the greater sensitivity of isolate A to UO(2) (2+), and the ability of isolate A to accumulate significant amounts of UO(2) (2+). The exclusive presence of negatively charged and stable UO(2) (2+)-carbonate complexes in the high bi-carbonate medium explained the diminished sensitivity of isolate A to UO(2) (2+) toxicity, and limited ability of isolate A to accumulate UO(2) (2+). (c) 2010 SETAC.
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HF treatment effect for carbon deposition on silicon (111) by DC sputtering technique
DOE Office of Scientific and Technical Information (OSTI.GOV)
Aji, A. S., E-mail: aji.ravazes70@gmail.com; Darma, Y., E-mail: aji.ravazes70@gmail.com
Surface modifications of Si (111) substrate by HF solution for thin film carbon deposition have been systematically studied. Thin film carbon on Si (111) has been deposited using DC Unbalanced Magnetron Sputtering with carbon pellet doped by 5% Fe as the target. EDAX characterization confirmed that the carbon fraction on Si substrate much higher by dipping a clean Si substrate by HF solution before sputtering process in comparison with carbon fraction on Si substrate just after conventional RCA. Moreover, SEM and AFM images show the uniform thin film carbon on Si with HF treatment, in contrast to the Si withoutmore » HF solution treatment. These experimental results suggest that HF treatment of Si surface provide Si-H bonds on top Si surface that useful to enhance the carbon deposition during sputtering process. Furthermore, we investigate the thermal stability of thin film carbon on Si by thermal annealing process up to 900 °C. Atomic arrangements during annealing process were characterized by Raman spectroscopy. Raman spectra indicate that thin film carbon on Si is remaining unchanged until 600 °C and carbon atoms start to diffuse toward Si substrate after annealing at 900 °C.« less
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Filtered cathodic arc deposition with ion-species-selective bias.
Anders, André; Pasaja, Nitisak; Sansongsiri, Sakon
2007-06-01
A dual-cathode arc plasma source was combined with a computer-controlled bias amplifier to synchronize substrate bias with the pulsed production of plasma. In this way, bias can be applied in a material-selective way. The principle has been applied to the synthesis of metal-doped diamondlike carbon films, where the bias was applied and adjusted when the carbon plasma was condensing and the substrate was at ground when the metal was incorporated. In doing so, excessive sputtering by energetic metal ions can be avoided while the sp(3)sp(2) ratio can be adjusted. It is shown that the resistivity of the film can be tuned by this species-selective bias; Raman spectroscopy was used to confirm expected changes of the amorphous ta-C:Mo films. The species-selective bias principle could be extended to multiple material plasma sources and complex materials.
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Selective Aliphatic Carbon-Carbon Bond Activation by Rhodium Porphyrin Complexes.
To, Ching Tat; Chan, Kin Shing
2017-07-18
The carbon-carbon bond activation of organic molecules with transition metal complexes is an attractive transformation. These reactions form transition metal-carbon bonded intermediates, which contribute to fundamental understanding in organometallic chemistry. Alternatively, the metal-carbon bond in these intermediates can be further functionalized to construct new carbon-(hetero)atom bonds. This methodology promotes the concept that the carbon-carbon bond acts as a functional group, although carbon-carbon bonds are kinetically inert. In the past few decades, numerous efforts have been made to overcome the chemo-, regio- and, more recently, stereoselectivity obstacles. The synthetic usefulness of the selective carbon-carbon bond activation has been significantly expanded and is becoming increasingly practical: this technique covers a wide range of substrate scopes and transition metals. In the past 16 years, our laboratory has shown that rhodium porphyrin complexes effectively mediate the intermolecular stoichiometric and catalytic activation of both strained and nonstrained aliphatic carbon-carbon bonds. Rhodium(II) porphyrin metalloradicals readily activate the aliphatic carbon(sp 3 )-carbon(sp 3 ) bond in TEMPO ((2,2,6,6-tetramethylpiperidin-1-yl)oxyl) and its derivatives, nitriles, nonenolizable ketones, esters, and amides to produce rhodium(III) porphyrin alkyls. Recently, the cleavage of carbon-carbon σ-bonds in unfunctionalized and noncoordinating hydrocarbons with rhodium(II) porphyrin metalloradicals has been developed. The absence of carbon-hydrogen bond activation in these systems makes the reaction unique. Furthermore, rhodium(III) porphyrin hydroxide complexes can be generated in situ to selectively activate the carbon(α)-carbon(β) bond in ethers and the carbon(CO)-carbon(α) bond in ketones under mild conditions. The addition of PPh 3 promotes the reaction rate and yield of the carbon-carbon bond activation product. Thus, both rhodium(II) porphyrin metalloradical and rhodium(III) porphyrin hydroxide are very reactive to activate the aliphatic carbon-carbon bonds. Recently, we successfully demonstrated the rhodium porphyrin catalyzed reduction or oxidation of aliphatic carbon-carbon bonds using water as the reductant or oxidant, respectively, in the absence of sacrificial reagents and neutral conditions. This Account presents our contribution in this domain. First, we describe the chemistry of equilibria among the reactive rhodium porphyrin complexes in oxidation states from Rh(I) to Rh(III). Then, we present the serendipitous discovery of the carbon-carbon bond activation reaction and subsequent developments in our laboratory. These aliphatic carbon-carbon bond activation reactions can generally be divided into two categories according to the reaction type: (i) homolytic radical substitution of a carbon(sp 3 )-carbon(sp 3 ) bond with a rhodium(II) porphyrin metalloradical and (ii) σ-bond metathesis of a carbon-carbon bond with a rhodium(III) porphyrin hydroxide. Finally, representative examples of catalytic carbon-carbon bond hydrogenation and oxidation through strategic design are covered. The progress in this area broadens the chemistry of rhodium porphyrin complexes, and these transformations are expected to find applications in organic synthesis.
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NASA Astrophysics Data System (ADS)
Popescu, C.; Dorcioman, G.; Bita, B.; Besleaga, C.; Zgura, I.; Himcinschi, C.; Popescu, A. C.
2016-12-01
Thin films of carbon were synthesized by ns pulsed laser deposition in vacuum on silicon substrates, starting from graphite targets. Further on, the films were irradiated with a picosecond laser source emitting in visible at 532 nm. After tuning of laser parameters, we obtained a film surface covered by laser induced periodical surface structures (LIPSS). They were investigated by optical, scanning electron and atomic force microscopy. It was observed that changing the irradiation angle influences the LIPSS covered area. At high magnification it was revealed that the LIPSS pattern was quite complex, being composed of other small LIPSS islands, interconnected by bridges of nanoparticles. Raman spectra for the non-irradiated carbon films were typical for a-C type of diamond-like carbon, while the LIPSS spectra were characteristic to nano-graphite. The pristine carbon film was hydrophilic, while the LIPSS covered film surface was hydrophobic.
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Hybridized boron-carbon nitride fibrous nanostructures on Ni substrates
NASA Astrophysics Data System (ADS)
Yap, Yoke Khin; Yoshimura, Masashi; Mori, Yusuke; Sasaki, Takatomo
2002-04-01
Stoichiometric BC2N films can be deposited on Si (100) at 800 °C, however, they are phase separated as pure carbon and BN phases. Likewise, hybridized boron-carbon nitride (BCN) films can be synthesized on Ni substrates. On Ni, the carbon and BN phases are hybridized through carbon nitride and boron carbide bonds. These films appeared as fibrous nanostructures. Evidence indicates that the Ni substrate acts as a sink for the carbon and forces the carbon composites to grow on top of the B and N atoms. However, as these films are grown thicker, phase separation occurs again. These results indicate that hybridized BCN phases should now be regarded as semiconducting or superhard nanostructures. High-temperature deposition on Ni substrates might be a solution to the obstacle of preparing hybridized BCN phases.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Chen, Cheng; Key Laboratory of Optoelectronic Devices and Systems of Ministry of Education and Guangdong Province, College of Optoelectronic Engineering, Shenzhen University, Shenzhen 518060; Wang, Chao, E-mail: cwang367@szu.edu.cn, E-mail: dfdiao@szu.edu.cn
2016-08-01
We report low-energy (50–200 eV) electron irradiation induced etching of thin carbon films on a SiO{sub 2} substrate. The etching mechanism was interpreted that electron irradiation stimulated the dissociation of the carbon film and SiO{sub 2}, and then triggered the carbon film reacting with oxygen from the SiO{sub 2} substrate. A requirement for triggering the etching of the carbon film is that the incident electron penetrates through the whole carbon film, which is related to both irradiation energy and film thickness. This study provides a convenient electron-assisted etching with the precursor substrate, which sheds light on an efficient pathway to themore » fabrication of nanodevices and nanosurfaces.« less
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Lahoda, Maryna; Mesters, Jeroen R; Stsiapanava, Alena; Chaloupkova, Radka; Kuty, Michal; Damborsky, Jiri; Kuta Smatanova, Ivana
2014-02-01
Haloalkane dehalogenases catalyze the hydrolytic cleavage of carbon-halogen bonds, which is a key step in the aerobic mineralization of many environmental pollutants. One important pollutant is the toxic and anthropogenic compound 1,2,3-trichloropropane (TCP). Rational design was combined with saturation mutagenesis to obtain the haloalkane dehalogenase variant DhaA31, which displays an increased catalytic activity towards TCP. Here, the 1.31 Å resolution crystal structure of substrate-free DhaA31, the 1.26 Å resolution structure of DhaA31 in complex with TCP and the 1.95 Å resolution structure of wild-type DhaA are reported. Crystals of the enzyme-substrate complex were successfully obtained by adding volatile TCP to the reservoir after crystallization at pH 6.5 and room temperature. Comparison of the substrate-free structure with that of the DhaA31 enzyme-substrate complex reveals that the nucleophilic Asp106 changes its conformation from an inactive to an active state during the catalytic cycle. The positions of three chloride ions found inside the active site of the enzyme indicate a possible pathway for halide release from the active site through the main tunnel. Comparison of the DhaA31 variant with wild-type DhaA revealed that the introduced substitutions reduce the volume and the solvent-accessibility of the active-site pocket.
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Carbon nanotube network thin-film transistors on flexible/stretchable substrates
Takei, Kuniharu; Takahashi, Toshitake; Javey, Ali
2016-03-29
This disclosure provides systems, methods, and apparatus for flexible thin-film transistors. In one aspect, a device includes a polymer substrate, a gate electrode disposed on the polymer substrate, a dielectric layer disposed on the gate electrode and on exposed portions of the polymer substrate, a carbon nanotube network disposed on the dielectric layer, and a source electrode and a drain electrode disposed on the carbon nanotube network.
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Method for fabricating thin films of pyrolytic carbon
Brassell, G.W.; Lewis, J. Jr.; Weber, G.W.
1980-03-13
The present invention relates to a method for fabricating ultrathin films of pyrolytic carbon. Pyrolytic carbon is vapor deposited onto a concave surface of a heated substrate to a total uniform thickness in the range of about 0.1 to 1.0 micrometer. The carbon film on the substrate is provided with a layer of adherent polymeric resin. The resulting composite film of pyrolytic carbon and polymeric resin is then easily separated from the substrate by shrinking the 10 polymeric resin coating with thermally induced forces.
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Method for fabricating thin films of pyrolytic carbon
Brassell, Gilbert W.; Lewis, Jr., John; Weber, Gary W.
1982-01-01
The present invention relates to a method for fabricating ultra-thin films of pyrolytic carbon. Pyrolytic carbon is vapor deposited onto a concave surface of a heated substrate to a total uniform thickness in the range of about 0.1 to 1.0 micrometer. The carbon film on the substrate is provided with a layer of adherent polymeric resin. The resulting composite film of pyrolytic carbon and polymeric resin is then easily separated from the substrate by shrinking the polymeric resin coating with thermally induced forces.
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Visualizing the Reaction Cycle in an Iron(II)- and 2-(Oxo)-glutarate-Dependent Hydroxylase.
Mitchell, Andrew J; Dunham, Noah P; Martinie, Ryan J; Bergman, Jonathan A; Pollock, Christopher J; Hu, Kai; Allen, Benjamin D; Chang, Wei-Chen; Silakov, Alexey; Bollinger, J Martin; Krebs, Carsten; Boal, Amie K
2017-10-04
Iron(II)- and 2-(oxo)-glutarate-dependent oxygenases catalyze diverse oxidative transformations that are often initiated by abstraction of hydrogen from carbon by iron(IV)-oxo (ferryl) complexes. Control of the relative orientation of the substrate C-H and ferryl Fe-O bonds, primarily by direction of the oxo group into one of two cis-related coordination sites (termed inline and offline), may be generally important for control of the reaction outcome. Neither the ferryl complexes nor their fleeting precursors have been crystallographically characterized, hindering direct experimental validation of the offline hypothesis and elucidation of the means by which the protein might dictate an alternative oxo position. Comparison of high-resolution X-ray crystal structures of the substrate complex, an Fe(II)-peroxysuccinate ferryl precursor, and a vanadium(IV)-oxo mimic of the ferryl intermediate in the l-arginine 3-hydroxylase, VioC, reveals coordinated motions of active site residues that appear to control the intermediate geometries to determine reaction outcome.
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Benoit, Isabelle; Zhou, Miaomiao; Vivas Duarte, Alexandra; Downes, Damien J.; Todd, Richard B.; Kloezen, Wendy; Post, Harm; Heck, Albert J. R.; Maarten Altelaar, A. F.; de Vries, Ronald P.
2015-01-01
Degradation of plant biomass to fermentable sugars is of critical importance for the use of plant materials for biofuels. Filamentous fungi are ubiquitous organisms and major plant biomass degraders. Single colonies of some fungal species can colonize massive areas as large as five soccer stadia. During growth, the mycelium encounters heterogeneous carbon sources. Here we assessed whether substrate heterogeneity is a major determinant of spatial gene expression in colonies of Aspergillus niger. We analyzed whole-genome gene expression in five concentric zones of 5-day-old colonies utilizing sugar beet pulp as a complex carbon source. Growth, protein production and secretion occurred throughout the colony. Genes involved in carbon catabolism were expressed uniformly from the centre to the periphery whereas genes encoding plant biomass degrading enzymes and nitrate utilization were expressed differentially across the colony. A combined adaptive response of carbon-catabolism and enzyme production to locally available monosaccharides was observed. Finally, our results demonstrate that A. niger employs different enzymatic tools to adapt its metabolism as it colonizes complex environments. PMID:26314379
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Benoit, Isabelle; Zhou, Miaomiao; Vivas Duarte, Alexandra; Downes, Damien J; Todd, Richard B; Kloezen, Wendy; Post, Harm; Heck, Albert J R; Maarten Altelaar, A F; de Vries, Ronald P
2015-08-28
Degradation of plant biomass to fermentable sugars is of critical importance for the use of plant materials for biofuels. Filamentous fungi are ubiquitous organisms and major plant biomass degraders. Single colonies of some fungal species can colonize massive areas as large as five soccer stadia. During growth, the mycelium encounters heterogeneous carbon sources. Here we assessed whether substrate heterogeneity is a major determinant of spatial gene expression in colonies of Aspergillus niger. We analyzed whole-genome gene expression in five concentric zones of 5-day-old colonies utilizing sugar beet pulp as a complex carbon source. Growth, protein production and secretion occurred throughout the colony. Genes involved in carbon catabolism were expressed uniformly from the centre to the periphery whereas genes encoding plant biomass degrading enzymes and nitrate utilization were expressed differentially across the colony. A combined adaptive response of carbon-catabolism and enzyme production to locally available monosaccharides was observed. Finally, our results demonstrate that A. niger employs different enzymatic tools to adapt its metabolism as it colonizes complex environments.
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Aerobic microbial mineralization of dichloroethene as sole carbon substrate
Bradley, P.M.; Chapelle, F.H.
2000-01-01
Microorganisms indigenous to the bed sediments of a black- water stream utilized 1,2-dichloroethene (1,2-DCE) as a sole carbon substrate for aerobic metabolism. Although no evidence of growth was observed in the minimal salts culture media used in this study, efficient aerobic microbial mineralization of 1,2-DCE as sole carbon substrate was maintained through three sequential transfers (107 final dilution) of the original environmental innoculum. These results indicate that 1,2-DCE can be utilized as a primary substrate to support microbial metabolism under aerobic conditions.Microorganisms indigenous to the bed sediments of a black-water stream utilized 1,2-dichloroethene (1,2-DCE) as a sole carbon substrate for aerobic metabolism. Although no evidence of growth was observed in the minimal salts culture media used in this study, efficient aerobic microbial mineralization of 1,2-DCE as sole carbon substrate was maintained through three sequential transfers (107 final dilution) of the original environmental innoculum. These results indicate that 1,2-DCE can be utilized as a primary substrate to support microbial metabolism under aerobic conditions.
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Fendt, Sarah-Maria; Sauer, Uwe
2010-02-18
Depending on the carbon source, Saccharomyces cerevisiae displays various degrees of respiration. These range from complete respiration as in the case of ethanol, to almost complete fermentation, and thus very low degrees of respiration on glucose. While many key regulators are known for these extreme cases, we focus here on regulators that are relevant at intermediate levels of respiration. We address this question by linking the functional degree of respiration to transcriptional regulation via enzyme abundances. Specifically, we investigated aerobic batch cultures with the differently repressive carbon sources glucose, mannose, galactose and pyruvate. Based on 13C flux analysis, we found that the respiratory contribution to cellular energy production was largely absent on glucose and mannose, intermediate on galactose and highest on pyruvate. In vivo abundances of 40 respiratory enzymes were quantified by GFP-fusions under each condition. During growth on the partly and fully respired substrates galactose and pyruvate, several TCA cycle and respiratory chain enzymes were significantly up-regulated. From these enzyme levels and the known regulatory network structure, we determined the probability for a given transcription factor to cause the coordinated expression changes. The most probable transcription factors to regulate the different degrees of respiration were Gcr1p, Cat8p, the Rtg-proteins and the Hap-complex. For the latter three ones we confirmed their importance for respiration by quantifying the degree of respiration and biomass yields in the corresponding deletion strains. Cat8p is required for wild-type like respiration, independent of its known activation of gluconeogenic genes. The Rtg-proteins and the Hap-complex are essential for wild-type like respiration under partially respiratory conditions. Under fully respiratory conditions, the Hap-complex, but not the Rtg-proteins are essential for respiration.
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Process for producing metal compounds from graphite oxide
NASA Technical Reports Server (NTRS)
Hung, Ching-Cheh (Inventor)
2000-01-01
A process for providing elemental metals or metal oxides distributed on a carbon substrate or self-supported utilizing graphite oxide as a precursor. The graphite oxide is exposed to one or more metal chlorides to form an intermediary product comprising carbon, metal, chloride, and oxygen This intermediary product can be flier processed by direct exposure to carbonate solutions to form a second intermediary product comprising carbon, metal carbonate, and oxygen. Either intermediary product may be further processed: a) in air to produce metal oxide; b) in an inert environment to produce metal oxide on carbon substrate; c) in a reducing environment to produce elemental metal distributed on carbon substrate. The product generally takes the shape of the carbon precursor.
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Process for Producing Metal Compounds from Graphite Oxide
NASA Technical Reports Server (NTRS)
Hung, Ching-Cheh (Inventor)
2000-01-01
A process for providing elemental metals or metal oxides distributed on a carbon substrate or self-supported utilizing graphite oxide as a precursor. The graphite oxide is exposed to one or more metal chlorides to form an intermediary product comprising carbon. metal. chloride. and oxygen This intermediary product can be flier processed by direct exposure to carbonate solutions to form a second intermediary product comprising carbon. metal carbonate. and oxygen. Either intermediary product may be further processed: a) in air to produce metal oxide: b) in an inert environment to produce metal oxide on carbon substrate: c) in a reducing environment. to produce elemental metal distributed on carbon substrate. The product generally takes the shape of the carbon precursor.
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Breault, Richard D.; Goller, Glen J.
1983-01-01
A ribbed substrate for an electrochemical cell electrode is made from a mixture of carbon fibers and carbonizable resin and has a mean pore size in the ribs which is 60-75% of the mean pore size of the web portions of the substrate which interconnect the ribs. Preferably the mean pore size of the web portion is 25-45 microns; and, if the substrate includes edge seals parallel to the ribs, the edge seals preferably have a mean pore size no greater than about ten microns. Most preferably the substrate has the same ratio of carbon fibers to polymeric carbon in all areas, including the ribs, webs, and edge seals. A substrate according to the present invention will have better overall performance than prior art substrates and minimizes the substrate thickness required for the substrate to perform all its functions well.
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Direct /TEM/ observation of the catalytic oxidation of amorphous carbon by Pd particles
NASA Technical Reports Server (NTRS)
Moorhead, R. D.; Poppa, H.; Heinemann, K.
1980-01-01
The catalytic oxidation of amorphous carbon substrates by Pd particles is observed by in situ transmission electron microscopy. Various modes of selective attack of the carbon substrate in the immediate neighborhood of Pd particles are observed, which can be correlated with different degrees of particle mobility. Using amorphous substrates we have been able to demonstrate that the particle-substrate interaction is influenced by the structure of the particle. This has not previously been noted.
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Photovoltaic device using single wall carbon nanotubes and method of fabricating the same
Biris, Alexandru S.; Li, Zhongrui
2012-11-06
A photovoltaic device and methods for forming the same. In one embodiment, the photovoltaic device has a silicon substrate, and a film comprising a plurality of single wall carbon nanotubes disposed on the silicon substrate, wherein the plurality of single wall carbon nanotubes forms a plurality of heterojunctions with the silicon in the substrate.
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Arceo, Elena; Jurberg, Igor D; Alvarez-Fernández, Ana; Melchiorre, Paolo
2013-09-01
Asymmetric catalytic variants of sunlight-driven photochemical processes hold extraordinary potential for the sustainable preparation of chiral molecules. However, the involvement of short-lived electronically excited states inherent to any photochemical reaction makes it challenging for a chiral catalyst to dictate the stereochemistry of the products. Here, we report that readily available chiral organic catalysts, with well-known utility in thermal asymmetric processes, can also confer a high level of stereocontrol in synthetically relevant intermolecular carbon-carbon bond-forming reactions driven by visible light. A unique mechanism of catalysis is proposed, wherein the catalyst is involved actively in both the photochemical activation of the substrates (by inducing the transient formation of chiral electron donor-acceptor complexes) and the stereoselectivity-defining event. We use this approach to enable transformations that are extremely difficult under thermal conditions, such as the asymmetric α-alkylation of aldehydes with alkyl halides, the formation of all-carbon quaternary stereocentres and the control of remote stereochemistry.
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Han, Qianji; Wang, Hongrui; Liu, Yali; Yan, Yajing; Wu, Mingxing
2017-11-15
A monodisperse carbon sphere with high uniformity, high catalytic activity and conductivity are successfully synthesized. Versatile counter electrodes using this carbon sphere catalyst on different substrates of fluorine-doped tin oxide (FTO) glass, indium-doped tin oxide polyethylenena phthalate (ITO-PEN), and Ti foil are fabricated for dye-sensitized solar cell (DSC). The impacts of substrates on the catalytic activities of the carbon sphere counter electrodes have been also evaluated by electrochemical analysis technologies, such as cyclic voltammetry, electrochemical impedance spectroscopy and Tafel polarization curves. With cobalt electrolyte, the DSC using carbon sphere counter electrodes based on FTO glass, ITO-PEN, and Ti substrates yield high power conversion efficiency values of 8.57%, 6.66%, and 9.10%, respectively. The catalytic activities of the prepared carbon sphere counter electrodes on different substrates are determined by the apparent activation energy for the cobalt redox couple regeneration on these electrodes. Copyright © 2017 Elsevier Inc. All rights reserved.
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Pretreatment process for forming a smooth surface diamond film on a carbon-coated substrate
Feng, Zhu; Brewer, Marilee; Brown, Ian; Komvopoulos, Kyriakos
1994-01-01
A process is disclosed for the pretreatment of a carbon-coated substrate to provide a uniform high density of nucleation sites thereon for the subsequent deposition of a continuous diamond film without the application of a bias voltage to the substrate. The process comprises exposing the carbon-coated substrate, in a microwave plasma enhanced chemical vapor deposition system, to a mixture of hydrogen-methane gases, having a methane gas concentration of at least about 4% (as measured by partial pressure), while maintaining the substrate at a pressure of about 10 to about 30 Torr during the pretreatment.
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Chemically Functionalized Carbon Nanotubes as Substrates for Neuronal Growth
Hu, Hui; Ni, Yingchun; Montana, Vedrana; Haddon, Robert C.; Parpura, Vladimir
2009-01-01
We report the use of chemically modified carbon nanotubes as a substrate for cultured neurons. The morphological features of neurons that directly reflect their potential capability in synaptic transmission are characterized. The chemical properties of carbon nanotubes are systematically varied by attaching different functional groups that confer known characteristics to the substrate. By manipulating the charge carried by functionalized carbon nanotubes we are able to control the outgrowth and branching pattern of neuronal processes. PMID:21394241
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Interstellar Communication Channel Based on a Biological Universal
NASA Technical Reports Server (NTRS)
Weber, Arthur L.; DeVincenzi, Donald L. (Technical Monitor)
1999-01-01
Cellular biosynthesis starts with sugar substrates and continues energetically downhill to yield amino acid, rapid, and nucleotide products. To understand the energetics of these processes, we calculated the energy for biosynthesis from sugars of E. cali's amino acids, nucleotides, and lipids. We found that the biosynthesis of amino acids and lipids from sugar substrates proceeds by redox disproportionation. of sugar carbon with a favorable energy of about -11 kcal/mole of carbon. Overall, redox disproportion of sugar carbon accounted for 84% and 96% (ATP only 6% and 1%) of the total biosynthetic energy of amino acids and lipids (the major cellular constituents). Next, we calculated for all 48 possible 3-carbon substrates the energy of maximal disproportionation to carbon dioxide and methane. We found no other carbon substrates than matched sugars in biosynthetic energy, efficiency, and simplicity. From this, we concluded that sugars are the optimal biosynthetic substrate. Since this conclusion is based on universal properties of carbon chemistry, other carbon-based life throughout the Universe would also use optimal sugar substrates. Furthermore, this rather obvious universal role of sugars as the optimal biosubstrate would probably be common knowledge of technological civilizations throughout the Universe. Since the elemental building block of all sugars is formaldehyde, the common knowledge that sugars are the universal optimal biosubstrate could reasonably lead to the selection of a line(s) in the microwave spectrum of formaldehyde as a frequency for interstellar communication.
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Pinus sylvestris switches respiration substrates under shading but not during drought
NASA Astrophysics Data System (ADS)
Hartmann, Henrik; Fischer, Sarah; Hanf, Stefan; Frosch, Torsten; Poppp, Jürgen; Trumbore, Susan
2015-04-01
Reduced carbon assimilation during prolonged drought forces trees to rely on stored carbon to maintain vital processes like respiration. It has been shown, however, that the use of carbohydrates, a major carbon storage pool and main respiratory substrate in plants, strongly declines with deceasing plant hydration. Yet, no empirical evidence has been produced to what degree other carbon storage compounds like lipids and proteins may fuel respiration during drought. We exposed young scots pine trees to carbon limitation using either drought or shading and assessed respiratory substrate use by monitoring the respiratory quotient, δ13C of respired CO2and concentrations of the major storage compounds, i.e. carbohydrates (COH), lipids and amino acids. Generally, respiration was dominated by the most abundant substrate. Only shaded trees shifted from carbohydrate-dominated to lipid-dominated respiration and showed progressive carbohydrate depletion. In drought trees respiration was strongly reduced and fueled with carbohydrates from also strongly reduced carbon assimilation. Initial COH content was maintained during drought probably due to reduced COH mobilization and use and the maintained COH content may have prevented lipid catabolism via sugar signaling. Our results suggest that respiratory substrates other than carbohydrates are used under carbohydrate limitation but not during drought. Thus, respiratory substrate change cannot provide an efficient means to counterbalance carbon limitation under natural drought.
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Ardèvol, Albert; Biarnés, Xevi; Planas, Antoni; Rovira, Carme
2010-11-17
The mechanism of glycosidic bond cleavage by glycosidases involves substrate ring distortions in the Michaelis complex that favor catalysis. Retaining β-mannosidases bind the substrate in a (1)S(5) conformation, and recent experiments have proposed an unusual substrate conformational pathway ((1)S(5) → B(2,5) → (O)S(2)) for the hydrolysis reaction. By means of Car-Parrinello metadynamics simulations, we have obtained the conformational free-energy surface (FES) of a β-d-mannopyranose molecule associated with the ideal Stoddart conformational diagram. We have found that (1)S(5) is among the most stable conformers and simultaneously is the most preactivated conformation in terms of elongation/shortening of the C1-O1/C1-O5 bonds, C1-O1 orientation, and charge development at the anomeric carbon. Analysis of the computed FES gives support to the proposed (1)S(5) → B(2,5) → (O)S(2) catalytic itinerary, showing that the degree of preactivation of the substrate in glycoside hydrolases (GHs) is related to the properties of an isolated sugar ring. We introduce a simple preactivation index integrating several structural, electronic, and energetic properties that can be used to predict the conformation of the substrate in the Michaelis complex of any GH.
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Insights from intercomparison of microbial and conventional soil models
NASA Astrophysics Data System (ADS)
Allison, S. D.; Li, J.; Luo, Y.; Mayes, M. A.; Wang, G.
2014-12-01
Changing the structure of soil biogeochemical models to represent coupling between microbial biomass and carbon substrate pools could improve predictions of carbon-climate feedbacks. So-called "microbial models" with this structure make very different predictions from conventional models based on first-order decay of carbon substrate pools. Still, the value of microbial models is uncertain because microbial physiological parameters are poorly constrained and model behaviors have not been fully explored. To address these issues, we developed an approach for inter-comparing microbial and conventional models. We initially focused on soil carbon responses to microbial carbon use efficiency (CUE) and temperature. Three scenarios were implemented in all models at a common reference temperature (20°C): constant CUE (held at 0.31), varied CUE (-0.016°C-1), and 50% acclimated CUE (-0.008°C-1). Whereas the conventional model always showed soil carbon losses with increasing temperature, the microbial models each predicted a temperature threshold above which warming led to soil carbon gain. The location of this threshold depended on CUE scenario, with higher temperature thresholds under the acclimated and constant scenarios. This result suggests that the temperature sensitivity of CUE and the structure of the soil carbon model together regulate the long-term soil carbon response to warming. Compared to the conventional model, all microbial models showed oscillatory behavior in response to perturbations and were much less sensitive to changing inputs. Oscillations were weakest in the most complex model with explicit enzyme pools, suggesting that multi-pool coupling might be a more realistic representation of the soil system. This study suggests that model structure and CUE parameterization should be carefully evaluated when scaling up microbial models to ecosystems and the globe.
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Identification and characterization of multiple rubisco activases in chemoautotrophic bacteria
Tsai, Yi-Chin Candace; Lapina, Maria Claribel; Bhushan, Shashi; Mueller-Cajar, Oliver
2015-01-01
Ribulose-1,5-bisphosphate carboxylase/oxygenase (rubisco) is responsible for almost all biological CO2 assimilation, but forms inhibited complexes with its substrate ribulose-1,5-bisphosphate (RuBP) and other sugar phosphates. The distantly related AAA+ proteins rubisco activase and CbbX remodel inhibited rubisco complexes to effect inhibitor release in plants and α-proteobacteria, respectively. Here we characterize a third class of rubisco activase in the chemolithoautotroph Acidithiobacillus ferrooxidans. Two sets of isoforms of CbbQ and CbbO form hetero-oligomers that function as specific activases for two structurally diverse rubisco forms. Mutational analysis supports a model wherein the AAA+ protein CbbQ functions as motor and CbbO is a substrate adaptor that binds rubisco via a von Willebrand factor A domain. Understanding the mechanisms employed by nature to overcome rubisco's shortcomings will increase our toolbox for engineering photosynthetic carbon dioxide fixation. PMID:26567524
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NASA Technical Reports Server (NTRS)
Vishniac, H. S.
1981-01-01
The multiple stresses temperature, moisture, and for chemoheterotrophs, sources of carbon and energy of the Dry Valley Antarctica soils allow at best depauperate communities, low in species diversity and population density. The nature of community structure, the operation of biogeochemical cycles, the evolution and mechanisms of adaptation to this habitat are of interest in informing speculations upon life on other planets as well as in modeling the limits of gene life. Yeasts of the Cryptococcus vishniacil complex (Basidiobiastomycetes) are investigated, as the only known indigenes of the most hostile, lichen free, parts of the Dry Valleys. Methods were developed for isolating these yeasts (methods which do not exclude the recovery of other microbiota). The definition of the complex was refined and the importance of nitrogen sources was established as well as substrate competition in fitness to the Dry Valley habitats.
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Light-Weight Low-Loss Dielectric Polymer Composites Containing Carbon Nanostructure
2014-10-17
increases in temperature. Subsequent thermal breakdown and carbonization of the polyurethane coating and polyimide substrate significantly reduced the RF...measurements through HD-GNR films. For the highly uniform films produced in separate experiments on a glass substrate with sufficient thermal conductivity ...further carbonized the polyurethane- coated polyimide substrate. This was attributed to the electromagnetic and the resulting thermal energy
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Garrett, David J; Flavel, Benjamin S; Baronian, Keith H R; Downard, Alison J
2013-01-01
A simple method for producing patterned forests of multiwalled carbon nanotubes (MWCNTs) is described. An aqueous metal salt solution is spin-coated onto a substrate patterned with photoresist by standard methods. The photoresist is removed by acetone washing leaving the acetone-insoluble catalyst pattern on the substrate. Dense forests of vertically aligned (VA) MWCNTs are grown on the patterned catalyst layers by chemical vapour deposition. The procedures have been demonstrated by growing MWCNT forests on two substrates: silicon and conducting graphitic carbon films. The forests adhere strongly to the substrates and when grown directly on carbon film, offer a simple method of preparing MWCNT electrodes.
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Mapping Microbial Carbon Substrate Utilization Across Permafrost Thaw
NASA Astrophysics Data System (ADS)
Anderson, D.; Rich, V. I.; Hodgkins, S. B.; Tfaily, M.; Chanton, J.
2014-12-01
Permafrost thaw is likely to create a substantial positive feedback to climate warming, as previously frozen carbon becomes bioavailable and is released to the atmosphere. Microbes mediate this release, while also consuming "new" carbon from plant inputs and middle-aged soil carbon pools in the seasonally-thawed active layer overlying permafrost. This carbon consumption releases carbon dioxide (CO2) and methane (CH4), both potent greenhouse gases. To investigate microbial carbon cycling in this changing habitat, we examined how microbial communities' carbon substrate degradation changes along a natural permafrost thaw gradient in Stordalen Mire (68.35°N, 19.05°E), northern Sweden. At this location, intermediate thaw creates Sphagnum moss-dominated bogs, while complete thaw results in Eriophorum sedge-dominated fens. The progression of thaw results in increasing organic matter lability (Hodgkins et al, 2014), shifting microbial community composition (Mondav & Woodcroft et al 2014), and changing carbon gas emissions (McCalley et al, in review). However, the inter-relationship of the first two in producing the third remains unclear. We analyzed microbial carbon substrate utilization in the intermediate-thaw and full-thaw sites by two incubation-based methods. We used Biolog EcoPlates, which contain 31 ecologically relevant carbon substrates and a colorimetric marker of their consumption, and into which we added a soil liquid suspension. In addition, we performed mason-jar incubations of peat with carbon substrate amendments and measured CH4 and CO2 emissions. Preliminary Biolog Ecoplate incubations showed that intermediate-thaw features responded faster and more strongly overall to a wide range of substrates relative to the full-thaw features. Preliminary mason jar incubations showed that acetate amendment elicited the greatest response increase in CH4 production and the second greatest increase in CO2 production relative to the controls, in samples from both habitats. In addition, the lowest CH4 and CO2 production was seen in amendments of sphagnum acid. It is important to understand the carbon substrate utilization occurring at these initial and advanced thaw features to speculate the degree to which various carbon inputs are being metabolized to produce the observed gas emissions.
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Allene formation by gold catalyzed cross-coupling of masked carbenes and vinylidenes
Lavallo, Vincent; Frey, Guido D.; Kousar, Shazia; Donnadieu, Bruno; Bertrand, Guy
2007-01-01
Addition of a sterically demanding cyclic (alkyl)(amino)carbene (CAAC) to AuCl(SMe2) followed by treatment with [Et3Si(Tol)]+[B(C6F5)4]− in toluene affords the isolable [(CAAC)Au(η2-toluene)]+[B(C6F5)4]− complex. This cationic Au(I) complex efficiently mediates the catalytic coupling of enamines and terminal alkynes to yield allenes and not propargyl amines as observed with other catalysts. Mono-, di-, and tri-substituted enamines can be used, as well as aryl-, alkyl-, and trimethylsilyl-substituted terminal alkynes. The reaction tolerates sterically hindered substrates and is diastereoselective. This general catalytic protocol directly couples two unsaturated carbon centers to form the three-carbon allenic core. The reaction most probably proceeds through an unprecedented “carbene/vinylidene cross-coupling.” PMID:17698808
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Carbon-carbon mirrors for exoatmospheric and space applications
NASA Astrophysics Data System (ADS)
Krumweide, Duane E.; Wonacott, Gary D.; Woida, Patrick M.; Woida, Rigel Q.; Shih, Wei
2007-09-01
The cost and leadtime associated with beryllium has forced the MDA and other defense agencies to look for alternative materials with similar structural and thermal properties. The use of carbon-carbon material, specifically in optical components has been demonstrated analytically in prior SBIR work at San Diego Composites. Carbon-carbon material was chosen for its low in-plane and through-thickness CTE (athermal design), high specific stiffness, near-zero coefficient of moisture expansion, availability of material (specifically c-c honeycomb for lightweight substrates), and compatibility with silicon monoxide (SiO) and silicon dioxide (SiO II) coatings. Subsequent development work has produced shaped carbon-carbon sandwich substrates which have been ground, polished, coated and figured using traditional optical processing. Further development has also been done on machined monolithic carbon-carbon mirror substrates which have also been processed using standard optical finishing techniques.
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NASA Astrophysics Data System (ADS)
Kilic, Ahmet; Palali, Ahmet Arif; Durgun, Mustafa; Tasci, Zeynep; Ulusoy, Mahmut
2013-09-01
A series of the mononuclear Cu(II) metal complexes containing the ligand Bdppz [(9a,13a-dihydro-4,5,9,14-tetraaza-benzo[b]triphenylene-11-yl)-phenyl-methanone] (L1) and Aqphen [(12,17-dihydronaphthol[2,3-h]dipyrido[3,2-a:2‧,3‧-c]-phenazine-12,17-dione)] (L2) were synthesized and used as catalyst for the coupling of carbon dioxide (CO2) and liquid epoxide which served as both reactant and solvent. Dimethylamino pyridine (DMAP) was used as co-catalyst. The yields of epoxides to corresponding cyclic carbonates were determined by comparing the ratio of product to substrate in the 1H NMR spectrum of an aliquot of the reaction mixture. The mononuclear Cu(II) complexes of these ligands were synthesized by treating an ethanol solvent of the appropriate ligand with a different molar amount of CuCl2·2H2O. The Cu(II) complexes were characterized by FT-IR, UV-Vis, elemental analysis, melting point analysis, mass spectra, molar conductivity measurements and magnetic susceptibility techniques. The reaction of the Bdppz and Aqphen ligands in a 1:1, 1:2 or 1:3 mole ratio with CuCl2·2H2O afforded ionic Cu(II) complexes in the presence of Et3N.
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Li, Huei-Jiun; Li, Xiaokai; Liu, Nina; Zhang, Huaning; Truglio, James J.; Mishra, Shambhavi; Kisker, Caroline; Garcia-Diaz, Miguel; Tonge, Peter J.
2014-01-01
MenB, the 1,4-dihydroxy-2-naphthoyl-CoA synthase from the bacterial menaquinone biosynthesis pathway, catalyzes an intramolecular Claisen condensation (Dieckmann reaction) in which the electrophile is an unactivated carboxylic acid. Mechanistic studies on this crotonase family member have been hindered by partial active site disorder in existing MenB X-ray structures. In the current work the 2.0 Å structure of O-succinylbenzoyl-aminoCoA (OSB-NCoA) bound to the MenB from Escherichia coli provides important insight into the catalytic mechanism by revealing the position of all active site residues. This has been accomplished by the use of a stable analogue of the O-succinylbenzoyl-CoA (OSB-CoA) substrate in which the CoA thiol has been replaced by an amine. The resulting OSB-NCoA is stable and the X-ray structure of this molecule bound to MenB reveals the structure of the enzyme-substrate complex poised for carbon-carbon bond formation. The structural data support a mechanism in which two conserved active site Tyr residues, Y97 and Y258, participate directly in the intramolecular transfer of the substrate α-proton to the benzylic carboxylate of the substrate, leading to protonation of the electrophile and formation of the required carbanion. Y97 and Y258 are also ideally positioned to function as the second oxyanion hole required for stabilization of the tetrahedral intermediate formed during carbon-carbon bond formation. In contrast, D163, which is structurally homologous to the acid-base catalyst E144 in crotonase, is not directly involved in carbanion formation and may instead play a structural role by stabilizing the loop that carries Y97. When similar studies were performed on the MenB from Mycobacterium tuberculosis, a twisted hexamer was unexpectedly observed, demonstrating the flexibility of the interfacial loops that are involved in the generation of the novel tertiary and quaternary structures found in the crotonase superfamily. This work reinforces the utility of using a stable substrate analogue as a mechanistic probe in which only one atom has been altered leading to a decrease in α-proton acidity. PMID:21830810
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Li, Huei-Jiun; Li, Xiaokai; Liu, Nina; Zhang, Huaning; Truglio, James J; Mishra, Shambhavi; Kisker, Caroline; Garcia-Diaz, Miguel; Tonge, Peter J
2011-11-08
MenB, the 1,4-dihydroxy-2-naphthoyl-CoA synthase from the bacterial menaquinone biosynthesis pathway, catalyzes an intramolecular Claisen condensation (Dieckmann reaction) in which the electrophile is an unactivated carboxylic acid. Mechanistic studies on this crotonase family member have been hindered by partial active site disorder in existing MenB X-ray structures. In the current work the 2.0 Å structure of O-succinylbenzoyl-aminoCoA (OSB-NCoA) bound to the MenB from Escherichia coli provides important insight into the catalytic mechanism by revealing the position of all active site residues. This has been accomplished by the use of a stable analogue of the O-succinylbenzoyl-CoA (OSB-CoA) substrate in which the CoA thiol has been replaced by an amine. The resulting OSB-NCoA is stable, and the X-ray structure of this molecule bound to MenB reveals the structure of the enzyme-substrate complex poised for carbon-carbon bond formation. The structural data support a mechanism in which two conserved active site Tyr residues, Y97 and Y258, participate directly in the intramolecular transfer of the substrate α-proton to the benzylic carboxylate of the substrate, leading to protonation of the electrophile and formation of the required carbanion. Y97 and Y258 are also ideally positioned to function as the second oxyanion hole required for stabilization of the tetrahedral intermediate formed during carbon-carbon bond formation. In contrast, D163, which is structurally homologous to the acid-base catalyst E144 in crotonase (enoyl-CoA hydratase), is not directly involved in carbanion formation and may instead play a structural role by stabilizing the loop that carries Y97. When similar studies were performed on the MenB from Mycobacterium tuberculosis, a twisted hexamer was unexpectedly observed, demonstrating the flexibility of the interfacial loops that are involved in the generation of the novel tertiary and quaternary structures found in the crotonase superfamily. This work reinforces the utility of using a stable substrate analogue as a mechanistic probe in which only one atom has been altered leading to a decrease in α-proton acidity.
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Human Cytochrome P450 21A2, the Major Steroid 21-Hydroxylase
Pallan, Pradeep S.; Wang, Chunxue; Lei, Li; Yoshimoto, Francis K.; Auchus, Richard J.; Waterman, Michael R.; Guengerich, F. Peter; Egli, Martin
2015-01-01
Cytochrome P450 (P450) 21A2 is the major steroid 21-hydroxylase, and deficiency of this enzyme is involved in ∼95% of cases of human congenital adrenal hyperplasia, a disorder of adrenal steroidogenesis. A structure of the bovine enzyme that we published previously (Zhao, B., Lei, L., Kagawa, N., Sundaramoorthy, M., Banerjee, S., Nagy, L. D., Guengerich, F. P., and Waterman, M. R. (2012) Three-dimensional structure of steroid 21-hydroxylase (cytochrome P450 21A2) with two substrates reveals locations of disease-associated variants. J. Biol. Chem. 287, 10613–10622), containing two molecules of the substrate 17α-hydroxyprogesterone, has been used as a template for understanding genetic deficiencies. We have now obtained a crystal structure of human P450 21A2 in complex with progesterone, a substrate in adrenal 21-hydroxylation. Substrate binding and release were fast for human P450 21A2 with both substrates, and pre-steady-state kinetics showed a partial burst but only with progesterone as substrate and not 17α-hydroxyprogesterone. High intermolecular non-competitive kinetic deuterium isotope effects on both kcat and kcat/Km, from 5 to 11, were observed with both substrates, indicative of rate-limiting C–H bond cleavage and suggesting that the juxtaposition of the C21 carbon in the active site is critical for efficient oxidation. The estimated rate of binding of the substrate progesterone (kon 2.4 × 107 m−1 s−1) is only ∼2-fold greater than the catalytic efficiency (kcat/Km = 1.3 × 107 m−1 s−1) with this substrate, suggesting that the rate of substrate binding may also be partially rate-limiting. The structure of the human P450 21A2-substrate complex provides direct insight into mechanistic effects of genetic variants. PMID:25855791
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Vriamont, Charles; Devillers, Michel; Riant, Olivier; Hermans, Sophie
2013-09-02
A new pyrene-tagged gold(I) complex has been synthesised and tested as a homogeneous catalyst. First, a simple 1,6-enyne was chosen as a model substrate for cyclisation by using different solvents to optimise the reaction conditions. The non-covalent immobilisation of our pyrene-tagged gold complex onto multi-walled carbon nanotubes through π-π stacking interactions was then explored to obtain a supported homogeneous catalyst. The heterogenised catalyst and its homogeneous counterpart exhibited similar activity in a range of enyne cyclisation reactions. Bearing in mind that π-π interactions are affected by temperature and solvent polarity, the reuse and robustness of the supported homogeneous catalyst was tested to explore the scope and limitations of the recyclability of this catalyst. Under the optimised conditions, recyclability was observed by using the concept of the boomerang effect. Copyright © 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.
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Pretreatment process for forming a smooth surface diamond film on a carbon-coated substrate
Feng, Z.; Brewer, M.; Brown, I.; Komvopoulos, K.
1994-05-03
A process is disclosed for the pretreatment of a carbon-coated substrate to provide a uniform high density of nucleation sites thereon for the subsequent deposition of a continuous diamond film without the application of a bias voltage to the substrate. The process comprises exposing the carbon-coated substrate, in a microwave plasma enhanced chemical vapor deposition system, to a mixture of hydrogen-methane gases, having a methane gas concentration of at least about 4% (as measured by partial pressure), while maintaining the substrate at a pressure of about 10 to about 30 Torr during the pretreatment. 6 figures.
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Starch and starch hydrolysates are favorable carbon sources for bifidobacteria in the human gut.
Liu, Songling; Ren, Fazheng; Zhao, Liang; Jiang, Lu; Hao, Yanling; Jin, Junhua; Zhang, Ming; Guo, Huiyuan; Lei, Xingen; Sun, Erna; Liu, Hongna
2015-03-01
Bifidobacteria are key commensals in human gut, and their abundance is associated with the health of their hosts. Although they are dominant in infant gut, their number becomes lower in adult gut. The changes of the diet are considered to be main reason for this difference. Large amounts of whole-genomic sequence data of bifidobacteria make it possible to elucidate the genetic interpretation of their adaptation to the nutrient environment. Among the nutrients in human gut, starch is a highly fermentable substrate and can exert beneficial effects by increasing bifidobacteria and/or being fermented to short chain fatty acids. In order to determine the potential substrate preference of bifidobacteria, we compared the glycoside hydrolase (GH) profiles of a pooled-bifidobacterial genome (PBG) with a representative microbiome (RM) of the human gut. In bifidobacterial genomes, only 15% of GHs contained signal peptides, suggesting their weakness in utilization of complex carbohydrate, such as plant cell wall polysaccharides. However, compared with other intestinal bacteria, bifidobacteiral genomes encoded more GH genes for degrading starch and starch hydrolysates, indicating that they have genetic advantages in utilizing these substrates. Bifidobacterium longum subsp. longum BBMN68 isolated from centenarian's faeces was used as a model strain to further investigate the carbohydrate utilization. The pathway for degrading starch and starch hydrolysates was the only complete pathway for complex carbohydrates in human gut. It is noteworthy that all of the GH genes for degrading starch and starch hydrolysates in the BBMN68 genome were conserved in all studied bifidobacterial strains. The in silico analyses of BBMN68 were further confirmed by growth experiments, proteomic and real-time quantitative PCR (RT-PCR) analyses. Our results demonstrated that starch and starch hydrolysates were the most universal and favorable carbon sources for bifidobacteria. The low amount of these carbon sources in adult intestine was speculated to contribute to the low relative abundance of bifidobacteria.
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Rochelet, Murielle; Solanas, Sébastien; Betelli, Laetitia; Chantemesse, Benoît; Vienney, Fabienne; Hartmann, Alain
2015-09-10
An assay on the indirect amperometric quantification of the β-D-Glucuronidase (GLUase) activity was developed for the rapid and specific detection of Escherichia coli (E. coli) in complex environmental samples. The p-aminophenyl β-D-glucopyranoside (PAPG) was selected as an electrochemical substrate for GLUase measurement and the p-aminophenol (PAP) released during the enzymatic hydrolysis was monitored by cyclic voltammetry with disposable carbon screen-printed sensors. The intensity of the measured anodic peak current was proportional to the amount of GLUase, and therefore to the number of E. coli in the tested sample. Once the substrate concentration and pH values optimized, a GLUase detection limit of 10 ng mL(-1) was achieved. Using a procedure involving a filtration step of the bacteria followed by their incubation with the substrate solution containing both the nonionic detergent Triton X-100 as permeabilization agent and the culture media Luria broth to monitor the growth, filtered bacterial cells ranging from 5 × 10(4) to 10(8) UFC/membrane were detected within 3 h. The amperometric assay was applied to the determination of fecal contamination in raw and treated wastewater samples and it was successfully compared with conventional bacterial plating methods and uidA gene quantitative PCR. Owing to its ability to perform measurements in turbid media, the GLUase amperometric method is a reliable tool for the rapid and decentralized quantification of viable but also nonculturable E. coli in complex environmental samples. Copyright © 2015 Elsevier B.V. All rights reserved.
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Silvering substrates after CO2 snow cleaning
NASA Astrophysics Data System (ADS)
Zito, Richard R.
2005-09-01
There have been some questions in the astronomical community concerning the quality of silver coatings deposited on substrates that have been cleaned with carbon dioxide snow. These questions center around the possible existence of carbonate ions left behind on the substrate by CO2. Such carbonate ions could react with deposited silver to produce insoluble silver carbonate, thereby reducing film adhesion and reflectivity. Carbonate ions could be produced from CO2 via the following mechanism. First, during CO2 snow cleaning, a small amount of moisture can condense on a surface. This is especially true if the jet of CO2 is allowed to dwell on one spot. CO2 gas can dissolve in this moisture, producing carbonic acid, which can undergo two acid dissociations to form carbonate ions. In reality, it is highly unlikely that charged carbonate ions will remain stable on a substrate for very long. As condensed water evaporates, Le Chatelier's principle will shift the equilibrium of the chain of reactions that produced carbonate back to CO2 gas. Furthermore, the hydration of CO2 reaction of CO2 with H20) is an extremely slow process, and the total dehydrogenation of carbonic acid is not favored. Living tissues that must carry out the equilibration of carbonic acid and CO2 use the enzyme carbonic anhydrase to speed up the reaction by a factor of one million. But no such enzymatic action is present on a clean mirror substrate. In short, the worst case analysis presented below shows that the ratio of silver atoms to carbonate radicals must be at least 500 million to one. The results of chemical tests presented here support this view. Furthermore, film lift-off tests, also presented in this report, show that silver film adhesion to fused silica substrates is actually enhanced by CO2 snow cleaning.
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Direct nitration and azidation of aliphatic carbons by an iron-dependent halogenase
Chang, Wei-chen; Layne, Andrew P; Miles, Linde A; Krebs, Carsten
2014-01-01
Iron-dependent halogenases employ cis-halo-Fe(IV)-oxo (haloferryl) complexes to functionalize unactivated aliphatic carbon centers, a capability elusive to synthetic chemists. Halogenation requires (1) coordination of a halide anion (Cl− or Br−) to the enzyme's Fe(II) cofactor; (2) coupled activation of O2 and decarboxylation of α-ketoglutarate to generate the haloferryl intermediate; (3) abstraction of hydrogen (H•) from the substrate by the ferryl oxo group; and (4) transfer of the cis halogen as Cl• or Br• to the substrate radical. This enzymatic solution to an unsolved chemical challenge is potentially generalizable to installation of other functional groups, provided that the corresponding anions can support the four requisite steps. We show here that the wild-type halogenase SyrB2 can indeed direct aliphatic nitration and azidation reactions by the same chemical logic. The discovery and enhancement by mutagenesis of these previously unknown reaction types suggests unrecognized or untapped versatility in ferryl-mediated enzymatic C–H-bond activation. PMID:24463698
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Liebetrau, Jan; Sträuber, Heike; Kretzschmar, Jörg; Denysenko, Velina; Nelles, Michael
2017-04-09
The term anaerobic digestion usually refers to the microbial conversion of organic material to biogas, which mainly consists of methane and carbon dioxide. The technical application of the naturally-occurring process is used to provide a renewable energy carrier and - as the substrate is often waste material - to reduce the organic matter content of the substrate prior to disposal.Applications can be found in sewage sludge treatment, the treatment of industrial and municipal solid wastes and wastewaters (including landfill gas utilization), and the conversion of agricultural residues and energy crops.For biorefinery concepts, the anaerobic digestion (AD) process is, on the one hand, an option to treat organic residues from other production processes. Concomitant effects are the reduction of organic carbon within the treated substance, the conversion of nitrogen and sulfur components, and the production of an energy-rich gas - the biogas. On the other hand, the multistep conversion of complex organic material offers the possibility of interrupting the conversion chain and locking out intermediates for utilization as basic material within the chemical industry.
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Rentz, Jeremy A; Alvarez, Pedro J J; Schnoor, Jerald L
2004-06-01
The phenanthrene-degrading activity (PDA) of Pseudomonas putida ATCC 17484 was repressed after incubation with plant root extracts of oat (Avena sativa), osage orange (Maclura pomifera), hybrid willow (Salix alba x matsudana), kou (Cordia subcordata) and milo (Thespesia populnea) and plant root exudates of oat (Avena sativa) and hybrid poplar (Populus deltoides x nigra DN34). Total organic carbon content of root extracts ranged from 103 to 395 mg l(-1). Characterization of root extracts identified acetate (not detectable to 8.0 mg l(-1)), amino acids (1.7-17.3 mg l(-1)) and glucose (1.6-14.0 mg l(-1)), indicating a complex mixture of substrates. Repression was also observed after exposure to potential root-derived substrates, including organic acids, glucose (carbohydrate) and glutamate (amino acid). Carbon source regulation (e.g. catabolite repression) was apparently responsible for the observed repression of P. putida PDA by root extracts. However, we showed that P. putida grows on root extracts and exudates as sole carbon and energy sources. Enhanced growth on root products may compensate for partial repression, because larger microbial populations are conducive to faster degradation rates. This would explain the commonly reported increase in phenanthrene removal in the rhizosphere.
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Zeng, Ruijie; Sheng, Hongting; Zhang, Yongcang; Feng, Yan; Chen, Zhi; Wang, Junfeng; Chen, Man; Zhu, Manzhou; Guo, Qingxiang
2014-10-03
A practical lanthanide(III)-catalyzed transesterification of carboxylic esters, weakly reactive carbonates, and much less-reactive ethyl silicate with primary and secondary alcohols was developed. Heterobimetallic dinuclear lanthanide alkoxide complexes [Ln2Na8{(OCH2CH2NMe2)}12(OH)2] (Ln = Nd (I), Sm (II), and Yb (III)) were used as highly active catalysts for this reaction. The mild reaction conditions enabled the transesterification of various substrates to proceed in good to high yield. Efficient activation of transesterification may be endowed by the above complexes as cooperative acid-base difunctional catalysts, which is proposed to be responsible for the higher reactivity in comparison with simple acid/base catalysts.
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NASA Astrophysics Data System (ADS)
Reynolds, L. L.; Lajtha, K.; Bowden, R.; Johnson, B. R.; Bridgham, S. D.
2013-12-01
The decomposition of soil organic matter is expected to increase with global warming and has been commonly described by kinetic models with at least two pools with differing turnover times. Pools characterized by rapid turnover are thought to consist of labile substrates. Meanwhile, slower turnover is attributed, in part, to greater chemical complexity and a necessarily higher activation energy which should in turn lead to a higher sensitivity (Q10) to temperature and a proportionally larger response to warming. Experimental tests of the relative Q10 of these pools have been inconclusive and contradictory in part due the fact that all pools are decomposing simultaneously and soils kept under differing conditions over long periods of time diverge in more than the Q10 response making them less comparable over time. We present here a test of the temperature response on soils from a 20 yr litter manipulation experiment incubated under an experimental regime that minimizes divergence among the soils. We hypothesize that 1) if exclusion of inputs has depleted labile substrates and 2) the remaining carbon is more chemically complex, then the input exclusion treatments should show a higher Q10 compared to the ambient or increased input treatments. The soils are taken from the Detritus Input and Removal Treatment (DIRT) plots in the Bousson Forest, Pennsylvania, US. The DIRT treatments consist of litter and root exclusion (no inputs = NI), no roots (NR), no litter (NL), double litter (DL), and ambient conditions (C). Soils were incubated at 25oC for 525 days. Periodically, replicate sets were rotated into 15oC, 35oC or remained at 25oC for 24 hr. The headspace CO2 concentration was measured before and after the 24 hr temperature treatments, and then all replicate sets were returned to 25oC. Twenty years of input exclusion decreased respiration rate, with NI < NR = NL < C = DL, and total carbon content, and thus, we conclude, labile substrates. The respiration rate at 25oC was the same for all replicate sets throughout, indicating no divergence due to the temperature rotations. Contrary to our hypothesis, our data indicates that Q10 was similar among the DIRT treatments, despite the clear differences in their carbon pools. Similar studies have examined the temperature response due to depletion labile substrate through laboratory incubation, rather beginning with presumably very different initial labile pools. Our results would suggest that soils with differing soil carbon content and presumably differing carbon quality have the same relative temperature responses. Recent studies have questioned the putative importance of chemical recalcitrance in soils, which would explain our results relative to the predictions of enzymatic kinetic theory.
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Density functional theory studies of oxygen and carbonate binding to a dicopper patellamide complex.
Latifi, Reza; Bagherzadeh, Mojtaba; Milne, Bruce F; Jaspars, Marcel; de Visser, Sam P
2008-12-01
In this work we present results of density functional theory (DFT) calculations on dicopper patellamides and their affinity for molecular oxygen and carbonate. Patellamides are cyclic octapeptides that are produced by a cyanobacterium, and may show promise as therapeutics. Thus, carbonate binding to a dicopper patellamide center gives a stable cyclic octapeptide with a twist of almost 90 degrees . The system exists in close-lying open-shell singlet and triplet spin states with two unpaired electrons in orthogonal sigma* orbitals on each metal center. Subsequently, we replaced carbonate with dioxygen and found a stable Cu2(mu-O)2 diamond shaped patellamide core. In this structure the original dioxygen bond is significantly weakened to essentially a single bond, which should enable the system to transfer these oxygen atoms to substrates. We predicted the IR and Raman spectra of the Cu2(mu-O)2 diamond shaped patellamide structure using density functional theory and found a considerable isotope effect on the O-O stretch vibration for 16O2 versus 18O2 bound structures. Our studies reveal that carbonate forms an extremely stable complex with dicopper patellamide, but that additional molecular oxygen to this system does not give a potential oxidant. Therefore, it is more likely that carbonate prepares the system for dioxygen binding by folding it into the correct configuration followed in the proposed catalytic cycle by a protonation event preceding dioxygen binding to enable the system to reorganize to form a stable Cu2(mu-O)2-patellamide cluster. Alternatively, carbonate may act as an inhibitor that blocks the catalytic activity of the system. It is anticipated that the Cu2(mu-O)2-patellamide structure is a potential active oxidant of the dicopper patellamide complex.
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NASA Astrophysics Data System (ADS)
Kolo, K.; Claeys, Ph.
2005-04-01
This study investigates the in vitro formation of Ca-oxalates and glushinskite through fungal interaction with carbonate substrates and seawater. In the first experiment, thin-sections prepared from dolomitic rock samples of Terwagne Formation (Carboniferous, Viséan, northern France) served as substrates. The thin sections placed in Petri dishes were exposed to fungi grown from naturally existing airborne spores. In the second experiment, fungal growth and mineral formation was monitored using only standard seawater (SSW) as substrate. Fungal growth media consisted of a high protein/carbohydrates and sugar diet with demineralised water for irrigation. Fungal growth process reached completion under uncontrolled laboratory conditions. The fungal interaction and attack on the carbonate substrates resulted in the formation of Ca-oxalates (weddellite CaC2O4·2(H2O), whewellite (CaC2O4·(H2O)) and glushinskite MgC2O4·2(H2O) associated with the destruction of the original substrate and its replacement by the new minerals. The seawater substrate resulted also in the formation of glushinskite and Ca-oxalates. Both of Ca and Mg were mobilized from the experimental substrates by fungi. The newly formed minerals and textural changes caused by fungal attack on the carbonate substrate were investigated using light and scanning electron microscopy (SEM-EDX), x-ray diffraction (XRD) and Raman spectroscopy. The results document the role of microorganisms in biomineralization, neo-mineral formation and sediment diagenesis. They also reveal the capacity of living fungi to interact with liquid substrates and precipitate new minerals. This work is the first report on the in vitro formation of the mineral glushinskite through fungal-carbonate and sea water substrates interactions processes.
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Sugars as the Optimal Biosynthetic Carbon Substrate of Aqueous Life throughout the Universe
NASA Technical Reports Server (NTRS)
Weber, Arthur L.
1999-01-01
Our previous analysis of the energetics of metabolism showed that both the biosynthesis of amino acids and lipids from sugars, and the fermentation of organic substrates, were energetically driven by electron transfer reactions resulting in carbon redox disproportionation (Weber 1997). Redox disproportionation -- the spontaneous (energetically favorable) direction of carbon group transformation in biosynthesis -- is brought about and driven by the energetically downhill transfer of electron pairs from more oxidized carbon groups (with lower half-cell reduction potentials) to more reduced carbon groups (with higher half-cell reduction potentials). In this report, we compare the redox and kinetic properties of carbon groups in order to evaluate the relative biosynthetic capability of organic substrates, and to identify the optimal biosubstrate. This analysis revealed that sugars (monocarbonyl alditols) are the optimal biosynthetic substrate because they contain the maximum number of biosynthetically useful .high energy electrons/carbon atom , while still containing a single carbonyl group needed to kinetically facilitate their conversion to useful biosynthetic intermediates. This conclusion applies to aqueous life throughout the Universe because it is based on invariant aqueous carbon chemistry -- primarily, the universal reduction potentials of carbon groups.
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Sugars as the optimal biosynthetic carbon substrate of aqueous life throughout the universe
NASA Technical Reports Server (NTRS)
Weber, A. L.
2000-01-01
Our previous analysis of the energetics of metabolism showed that both the biosynthesis of amino acids and lipids from sugars, and the fermentation of organic substrates, were energetically driven by electron transfer reactions resulting in carbon redox disproportionation (Weber, 1997). Redox disproportionation--the spontaneous (energetically favorable) direction of carbon group transformation in biosynthesis--is brought about and driven by the energetically downhill transfer of electron pairs from more oxidized carbon groups (with lower half-cell reduction potentials) to more reduced carbon groups (with higher half-cell reduction potentials). In this report, we compare the redox and kinetic properties of carbon groups in order to evaluate the relative biosynthetic capability of organic substrates, and to identify the optimal biosubstrate. This analysis revealed that sugars (monocarbonyl alditols) are the optimal biosynthetic substrate because they contain the maximum number of biosynthetically useful high energy electrons/carbon atom while still containing a single carbonyl group needed to kinetically facilitate their conversion to useful biosynthetic intermediates. This conclusion applies to aqueous life throughout the Universe because it is based on invariant aqueous carbon chemistry--primarily, the universal reduction potentials of carbon groups.
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He, Yu; Gorden, John D; Goldsmith, Christian R
2011-12-19
Iron complexes with the tetradentate N-donor ligand N,N'-di(phenylmethyl)-N,N'-bis(2-pyridinylmethyl)-1,2-cyclohexanediamine (bbpc) are reported. Despite the benzyl groups present on the amines, the iron compounds catalyze the oxygenation of cyclohexane to an extent similar to those employing less sterically encumbered ligands. The catalytic activity is strongly dependent on the counterion, with the highest activity and the strongest preference for alkane hydroxylation correlating to the most weakly coordinating anion, SbF(6)(-). The selectivity for the alcohol product over the ketone is amplified when acetic acid is present as an additive. When hydrocarbon substrates with both secondary and tertiary carbons are oxidized by H(2)O(2), the catalyst directs oxidation toward the secondary carbons to a greater degree than other previously reported iron-containing homogeneous catalysts. © 2011 American Chemical Society
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Seasonal variation in functional properties of microbial communities in beech forest soil
Koranda, Marianne; Kaiser, Christina; Fuchslueger, Lucia; Kitzler, Barbara; Sessitsch, Angela; Zechmeister-Boltenstern, Sophie; Richter, Andreas
2013-01-01
Substrate quality and the availability of nutrients are major factors controlling microbial decomposition processes in soils. Seasonal alteration in resource availability, which is driven by plants via belowground C allocation, nutrient uptake and litter fall, also exerts effects on soil microbial community composition. Here we investigate if seasonal and experimentally induced changes in microbial community composition lead to alterations in functional properties of microbial communities and thus microbial processes. Beech forest soils characterized by three distinct microbial communities (winter and summer community, and summer community from a tree girdling plot, in which belowground carbon allocation was interrupted) were incubated with different 13C-labeled substrates with or without inorganic N supply and analyzed for substrate use and various microbial processes. Our results clearly demonstrate that the three investigated microbial communities differed in their functional response to addition of various substrates. The winter communities revealed a higher capacity for degradation of complex C substrates (cellulose, plant cell walls) than the summer communities, indicated by enhanced cellulase activities and reduced mineralization of soil organic matter. In contrast, utilization of labile C sources (glucose) was lower in winter than in summer, demonstrating that summer and winter community were adapted to the availability of different substrates. The saprotrophic community established in girdled plots exhibited a significantly higher utilization of complex C substrates than the more plant root associated community in control plots if additional nitrogen was provided. In this study we were able to demonstrate experimentally that variation in resource availability as well as seasonality in temperate forest soils cause a seasonal variation in functional properties of soil microorganisms, which is due to shifts in community structure and physiological adaptations of microbial communities to altered resource supply. PMID:23645937
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CHEMISTRY OF OXIDATION OF POLYCYCLIC AROMATIC HYDROCARBONS BY SOIL PSEUDOMONADS
Rogoff, Martin H.
1962-01-01
Rogoff, Martin H. (U.S. Bureau of Mines, Pittsburgh, Pa.). Oxidation of polycyclic aromatic hydrocarbons by soil pseudomonads. J. Bacteriol. 83:998–1004. 1962.—Substitution of phenanthrene by a methyl group at the 9-carbon blocks oxidation of the compound by a resting-cell suspension of a phenanthrene-grown soil pseudomonad. When 2-methylphenanthrene is provided, the oxidation rate is considerably higher; 3-methylphenanthrene is oxidized at a rate intermediate between the other two, even though the methyl group is attached to a carbon directly involved in ring splitting. Cells grown on naphthalene or anthracene oxidize phenanthrene at a much lower rate than cells grown with phenanthrene or 2-methylnaphthalene as the source of carbon. Naphthalene-grown cells also absorb less phenanthrene from aqueous solution than do their phenanthrene-grown counterparts. The data are in keeping with the hypothesis that polynuclear aromatic hydrocarbons attach to the relevant bacterial enzymes at carbon-carbon bonds of high electron density (K regions; localized double bonds), and that the ring-splitting reactions then occur at other bonds on the substrate molecule. The actual bond that undergoes fission is determined by the electronic and steric configurations of the enzyme-substrate complex. When linearly arranged aromatic compounds such as naphthalene or anthracene are attacked, attachment to an enzyme and ring splitting may take place on the same ring; angular aromatic compounds such as phenanthrene afford attachment to an enzyme at a bond in a ring other than the one containing the ring-splitting site. PMID:14493381
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NASA Astrophysics Data System (ADS)
Ogée, J.; Barbour, M. M.; Dewar, R. C.; Wingate, L.; Bert, D.; Bosc, A.; Lambrot, C.; Stievenard, M.; Bariac, T.; Berbigier, P.; Loustau, D.
2007-12-01
High-resolution measurements of the carbon and oxygen stable isotope composition of cellulose in annual tree rings (δ13Ccellulose and δ18Ocellulose, respectively) reveal well-defined seasonal patterns that could contain valuable records of past climate and tree function. Interpreting these signals is nonetheless complex because they not only record the signature of current assimilates, but also depend on carbon allocation dynamics within the trees. Here, we will present a single-substrate model for wood growth in order to interpret qualitatively and quantitatively these seasonal isotopic signals. We will also show how this model can relate to more complex models of phloem transport and cambial activity. The model will then be tested against an isotopic intra-annual chronology collected on a Pinus pinaster tree equipped with point dendrometers and growing on a Carboeurope site where climate, soil and flux variables are also monitored. The empirical δ13Ccellulose and δ18Ocellulose signals exhibit dynamic seasonal patterns with clear differences between years, which makes it suitable for model testing. We will show how our simple model of carbohydrate reserves, forced by sap flow and eddy covariance measurements, enables us to interpret these seasonal and inter-annual patterns. Finally, we will present a sensitivity analysis of the model, showing how gas-exchange parameters, carbon and water pool sizes or wood maturation times affect these isotopic signals. Acknowledgements: this study benefited from the CarboEurope-IP Bray site facilities and was funded by the French INSU programme Eclipse, with an additional support from the INRA department EFPA.
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Burton, George L.; Diercks, David R.; Perkins, Craig L.; ...
2017-07-01
Recent studies have demonstrated that growth of CdTe on CdTe (100) and (211)B substrates via molecular beam epitaxy (MBE) results in planar defect densities 2 and 3 orders of magnitude higher than growth on InSb (100) substrates, respectively. To understand this shortcoming, MBE growth on CdTe substrates with a variety of substrate preparation methods is studied by scanning electron microscopy, secondary ion mass spectrometry, x-ray photoelectron spectroscopy, cross sectional transmission electron microscopy, and atom probe tomography (APT). Prior to growth, carbon is shown to remain on substrate surfaces even after atomic hydrogen cleaning. APT revealed that following the growth ofmore » films, trace amounts of carbon remained at the substrate/film interface. This residual carbon may lead to structural degradation, which was determined as the main cause of higher defect density.« less
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Vitreous carbon mask substrate for X-ray lithography
Aigeldinger, Georg [Livermore, CA; Skala, Dawn M [Fremont, CA; Griffiths, Stewart K [Livermore, CA; Talin, Albert Alec [Livermore, CA; Losey, Matthew W [Livermore, CA; Yang, Chu-Yeu Peter [Dublin, CA
2009-10-27
The present invention is directed to the use of vitreous carbon as a substrate material for providing masks for X-ray lithography. The new substrate also enables a small thickness of the mask absorber used to pattern the resist, and this enables improved mask accuracy. An alternative embodiment comprised the use of vitreous carbon as a LIGA substrate wherein the VC wafer blank is etched in a reactive ion plasma after which an X-ray resist is bonded. This surface treatment provides a surface enabling good adhesion of the X-ray photoresist and subsequent nucleation and adhesion of the electrodeposited metal for LIGA mold-making while the VC substrate practically eliminates secondary radiation effects that lead to delamination of the X-ray resist form the substrate, the loss of isolated resist features, and the formation of a resist layer adjacent to the substrate that is insoluble in the developer.
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Li, Yanbo; Wang, Xu; Butler, David; Liu, Junxin; Qu, Jiuhui
2017-03-21
Energy neutrality and reduction of carbon emissions are significant challenges to the enhanced sustainability of wastewater treatment plants (WWTPs). Harvesting energy from wastewater carbonaceous substrates can offset energy demands and enable net power generation; yet, there is limited research about how carbonaceous substrates influence energy and carbon implications of WWTPs with integrated energy recovery at systems-level. Consequently, this research uses biokinetics modelling and life cycle assessment philology to explore this notion, by tracing and assessing the quantitative flows of energy embodied or captured, and by exploring the carbon footprint throughout an energy-intensive activated sludge process with integrated energy recovery facilities. The results indicate that energy use and carbon footprint per cubic meter of wastewater treated, varies markedly with the carbon substrate. Compared with systems driven with proteins, carbohydrates or other short-chain fatty acids, systems fed with acetic acid realized energy neutrality with maximal net gain of power from methane combustion (0.198 kWh) and incineration of residual biosolids (0.153 kWh); and also achieved a negative carbon footprint (72.6 g CO 2 ). The findings from this work help us to better understand and develop new technical schemes for improving the energy efficiency of WWTPs by repurposing the stream of carbon substrates across systems.
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NASA Astrophysics Data System (ADS)
Hopkins, F. M.; Trumbore, S.
2011-12-01
The role of substrate availability on soil carbon turnover is a critical unknown in predicting future soil carbon stocks. Substrate composition and availability can be altered by land cover change, warming, and nitrogen deposition, which can in turn affect soil carbon stocks through the priming effect. In particular, little is understood about the interaction between warming and changing substrate concentration. We examined the interactions between global change factors and the priming effect using sucrose addition to incubations of soils from two forest Free Air CO2 Enrichment (FACE) sites (Duke and Aspen). In addition to the in situ global change manipulations conducted at these sites, the CO2 fertilization procedure over the decade-long experiment labeled soil carbon pools with fossil-derived carbon (depleted in 14C relative to the background isotope content of soil carbon), allowing us to determine the effect of priming on respiration of soil carbon substrates of different ages. Thus, we used the carbon-13 signature of sucrose-derived CO2 to account for losses of substrate C, and the carbon-14 signature to partition fluxes of soil-derived CO2 between pre-FACE (> 10 y) and FACE derived (< 10 y) carbon sources. At both sites, we observed a positive priming effect-an increase in the rate of soil carbon derived respiration due to sucrose addition. However, the effect of substrate addition on respiratory source pools, as measured by 14C of respiration, varied greatly. At Duke FACE, we observed an increase in 14C content of CO2 of primed soil carbon, whereas at Aspen, we observed no difference. The amount of CO2 released by priming increased with temperature, but was proportionally similar to the amount of increase in basal respiration rates (no differences in Q10). At Duke, both warming and priming served to increase the 14C of respiration, whereas only warming changed 14C of respiration at Aspen. Despite similar overall carbon stocks, differences in the source of the priming effect between the two sites may be due to inherent differences in the relative role of stabilization factors within the soil carbon stock.
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NASA Astrophysics Data System (ADS)
Koga, Yoshihiro; Kadono, Takeshi; Shigematsu, Satoshi; Hirose, Ryo; Onaka-Masada, Ayumi; Okuyama, Ryousuke; Okuda, Hidehiko; Kurita, Kazunari
2018-06-01
We propose a fabrication process for silicon wafers by combining carbon-cluster ion implantation and room-temperature bonding for advanced CMOS image sensors. These carbon-cluster ions are made of carbon and hydrogen, which can passivate process-induced defects. We demonstrated that this combination process can be used to form an epitaxial layer on a carbon-cluster ion-implanted Czochralski (CZ)-grown silicon substrate with a high dose of 1 × 1016 atoms/cm2. This implantation condition transforms the top-surface region of the CZ-grown silicon substrate into a thin amorphous layer. Thus, an epitaxial layer cannot be grown on this implanted CZ-grown silicon substrate. However, this combination process can be used to form an epitaxial layer on the amorphous layer of this implanted CZ-grown silicon substrate surface. This bonding wafer has strong gettering capability in both the wafer-bonding region and the carbon-cluster ion-implanted projection range. Furthermore, this wafer inhibits oxygen out-diffusion to the epitaxial layer from the CZ-grown silicon substrate after device fabrication. Therefore, we believe that this bonding wafer is effective in decreasing the dark current and white-spot defect density for advanced CMOS image sensors.
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NASA Astrophysics Data System (ADS)
Li, Shizhe; Zhang, Yan; Ferraris Araneta, Maria; Xiang, Yun; Johnson, Christopher; Innis, Robert B.; Shen, Jun
2012-05-01
This study demonstrates the feasibility of simultaneously detecting human brain metabolites labeled by two substrates infused in a sequential order. In vivo 13C spectra of carboxylic/amide carbons were acquired only during the infusion of the second substrate. This approach allowed dynamic detection of 13C labeling from two substrates with considerably different labeling patterns. [2-13C]glucose and [U-13C6]glucose were used to generate singlet and doublet signals of the same carboxylic/amide carbon atom, respectively. Because of the large one-bond 13C-13C homonuclear J coupling between a carboxylic/amide carbon and an aliphatic carbon (˜50 Hz), the singlet and doublet signals of the same carboxylic/amide carbon were well distinguished. The results demonstrated that different 13C isotopomer patterns could be simultaneously and distinctly measured in vivo in a clinical setting at 3 T.
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Jiao, Yunzhe; Morris, James; Brennessel, William W; Jones, William D
2013-10-30
Tp'Rh(PMe3)(CH3)H was synthesized as a precursor to produce the coordinatively unsaturated fragment [Tp'Rh(PMe3)], which reacts with benzene, mesitylene, 3,3-dimethyl-1-butene, 2-methoxy-2-methylpropane, 2-butyne, acetone, pentane, cyclopentane, trifluoroethane, fluoromethane, dimethyl ether, and difluoromethane at ambient temperature to give only one product in almost quantitative yield in each case. All of the complexes Tp'Rh(PMe3)(R)H were characterized by NMR spectroscopy, and their halogenated derivatives were fully characterized by NMR spectroscopy, elemental analysis, and X-ray crystallography. The active species [Tp'Rh(PMe3)] was also able to activate the alkynyl C-H bond of terminal alkynes to give activation products of the type Tp'Rh(PMe3)(C≡CR)H (R = t-Bu, SiMe3, hexyl, CF3, Ph, p-MeOC6H4, and p-CF3C6H4). The measured relative rhodium-carbon bond strengths display two linear correlations with the corresponding carbon-hydrogen bond strengths, giving a slope of 1.54 for α-unsubstituted hydrocarbons and a slope of 1.71 for substrates with α-substitution. Similar trends of energy correlations were established by DFT calculated metal-carbon bond strengths for the same groups of substrates.
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NASA Astrophysics Data System (ADS)
Sahatiya, Parikshit; Badhulika, Sushmee
2017-03-01
This paper reports a new type of electronic, recoverable skin-like pressure and strain sensor, produced on a flexible, biodegradable pencil-eraser substrate and fabricated using a solvent-free, low-cost and energy efficient process. Multi-walled carbon nanotube (MWCNT) film, the strain sensing element, was patterned on pencil eraser with a rolling pin and a pre-compaction mechanical press. This induces high interfacial bonding between the MWCNTs and the eraser substrate, which enables the sensor to achieve recoverability under ambient conditions. The eraser serves as a substrate for strain sensing, as well as acting as a dielectric for capacitive pressure sensing, thereby eliminating the dielectric deposition step, which is crucial in capacitive-based pressure sensors. The strain sensing transduction mechanism is attributed to the tunneling effect, caused by the elastic behavior of the MWCNTs and the strong mechanical interlock between MWCNTs and the eraser substrate, which restricts slippage of MWCNTs on the eraser thereby minimizing hysteresis. The gauge factor of the strain sensor was calculated to be 2.4, which is comparable to and even better than most of the strain and pressure sensors fabricated with more complex designs and architectures. The sensitivity of the capacitive pressure sensor was found to be 0.135 MPa-1.To demonstrate the applicability of the sensor as artificial electronic skin, the sensor was assembled on various parts of the human body and corresponding movements and touch sensation were monitored. The entire fabrication process is scalable and can be integrated into large areas to map spatial pressure distributions. This low-cost, easily scalable MWCNT pin-rolled eraser-based pressure and strain sensor has huge potential in applications such as artificial e-skin in flexible electronics and medical diagnostics, in particular in surgery as it provides high spatial resolution without a complex nanostructure architecture.
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Sahatiya, Parikshit; Badhulika, Sushmee
2017-03-03
This paper reports a new type of electronic, recoverable skin-like pressure and strain sensor, produced on a flexible, biodegradable pencil-eraser substrate and fabricated using a solvent-free, low-cost and energy efficient process. Multi-walled carbon nanotube (MWCNT) film, the strain sensing element, was patterned on pencil eraser with a rolling pin and a pre-compaction mechanical press. This induces high interfacial bonding between the MWCNTs and the eraser substrate, which enables the sensor to achieve recoverability under ambient conditions. The eraser serves as a substrate for strain sensing, as well as acting as a dielectric for capacitive pressure sensing, thereby eliminating the dielectric deposition step, which is crucial in capacitive-based pressure sensors. The strain sensing transduction mechanism is attributed to the tunneling effect, caused by the elastic behavior of the MWCNTs and the strong mechanical interlock between MWCNTs and the eraser substrate, which restricts slippage of MWCNTs on the eraser thereby minimizing hysteresis. The gauge factor of the strain sensor was calculated to be 2.4, which is comparable to and even better than most of the strain and pressure sensors fabricated with more complex designs and architectures. The sensitivity of the capacitive pressure sensor was found to be 0.135 MPa -1 .To demonstrate the applicability of the sensor as artificial electronic skin, the sensor was assembled on various parts of the human body and corresponding movements and touch sensation were monitored. The entire fabrication process is scalable and can be integrated into large areas to map spatial pressure distributions. This low-cost, easily scalable MWCNT pin-rolled eraser-based pressure and strain sensor has huge potential in applications such as artificial e-skin in flexible electronics and medical diagnostics, in particular in surgery as it provides high spatial resolution without a complex nanostructure architecture.
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Expression-based clustering of CAZyme-encoding genes of Aspergillus niger.
Gruben, Birgit S; Mäkelä, Miia R; Kowalczyk, Joanna E; Zhou, Miaomiao; Benoit-Gelber, Isabelle; De Vries, Ronald P
2017-11-23
The Aspergillus niger genome contains a large repertoire of genes encoding carbohydrate active enzymes (CAZymes) that are targeted to plant polysaccharide degradation enabling A. niger to grow on a wide range of plant biomass substrates. Which genes need to be activated in certain environmental conditions depends on the composition of the available substrate. Previous studies have demonstrated the involvement of a number of transcriptional regulators in plant biomass degradation and have identified sets of target genes for each regulator. In this study, a broad transcriptional analysis was performed of the A. niger genes encoding (putative) plant polysaccharide degrading enzymes. Microarray data focusing on the initial response of A. niger to the presence of plant biomass related carbon sources were analyzed of a wild-type strain N402 that was grown on a large range of carbon sources and of the regulatory mutant strains ΔxlnR, ΔaraR, ΔamyR, ΔrhaR and ΔgalX that were grown on their specific inducing compounds. The cluster analysis of the expression data revealed several groups of co-regulated genes, which goes beyond the traditionally described co-regulated gene sets. Additional putative target genes of the selected regulators were identified, based on their expression profile. Notably, in several cases the expression profile puts questions on the function assignment of uncharacterized genes that was based on homology searches, highlighting the need for more extensive biochemical studies into the substrate specificity of enzymes encoded by these non-characterized genes. The data also revealed sets of genes that were upregulated in the regulatory mutants, suggesting interaction between the regulatory systems and a therefore even more complex overall regulatory network than has been reported so far. Expression profiling on a large number of substrates provides better insight in the complex regulatory systems that drive the conversion of plant biomass by fungi. In addition, the data provides additional evidence in favor of and against the similarity-based functions assigned to uncharacterized genes.
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Carbon-tuned bonding method significantly enhanced the hydrogen storage of BN-Li complexes.
Deng, Qing-ming; Zhao, Lina; Luo, You-hua; Zhang, Meng; Zhao, Li-xia; Zhao, Yuliang
2011-11-01
Through first-principles calculations, we found doping carbon atoms onto BN monolayers (BNC) could significantly strengthen the Li bond on this material. Unlike the weak bond strength between Li atoms and the pristine BN layer, it is observed that Li atoms are strongly hybridized and donate their electrons to the doped substrate, which is responsible for the enhanced binding energy. Li adsorbed on the BNC layer can serve as a high-capacity hydrogen storage medium, without forming clusters, which can be recycled at room temperature. Eight polarized H(2) molecules are attached to two Li atoms with an optimal binding energy of 0.16-0.28 eV/H(2), which results from the electrostatic interaction of the polarized charge of hydrogen molecules with the electric field induced by positive Li atoms. This practical carbon-tuned BN-Li complex can work as a very high-capacity hydrogen storage medium with a gravimetric density of hydrogen of 12.2 wt%, which is much higher than the gravimetric goal of 5.5 wt % hydrogen set by the U.S. Department of Energy for 2015.
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Graphitic carbon grown on fluorides by molecular beam epitaxy.
Jerng, Sahng-Kyoon; Lee, Jae Hong; Kim, Yong Seung; Chun, Seung-Hyun
2013-01-03
We study the growth mechanism of carbon molecules supplied by molecular beam epitaxy on fluoride substrates (MgF2, CaF2, and BaF2). All the carbon layers form graphitic carbon with different crystallinities depending on the cation. Especially, the growth on MgF2 results in the formation of nanocrystalline graphite (NCG). Such dependence on the cation is a new observation and calls for further systematic studies with other series of substrates. At the same growth temperature, the NCG on MgF2 has larger clusters than those on oxides. This is contrary to the general expectation because the bond strength of the carbon-fluorine bond is larger than that of the carbon-oxygen bond. Our results show that the growth of graphitic carbon does not simply depend on the chemical bonding between the carbon and the anion in the substrate.
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Graphitic carbon grown on fluorides by molecular beam epitaxy
2013-01-01
We study the growth mechanism of carbon molecules supplied by molecular beam epitaxy on fluoride substrates (MgF2, CaF2, and BaF2). All the carbon layers form graphitic carbon with different crystallinities depending on the cation. Especially, the growth on MgF2 results in the formation of nanocrystalline graphite (NCG). Such dependence on the cation is a new observation and calls for further systematic studies with other series of substrates. At the same growth temperature, the NCG on MgF2 has larger clusters than those on oxides. This is contrary to the general expectation because the bond strength of the carbon-fluorine bond is larger than that of the carbon-oxygen bond. Our results show that the growth of graphitic carbon does not simply depend on the chemical bonding between the carbon and the anion in the substrate. PMID:23286607
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Warming accelerates decomposition of decades-old carbon in forest soils
Hopkins, F. M.; Torn, M. S.; Trumbore, S. E.
2012-06-11
Global climate carbon-cycle models predict acceleration of soil organic carbon losses to the atmosphere with warming, but the size of this feedback is poorly known. The temperature sensitivity of soil carbon decomposition is commonly determined by measuring changes in the rate of carbon dioxide (CO 2) production under controlled laboratory conditions. We added measurements of carbon isotopes in respired CO 2 to constrain the age of carbon substrates contributing to the temperature response of decomposition for surface soils from two temperate forest sites with very different overall rates of carbon cycling. Roughly one-third of the carbon respired at any temperaturemore » was fixed from the atmosphere more than 10 y ago, and the mean age of respired carbon reflected a mixture of substrates of varying ages. Consistent with global ecosystem model predictions, the temperature sensitivity of the carbon fixed more than a decade ago was the same as the temperature sensitivity for carbon fixed less than 10 y ago. However, we also observed an overall increase in the mean age of carbon respired at higher temperatures, even correcting for potential substrate limitation effects. The combination of several age constraints from carbon isotopes showed that warming had a similar effect on respiration of decades-old and younger (<10 y) carbon but a greater effect on decomposition of substrates of intermediate (between 7 and 13 y) age. Our results highlight the vulnerability of soil carbon to warming that is years-to-decades old, which makes up a large fraction of total soil carbon in forest soils globally.« less
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Warming accelerates decomposition of decades-old carbon in forest soils.
Hopkins, Francesca M; Torn, Margaret S; Trumbore, Susan E
2012-06-26
Global climate carbon-cycle models predict acceleration of soil organic carbon losses to the atmosphere with warming, but the size of this feedback is poorly known. The temperature sensitivity of soil carbon decomposition is commonly determined by measuring changes in the rate of carbon dioxide (CO(2)) production under controlled laboratory conditions. We added measurements of carbon isotopes in respired CO(2) to constrain the age of carbon substrates contributing to the temperature response of decomposition for surface soils from two temperate forest sites with very different overall rates of carbon cycling. Roughly one-third of the carbon respired at any temperature was fixed from the atmosphere more than 10 y ago, and the mean age of respired carbon reflected a mixture of substrates of varying ages. Consistent with global ecosystem model predictions, the temperature sensitivity of the carbon fixed more than a decade ago was the same as the temperature sensitivity for carbon fixed less than 10 y ago. However, we also observed an overall increase in the mean age of carbon respired at higher temperatures, even correcting for potential substrate limitation effects. The combination of several age constraints from carbon isotopes showed that warming had a similar effect on respiration of decades-old and younger (<10 y) carbon but a greater effect on decomposition of substrates of intermediate (between 7 and 13 y) age. Our results highlight the vulnerability of soil carbon to warming that is years-to-decades old, which makes up a large fraction of total soil carbon in forest soils globally.
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NASA Astrophysics Data System (ADS)
Jung, Sunshin; Chun, Su Jin; Han, Joong Tark; Woo, Jong Seok; Shon, Cha-Hwa; Lee, Geon-Woong
2016-02-01
A method of microwave sintering that is mediated by carbon nanotubes (CNTs) has been developed to obtain high-conductivity Ag patterns on the top of heat-sensitive plastic substrates within a short time. The Ag patterns are printed on CNTs formed on plastic substrates and rapidly heated to a great extent by the heat transferred from the microwave-heated CNTs. The conductivity of the microwave-sintered Ag patterns reaches ~39% that of bulk Ag within 1 s without substrate deformation. Furthermore, microwave sintering enhances the adhesion of Ag patterns to the thermoplastic substrates because the sintering causes interfacial fusion between the Ag patterns and the substrates, and CNTs physically connect the patterns with the substrates.A method of microwave sintering that is mediated by carbon nanotubes (CNTs) has been developed to obtain high-conductivity Ag patterns on the top of heat-sensitive plastic substrates within a short time. The Ag patterns are printed on CNTs formed on plastic substrates and rapidly heated to a great extent by the heat transferred from the microwave-heated CNTs. The conductivity of the microwave-sintered Ag patterns reaches ~39% that of bulk Ag within 1 s without substrate deformation. Furthermore, microwave sintering enhances the adhesion of Ag patterns to the thermoplastic substrates because the sintering causes interfacial fusion between the Ag patterns and the substrates, and CNTs physically connect the patterns with the substrates. Electronic supplementary information (ESI) available: Temperature difference in Ag/CNT/PC samples; the carbon content and electrical performance after microwave sintering; microwave sintering of Ag/CNT patterns; physical connection between the substrate and sintered Ag lines; touch-piano (figure and movie). See DOI: 10.1039/c5nr08082g
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Dynamics of Marine Microbial Metabolism and Physiology at Station ALOHA
NASA Astrophysics Data System (ADS)
Casey, John R.
Marine microbial communities influence global biogeochemical cycles by coupling the transduction of free energy to the transformation of Earth's essential bio-elements: H, C, N, O, P, and S. The web of interactions between these processes is extraordinarily complex, though fundamental physical and thermodynamic principles should describe its dynamics. In this collection of 5 studies, aspects of the complexity of marine microbial metabolism and physiology were investigated as they interact with biogeochemical cycles and direct the flow of energy within the Station ALOHA surface layer microbial community. In Chapter 1, and at the broadest level of complexity discussed, a method to relate cell size to metabolic activity was developed to evaluate allometric power laws at fine scales within picoplankton populations. Although size was predictive of metabolic rates, within-population power laws deviated from the broader size spectrum, suggesting metabolic diversity as a key determinant of microbial activity. In Chapter 2, a set of guidelines was proposed by which organic substrates are selected and utilized by the heterotrophic community based on their nitrogen content, carbon content, and energy content. A hierarchical experimental design suggested that the heterotrophic microbial community prefers high nitrogen content but low energy density substrates, while carbon content was not important. In Chapter 3, a closer look at the light-dependent dynamics of growth on a single organic substrate, glycolate, suggested that growth yields were improved by photoheterotrophy. The remaining chapters were based on the development of a genome-scale metabolic network reconstruction of the cyanobacterium Prochlorococcus to probe its metabolic capabilities and quantify metabolic fluxes. Findings described in Chapter 4 pointed to evolution of the Prochlorococcus metabolic network to optimize growth at low phosphate concentrations. Finally, in Chapter 5 and at the finest scale of complexity, a method was developed to predict hourly changes in both physiology and metabolic fluxes in Prochlorococcus by incorporating gene expression time-series data within the metabolic network model. Growth rates predicted by this method more closely matched experimental data, and diel changes in elemental composition and the energy content of biomass were predicted. Collectively, these studies identify and quantify the potential impact of variations in metabolic and physiological traits on the melee of microbial community interactions.
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Patra, Ayan; Bera, Manindranath
2014-01-30
In methanol, the reaction of stoichiometric amounts of Mn(OAc)(2)·4H(2)O and the ligand H(3)hpnbpda [H(3)hpnbpda=N,N'-bis(2-pyridylmethyl)-2-hydroxy-1,3-propanediamine-N,N'-diacetic acid] in the presence of NaOH, afforded a new water soluble dinuclear manganese(II) complex, [Mn2(hpnbpda)(μ-OAc)] (1). Similarly, the reaction of Mg(OAc)(2)·4H(2)O and the ligand H3hpnbpda in the presence of NaOH, in methanol, yielded a new water soluble dinuclear magnesium(II) complex, [Mg2(hpnbpda)(μ-OAc)(H2O)2] (2). DFT calculations have been performed for the structural optimization of complexes 1 and 2. The DFT optimized structure of complex 1 shows that two manganese(II) centers are in a distorted square pyramidal geometry, whereas the DFT optimized structure of complex 2 reveals that two magnesium(II) centers adopt a six-coordinate distorted octahedral geometry. To understand the mode of substrate binding and the mechanistic details of the active site metals in xylose/glucose isomerases (XGI), we have investigated the binding interactions of biologically important monosaccharides d-glucose and d-xylose with complexes 1 and 2, in aqueous alkaline solution by a combined approach of FTIR, UV-vis, fluorescence, and (13)C NMR spectroscopic techniques. Fluorescence spectra show the binding-induced gradual decrease in emission of complexes 1 and 2 accompanied by a significant blue shift upon increasing the concentration of sugar substrates. The binding modes of d-glucose and d-xylose with complex 2 are indicated by their characteristic coordination induced shift (CIS) values in (13)C NMR spectra for C1 and C2 carbon atoms. Copyright © 2013 Elsevier Ltd. All rights reserved.
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Morphology and topography study of graphene synthesized from plant oil
NASA Astrophysics Data System (ADS)
Robaiah, M.; Rusop, M.; Abdullah, S.; Khusaimi, Z.; Azhan, H.; Laila, M. O.; Salifairus, M. J.; Asli, N. A.
2018-05-01
The graphene is material consists of bonded atom carbon atoms in sheet form one atom thick. The different types of carbon sources which are refined corn oil, palm oil and waste cooking palm oil were used as carbon feedstock to supply carbon atom for synthesizing graphene on the nickel substrate by thermal chemical vapour deposition. The substrate and carbon sources were placed in double zone furnaces. The carbon sources and the substrate were heated at 300 °C and 900 °C respectively. The both furnaces were switched off after synthesis time for cooling process finish. The formation of the graphene on the Ni surface appears due to segregation and precipitation of a high amount of carbon from the source material during the cooling process. FESEM, AFM, UV-VIS Spectroscopy and Raman Spectroscopy were used to characterize and synthesized graphene.
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Mehra, S; Morrison, P D; Coates, F; Lawrie, A C
2017-02-01
Terrestrial orchids depend on orchid mycorrhizal fungi (OMF) as symbionts for their survival, growth and nutrition. The ability of OMF from endangered orchid species to compete for available resources with OMF from common species may affect the distribution, abundance and therefore conservation status of their orchid hosts. Eight symbiotically effective OMF from endangered and more common Caladenia species were tested for their ability to utilise complex insoluble and simple soluble carbon sources produced during litter degradation by growth with different carbon sources in liquid medium to measure the degree of OMF variation with host conservation status or taxonomy. On simple carbon sources, fungal growth was assessed by biomass. On insoluble substrates, ergosterol content was assessed using ultra-performance liquid chromatography (UPLC). The OMF grew on all natural materials and complex carbon sources, but produced the greatest biomass on xylan and starch and the least on bark and chitin. On simple carbon sources, the greatest OMF biomass was measured on most hexoses and disaccharides and the least on galactose and arabinose. Only some OMF used sucrose, the most common sugar in green plants, with possible implications for symbiosis. OMF from common orchids produced more ergosterol and biomass than those from endangered orchids in the Dilatata and Reticulata groups but not in the Patersonii and Finger orchids. This suggests that differences in carbon source utilisation may contribute to differences in the distribution of some orchids, if these differences are retained on site.
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Foster, Christopher W.; Pillay, Jeseelan; Metters, Jonathan P.; Banks, Craig E.
2014-01-01
Cobalt phthalocyanine (CoPC) compounds have been reported to provide electrocatalytic performances towards a substantial number of analytes. In these configurations, electrodes are typically constructed via drop casting the CoPC onto a supporting electrode substrate, while in other cases the CoPC complex is incorporated within the ink of a screen-printed sensor, providing a one-shot economical and disposable electrode configuration. In this paper we critically compare CoPC modified electrodes prepared by drop casting CoPC nanoparticles (nano-CoPC) onto a range of carbon based electrode substrates with that of CoPC bulk modified screen-printed electrodes in the sensing of the model analytes l-ascorbic acid, oxygen and hydrazine. It is found that no “electrocatalysis” is observed towards l-ascorbic acid using either of these CoPC modified electrode configurations and that the bare underlying carbon electrode is the origin of the obtained voltammetric signal, which gives rise to useful electroanalytical signatures, providing new insights into literature reports where “electrocatalysis” has been reported with no clear control experiments undertaken. On the other hand true electrocatalysis is observed towards hydrazine, where no such voltammetric features are witnessed on the bare underlying electrode substrate. PMID:25414969
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Jing, Qing; Okrasa, Krzysztof; Kazlauskas, Romas J
2009-01-01
One useful synthetic reaction missing from nature's toolbox is the direct hydrogenation of substrates using hydrogen. Instead nature uses cofactors like NADH to reduce organic substrates, which adds complexity and cost to these reductions. To create an enzyme that can directly reduce organic substrates with hydrogen, researchers have combined metal hydrogenation catalysts with proteins. One approach is an indirect link where a ligand is linked to a protein and the metal binds to the ligand. Another approach is direct linking of the metal to protein, but nonspecific binding of the metal limits this approach. Herein, we report a direct hydrogenation of olefins catalyzed by rhodium(I) bound to carbonic anhydrase (CA-[Rh]). We minimized nonspecific binding of rhodium by replacing histidine residues on the protein surface using site-directed mutagenesis or by chemically modifying the histidine residues. Hydrogenation catalyzed by CA-[Rh] is slightly slower than for uncomplexed rhodium(I), but the protein environment induces stereoselectivity favoring cis- over trans-stilbene by about 20:1. This enzyme is the first cofactor-independent reductase that reduces organic molecules using hydrogen. This catalyst is a good starting point to create variants with tailored reactivity and selectivity. This strategy to insert transition metals in the active site of metalloenzymes opens opportunities to a wider range of enzyme-catalyzed reactions.
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NASA Technical Reports Server (NTRS)
Debolt, H. E.; Krukonis, V. J.
1973-01-01
Silicon carbide (SiC) ribbon filaments were produced on a carbon ribbon substrate, about 1500 microns (60 mils) wide and 100 microns (4 mils) thick in lengths up to 2 meters (6 ft), and with tensile strengths up to 142 KN/cm sq (206 Ksi). During the course of the study, ribbon filaments of boron were also produced on the carbon ribbon substrate; the boron ribbon produced was extremely fragile. The tensile strength of the SiC ribbon was limited by large growths or flaws caused by anomalies at the substrate surface; these anomalies were either foreign dirt or substrate imperfections or both. Related work carried out on round 100 micron (4 mils) diameter SiC filaments on a 33 micron (1.3 mil) diameter, very smooth carbon monofilament substrate has shown that tensile strengths as high as 551 KN/cm sq (800 Ksi) are obtainable with the SiC-carbon round substrate combination, and indicates that if the ribbon substrate surface and ribbon deposition process can be improved similar strengths can be realizable. Cost analysis shows that 100 micron x 5-10 micron SiC ribbon can be very low cost reinforcement material.
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Steinbacher, Stefan; Schiffmann, Susanne; Richter, Gerald; Huber, Robert; Bacher, Adelbert; Fischer, Markus
2003-10-24
Skeletal rearrangements of carbohydrates are crucial for many biosynthetic pathways. In riboflavin biosynthesis ribulose 5-phosphate is converted into 3,4-dihydroxy-2-butanone 4-phosphate while its C4 atom is released as formate in a sequence of metal-dependent reactions. Here, we present the crystal structure of Methanococcus jannaschii 3,4-dihydroxy-2-butanone 4-phosphate synthase in complex with the substrate ribulose 5-phosphate at a dimetal center presumably consisting of non-catalytic zinc and calcium ions at 1.7-A resolution. The carbonyl group (O2) and two out of three free hydroxyl groups (OH3 and OH4) of the substrate are metal-coordinated. We correlate previous mutational studies on this enzyme with the present structural results. Residues of the first coordination sphere involved in metal binding are indispensable for catalytic activity. Only Glu-185 of the second coordination sphere cannot be replaced without complete loss of activity. It contacts the C3 hydrogen atom directly and probably initiates enediol formation in concert with both metal ions to start the reaction sequence. Mechanistic similarities to Rubisco acting on the similar substrate ribulose 1,5-diphosphate in carbon dioxide fixation as well as other carbohydrate (reducto-) isomerases are discussed.
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NASA Astrophysics Data System (ADS)
Afre, Rakesh A.; Soga, T.; Jimbo, T.; Kumar, Mukul; Ando, Y.; Sharon, M.
2005-10-01
Vertically aligned carbon nanotubes (VACNTs) were grown by spray pyrolysis of turpentine oil and ferrocene mixture at 700 °C. Using this simple method, we report the successful growth of vertically aligned nanotubes of 300 μm length and diameter in the range of 50-100 nm on Si(1 0 0) substrate. The ferrocene act as an in situ Fe catalyst precursor and forming the nanosize iron particles for formation of VACNTs on Si and quartz substrates. Morphological differences between aligned carbon nanotubes grown on different substrates are studied and discussed by SEM, TEM and Raman spectroscopy characterizations.
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Reusable crucible for containing corrosive liquids
de Pruneda, Jean A. H.
1995-01-01
A reusable, non-wetting, corrosion-resistant material suitable for containment of corrosive liquids is formed of a tantalum or tantalum alloy substrate that is permeated with carbon atoms. The substrate is carburized to form surface layers of TaC and Ta.sub.2 C, and then is heated at high temperature under vacuum until the carbon atoms in the carbide layers diffuse throughout the substrate to form a solid solution of carbon atoms randomly interspersed in the tantalum or tantalum alloy lattice.
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Reusable crucible for containing corrosive liquids
Pruneda, J.A.H. de.
1995-01-24
A reusable, non-wetting, corrosion-resistant material suitable for containment of corrosive liquids is formed of a tantalum or tantalum alloy substrate that is permeated with carbon atoms. The substrate is carburized to form surface layers of TaC and Ta[sub 2]C, and then is heated at high temperature under vacuum until the carbon atoms in the carbide layers diffuse throughout the substrate to form a solid solution of carbon atoms randomly interspersed in the tantalum or tantalum alloy lattice. 10 figures.
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Ovez, B; Mergaert, J; Saglam, M
2006-04-01
Chemical and microbiological aspects were investigated with regard to biological denitrification of drinking water using the seaweed Gracilaria verrucosa as the carbon and energy substrate and as physical support for the microbial flora in semibatch, fixed-bed reactors. Complete removal of nitrate (100 mg/L) was readily achieved without accumulation of nitrite. Microbiological analysis indicated that the effluent of the reactor contained high numbers of bacteria (>10(6)/mL total count). Among the 44 bacterial strains isolated directly from the samples or isolated after enrichment at 37 degrees C, 25 different fatty acid profiles were found, indicating a complex microflora, including potential pathogens.
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NASA Technical Reports Server (NTRS)
Harder, Theodore (Inventor); Konishi, Satoshi (Inventor); Miserendino, Scott (Inventor); Tai, Yu-Chong (Inventor); Liger, Matthieu (Inventor)
2010-01-01
A method of making carbon thin films comprises depositing a catalyst on a substrate, depositing a hydrocarbon in contact with the catalyst and pyrolyzing the hydrocarbon. A method of controlling a carbon thin film density comprises etching a cavity into a substrate, depositing a hydrocarbon into the cavity, and pyrolyzing the hydrocarbon while in the cavity to form a carbon thin film. Controlling a carbon thin film density is achieved by changing the volume of the cavity. Methods of making carbon containing patterned structures are also provided. Carbon thin films and carbon containing patterned structures can be used in NEMS, MEMS, liquid chromatography, and sensor devices.
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Reversible interactions with para-hydrogen enhance NMR sensitivity by polarization transfer.
Adams, Ralph W; Aguilar, Juan A; Atkinson, Kevin D; Cowley, Michael J; Elliott, Paul I P; Duckett, Simon B; Green, Gary G R; Khazal, Iman G; López-Serrano, Joaquín; Williamson, David C
2009-03-27
The sensitivity of both nuclear magnetic resonance spectroscopy and magnetic resonance imaging is very low because the detected signal strength depends on the small population difference between spin states even in high magnetic fields. Hyperpolarization methods can be used to increase this difference and thereby enhance signal strength. This has been achieved previously by incorporating the molecular spin singlet para-hydrogen into hydrogenation reaction products. We show here that a metal complex can facilitate the reversible interaction of para-hydrogen with a suitable organic substrate such that up to an 800-fold increase in proton, carbon, and nitrogen signal strengths are seen for the substrate without its hydrogenation. These polarized signals can be selectively detected when combined with methods that suppress background signals.
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Behenna, Douglas C.; Mohr, Justin T.; Sherden, Nathaniel H.; Marinescu, Smaranda C.; Harned, Andrew M.; Tani, Kousuke; Seto, Masaki; Ma, Sandy; Novák, Zoltán; Krout, Michael R.; McFadden, Ryan M.; Roizen, Jennifer L.; Enquist, John A.; White, David E.; Levine, Samantha R.; Petrova, Krastina V.; Iwashita, Akihiko; Virgil, Scott C.; Stoltz, Brian M.
2012-01-01
α-Quaternary ketones are accessed through novel enantioselective alkylations of allyl and propargyl electrophiles by unstabilized prochiral enolate nucleophiles in the presence of palladium complexes with various phosphinooxazoline (PHOX) ligands. Excellent yields and high enantiomeric excesses are obtained from three classes of enolate precursors: enol carbonates, enol silanes, and racemic β-ketoesters. Each of these substrate classes functions with nearly identical efficiency in terms of yield and enantioselectivity. Catalyst discovery and development, the optimization of reaction conditions, the exploration of reaction scope, and applications in target-directed synthesis are reported. Experimental observations suggest that these alkylation reactions occur through an unusual inner-sphere mechanism involving binding of the prochiral enolate nucleophile directly to the palladium center. PMID:22083969
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Yokoyama, Kenichi; Lilla, Edward A
2018-04-10
Covering: up to the end of 2017C-C bond formations are frequently the key steps in cofactor and natural product biosynthesis. Historically, C-C bond formations were thought to proceed by two electron mechanisms, represented by Claisen condensation in fatty acids and polyketide biosynthesis. These types of mechanisms require activated substrates to create a nucleophile and an electrophile. More recently, increasing number of C-C bond formations catalyzed by radical SAM enzymes are being identified. These free radical mediated reactions can proceed between almost any sp3 and sp2 carbon centers, allowing introduction of C-C bonds at unconventional positions in metabolites. Therefore, free radical mediated C-C bond formations are frequently found in the construction of structurally unique and complex metabolites. This review discusses our current understanding of the functions and mechanisms of C-C bond forming radical SAM enzymes and highlights their important roles in the biosynthesis of structurally complex, naturally occurring organic molecules. Mechanistic consideration of C-C bond formation by radical SAM enzymes identifies the significance of three key mechanistic factors: radical initiation, acceptor substrate activation and radical quenching. Understanding the functions and mechanisms of these characteristic enzymes will be important not only in promoting our understanding of radical SAM enzymes, but also for understanding natural product and cofactor biosynthesis.
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NASA Astrophysics Data System (ADS)
de Oliveira, Luiz Carlos Alves; da Silva, Adilson Cândido; Machado, Alan Rodrigues Teixeira; Diniz, Renata; Pereira, Márcio César
2013-05-01
We have produced carbon nanofibers (CNFs) using leather waste that had been tanned with a chromium bath, and when dried contained Cr2O3. Suitable reduction processing produced a carbon substrate with supported nanoparticles of chromium metal. Powder X-ray diffraction showed that the Cr2O3 is reduced on the carbon surface to produce CrC and metal Cr, which is the effective catalyst for the CNFs growth. The CNF arrays were confirmed by TEM images. Raman data revealed that the synthesized CNFs have a poor-quality graphite structure which favors their use in adsorption processes. These CNFs presented higher affinity to adsorb anionic dyes, whereas the cationic dyes are better adsorbed on the carbon substrate. The low-cost and availability of the carbon precursor makes their potential use to produce CNFs of interest.
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Epitaxial Relationships between Calcium Carbonate and Inorganic Substrates
Yang, Taewook; Jho, Jae Young; Kim, Il Won
2014-01-01
The polymorph-selective crystallization of calcium carbonate has been studied in terms of epitaxial relationship between the inorganic substrates and the aragonite/calcite polymorphs with implication in bioinspired mineralization. EpiCalc software was employed to assess the previously published experimental results on two different groups of inorganic substrates: aragonitic carbonate crystals (SrCO3, PbCO3, and BaCO3) and a hexagonal crystal family (α-Al2O3, α-SiO2, and LiNbO3). The maximum size of the overlayer (aragonite or calcite) was calculated for each substrate based on a threshold value of the dimensionless potential to estimate the relative nucleation preference of the polymorphs of calcium carbonate. The results were in good agreement with previous experimental observations, although stereochemical effects between the overlayer and substrate should be separately considered when existed. In assessing the polymorph-selective nucleation, the current method appeared to provide a better tool than the oversimplified mismatch parameters without invoking time-consuming molecular simulation\\. PMID:25226539
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Is hexagonal boron nitride always good as a substrate for carbon nanotube-based devices?
Kang, Seoung-Hun; Kim, Gunn; Kwon, Young-Kyun
2015-02-21
Hexagonal boron nitride sheets have been noted especially for their enhanced properties as substrates for sp(2) carbon-based nanodevices. To evaluate whether such enhanced properties would be retained under various realistic conditions, we investigate the structural and electronic properties of semiconducting carbon nanotubes on perfect and defective hexagonal boron nitride sheets under an external electric field as well as with a metal impurity, using density functional theory. We verify that the use of a perfect hexagonal boron nitride sheet as a substrate indeed improves the device performances of carbon nanotubes, compared with the use of conventional substrates such as SiO2. We further show that even the hexagonal boron nitride with some defects can show better performance as a substrate. Our calculations, on the other hand, also suggest that some defective boron nitride layers with a monovacancy and a nickel impurity could bring about poor device behavior since the imperfections impair electrical conductivity due to residual scattering under an applied electric field.
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Preparation of arrays of long carbon nanotubes using catalyst structure
Zhu, Yuntian T.; Arendt, Paul; Li, Qingwen; Zhang, Xiefie
2016-03-22
A structure for preparing an substantially aligned array of carbon nanotubes include a substrate having a first side and a second side, a buffer layer on the first side of the substrate, a catalyst on the buffer layer, and a plurality of channels through the structure for allowing a gaseous carbon source to enter the substrate at the second side and flow through the structure to the catalyst. After preparing the array, a fiber of carbon nanotubes may be spun from the array. Prior to spinning, the array can be immersed in a polymer solution. After spinning, the polymer can be cured.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Scott, R.W.; Fernandez-Mendiola, P.A.; Gili, E.
During the Early Cretaceous, coral-algal communities occupied deeper water habitats in the reef ecosystem, and rudist communities generally populated the shallow-water, carbonate-sand substrates. During the middle Cretaceous, however, coral-algal communities became less common, and Late Cretaceous reef communities consisted of both rudist-dominated and rudist-coral communities. In the Pyrenean basins and other basins in the Mediterranean, coral associations co-existed with rudists forming complex buildups at the shelf-edge. In some parts of these buildups corals were nearly as abundant as rudists; in some complex buildups large coral colonies encrusted the rudists. Behind the shelf margin cylindrical, elevator rudists dominated the lenticular thicketsmore » that were interspersed with carbonate sands. Global changes in oceanic conditions, such as marine productivity and oxygen content, may have stressed the deeper coral-algal reef communities leaving rudists as the major shallow reef biota in Caribbean reefs. However, the co-occurrence of corals with rudists in these Pyrenean complex buildups suggests that corals were able to compete with rudists for resources. The corals in the complex buildups generally belong to genera different from those in the coral-algal communities. Perhaps this ecological stress in the mid-Cretaceous resulted in the evolution of new coral taxa.« less
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Isotope effect studies of the pyruvate-dependent histidine decarboxylase from Lactobacillus 30a
DOE Office of Scientific and Technical Information (OSTI.GOV)
Abell, L.M.; O'Leary, M.H.
1988-08-09
The decarboxylation of histidine by the pyruvate-dependent histidine decarboxylase of Lactobacillus 30 a shows a carbon isotope effect k/sup 12//k/sup 13/ = 1.0334 +/- 0.0005 and a nitrogen isotope effect k/sup 14//k/sup 15/ = 0.9799 +/- 0.0006 at pH 4.8, 37/sup 0/C. The carbon isotope effect is slightly increased by deuteriation of the substrate and slightly decreased in D/sub 2/O. The observed nitrogen isotope effect indicates that the imine nitrogen in the substrate-Schiff base intermediate complex is ordinarily protonated, and the pH dependence of the carbon isotope effect indicates that both protonated and unprotonated forms of this intermediate are capablemore » of undergoing decarboxylation. As with the pyridoxal 5'-phosphate dependent enzyme, Schiff base formation and decarboxylation are jointly rate-limiting, with the intermediate histidine-pyruvate Schiff base showing a decarboxylation/Schiff base hydrolysis ratio of 0.5-1.0 at pH 4.8. The decarboxylation transition state is more reactant-like for the pyruvate-dependent enzyme than for the pyridoxal 5'-phosphate dependent enzyme. These studies find no particular energetic or catalytic advantage to the use of pyridoxal 5'-phosphate over covalently bound pyruvate in catalysis of the decarboxylation of histidine.« less
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Increased Alignment in Carbon Nanotube Growth
NASA Technical Reports Server (NTRS)
Delzeit, Lance D. (Inventor)
2007-01-01
Method and system for fabricating an array of two or more carbon nanotube (CNT) structures on a coated substrate surface, the structures having substantially the same orientation with respect to a substrate surface. A single electrode, having an associated voltage source with a selected voltage, is connected to a substrate surface after the substrate is coated and before growth of the CNT structures, for a selected voltage application time interval. The CNT structures are then grown on a coated substrate surface with the desired orientation. Optionally, the electrode can be disconnected before the CNT structures are grown.
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NASA Astrophysics Data System (ADS)
Yoon, Im Taek; Cho, Hak Dong; Lee, Sejoon; Roshchupkin, Dmitry V.
2018-02-01
We have fabricated as-grown ZnO nanorods (NRs) and carbon-assisted NR arrays on semi-insulating (100)-oriented Si substrates. We compared the structural and luminescent properties of them. High-resolution transmission microscopy, field emission scanning electron microscopy, x-ray diffraction and energy-dispersive x-ray revealed that the as-grown ZnO NRs and carbon-assisted ZnO NRs were single crystals with a hexagonal wurtzite structure, and grew with a c-axis orientation perpendicular to the Si substrate. These measurements show that the carbon-assisted ZnO NRs were better synthesized vertically on an Si substrate compared to the as-grown ZnO NRs. Photoluminescence measurements showed that luminescence intensity of the carbon-assisted ZnO NRs was enhanced compared to the as-grown ZnO NRs. The enhanced luminescence intensity of the carbon-assisted ZnO demonstrates the possible improvement in the performance of photovoltaic nanodevices based on ZnO-like materials. This method can be applied to the fabrication of well-aligned ZnO NRs used widely in optoelectronic devices.
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Strain Sensors, Methods of Making Same, and Applications of Same
NASA Technical Reports Server (NTRS)
Hatfield, Walter (Inventor); Biris, Alexandru S. (Inventor); Trigwell, Steven (Inventor)
2015-01-01
In one aspect, the present invention relates to a layered structure usable in a strain sensor. In one embodiment, the layered structure has a substrate with a first surface and an opposite, second surface defining a body portion therebetween; and a film of carbon nanotubes deposited on the first surface of the substrate, wherein the film of carbon nanotubes is conductive and characterized with an electrical resistance. In one embodiment, the carbon nanotubes are aligned in a preferential direction. In one embodiment, the carbon nanotubes are formed in a yarn such that any mechanical stress increases their electrical response. In one embodiment, the carbon nanotubes are incorporated into a polymeric scaffold that is attached to the surface of the substrate. In one embodiment, the surfaces of the carbon nanotubes are functionalized such that its electrical conductivity is increased.
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Strain sensors, methods of making same, and applications of same
Biris, Alexandru S.; Trigwell, Steven; Hatfield, Walter
2015-06-30
In one aspect, the present invention relates to a layered structure usable in a strain sensor. In one embodiment, the layered structure has a substrate with a first surface and an opposite, second surface defining a body portion therebetween; and a film of carbon nanotubes deposited on the first surface of the substrate, wherein the film of carbon nanotubes is conductive and characterized with an electrical resistance. In one embodiment, the carbon nanotubes are aligned in a preferential direction. In one embodiment, the carbon nanotubes are formed in a yarn such that any mechanical stress increases their electrical response. In one embodiment, the carbon nanotubes are incorporated into a polymeric scaffold that is attached to the surface of the substrate. In one embodiment, the surfaces of the carbon nanotubes are functionalized such that its electrical conductivity is increased.
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Kumar, Ramasamy P; Morehouse, Benjamin R; Matos, Jason O; Malik, Karan; Lin, Hongkun; Krauss, Isaac J; Oprian, Daniel D
2017-03-28
The stereochemical course of monoterpene synthase reactions is thought to be determined early in the reaction sequence by selective binding of distinct conformations of the geranyl diphosphate (GPP) substrate. We explore here formation of early Michaelis complexes of the (+)-limonene synthase [(+)-LS] from Citrus sinensis using monofluorinated substrate analogues 2-fluoro-GPP (FGPP) and 2-fluoroneryl diphosphate (FNPP). Both are competitive inhibitors for (+)-LS with K I values of 2.4 ± 0.5 and 39.5 ± 5.2 μM, respectively. The K I values are similar to the K M for the respective nonfluorinated substrates, indicating that fluorine does not significantly perturb binding of the ligand to the enzyme. FGPP and FNPP are also substrates, but with dramatically reduced rates (k cat values of 0.00054 ± 0.00005 and 0.00024 ± 0.00002 s -1 , respectively). These data are consistent with a stepwise mechanism for (+)-LS involving ionization of the allylic GPP substrate to generate a resonance-stabilized carbenium ion in the rate-limiting step. Crystals of apo-(+)-LS were soaked with FGPP and FNPP to obtain X-ray structures at 2.4 and 2.2 Å resolution, respectively. The fluorinated analogues are found anchored in the active site through extensive interactions involving the diphosphate, three metal ions, and three active-site Asp residues. Electron density for the carbon chains extends deep into a hydrophobic pocket, while the enzyme remains mostly in the open conformation observed for the apoprotein. While FNPP was found in multiple conformations, FGPP, importantly, was in a single, relatively well-defined, left-handed screw conformation, consistent with predictions for the mechanism of stereoselectivity in the monoterpene synthases.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Xu, Xiaofeng; Schimel, Joshua; Thornton, Peter E
2014-01-01
Microbial assimilation of soil organic carbon is one of the fundamental processes of global carbon cycling and it determines the magnitude of microbial biomass in soils. Mechanistic understanding of microbial assimilation of soil organic carbon and its controls is important for to improve Earth system models ability to simulate carbon-climate feedbacks. Although microbial assimilation of soil organic carbon is broadly considered to be an important parameter, it really comprises two separate physiological processes: one-time assimilation efficiency and time-dependent microbial maintenance energy. Representing of these two mechanisms is crucial to more accurately simulate carbon cycling in soils. In this study, amore » simple modeling framework was developed to evaluate the substrate and environmental controls on microbial assimilation of soil organic carbon using a new term: microbial annual active period (the length of microbes remaining active in one year). Substrate quality has a positive effect on microbial assimilation of soil organic carbon: higher substrate quality (lower C:N ratio) leads to higher ratio of microbial carbon to soil organic carbon and vice versa. Increases in microbial annual active period from zero stimulate microbial assimilation of soil organic carbon; however, when microbial annual active period is longer than an optimal threshold, increasing this period decreases microbial biomass. The simulated ratios of soil microbial biomass to soil organic carbon are reasonably consistent with a recently compiled global dataset at the biome-level. The modeling framework of microbial assimilation of soil organic carbon and its controls developed in this study offers an applicable ways to incorporate microbial contributions to the carbon cycling into Earth system models for simulating carbon-climate feedbacks and to explain global patterns of microbial biomass.« less
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Surface protection of austenitic steels by carbon nanotube coatings
NASA Astrophysics Data System (ADS)
MacLucas, T.; Schütz, S.; Suarez, S.; Mücklich, F.
2018-03-01
In the present study, surface protection properties of multiwall carbon nanotubes (CNTs) deposited on polished austenitic stainless steel are evaluated. Electrophoretic deposition is used as a coating technique. Contact angle measurements reveal hydrophilic as well as hydrophobic wetting characteristics of the carbon nanotube coating depending on the additive used for the deposition. Tribological properties of carbon nanotube coatings on steel substrate are determined with a ball-on-disc tribometer. Effective lubrication can be achieved by adding magnesium nitrate as an additive due to the formation of a holding layer detaining CNTs in the contact area. Furthermore, wear track analysis reveals minimal wear on the coated substrate as well as carbon residues providing lubrication. Energy dispersive x-ray spectroscopy is used to qualitatively analyse the elemental composition of the coating and the underlying substrate. The results explain the observed wetting characteristics of each coating. Finally, merely minimal oxidation is detected on the CNT-coated substrate as opposed to the uncoated sample.
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Pratter, Sarah M; Light, Kenneth M; Solomon, Edward I; Straganz, Grit D
2014-07-02
Mononuclear nonheme Fe(II) (MNH) and α-ketoglutarate (α-KG) dependent halogenases activate O2 to perform oxidative halogenations of activated and nonactivated carbon centers. While the mechanism of halide incorporation into a substrate has been investigated, the mechanism by which halogenases prevent oxidations in the absence of chloride is still obscure. Here, we characterize the impact of chloride on the metal center coordination and reactivity of the fatty acyl-halogenase HctB. Stopped-flow kinetic studies show that the oxidative transformation of the Fe(II)-α-KG-enzyme complex is >200-fold accelerated by saturating concentrations of chloride in both the absence and presence of a covalently bound substrate. By contrast, the presence of substrate, which generally brings about O2 activation at enzymatic MNH centers, only has an ∼10-fold effect in the absence of chloride. Circular dichroism (CD) and magnetic CD (MCD) studies demonstrate that chloride binding triggers changes in the metal center ligation: chloride binding induces the proper binding of the substrate as shown by variable-temperature, variable-field (VTVH) MCD studies of non-α-KG-containing forms and the conversion from six-coordinate (6C) to 5C/6C mixtures when α-KG is bound. In the presence of substrate, a site with square pyramidal five-coordinate (5C) geometry is observed, which is required for O2 activation at enzymatic MNH centers. In the absence of substrate an unusual trigonal bipyramidal site is formed, which accounts for the observed slow, uncoupled reactivity. Molecular dynamics simulations suggest that the binding of chloride to the metal center of HctB leads to a conformational change in the enzyme that makes the active site more accessible to the substrate and thus facilitates the formation of the catalytically competent enzyme-substrate complex. Results are discussed in relation to other MNH dependent halogenases.
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Microfluidic sieve using intertwined, free-standing carbon nanotube mesh as active medium
Bakajin, Olgica; Noy, Aleksandr
2007-11-06
A microfluidic sieve having a substrate with a microfluidic channel, and a carbon nanotube mesh. The carbon nanotube mesh is formed from a plurality of intertwined free-standing carbon nanotubes which are fixedly attached within the channel for separating, concentrating, and/or filtering molecules flowed through the channel. In one embodiment, the microfluidic sieve is fabricated by providing a substrate having a microfluidic channel, and growing the intertwined free-standing carbon nanotubes from within the channel to produce the carbon nanotube mesh attached within the channel.
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Method for joining carbon-carbon composites to metals
Lauf, Robert J.; McMillan, April D.; Moorhead, Arthur J.
1997-01-01
A method for joining carbon-carbon composites to metals by brazing. Conventional brazing of recently developed carbon-bonded carbon fiber (CBCF) material to a metal substrate is limited by the tendency of the braze alloy to "wick" into the CBCF composite rather than to form a strong bond. The surface of the CBCF composite that is to be bonded is first sealed with a fairly dense carbonaceous layer achieved by any of several methods. The sealed surface is then brazed to the metal substrate by vacuum brazing with a Ti-Cu-Be alloy.
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Method for joining carbon-carbon composites to metals
Lauf, R.J.; McMillan, A.D.; Moorhead, A.J.
1997-07-15
A method for joining carbon-carbon composites to metals by brazing. Conventional brazing of recently developed carbon-bonded carbon fiber (CBCF) material to a metal substrate is limited by the tendency of the braze alloy to ``wick`` into the CBCF composite rather than to form a strong bond. The surface of the CBCF composite that is to be bonded is first sealed with a fairly dense carbonaceous layer achieved by any of several methods. The sealed surface is then brazed to the metal substrate by vacuum brazing with a Ti-Cu-Be alloy. 1 fig.
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Zhang, Liuyang; Gong, Hao
2015-12-08
Carbon-based substrates offer unprecedented advantages in lightweight supercapacitors. However, it is still challenging to achieve high coverage or loading. Different from the traditional belief that a lack of defects or functional groups is the cause of poor growth on carbon-based substrates, we reckon that the major cause is the discrepancy between the hydrophilic nature of the metal oxide/hydroxide and the hydrophobic nature of carbon. To solve this incompatibility, we introduced ethanol into the precursor solution. The method to synthesize nickel copper hydroxide on carbon fiber paper employs only water and ethanol, in addition to nickel acetate and copper acetate. The results revealed good growth and tight adhesion of active materials on carbon fiber paper substrates. The specific capacitance and energy density per total weight of the active material plus substrate (carbon fiber paper, current collector) reached 770 F g(-1) and 33 Wh kg(-1) (1798 F g(-1) and 54 Wh kg(-1) per weight of the active materials), owing to the high loading of active material and the light weight of carbon fiber paper. These results signified the achievability of light, cheap and high-performance supercapacitors by an environmental-friendly approach.
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NASA Astrophysics Data System (ADS)
Zhang, Liuyang; Gong, Hao
2015-12-01
Carbon-based substrates offer unprecedented advantages in lightweight supercapacitors. However, it is still challenging to achieve high coverage or loading. Different from the traditional belief that a lack of defects or functional groups is the cause of poor growth on carbon-based substrates, we reckon that the major cause is the discrepancy between the hydrophilic nature of the metal oxide/hydroxide and the hydrophobic nature of carbon. To solve this incompatibility, we introduced ethanol into the precursor solution. The method to synthesize nickel copper hydroxide on carbon fiber paper employs only water and ethanol, in addition to nickel acetate and copper acetate. The results revealed good growth and tight adhesion of active materials on carbon fiber paper substrates. The specific capacitance and energy density per total weight of the active material plus substrate (carbon fiber paper, current collector) reached 770 F g-1 and 33 Wh kg-1 (1798 F g-1 and 54 Wh kg-1 per weight of the active materials), owing to the high loading of active material and the light weight of carbon fiber paper. These results signified the achievability of light, cheap and high-performance supercapacitors by an environmental-friendly approach.
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Zhang, Liuyang; Gong, Hao
2015-01-01
Carbon-based substrates offer unprecedented advantages in lightweight supercapacitors. However, it is still challenging to achieve high coverage or loading. Different from the traditional belief that a lack of defects or functional groups is the cause of poor growth on carbon-based substrates, we reckon that the major cause is the discrepancy between the hydrophilic nature of the metal oxide/hydroxide and the hydrophobic nature of carbon. To solve this incompatibility, we introduced ethanol into the precursor solution. The method to synthesize nickel copper hydroxide on carbon fiber paper employs only water and ethanol, in addition to nickel acetate and copper acetate. The results revealed good growth and tight adhesion of active materials on carbon fiber paper substrates. The specific capacitance and energy density per total weight of the active material plus substrate (carbon fiber paper, current collector) reached 770 F g−1 and 33 Wh kg−1 (1798 F g−1 and 54 Wh kg−1 per weight of the active materials), owing to the high loading of active material and the light weight of carbon fiber paper. These results signified the achievability of light, cheap and high-performance supercapacitors by an environmental-friendly approach. PMID:26643665
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Microfabricated triggered vacuum switch
Roesler, Alexander W [Tijeras, NM; Schare, Joshua M [Albuquerque, NM; Bunch, Kyle [Albuquerque, NM
2010-05-11
A microfabricated vacuum switch is disclosed which includes a substrate upon which an anode, cathode and trigger electrode are located. A cover is sealed over the substrate under vacuum to complete the vacuum switch. In some embodiments of the present invention, a metal cover can be used in place of the trigger electrode on the substrate. Materials used for the vacuum switch are compatible with high vacuum, relatively high temperature processing. These materials include molybdenum, niobium, copper, tungsten, aluminum and alloys thereof for the anode and cathode. Carbon in the form of graphitic carbon, a diamond-like material, or carbon nanotubes can be used in the trigger electrode. Channels can be optionally formed in the substrate to mitigate against surface breakdown.
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Acidotolerant Bacteria and Fungi as a Sink of Methanol-Derived Carbon in a Deciduous Forest Soil
Morawe, Mareen; Hoeke, Henrike; Wissenbach, Dirk K.; Lentendu, Guillaume; Wubet, Tesfaye; Kröber, Eileen; Kolb, Steffen
2017-01-01
Methanol is an abundant atmospheric volatile organic compound that is released from both living and decaying plant material. In forest and other aerated soils, methanol can be consumed by methanol-utilizing microorganisms that constitute a known terrestrial sink. However, the environmental factors that drive the biodiversity of such methanol-utilizers have been hardly resolved. Soil-derived isolates of methanol-utilizers can also often assimilate multicarbon compounds as alternative substrates. Here, we conducted a comparative DNA stable isotope probing experiment under methylotrophic (only [13C1]-methanol was supplemented) and combined substrate conditions ([12C1]-methanol and alternative multi-carbon [13Cu]-substrates were simultaneously supplemented) to (i) identify methanol-utilizing microorganisms of a deciduous forest soil (European beech dominated temperate forest in Germany), (ii) assess their substrate range in the soil environment, and (iii) evaluate their trophic links to other soil microorganisms. The applied multi-carbon substrates represented typical intermediates of organic matter degradation, such as acetate, plant-derived sugars (xylose and glucose), and a lignin-derived aromatic compound (vanillic acid). An experimentally induced pH shift was associated with substantial changes of the diversity of active methanol-utilizers suggesting that soil pH was a niche-defining factor of these microorganisms. The main bacterial methanol-utilizers were members of the Beijerinckiaceae (Bacteria) that played a central role in a detected methanol-based food web. A clear preference for methanol or multi-carbon substrates as carbon source of different Beijerinckiaceae-affiliated phylotypes was observed suggesting a restricted substrate range of the methylotrophic representatives. Apart from Bacteria, we also identified the yeasts Cryptococcus and Trichosporon as methanol-derived carbon-utilizing fungi suggesting that further research is needed to exclude or prove methylotrophy of these fungi. PMID:28790984
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Hierarchically ordered carbon tubes
NASA Astrophysics Data System (ADS)
Pan, Zheng-Wei; Zhu, Hao-Guo; Zhang, Zong-Tao; Im, Hee-Jung; Dai, Sheng; Beach, David B.; Lowndes, Douglas H.
2003-04-01
Micropatterns of hierarchically ordered carbon tubes (i.e., ordered carbon microtubes composed of aligned carbon nanotubes) were grown on a film-like iron/silica substrate consisting of ring-like catalyst patterns. The substrates were prepared by a combined technique, in which the sol-gel method was used to prepare catalyst film and transmission electron microscope grids were used as a shadow mask. In comparison with other techniques that involve sophisticated lithography, this approach represents a simple and low-cost way to the micropatterning of aligned carbon nanotubes.
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Yoon, Jinsu; Han, Jungmin; Choi, Bongsik; Lee, Yongwoo; Kim, Yeamin; Park, Jinhee; Lim, Meehyun; Kang, Min-Ho; Kim, Dae Hwan; Kim, Dong Myong; Kim, Sungho; Choi, Sung-Jin
2018-05-25
Electronics that degrade after stable operation for a desired operating time, called transient electronics, are of great interest in many fields, including biomedical implants, secure memory devices, and environmental sensors. Thus, the development of transient materials is critical for the advancement of transient electronics and their applications. However, previous reports have mostly relied on achieving transience in aqueous solutions, where the transience time is largely predetermined based on the materials initially selected at the beginning of the fabrication. Therefore, accurate control of the transience time is difficult, thereby limiting their application. In this work, we demonstrate transient electronics based on a water-soluble poly(vinyl alcohol) (PVA) substrate on which carbon nanotube (CNT)-based field-effect transistors were fabricated. We regulated the structural parameters of the PVA substrate using a three-dimensional (3D) printer to accurately control and program the transience time of the PVA substrate in water. The 3D printing technology can produce complex objects directly, thus enabling the efficient fabrication of a transient substrate with a prescribed and controlled transience time. In addition, the 3D printer was used to develop a facile method for the selective and partial destruction of electronics.
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NASA Astrophysics Data System (ADS)
Fernández, R.; MacDonald, D.; Nastić, A.; Jodoin, B.; Tieu, A.; Vijay, M.
2016-12-01
Thick copper coatings have been envisioned as corrosion protection barriers for steel containers used in repositories for nuclear waste fuel bundles. Due to its high deposition rate and low oxidation levels, cold spray is considered as an option to produce these coatings as an alternative to traditional machining processes to create corrosion protective sleeves. Previous investigations on the deposition of thick cold spray copper coatings using only nitrogen as process gas on carbon steel substrates have continuously resulted in coating delamination. The current work demonstrates the possibility of using an innovative surface preparation process, forced pulsed waterjet, to induce a complex substrate surface morphology that serves as anchoring points for the copper particles to mechanically adhere to the substrate. The results of this work show that, through the use of this surface preparation method, adhesion strength can be drastically increased, and thick copper coatings can be deposited using nitrogen. Through finite element analysis, it was shown that it is likely that the bonding created is purely mechanical, explaining the lack of adhesion when conventional substrate preparation methods are used and why helium is usually required as process gas.
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Rahman, Masudur; Neff, David; Green, Nathaniel; Norton, Michael L.
2016-01-01
Although there is a long history of the study of the interaction of DNA with carbon surfaces, limited information exists regarding the interaction of complex DNA-based nanostructures with the important material graphite, which is closely related to graphene. In view of the capacity of DNA to direct the assembly of proteins and optical and electronic nanoparticles, the potential for combining DNA-based materials with graphite, which is an ultra-flat, conductive carbon substrate, requires evaluation. A series of imaging studies utilizing Atomic Force Microscopy has been applied in order to provide a unified picture of this important interaction of structured DNA and graphite. For the test structure examined, we observe a rapid destabilization of the complex DNA origami structure, consistent with a strong interaction of single-stranded DNA with the carbon surface. This destabilizing interaction can be obscured by an intentional or unintentional primary intervening layer of single-stranded DNA. Because the interaction of origami with graphite is not completely dissociative, and because the frustrated, expanded structure is relatively stable over time in solution, it is demonstrated that organized structures of pairs of the model protein streptavidin can be produced on carbon surfaces using DNA origami as the directing material. PMID:28335324
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Binding of dinitrogen to an iron-sulfur-carbon site
NASA Astrophysics Data System (ADS)
Čorić, Ilija; Mercado, Brandon Q.; Bill, Eckhard; Vinyard, David J.; Holland, Patrick L.
2015-10-01
Nitrogenases are the enzymes by which certain microorganisms convert atmospheric dinitrogen (N2) to ammonia, thereby providing essential nitrogen atoms for higher organisms. The most common nitrogenases reduce atmospheric N2 at the FeMo cofactor, a sulfur-rich iron-molybdenum cluster (FeMoco). The central iron sites that are coordinated to sulfur and carbon atoms in FeMoco have been proposed to be the substrate binding sites, on the basis of kinetic and spectroscopic studies. In the resting state, the central iron sites each have bonds to three sulfur atoms and one carbon atom. Addition of electrons to the resting state causes the FeMoco to react with N2, but the geometry and bonding environment of N2-bound species remain unknown. Here we describe a synthetic complex with a sulfur-rich coordination sphere that, upon reduction, breaks an Fe-S bond and binds N2. The product is the first synthetic Fe-N2 complex in which iron has bonds to sulfur and carbon atoms, providing a model for N2 coordination in the FeMoco. Our results demonstrate that breaking an Fe-S bond is a chemically reasonable route to N2 binding in the FeMoco, and show structural and spectroscopic details for weakened N2 on a sulfur-rich iron site.
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Composite substrate for bipolar electrodes
Tekkanat, Bora; Bolstad, James J.
1992-12-22
Substrates for electrode systems, particularly those to be used for bipolar electrodes in zinc-bromine batteries, are disclosed. The substrates preferably include carbon-black as a conductive filler in a polymeric matrix, with reinforcing materials such as glass fibers. Warpage of the zinc-bromine electrodes which was experienced in the prior art and which was believed to be caused by physical expansion of the electrodes due to bromine absorption by the carbon-black, is substantially eliminated when new substrate fabrication techniques are employed. In the pesent invention, substrates are prepared using a lamination process known as glass mat reinforced thermoplastics technology or, in an alternate embodiment, the substrate is made using a slurry process.
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Weiner, Ronald M.; Taylor, Larry E.; Henrissat, Bernard; Hauser, Loren; Land, Miriam; Coutinho, Pedro M.; Rancurel, Corinne; Saunders, Elizabeth H.; Longmire, Atkinson G.; Zhang, Haitao; Bayer, Edward A.; Gilbert, Harry J.; Larimer, Frank; Zhulin, Igor B.; Ekborg, Nathan A.; Lamed, Raphael; Richardson, Paul M.; Borovok, Ilya; Hutcheson, Steven
2008-01-01
The marine bacterium Saccharophagus degradans strain 2-40 (Sde 2-40) is emerging as a vanguard of a recently discovered group of marine and estuarine bacteria that recycles complex polysaccharides. We report its complete genome sequence, analysis of which identifies an unusually large number of enzymes that degrade >10 complex polysaccharides. Not only is this an extraordinary range of catabolic capability, many of the enzymes exhibit unusual architecture including novel combinations of catalytic and substrate-binding modules. We hypothesize that many of these features are adaptations that facilitate depolymerization of complex polysaccharides in the marine environment. This is the first sequenced genome of a marine bacterium that can degrade plant cell walls, an important component of the carbon cycle that is not well-characterized in the marine environment. PMID:18516288
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A Model of Extracellular Enzymes in Free-Living Microbes: Which Strategy Pays Off?
Thygesen, Uffe H.; Riemann, Lasse; Stedmon, Colin A.
2015-01-01
An initial modeling approach was applied to analyze how a single, nonmotile, free-living, heterotrophic bacterial cell may optimize the deployment of its extracellular enzymes. Free-living cells live in a dilute and complex substrate field, and to gain enough substrate, their extracellular enzymes must be utilized efficiently. The model revealed that surface-attached and free enzymes generate unique enzyme and substrate fields, and each deployment strategy has distinctive advantages. For a solitary cell, surface-attached enzymes are suggested to be the most cost-efficient strategy. This strategy entails potential substrates being reduced to very low concentrations. Free enzymes, on the other hand, generate a radically different substrate field, which suggests significant benefits for the strategy if free cells engage in social foraging or experience high substrate concentrations. Swimming has a slight positive effect for the attached-enzyme strategy, while the effect is negative for the free-enzyme strategy. The results of this study suggest that specific dissolved organic compounds in the ocean likely persist below a threshold concentration impervious to biological utilization. This could help explain the persistence and apparent refractory state of oceanic dissolved organic matter (DOM). Microbial extracellular enzyme strategies, therefore, have important implications for larger-scale processes, such as shaping the role of DOM in ocean carbon sequestration. PMID:26253668
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NASA Astrophysics Data System (ADS)
Lin, Meng-Yu; Wang, Cheng-Hung; Pao, Chun-Wei; Lin, Shih-Yen
2015-09-01
Graphitic carbon films prepared by using molecular beam epitaxy (MBE) on metal templates with different thicknesses deposited on SiO2/Si substrates are investigated in this paper. With thick Cu templates, only graphitic carbon flakes are obtained near the Cu grain boundaries at low growth temperatures on metal/SiO2 interfaces. By replacing the Cu templates with thin Ni templates, complete graphitic carbon films with superior crystalline quality is obtained at 600 °C on SiO2/Si substrates after removing the Ni templates. The enhanced attachment of the graphitic carbon film to the SiO2/Si substrates with reduced Ni thickness makes the approach a promising approach for transferring-free graphene preparation at low temperature by using MBE.
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Structural Analysis of a Carbon Nitride Film Prepared by Ion-Beam-Assisted Deposition
NASA Astrophysics Data System (ADS)
Hayashi, Toshiyuki; Matsumuro, Akihito; Muramatsu, Mutsuo; Kohzaki, Masao; Takahashi, Yutaka; Yamaguchi, Katsumi
1999-04-01
The microstructure of a carbon nitride (CNx) film formed by ion-beam-assisted deposition (IBAD) was investigated by transmission electron microscopy (TEM). This film was formed on the Si (100) substrate by IBAD with an N/C transport ratio of 1. Three different spacings (0.34 nm, 0.21 nm, 0.12 nm) were observed by transmission electron diffraction (TED) and the periodic structure corresponding to the spacing of 0.34 nm was aligned perpendicular to the substrate. The bending of this plane resembled a carbon nanotube; therefore, it seemed reasonable to suppose that the CNx film obtained consisted of numerous carbon-nanotube-like structural elements grown vertically, relative to the substrate, and it also seemed appropriate that these structural elements should be termed nanotube-like carbon nitride.
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Fabricating Large-Area Sheets of Single-Layer Graphene by CVD
NASA Technical Reports Server (NTRS)
Bronikowski, Michael; Manohara, Harish
2008-01-01
This innovation consists of a set of methodologies for preparing large area (greater than 1 cm(exp 2)) domains of single-atomic-layer graphite, also called graphene, in single (two-dimensional) crystal form. To fabricate a single graphene layer using chemical vapor deposition (CVD), the process begins with an atomically flat surface of an appropriate substrate and an appropriate precursor molecule containing carbon atoms attached to substituent atoms or groups. These molecules will be brought into contact with the substrate surface by being flowed over, or sprayed onto, the substrate, under CVD conditions of low pressure and elevated temperature. Upon contact with the surface, the precursor molecules will decompose. The substituent groups detach from the carbon atoms and form gas-phase species, leaving the unfunctionalized carbon atoms attached to the substrate surface. These carbon atoms will diffuse upon this surface and encounter and bond to other carbon atoms. If conditions are chosen carefully, the surface carbon atoms will arrange to form the lowest energy single-layer structure available, which is the graphene lattice that is sought. Another method for creating the graphene lattice includes metal-catalyzed CVD, in which the decomposition of the precursor molecules is initiated by the catalytic action of a catalytic metal upon the substrate surface. Another type of metal-catalyzed CVD has the entire substrate composed of catalytic metal, or other material, either as a bulk crystal or as a think layer of catalyst deposited upon another surface. In this case, the precursor molecules decompose directly upon contact with the substrate, releasing their atoms and forming the graphene sheet. Atomic layer deposition (ALD) can also be used. In this method, a substrate surface at low temperature is covered with exactly one monolayer of precursor molecules (which may be of more than one type). This is heated up so that the precursor molecules decompose and form one monolayer of the target material.
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Ma, Yuhui; Niu, Ruxuan; Wang, Xiaona; Wang, Qunhui; Wang, Xiaoqiang; Sun, Xiaohong
2014-11-01
This is the first study on the co-pyrolysis of spent substrate of Pleurotus ostreatus and coal tar pitch, and the activated carbon prepared from the pyrolytic char. Thermogravimetry (TG) analysis was carried out taking spent substrate, coal tar pitch and spent substrate-coal tar pitch mixture. The activation energies of pyrolysis reactions were obtained via the Flynn-Wall-Ozawa and Kissinger-Akahira-Sunose methods. The kinetic models were determined by the master-plots method. The activated carbons were characterised by N2-adsorption, Fourier transform infrared spectroscopy and X-ray diffraction. Experimental results demonstrated a synergistic effect happened during co-pyrolysis, which was characterised by a decreased maximum decomposition rate and an enhanced char yield. The average activation energies of the pyrolysis reactions of spent substrate, coal tar pitch and the mixture were 115.94, 72.92 and 94.38 kJ mol(-1) for the Flynn-Wall-Ozawa method, and 112.17, 65.62 and 89.91 kJ mol(-1) for the Kissinger-Akahira-Sunose method. The reaction model functions were f(α) = (1-α)(3.42), (1-α)(1.72) and (1-α)(3.07) for spent substrate, coal tar pitch and the mixture, respectively. The mixture char-derived activated carbon had a Brunauer-Emmett-Teller surface area up to 1337 m(2) g(-1) and a total pore volume of 0.680 cm(3) g(-1). Mixing spent substrate with coal tar pitch led to the creation of more micropores and a higher surface area compared with the single spent substrate and coal tar pitch char. Also, the mixture char-derived activated carbon had a higher proportion of aromatic stacking. This study provides a reference for the utilisation of spent substrate and coal tar pitch via co-pyrolysis, and their pyrolytic char as a promising precursor of activated carbon. © The Author(s) 2014.
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MnO2-Based Electrochemical Supercapacitors on Flexible Carbon Substrates
NASA Astrophysics Data System (ADS)
Tadjer, Marko J.; Mastro, Michael A.; Rojo, José M.; Mojena, Alberto Boscá; Calle, Fernando; Kub, Francis J.; Eddy, Charles R.
2014-04-01
Manganese dioxide films were grown on large area flexible carbon aerogel substrates. Characterization by x-ray diffraction confirmed α-MnO2 growth. Three types of films were compared as a function of hexamethylenetetramine (HMTA) concentration during growth. The highest concentration of HM TA produced MnO2 flower-like films, as observed by scanning electron microscopy, whose thickness and surface coverage lead to both a higher specific capacitance and higher series resistance. Specific capacitance was measured to be 64 F/g using a galvanostatic setup, compared to the 47 F/g-specific capacitance of the carbon aerogel substrate. Such supercapacitor devices can be fabricated on large area sheets of carbon aerogel to achieve high total capacitance.
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Zimmerman, Matthew D.; Proudfoot, Michael; Yakunin, Alexander; Minor, Wladek
2008-01-01
Summary HD-domain phosphohydrolases have nucleotidase and phosphodiesterase activities and play important roles in the metabolism of nucleotides and in signaling. We present three 2.1 Å resolution crystal structures (one in the free state and two complexed with natural substrates) of a HD-domain phosphohydrolase, the E. coli 5′-nucleotidase YfbR. The free-state structure of YfbR contains a large cavity accommodating the metal-coordinating HD motif (H33, H68, D69, and D137) and other conserved residues (R18, E72, and D77). Alanine scanning mutagenesis confirms that these residues are important for activity. Two structures of the catalytically inactive mutant E72A complexed with Co2+ and either TMP or dAMP disclose the novel binding mode of deoxyribonucleotides in the active site. Residue R18 stabilizes the phosphate on the Co2+, and residue D77 forms a strong hydrogen bond critical for binding the ribose. The indole side chain of W19 is located close to the 2′-carbon atom of the deoxyribose moiety and is proposed to act as the selectivity switch for deoxyribonucleotide, which is supported by comparison to YfdR, another 5′-nucleotidase in E. coli. The nucleotide bases of both dAMP and TMP make no specific hydrogen bonds with the protein, explaining the lack of nucleotide base selectivity. The YfbR E72A substrate complex structures also suggest a plausible single-step nucleophilic substitution mechanism. This is the first proposed molecular mechanism for a HD-domain phosphohydrolase based directly on substrate-bound crystal structures. PMID:18353368
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Gagnon, Susannah M. L.; Meloncelli, Peter J.; Zheng, Ruixiang B.; Haji-Ghassemi, Omid; Johal, Asha R.; Borisova, Svetlana N.; Lowary, Todd L.; Evans, Stephen V.
2015-01-01
Homologous glycosyltransferases α-(1→3)-N-acetylgalactosaminyltransferase (GTA) and α-(1→3)-galactosyltransferase (GTB) catalyze the final step in ABO(H) blood group A and B antigen synthesis through sugar transfer from activated donor to the H antigen acceptor. These enzymes have a GT-A fold type with characteristic mobile polypeptide loops that cover the active site upon substrate binding and, despite intense investigation, many aspects of substrate specificity and catalysis remain unclear. The structures of GTA, GTB, and their chimeras have been determined to between 1.55 and 1.39 Å resolution in complex with natural donors UDP-Gal, UDP-Glc and, in an attempt to overcome one of the common problems associated with three-dimensional studies, the non-hydrolyzable donor analog UDP-phosphono-galactose (UDP-C-Gal). Whereas the uracil moieties of the donors are observed to maintain a constant location, the sugar moieties lie in four distinct conformations, varying from extended to the “tucked under” conformation associated with catalysis, each stabilized by different hydrogen bonding partners with the enzyme. Further, several structures show clear evidence that the donor sugar is disordered over two of the observed conformations and so provide evidence for stepwise insertion into the active site. Although the natural donors can both assume the tucked under conformation in complex with enzyme, UDP-C-Gal cannot. Whereas UDP-C-Gal was designed to be “isosteric” with natural donor, the small differences in structure imposed by changing the epimeric oxygen atom to carbon appear to render the enzyme incapable of binding the analog in the active conformation and so preclude its use as a substrate mimic in GTA and GTB. PMID:26374898
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QEEN Workshop: "Quantifying Exposure to Engineered Nano ...
The measurement and characterization of nanomaterials in biological tissues is complicated by a number of factors including: the sensitivity of the assay to small sized particles or low concentrations of materials; the ability to distinguish different forms and transformations of the materials related to the biological matrix; distinguishing exogenous nanomaterials, which may be composed of biologically common elements such as carbon,from normal biological tissues; differentiating particle from ionic phases for materials that dissolve; localization of sparsely distributed materials in a complex substrate (the
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Catalyst free growth of CNTs by CVD on nanoscale rough surfaces of silicon substrates
NASA Astrophysics Data System (ADS)
Damodar, D.; Sahoo, R. K.; Jacob, C.
2013-06-01
Catalyst free growth of carbon nanotubes (CNT) has been achieved using atmospheric pressure chemical vapor deposition (APCVD) on surface modified Si(111) substrates. The effect of the substrate surface has been observed by partially etching with KOH (potassium hydroxide) solution which is an anisotropic etchant. Scanning electron microscopy (SEM) confirmed the formation of CNTs over most of the area of the substrate where substrates were anisotropically etched. Transmission electron microscopy (TEM) was used to observe the internal structure of the CNTs. Raman spectroscopy further confirmed the formation of the carbon nanostructures and also their graphitic crystallinity.
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Cho, Dae Won; Latham, John A; Park, Hea Jung; Yoon, Ung Chan; Langan, Paul; Dunaway-Mariano, Debra; Mariano, Patrick S
2011-04-15
New types of tetrameric lignin model compounds, which contain the common β-O-4 and β-1 structural subunits found in natural lignins, have been prepared and carbon-carbon bond fragmentation reactions of their cation radicals, formed by photochemical (9,10-dicyanoanthracene) and enzymatic (lignin peroxidase) SET-promoted methods, have been explored. The results show that cation radical intermediates generated from the tetrameric model compounds undergo highly regioselective C-C bond cleavage in their β-1 subunits. The outcomes of these processes suggest that, independent of positive charge and odd-electron distributions, cation radicals of lignins formed by SET to excited states of sensitizers or heme-iron centers in enzymes degrade selectively through bond cleavage reactions in β-1 vs β-O-4 moieties. In addition, the findings made in the enzymatic studies demonstrate that the sterically large tetrameric lignin model compounds undergo lignin peroxidase-catalyzed cleavage via a mechanism involving preliminary formation of an enzyme-substrate complex.
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Recent Advances in Electrochemical Immunosensors
Piro, Benoît; Reisberg, Steeve
2017-01-01
Immunosensors have experienced a very significant growth in recent years, driven by the need for fast, sensitive, portable and easy-to-use devices to detect biomarkers for clinical diagnosis or to monitor organic pollutants in natural or industrial environments. Advances in the field of signal amplification using enzymatic reactions, nanomaterials such as carbon nanotubes, graphene and graphene derivatives, metallic nanoparticles (gold, silver, various oxides or metal complexes), or magnetic beads show how it is possible to improve collection, binding or transduction performances and reach the requirements for realistic clinical diagnostic or environmental control. This review presents these most recent advances; it focuses first on classical electrode substrates, then moves to carbon-based nanostructured ones including carbon nanotubes, graphene and other carbon materials, metal or metal-oxide nanoparticles, magnetic nanoparticles, dendrimers and, to finish, explore the use of ionic liquids. Analytical performances are systematically covered and compared, depending on the detection principle, but also from a chronological perspective, from 2012 to 2016 and early 2017. PMID:28387718
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Chen, Nuo; Liao, Ting-ting; Wang, Rui; Zheng, Xun-hua; Hu, Rong-gui; Butterbach-Bahl, Klaus
2014-09-01
Understanding the effects of carbon and nitrogen substrates concentrations on the emissions of denitrification gases including nitrogen (N2) , nitrous oxide (N2O) and nitric oxide (NO), carbon dioxide (CO2) and methane (CH4) from anaerobic paddy soils is believed to be helpful for development of greenhouse gas mitigation strategies. Moreover, understanding the quantitative dependence of denitrification products compositions on carbon substrate concentration could provide some key parameters or parameterization scheme for developing process-oriented model(s) of nitrogen transformation. Using a silt loam soil collected from a paddy field, we investigated the influence of carbon substrate concentration on the emissions of the denitrification gases, CO2 and CH4 from anaerobically incubated soils by setting two treatments: control (CK) with initial soil nitrate and dissolved organic carbon (DOC) concentrations of ~ 50 mg.kg-1 and -28 mg kg-1 , respectively; and DOC added (C + ) with initial soil nitrate and DOC concentrations of ~50 mg.kg-1 and ~300 mg.kg-1 , respectively. The emissions of denitrification gases, CO2 and CH4, as well as concentrations of carbon and nitrogen substrates for each treatment were dynamically measured, using the gas-flow-soil-core technique and a paralleling substrate monitoring system. The results showed that CH4 emission was not observed in CK treatment while observed in C treatment. Aggregate emission of greenhouse gases for C + treatment was significantly higher comparing with the CK treatment (P <0. 01). The mass fractions of NO, N20 and N2 emissions in total nitrogen gases emissions were approximately 9% , 35% and 56% for CK treatment, respectively; and approximately 31% , 50% and 19% for C+ treatment, respectively, with significant differences between these two treatments (P < 0.01). The results indicated that carbon substrate concentrations can significantly change the composition of nitrogen gas emissions. The results also implicated that organic fertilizer should not be applied to nitrate-rich paddy soils prior to or during flooding so as to mitigate greenhouse gases emissions.
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Joining Carbon-Carbon Composites and High-Temperature Materials with High Energy Electron Beams
NASA Technical Reports Server (NTRS)
Goodman, Daniel; Singler, Robert
1998-01-01
1. Program goals addressed during this period. Experimental work was directed at formation of a low-stress bond between carbon- carbon and aluminum, with the objective of minimizing the heating of the aluminum substrate, thereby minimizing stresses resulting from the coefficient of thermal expansion (CTE) difference between the aluminum and carbon-carbon. A second objective was to form a bond between carbon-carbon and aluminum with good thermal conductivity for electronic thermal management (SEM-E) application. 2. Substrates and joining materials selected during this period. Carbon-Carbon Composite (CCC) to Aluminum. CCC (Cu coated) to Aluminum. Soldering compounds based on Sn/Pb and Sn/Ag/Cu/Bi compositions. 3. Soldering experiments performed. Conventional techniques. High Energy Electron Beam (HEEB) process.
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Porous substrates filled with nanomaterials
Worsley, Marcus A.; Baumann, Theodore F.; Satcher, Jr., Joe H.; Stadermann, Michael
2018-04-03
A composition comprising: at least one porous carbon monolith, such as a carbon aerogel, comprising internal pores, and at least one nanomaterial, such as carbon nanotubes, disposed uniformly throughout the internal pores. The nanomaterial can be disposed in the middle of the monolith. In addition, a method for making a monolithic solid with both high surface area and good bulk electrical conductivity is provided. A porous substrate having a thickness of 100 microns or more and comprising macropores throughout its thickness is prepared. At least one catalyst is deposited inside the porous substrate. Subsequently, chemical vapor deposition is used to uniformly deposit a nanomaterial in the macropores throughout the thickness of the porous substrate. Applications include electrical energy storage, such as batteries and capacitors, and hydrogen storage.
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Porous substrates filled with nanomaterials
Worsley, Marcus A.; Baumann, Theodore F.; Satcher, Jr., Joe H.; Stadermann, Michael
2014-08-19
A composition comprising: at least one porous carbon monolith, such as a carbon aerogel, comprising internal pores, and at least one nanomaterial, such as carbon nanotubes, disposed uniformly throughout the internal pores. The nanomaterial can be disposed in the middle of the monolith. In addition, a method for making a monolithic solid with both high surface area and good bulk electrical conductivity is provided. A porous substrate having a thickness of 100 microns or more and comprising macropores throughout its thickness is prepared. At least one catalyst is deposited inside the porous substrate. Subsequently, chemical vapor deposition is used to uniformly deposit a nanomaterial in the macropores throughout the thickness of the porous substrate. Applications include electrical energy storage, such as batteries and capacitors, and hydrogen storage.
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A carbon nanotube-polymer composite for T-cell therapy
NASA Astrophysics Data System (ADS)
Fadel, Tarek R.; Sharp, Fiona A.; Vudattu, Nalini; Ragheb, Ragy; Garyu, Justin; Kim, Dongin; Hong, Enping; Li, Nan; Haller, Gary L.; Pfefferle, Lisa D.; Justesen, Sune; Harold, Kevin C.; Fahmy, Tarek M.
2014-08-01
Clinical translation of cell therapies requires strategies that can manufacture cells efficiently and economically. One promising way to reproducibly expand T cells for cancer therapy is by attaching the stimuli for T cells onto artificial substrates with high surface area. Here, we show that a carbon nanotube-polymer composite can act as an artificial antigen-presenting cell to efficiently expand the number of T cells isolated from mice. We attach antigens onto bundled carbon nanotubes and combined this complex with polymer nanoparticles containing magnetite and the T-cell growth factor interleukin-2 (IL-2). The number of T cells obtained was comparable to clinical standards using a thousand-fold less soluble IL-2. T cells obtained from this expansion were able to delay tumour growth in a murine model for melanoma. Our results show that this composite is a useful platform for generating large numbers of cytotoxic T cells for cancer immunotherapy.
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Hovey, Raymond; Lentes, Sabine; Ehrenreich, Armin; Salmon, Kirsty; Saba, Karla; Gottschalk, Gerhard; Gunsalus, Robert P; Deppenmeier, Uwe
2005-05-01
Methansarcina mazei Gö1 DNA arrays were constructed and used to evaluate the genomic expression patterns of cells grown on either of two alternative methanogenic substrates, acetate or methanol, as sole carbon and energy source. Analysis of differential transcription across the genome revealed two functionally grouped sets of genes that parallel the central biochemical pathways in, and reflect many known features of, acetate and methanol metabolism. These include the acetate-induced genes encoding acetate activating enzymes, acetyl-CoA synthase/CO dehydrogenase, and carbonic anhydrase. Interestingly, additional genes expressed at significantly higher levels during growth on acetate included two energy-conserving complexes (the Ech hydrogenase, and the A1A0-type ATP synthase). Many previously unknown features included the induction by acetate of genes coding for ferredoxins and flavoproteins, an aldehyde:ferredoxin oxidoreductase, enzymes for the synthesis of aromatic amino acids, and components of iron, cobalt and oligopeptide uptake systems. In contrast, methanol-grown cells exhibited elevated expression of genes assigned to the methylotrophic pathway of methanogenesis. Expression of genes for components of the translation apparatus was also elevated in cells grown in the methanol medium relative to acetate, and was correlated with the faster growth rate observed on the former substrate. These experiments provide the first comprehensive insight into substrate-dependent gene expression in a methanogenic archaeon. This genome-wide approach, coupled with the complementary molecular and biochemical tools, should greatly accelerate the exploration of Methanosarcina cell physiology, given the present modest level of our knowledge of these large archaeal genomes.
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NASA Astrophysics Data System (ADS)
Vo, T. T.; Poulain, C.; Dijon, J.; Fournier, A.; Chevalier, N.; Mariolle, D.
2012-08-01
High density vertically aligned carbon nanotube (VACNT) forests are considered as a promising conductive material for many applications (interconnects in microelectronics or contact material layer in sliding contact applications). It is thus crucial to characterize the electrical resistance of these forests, especially in contact with the inherent top/bottom conductive substrates. This paper aims to develop an original method to determine the contribution of the different terms in this electrical resistance, which is measured with a tipless atomic force microscope used in high accuracy "force mode." VACNT stacks with different heights on AlCu substrate with or without Au/Pd top coating are studied. The electrical contact area between the probe tip and the forest is considered to be equivalent to the classical electrical contact area between a tip and a rough surface. With this assumption, the scattering resistance of a mono-wall CNT is 14.6 kΩ μm-1, the top/bottom contact resistance is, respectively, 265 kΩ/385 kΩ. The bottom resistance divided in half is obtained by an interface substrate/CNT catalyst treatment. The same assumption leads to an effective compressive modulus of 175 MPa. These results are consistent with the values published by other authors. The proposed method is effective to optimise the CNT interface contact resistance before integration in a more complex functional structure.
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Composite substrate for bipolar electrodes
Tekkanat, B.; Bolstad, J.J.
1992-12-22
Substrates for electrode systems, particularly those to be used for bipolar electrodes in zinc-bromine batteries, are disclosed. The substrates preferably include carbon-black as a conductive filler in a polymeric matrix, with reinforcing materials such as glass fibers. Warpage of the zinc-bromine electrodes which was experienced in the prior art and which was believed to be caused by physical expansion of the electrodes due to bromine absorption by the carbon-black, is substantially eliminated when new substrate fabrication techniques are employed. In the present invention, substrates are prepared using a lamination process known as glass mat reinforced thermoplastics technology or, in an alternate embodiment, the substrate is made using a slurry process. 4 figs.
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Deng, Shihai; Li, Desheng; Yang, Xue; Xing, Wei; Li, Jinlong; Zhang, Qi
2017-02-01
The phosphorus (P) adsorption properties of an iron [Fe(0)]-rich substrate (IRS) composed of iron scraps and activated carbon were investigated based on iron-carbon micro-electrolysis (IC-ME) and compared to the substrates commonly used in constructed wetlands (CWs) to provide an initial characterization of the [Fe(0)]-rich substrate. The results showed that P was precipitated by Fe(III) dissolved from the galvanic cell reactions in the IRS and the reaction was suppressed by the pH and stopped when the pH exceeded 8.90 ± 0.09. The adsorption capacity of the IRS decreased by only 4.6% in the second round of adsorption due to Fe(0) consumption in the first round. Substrates with high Ca- and Mg-oxide contents and high Fe- and Al-oxide contents had higher P adsorption capacities at high and low pH values, respectively. Substrates containing high Fe and Al concentrations and low Ca concentrations were more resistant to decreases in the P adsorption capacity resulting from organic matter (OM) accumulation. The IRS with an iron scrap to activated carbon volume ratio of 3:2 resulted in the highest P adsorption capacity (9.34 ± 0.14 g P kg -1 ), with minimal pH change and strong adaptability to OM accumulation. The Fe(0)-rich substrate has the considerable potential for being used as a CW substrate. Copyright © 2016 Elsevier Ltd. All rights reserved.
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Carbon Nanospikes Grown on Metal Wires as Microelectrode Sensors for Dopamine
Zestos, Alexander G.; Yang, Cheng; Jacobs, Christopher B.; Hensley, Dale; Venton, B. Jill
2015-01-01
Carbon nanomaterials are advantageous as electrodes for neurotransmitter detection, but the difficulty of nanomaterials deposition on electrode substrates limits the reproducibility and future applications. In this study, we used plasma enhanced chemical vapor deposition (PECVD) to directly grow a thin layer of carbon nanospikes (CNS) on cylindrical metal substrates. No catalyst is required and the CNS surface coverage is uniform over the cylindrical metal substrate. The CNS growth was characterized on several metallic substrates including tantalum, niobium, palladium, and nickel wires. Using fast-scan cyclic voltammetry (FSCV), bare metal wires could not detect 1 μM dopamine while carbon nanospike coated wires could. The highest sensitivity and optimized S/N ratio was recorded from carbon nanospike-tantalum (CNS-Ta) microwires grown for 7.5 minutes, which had a LOD of 8 ± 2 nM for dopamine with FSCV. CNS-Ta microelectrodes were more reversible and had a smaller ΔEp for dopamine than carbon-fiber microelectrodes, suggesting faster electron transfer kinetics. The kinetics of dopamine redox were adsorption controlled at CNS-Ta microelectrodes and repeated electrochemical measurements displayed stability for up to ten hours in vitro and over a ten day period as well. The oxidation potential was significantly different for ascorbic acid and uric acid compared to dopamine. Growing carbon nanospikes on metal wires is a promising method to produce uniformly-coated, carbon nanostructured cylindrical microelectrodes for sensitive dopamine detection. PMID:26389138
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NASA Astrophysics Data System (ADS)
Guo, Shusen; Cao, Yongzhi; Sun, Tao; Zhang, Junjie; Gu, Le; Zhang, Chuanwei; Xu, Zhiqiang
2018-05-01
Molecular dynamics (MD) simulations were used to provide insights into the influence of nano-scale surface morphology on adsorptive behavior of Potassium stearate molecules on diamond-like carbon (DLC) substrates. Particular focus was given to explain that how the distinctive geometric properties of different surface morphologies affect the equilibrium structures and substrate-molecules interactions of monolayers, which was achieved through adsorptive analysis methods including adsorptive process, density profile, density distribution and surface potential energy. Analysis on surface potential energy demonstrated that the adsorptivity of amorphous smooth substrate is uniformly distributed over the surface, while DLC substrates with different surface morphologies appear to be more potentially corrugated, which improves the adsorptivity significantly. Because of the large distance of molecules from carbon atoms located at the square groove bottom, substrate-molecules interactions vanish significantly, and thus potassium stearate molecules cannot penetrate completely into the square groove. It can be observed that the equilibrium substrate-molecules interactions of triangle groove and semi-circle groove are much more powerful than that of square groove due to geometrically advantageous properties. These findings provided key information of optimally design of solid substrates with controllable adsorptivity.
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NASA Astrophysics Data System (ADS)
Hoarfrost, Adrienne; Snider, Rachel; Arnosti, Carol
2017-02-01
Extracellular enzymatic activities initiate microbially-driven heterotrophic carbon cycling in subsurface sediments. While measurement of hydrolytic activities in sediments is fundamental to our understanding of carbon cycling, these measurements are often technically difficult due to sorption of organic substrates to the sediment matrix. Most methods that measure hydrolysis of organic substrates in sediments rely on recovery of a fluorophore or fluorescently-labeled target substrate from a sediment incubation. The tendency for substrates to sorb to sediments results in lower recovery of an added substrate, and can result in data that are unusable or difficult to interpret. We developed a treatment using competitive desorption of a fluorescently-labeled, high molecular weight organic substrate that improves recovery of the labeled substrate from sediment subsamples. Competitive desorption treatment improved recovery of the fluorescent substrate by a median of 66%, expanded the range of sediments for which activity measurements could be made, and was effective in sediments from a broad range of geochemical contexts. More reliable measurements of hydrolytic activities in sediments will yield usable and more easily interpretable data from a wider range of sedimentary environments, enabling better understanding of microbially-catalyzed carbon cycling in subsurface environments.
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Solar radiation absorbing material
Googin, John M.; Schmitt, Charles R.; Schreyer, James M.; Whitehead, Harlan D.
1977-01-01
Solar energy absorbing means in solar collectors are provided by a solar selective carbon surface. A solar selective carbon surface is a microporous carbon surface having pores within the range of 0.2 to 2 micrometers. Such a surface is provided in a microporous carbon article by controlling the pore size. A thermally conductive substrate is provided with a solar selective surface by adhering an array of carbon particles in a suitable binder to the substrate, a majority of said particles having diameters within the range of about 0.2-10 microns.
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Thermal stability of Pt nanoclusters interacting to carbon sublattice
NASA Astrophysics Data System (ADS)
Baidyshev, V. S.; Gafner, Yu. Ya.; Gafner, S. L.; Redel, L. V.
2017-12-01
The catalytic activity of Pt clusters is dependent not only on the nanoparticle size and its composition, but also on its internal structure. To determine the real structure of the nanoparticles used in catalysis, the boundaries of the thermal structure stability of Pt clusters to 8.0 nm in diameter interacting with carbon substrates of two types: a fixed α-graphite plane and a mobile substrate with the diamond structure. The effect of a substrate on the processes melting of Pt nanoclusters is estimated. The role of the cooling rate in the formation of the internal structure of Pt clusters during crystallization is studied. The regularities obtained in the case of "free" Pt clusters and Pt clusters on a substrate are compared. It is concluded that platinum nanoparticles with diameter D ≤ 4.0 nm disposed on a carbon substrate conserve the initial fcc structure during cooling.
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NASA Astrophysics Data System (ADS)
Yamagiwa, Kiyofumi; Kuwano, Jun
2017-06-01
This paper describes a unique and innovative synthesis technique for carbon nanotubes (CNTs) by a one-step liquid-phase process under ambient pressure. Vertically aligned multi-walled CNT arrays with a maximum height of 100 µm are prepared on stainless steel substrates, which are submerged and electrically heated in straight-chain primary alcohols with n C = 1-4 (n C: number of C atoms in the molecule) containing an appropriate amount of cobalt-based organometallic complex as a catalyst precursor. Structural isomers of butanol were also used for the synthesis to examine the effects of structural factors on the morphology of the deposited products. Notably, 2-methyl-2-propanol, which is a tertiary alcohol, produced only a small amount of low-crystallinity carbonaceous deposits, whereas vertically aligned CNTs were grown from the other isomers of butanol. These results suggest that the presence or absence of β-hydrogen in the molecular structure is a key factor for understanding the dissociation behavior of the carbon source molecules on the catalyst.
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NASA Astrophysics Data System (ADS)
Stiegler, J.; Lang, T.; von Kaenel, Y.; Michler, J.; Blank, E.
1997-01-01
The growth kinetics of diamond films deposited at low substrate temperatures (600-400 °C) from the carbon-hydrogen gas system have been studied. When the substrate temperature alone was varied, independently of all other process parameters in the microwave plasma reactor, an activation energy in the order of 7 kcal/mol was observed. This value did not change with different carbon concentrations in hydrogen. It is supposed that growth kinetics in this temperature range are controlled by a single chemical reaction, probably the abstraction of surface bonded hydrogen by gas phase atomic hydrogen.
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Reefs as cradles of evolution and sources of biodiversity in the Phanerozoic.
Kiessling, Wolfgang; Simpson, Carl; Foote, Michael
2010-01-08
Large-scale biodiversity gradients among environments and habitats are usually attributed to a complex array of ecological and evolutionary factors. We tested the evolutionary component of such gradients by compiling the environments of the geologically oldest occurrences of marine genera and using sampling standardization to assess if originations tended to be clustered in particular environments. Shallow, tropical environments and carbonate substrates all tend to have harbored high origination rates. Diversity within these environments tended to be preferentially generated in reefs, probably because of their habitat complexity. Reefs were also prolific at exporting diversity to other environments, which might be a consequence of low-diversity habitats being more susceptible to invasions.
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Yeh, Hui-Chun; Hsu, Pei-Yung; Tsai, Ah-Lim; Wang, Lee-Ho
2010-01-01
Prostacyclin synthase (PGIS) is a member of the cytochrome P450 family in which the oxyferrous complexes are generally labile in the absence of substrate. At 4 °C, the on-rate constants and off-rate constants of oxygen binding to PGIS in solution are 5.9 × 105 m−1 ·s−1 and 29 s−1, respectively. The oxyferrous complex decays to a ferric form at a rate of 12 s−1. We report, for the first time, a stable oxyferrous complex of PGIS in a transparent sol–gel monolith. The encapsulated ferric PGIS retained the same spectroscopic features as in solution. The binding capabilities of the encapsulated PGIS were demonstrated by spectral changes upon the addition of O-based, N-based and C-based ligands. The peroxidase activity of PGIS in sol–gel was three orders of magnitude slower than that in solution owing to the restricted diffusion of the substrate in sol–gel. The oxyferrous complex in sol–gel was observable for 24 h at room temperature and displayed a much red-shifted Soret peak. Stabilization of the ferrous–carbon monoxide complex in sol–gel was observed as an enrichment of the 450-nm species over the 420-nm species. This result suggests that the sol–gel method may be applied to other P450s to generate a stable intermediate in the di-oxygen activation. PMID:18397321
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Yoav, Shahar; Barak, Yoav; Shamshoum, Melina; Borovok, Ilya; Lamed, Raphael; Dassa, Bareket; Hadar, Yitzhak; Morag, Ely; Bayer, Edward A
2017-01-01
Bioethanol production processes involve enzymatic hydrolysis of pretreated lignocellulosic biomass into fermentable sugars. Due to the relatively high cost of enzyme production, the development of potent and cost-effective cellulolytic cocktails is critical for increasing the cost-effectiveness of bioethanol production. In this context, the multi-protein cellulolytic complex of Clostridium ( Ruminiclostridium ) thermocellum, the cellulosome, was studied here. C. thermocellum is known to assemble cellulosomes of various subunit (enzyme) compositions, in response to the available carbon source. In the current study, different carbon sources were used, and their influence on both cellulosomal composition and the resultant activity was investigated. Glucose, cellobiose, microcrystalline cellulose, alkaline-pretreated switchgrass, alkaline-pretreated corn stover, and dilute acid-pretreated corn stover were used as sole carbon sources in the growth media of C. thermocellum strain DSM 1313. The purified cellulosomes were compared for their activity on selected cellulosic substrates. Interestingly, cellulosomes derived from cells grown on lignocellulosic biomass showed no advantage in hydrolyzing the original carbon source used for their production. Instead, microcrystalline cellulose- and glucose-derived cellulosomes were equal or superior in their capacity to deconstruct lignocellulosic biomass. Mass spectrometry analysis revealed differential composition of catalytic and structural subunits (scaffoldins) in the different cellulosome samples. The most abundant catalytic subunits in all cellulosome types include Cel48S, Cel9K, Cel9Q, Cel9R, and Cel5G. Microcrystalline cellulose- and glucose-derived cellulosome samples showed higher endoglucanase-to-exoglucanase ratios and higher catalytic subunit-per-scaffoldin ratios compared to lignocellulose-derived cellulosome types. The results reported here highlight the finding that cellulosomes derived from cells grown on glucose and microcrystalline cellulose are more efficient in their action on cellulosic substrates than other cellulosome preparations. These results should be considered in the future development of C. thermocellum -based cellulolytic cocktails, designer cellulosomes, or engineering of improved strains for deconstruction of lignocellulosic biomass.
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NASA Astrophysics Data System (ADS)
Shu, Guoyang; Dai, Bing; Ralchenko, V. G.; Khomich, A. A.; Ashkinazi, E. E.; Bolshakov, A. P.; Bokova-Sirosh, S. N.; Liu, Kang; Zhao, Jiwen; Han, Jiecai; Zhu, Jiaqi
2017-04-01
We studied defects and stress distributions in mosaic epitaxial diamond film using a confocal Raman spectroscopy, with a special attention to the junction area between the crystals. The mosaics was grown by microwave plasma CVD on closely arranged (1 0 0)-oriented HPHT type Ib substrates. The width of stress affected and defect enriched region around the junction show a tendency of extending with the film thickness, from ≈40 μm on the film-substrate interface to ≈250 μm in the layer 500 μm above the substrate, as found from the mosaics analysis in cross-section. The stress field around the junction demonstrates a complex pattern, with mixed domains of tensile and compressive stress, with maximum value of σ ≈ 0.6 GPa. A similar non-uniform pattern was observed for defect distribution as well. No sign of amorphous sp2 carbon in the junction zone was revealed.
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Morillo, Jose Antonio; Aguilera, Margarita; Ramos-Cormenzana, Alberto; Monteoliva-Sánchez, Mercedes
2006-09-01
The present study investigated the use of two-phase olive mill waste (TPOMW) as substrate for the production of exopolysaccharide (EPS) by the endospore-forming bacilli Paenibacillus jamilae. This microorganism was able to grow and produce EPS in aqueous extracts of TPOMW as a unique source of carbon. The effects of substrate concentration and the addition of inorganic nutrients were investigated. Maximal polymer yield in 100-ml batch-culture experiments (2 g l(-1)) was obtained in cultures prepared with an aqueous extract of 20% TPOMW (w/v). An inhibitory effect was observed on growth and EPS production when TPOMW concentration was increased. Nutrient supplementation (nitrate, phosphate, and other inorganic nutrients) did not increase yield. Finally, an adsorption experiment of Pb (II), Cd (II), Cu (II), Zn (II), Co (II), and Ni (II) by EPS is reported. Lead was preferentially complexed by the polymer, with a maximal uptake of 230 mg/g EPS.
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Poelma, Saemi O; Burnett, G Leslie; Discekici, Emre H; Mattson, Kaila M; Treat, Nicolas J; Luo, Yingdong; Hudson, Zachary M; Shankel, Shelby L; Clark, Paul G; Kramer, John W; Hawker, Craig J; Read de Alaniz, Javier
2016-08-19
Despite the number of methods available for dehalogenation and carbon-carbon bond formation using aryl halides, strategies that provide chemoselectivity for systems bearing multiple carbon-halogen bonds are still needed. Herein, we report the ability to tune the reduction potential of metal-free phenothiazine-based photoredox catalysts and demonstrate the application of these catalysts for chemoselective carbon-halogen bond activation to achieve C-C cross-coupling reactions as well as reductive dehalogenations. This procedure works both for conjugated polyhalides as well as unconjugated substrates. We further illustrate the usefulness of this protocol by intramolecular cyclization of a pyrrole substrate, an advanced building block for a family of natural products known to exhibit biological activity.
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NASA Astrophysics Data System (ADS)
Werther, Tobias; Wahlefeld, Stefan; Salewski, Johannes; Kuhlmann, Uwe; Zebger, Ingo; Hildebrandt, Peter; Dobbek, Holger
2017-07-01
How an enzyme activates its substrate for turnover is fundamental for catalysis but incompletely understood on a structural level. With redox enzymes one typically analyses structures of enzyme-substrate complexes in the unreactive oxidation state of the cofactor, assuming that the interaction between enzyme and substrate is independent of the cofactors oxidation state. Here, we investigate the Michaelis complex of the flavoenzyme xenobiotic reductase A with the reactive reduced cofactor bound to its substrates by X-ray crystallography and resonance Raman spectroscopy and compare it to the non-reactive oxidized Michaelis complex mimics. We find that substrates bind in different orientations to the oxidized and reduced flavin, in both cases flattening its structure. But only authentic Michaelis complexes display an unexpected rich vibrational band pattern uncovering a strong donor-acceptor complex between reduced flavin and substrate. This interaction likely activates the catalytic ground state of the reduced flavin, accelerating the reaction within a compressed cofactor-substrate complex.
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Werther, Tobias; Wahlefeld, Stefan; Salewski, Johannes; Kuhlmann, Uwe; Zebger, Ingo; Hildebrandt, Peter; Dobbek, Holger
2017-01-01
How an enzyme activates its substrate for turnover is fundamental for catalysis but incompletely understood on a structural level. With redox enzymes one typically analyses structures of enzyme–substrate complexes in the unreactive oxidation state of the cofactor, assuming that the interaction between enzyme and substrate is independent of the cofactors oxidation state. Here, we investigate the Michaelis complex of the flavoenzyme xenobiotic reductase A with the reactive reduced cofactor bound to its substrates by X-ray crystallography and resonance Raman spectroscopy and compare it to the non-reactive oxidized Michaelis complex mimics. We find that substrates bind in different orientations to the oxidized and reduced flavin, in both cases flattening its structure. But only authentic Michaelis complexes display an unexpected rich vibrational band pattern uncovering a strong donor–acceptor complex between reduced flavin and substrate. This interaction likely activates the catalytic ground state of the reduced flavin, accelerating the reaction within a compressed cofactor–substrate complex.
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Elevated Colonization of Microborers at a Volcanically Acidified Coral Reef
Enochs, Ian C.; Manzello, Derek P.; Tribollet, Aline; Valentino, Lauren; Kolodziej, Graham; Donham, Emily M.; Fitchett, Mark D.; Carlton, Renee; Price, Nichole N.
2016-01-01
Experiments have demonstrated that ocean acidification (OA) conditions projected to occur by the end of the century will slow the calcification of numerous coral species and accelerate the biological erosion of reef habitats (bioerosion). Microborers, which bore holes less than 100 μm diameter, are one of the most pervasive agents of bioerosion and are present throughout all calcium carbonate substrates within the reef environment. The response of diverse reef functional groups to OA is known from real-world ecosystems, but to date our understanding of the relationship between ocean pH and carbonate dissolution by microborers is limited to controlled laboratory experiments. Here we examine the settlement of microborers to pure mineral calcium carbonate substrates (calcite) along a natural pH gradient at a volcanically acidified reef at Maug, Commonwealth of the Northern Mariana Islands (CNMI). Colonization of pioneer microborers was higher in the lower pH waters near the vent field. Depth of microborer penetration was highly variable both among and within sites (4.2–195.5 μm) over the short duration of the study (3 mo.) and no clear relationship to increasing CO2 was observed. Calculated rates of biogenic dissolution, however, were highest at the two sites closer to the vent and were not significantly different from each other. These data represent the first evidence of OA-enhancement of microboring flora colonization in newly available substrates and provide further evidence that microborers, especially bioeroding chlorophytes, respond positively to low pH. The accelerated breakdown and dissolution of reef framework structures with OA will likely lead to declines in structural complexity and integrity, as well as possible loss of essential habitat. PMID:27467570
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Elevated Colonization of Microborers at a Volcanically Acidified Coral Reef.
Enochs, Ian C; Manzello, Derek P; Tribollet, Aline; Valentino, Lauren; Kolodziej, Graham; Donham, Emily M; Fitchett, Mark D; Carlton, Renee; Price, Nichole N
2016-01-01
Experiments have demonstrated that ocean acidification (OA) conditions projected to occur by the end of the century will slow the calcification of numerous coral species and accelerate the biological erosion of reef habitats (bioerosion). Microborers, which bore holes less than 100 μm diameter, are one of the most pervasive agents of bioerosion and are present throughout all calcium carbonate substrates within the reef environment. The response of diverse reef functional groups to OA is known from real-world ecosystems, but to date our understanding of the relationship between ocean pH and carbonate dissolution by microborers is limited to controlled laboratory experiments. Here we examine the settlement of microborers to pure mineral calcium carbonate substrates (calcite) along a natural pH gradient at a volcanically acidified reef at Maug, Commonwealth of the Northern Mariana Islands (CNMI). Colonization of pioneer microborers was higher in the lower pH waters near the vent field. Depth of microborer penetration was highly variable both among and within sites (4.2-195.5 μm) over the short duration of the study (3 mo.) and no clear relationship to increasing CO2 was observed. Calculated rates of biogenic dissolution, however, were highest at the two sites closer to the vent and were not significantly different from each other. These data represent the first evidence of OA-enhancement of microboring flora colonization in newly available substrates and provide further evidence that microborers, especially bioeroding chlorophytes, respond positively to low pH. The accelerated breakdown and dissolution of reef framework structures with OA will likely lead to declines in structural complexity and integrity, as well as possible loss of essential habitat.
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NASA Astrophysics Data System (ADS)
Tang, Jin-Yun; Riley, William J.
2017-09-01
Several land biogeochemical models used for studying carbon-climate feedbacks have begun explicitly representing microbial dynamics. However, to our knowledge, there has been no theoretical work on how to achieve a consistent scaling of the complex biogeochemical reactions from microbial individuals to populations, communities, and interactions with plants and mineral soils. We focus here on developing a mathematical formulation of the substrate-consumer relationships for consumer-mediated redox reactions of the form A + BE→ products, where products could be, e.g., microbial biomass or bioproducts. Under the quasi-steady-state approximation, these substrate-consumer relationships can be formulated as the computationally difficult full equilibrium chemistry problem or approximated analytically with the dual Monod (DM) or synthesizing unit (SU) kinetics. We find that DM kinetics is scaling inconsistently for reaction networks because (1) substrate limitations are not considered, (2) contradictory assumptions are made regarding the substrate processing rate when transitioning from single- to multi-substrate redox reactions, and (3) the product generation rate cannot be scaled from one to multiple substrates. In contrast, SU kinetics consistently scales the product generation rate from one to multiple substrates but predicts unrealistic results as consumer abundances reach large values with respect to their substrates. We attribute this deficit to SU's failure to incorporate substrate limitation in its derivation. To address these issues, we propose SUPECA (SU plus the equilibrium chemistry approximation - ECA) kinetics, which consistently imposes substrate and consumer mass balance constraints. We show that SUPECA kinetics satisfies the partition principle, i.e., scaling invariance across a network of an arbitrary number of reactions (e.g., as in Newton's law of motion and Dalton's law of partial pressures). We tested SUPECA kinetics with the equilibrium chemistry solution for some simple problems and found SUPECA outperformed SU kinetics. As an example application, we show that a steady-state SUPECA-based approach predicted an aerobic soil respiration moisture response function that agreed well with laboratory observations. We conclude that, as an extension to SU and ECA kinetics, SUPECA provides a robust mathematical representation of complex soil substrate-consumer interactions and can be applied to improve Earth system model (ESM) land models.
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Franseen, E.K.; Goldstein, R.H.; Farr, M.R.
1997-01-01
Sequence stratigraphy, pinning-point relative sea-level curves, and magnetostratigraphy provide the quantitative data necessary to understand how rates of sea-level change and different substrate paleoslopes are dominant controls on accumulation rate, carbonate depositional sequence location, and internal architecture. Five third-order (1-10 my) and fourth-order (0.1-1.0 my) upper Miocene carbonate depositional sequences (DS1A, DS1B, DS2, DS3, TCC) formed with superimposed higher-frequency sea-level cycles in an archipelago setting in SE Spain. Overall, our study indicates when areas of high substrate slope (> 15??) are in shallow water, independent of climate, the location and internal architecture of carbonate deposits are not directly linked to sea-level position but, instead, are controlled by location of gently sloping substrates and processes of bypass. In contrast, if carbonate sediments are generated where substrates of low slope ( 15.6 cm/ky to ??? 2 cm/ky and overall relative sea level rose at rates of 17-21.4 cm/ky. Higher frequency sea-level rates were about 111 to more than 260 cm/ky, producing onlapping, fining- (deepening-) upward cycles. Decreasing accumulation rates resulted from decreasing surface area for shallow-water sediment production, drowning of shallow-water substrates, and complex sediment dispersal related to the archipelago setting. Typical systems tract and parasequence development should not be expected in "bypass ramp" settings; facies of onlapping strata do not track base level and are likely to be significantly different compared to onlapping strata associated with coastal onlap. Basal and upper DS2 reef megabreccias (indicating the transition from cool to warmer climatic conditions) were eroded from steep upslope positions and redeposited downslope onto areas of gentle substrate during rapid sea-level falls (> 22.7 cm/ky) of short duration. Such rapid sea-level falls and presence of steep slopes are not conducive to formation of forced regressive systems tracts composed of down-stepping reef clinoforms. The DS3 reefal platform formed where shallow water coincided with gently sloping substrates created by earlier deposition. Slow progradation (0.39-1.45 km/my) is best explained by the lack of an extensive bank top, progressively falling sea level, and low productivity resulting from siliciclastic debris and excess nutrients shed from nearby volcanic islands. Although DS3 strata were deposited during a third-order relative sea-level cycle, a typical transgressive systems tract is not recognizable, indicating that the initial relative rise in sea level was too rapid (??? 19 cm/ky). Downstepping reefs, forming a forced regressive systems tract, were deposited during the relative sea-level fall at the end of DS3, indicating that relatively slow rates of fall (10 cm/ky or less) over favorable paleoslope conditions are conducive to generation of forced regressive systems tracts consisting of downstepping reef clinoforms. The TCC sequence consists of four shallow-water sedimentary cycles that were deposited during a 400 ky to 100 ky time span. Such shallow-water cycles, typical of many platforms, form only where shallow water intersects gently sloping substrates. The relative thicknesses of cycles (< 2 m to 15 m thick), magnitudes of relative sea-level fluctuations associated with each cycle (25-30 m), high rates of relative sea-level fluctuations (minimum of 25-120 cm/ky), and the widespread distribution of similar TCC cycles in the Mediterranean and elsewhere are supportive of a glacio-eustatic
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Franseen, E.K.; Goldstein, R.H.; Farr, M.R.
1998-01-01
Sequence stratigraphy, pinning-point relative sea-level curves, and magnetostratigraphy provide the quantitative data necessary to understand how rates of sea-level change and different substrate paleoslopes are dominant controls on accumulation rate, carbonate depositional sequence location, and internal architecture. Five third-order (1-10 my) and fourth-order (0.1-1.0 my) upper Miocene carbonate depositional sequences (DS1A, DS1B, DS2, DS3, TCC) formed with superimposed higher-frequency sea-level cycles in an archipelago setting in SE Spain. Overall, our study indicates when areas of high substrate slope (> 15??) are in shallow water, independent of climate, the location and internal architecture of carbonate deposits are not directly linked to sea-level position but, instead, are controlled by location of gently sloping substrates and processes of bypass. In contrast, if carbonate sediments are generated where substrates of low slope ( 15.6 cm/ky to ??? 2 cm/ky and overall relative sea level rose at rates of 17-21.4 cm/ky. Higher frequency sea-level rates were about 111 to more than 260 cm/ky, producing onlapping, fining- (deepening-) upward cycles. Decreasing accumulation rates resulted from decreasing surface area for shallow-water sediment production, drowning of shallow-water substrates, and complex sediment dispersal related to the archipelago setting. Typical systems tract and parasequence development should not be expected in "bypass ramp" settings; facies of onlapping strata do not track base level and are likely to be significantly different compared to onlapping strata associated with coastal onlap. Basal and upper DS2 reef megabreccias (indicating the transition from cool to warmer climatic conditions) were eroded from steep upslope positions and redeposited downslope onto areas of gentle substrate during rapid sea-level falls (> 22.7 cm/ky) of short duration. Such rapid sea-level falls and presence of steep slopes are not conducive to formation of forced regressive systems tracts composed of downstepping reef clinoforms. The DS3 reefal platform formed where shallow water coincided with gently sloping substrates created by earlier deposition. Slow progradation (0.39-1.45 km/my) is best explained by the lack of an extensive bank top, progressively falling sea level, and low productivity resulting from siliciclastic debris and excess nutrients shed from nearby volcanic islands. Although DS3 strata were deposited during a third-order relative sea-level cycle, a typical transgresse??e systems tract is not recognizable, indicating that the initial relative rise in sea level was too rapid (??? 19 cm/ky). Downstepping reefs, forming a forced regressive systems tract, were deposited during the relative sea-level fall at the end of DS3, indicating that relatively slow rates of fall (10 cm/ky or less) over favorable paleoslope conditions are conducive to generation of forced regressive systems tracts consisting of downstepping reef clinoforms. The TCC sequence consists of four shallow -water sedimentary cycles that were deposited during a 400 ky to 100 ky time span. Such shallow-water cycles, typical of many platforms, form only where shallow water intersects gently sloping substrates. The relative thicknesses of cycles (< 2 m to 15 m thick), magnitudes of relative sea-level fluctuations associated with each cycle (25-30 m), high rates of relative sea-level fluctuations (minimum of 25-120 cm/ky), and the widespread distribution of similar TCC cycles in the Mediterranean and elsewhere are supportive of a glacio-eustati
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Liu, Li; Helbling, Damian E; Kohler, Hans-Peter E; Smets, Barth F
2014-11-18
Pollutants such as pesticides and their degradation products occur ubiquitously in natural aquatic environments at trace concentrations (μg L(-1) and lower). Microbial biodegradation processes have long been known to contribute to the attenuation of pesticides in contaminated environments. However, challenges remain in developing engineered remediation strategies for pesticide-contaminated environments because the fundamental processes that regulate growth-linked biodegradation of pesticides in natural environments remain poorly understood. In this research, we developed a model framework to describe growth-linked biodegradation of pesticides at trace concentrations. We used experimental data reported in the literature or novel simulations to explore three fundamental kinetic processes in isolation. We then combine these kinetic processes into a unified model framework. The three kinetic processes described were: the growth-linked biodegradation of micropollutant at environmentally relevant concentrations; the effect of coincidental assimilable organic carbon substrates; and the effect of coincidental microbes that compete for assimilable organic carbon substrates. We used Monod kinetic models to describe substrate utilization and microbial growth rates for specific pesticide and degrader pairs. We then extended the model to include terms for utilization of assimilable organic carbon substrates by the specific degrader and coincidental microbes, growth on assimilable organic carbon substrates by the specific degrader and coincidental microbes, and endogenous metabolism. The proposed model framework enables interpretation and description of a range of experimental observations on micropollutant biodegradation. The model provides a useful tool to identify environmental conditions with respect to the occurrence of assimilable organic carbon and coincidental microbes that may result in enhanced or reduced micropollutant biodegradation.
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Soil Carbon Decomposition: "Quality control" or logistic challenge?
NASA Astrophysics Data System (ADS)
Kleber, M.
2011-12-01
A long tradition of soil organic matter research has generated the belief that there is "stable" soil organic carbon, thought to be recalcitrant because molecular compounds such as aromatic rings and aliphatic chains are joined to polymeric macromolecules by processes of secondary syntheses. The Carbon-Quality Temperature (CQT) theory posits that such materials should be considered "low quality" substrates, because they would require large Arrhenius activation energies for full conversion to CO2. This, in turn, has generated the notion that recalcitrant organic matter should be more temperature sensitive to elevated temperatures than less complex, more "labile" soil organic matter. Yet the molecular properties of stable carbon are elusive - so far, it has not been possible to parameterize molecular recalcitrance in a context -independent fashion. Classic humic substances and even charcoal are readily broken down when placed in an environment where microorganisms with a suitable catabolic toolbox can resort to a plentiful supply of cometabolites and oxygen. At the same time we find labile substrates such as glucose to survive for decades when enclosed within soil aggregates. What then determines the temperature sensitivity of decomposition? Should the scientific community continue to hunt for some molecular proxy for organic matter quality (such as degree of polymerization, aromaticity, aqueous solubility etc) to predict the fate of soil organic carbon in a changing world? This contribution proposes a fundamentally different approach by treating soils as reaction vessels analogous to an industrial bioreactor. Soils are considered as capable of processing dead plant material in all its molecular variations. Decomposition is seen as constrained by environmental drivers, microbial ecology and community composition, and the physical structure of the soil environment. The hypotheses is put forward that, compared to variations in the logistic status of the soil reactor, molecular variations within the substrate are insignificant for the response of the system to rising temperatures. Three functional soil reactor types are distinguished, each representing a specific process space with unique, rate controlling logistics: a) the litter layer, b) the rhizosphere and c) the subsoil.
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NASA Astrophysics Data System (ADS)
Žáková, Pavlína; Slepičková Kasálková, Nikola; Slepička, Petr; Kolská, Zdeňka; Karpíšková, Jana; Stibor, Ivan; Švorčík, Václav
2017-11-01
Various carbon nanostructures are widely researched as scaffolds for tissue engineering. We evaluated the surface properties and cell-substrate interactions of carbon nanoparticles functionalized with triethylenetetramine (CNPs) grafted polymer film. Two forms of polyethylene (HDPE, LDPE) were treated in an inert argon plasma discharge and, subsequently, grafted with CNPs. The surface properties were studied using multiple methods, including Raman spectroscopy, goniometry, atomic force microscopy, X-ray photoelectron spectroscopy and electrokinetic analysis. Cell-substrate interactions were determined in vitro by studying adhesion, proliferation and viability of vascular smooth muscle cells (VSMCs) from the aorta of a rat. Cell-substrate interactions on pristine and modified substrates were compared to standard tissue culture polystyrene. Our results show that CNPs affect surface morphology and wettability and therefore adhesion, proliferation and viability of cultured muscle cells.
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NASA Astrophysics Data System (ADS)
Kopf, S.; McGlynn, S.; Cowley, E.; Green, A.; Newman, D. K.; Orphan, V. J.
2014-12-01
Metabolic rates of microbial communities constitute a key physiological parameter for understanding the in situ growth constraints for life in any environment. Isotope labeling techniques provide a powerful approach for measuring such biological activity, due to the use of isotopically enriched substrate tracers whose incorporation into biological materials can be detected with high sensitivity by isotope-ratio mass spectrometry. Nano-meter scale secondary ion mass spectrometry (NanoSIMS) combined with stable isotope labeling provides a unique tool for studying the spatiometabolic activity of microbial populations at the single cell level in order to assess both community structure and population diversity. However, assessing the distribution and range of microbial activity in complex environmental systems with slow-growing organisms, diverse carbon and nitrogen sources, or heterotrophic subpopulations poses a tremendous technical challenge because the introduction of isotopically labeled substrates frequently changes the nutrient availability and can inflate or bias measures of activity. Here, we present the use of hydrogen isotope labeling with deuterated water as an important new addition to the isotopic toolkit and apply it for the determination of single cell microbial activities by NanoSIMS imaging. This tool provides a labeling technique that minimally alters any aquatic chemical environment, can be administered with strong labels even in minimal addition (natural background is very low), is an equally universal substrate for all forms of life even in complex, carbon and nitrogen saturated systems, and can be combined with other isotopic tracers. The combination of heavy water labeling with the most commonly used NanoSIMS tracer, 15N, is technically challenging but opens up a powerful new set of multi-tracer experiments for the study of microbial activity in complex communities. We present the first truly simultaneous single cell triple isotope system measurements of 2H/1H, 13C/12C and 15N/14N and apply it to study of microbial metabolic heterogeneity and nitrogen metabolism in a continuous culture case study. Our data provide insight into both the diversity of microbial activity rates, as well as patterns of ammonium utilization at the single cell level.
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Liang, Yu Teng; Vijayan, Baiju K.; Gray, Kimberly A.; Hersam, Mark C.
2016-07-19
In one aspect, a method of making non-covalently bonded carbon-titania nanocomposite thin films includes: forming a carbon-based ink; forming a titania (TiO.sub.2) solution; blade-coating a mechanical mixture of the carbon-based ink and the titania solution onto a substrate; and annealing the blade-coated substrate at a first temperature for a first period of time to obtain the carbon-based titania nanocomposite thin films. In certain embodiments, the carbon-based titania nanocomposite thin films may include solvent-exfoliated graphene titania (SEG-TiO.sub.2) nanocomposite thin films, or single walled carbon nanotube titania (SWCNT-TiO.sub.2) nanocomposite thin films.
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Germination and seedling establishment in orchids: a complex of requirements
Rasmussen, Hanne N.; Dixon, Kingsley W.; Jersáková, Jana; Těšitelová, Tamara
2015-01-01
Background Seedling recruitment is essential to the sustainability of any plant population. Due to the minute nature of seeds and early-stage seedlings, orchid germination in situ was for a long time practically impossible to observe, creating an obstacle towards understanding seedling site requirements and fluctuations in orchid populations. The introduction of seed packet techniques for sowing and retrieval in natural sites has brought with it important insights, but many aspects of orchid seed and germination biology remain largely unexplored. Key Considerations The germination niche for orchids is extremely complex, because it is defined by requirements not only for seed lodging and germination, but also for presence of a fungal host and its substrate. A mycobiont that the seedling can parasitize is considered an essential element, and a great diversity of Basidiomycota and Ascomycota have now been identified for their role in orchid seed germination, with fungi identifiable as imperfect Rhizoctonia species predominating. Specificity patterns vary from orchid species employing a single fungal lineage to species associating individually with a limited selection of distantly related fungi. A suitable organic carbon source for the mycobiont constitutes another key requirement. Orchid germination also relies on factors that generally influence the success of plant seeds, both abiotic, such as light/shade, moisture, substrate chemistry and texture, and biotic, such as competitors and antagonists. Complexity is furthermore increased when these factors influence seeds/seedling, fungi and fungal substrate differentially. Conclusions A better understanding of germination and seedling establishment is needed for conservation of orchid populations. Due to the obligate association with a mycobiont, the germination niches in orchid species are extremely complex and varied. Microsites suitable for germination can be small and transient, and direct observation is difficult. An experimental approach using several levels of environmental manipulation/control is recommended. PMID:26271118
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Nanocatalyst shape and composition during nucleation of single-walled carbon nanotubes
Gomez-Ballesteros, Jose L.; Burgos, Juan C.; Lin, Pin Ann; ...
2015-12-07
The dynamic evolution of nanocatalyst particle shape and carbon composition during the initial stages of single-walled carbon nanotube growth by chemical vapor deposition synthesis is investigated. Classical reactive and ab initio molecular dynamics simulations are used, along with environmental transmission electron microscope video imaging analyses. A clear migration of carbon is detected from the nanocatalyst/substrate interface, leading to a carbon gradient showing enrichment of the nanocatalyst layers in the immediate vicinity of the contact layer. However, as the metal nanocatalyst particle becomes saturated with carbon, a dynamic equilibrium is established, with carbon precipitating on the surface and nucleating a carbonmore » cap that is the precursor of nanotube growth. A carbon composition profile decreasing towards the nanoparticle top is clearly revealed by the computational and experimental results that show a negligible amount of carbon in the nanoparticle region in contact with the nucleating cap. The carbon composition profile inside the nanoparticle is accompanied by a well-defined shape evolution of the nanocatalyst driven by the various opposing forces acting upon it both from the substrate and from the nascent carbon nanostructure. In conclusion, this new understanding suggests that tuning the nanoparticle/substrate interaction would provide unique ways of controlling the nanotube synthesis.« less
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van Munster, Jolanda M.; Daly, Paul; Delmas, Stéphane; Pullan, Steven T.; Blythe, Martin J.; Malla, Sunir; Kokolski, Matthew; Noltorp, Emelie C.M.; Wennberg, Kristin; Fetherston, Richard; Beniston, Richard; Yu, Xiaolan; Dupree, Paul; Archer, David B.
2014-01-01
Fungi are an important source of enzymes for saccharification of plant polysaccharides and production of biofuels. Understanding of the regulation and induction of expression of genes encoding these enzymes is still incomplete. To explore the induction mechanism, we analysed the response of the industrially important fungus Aspergillus niger to wheat straw, with a focus on events occurring shortly after exposure to the substrate. RNA sequencing showed that the transcriptional response after 6 h of exposure to wheat straw was very different from the response at 24 h of exposure to the same substrate. For example, less than half of the genes encoding carbohydrate active enzymes that were induced after 24 h of exposure to wheat straw, were also induced after 6 h exposure. Importantly, over a third of the genes induced after 6 h of exposure to wheat straw were also induced during 6 h of carbon starvation, indicating that carbon starvation is probably an important factor in the early response to wheat straw. The up-regulation of the expression of a high number of genes encoding CAZymes that are active on plant-derived carbohydrates during early carbon starvation suggests that these enzymes could be involved in a scouting role during starvation, releasing inducing sugars from complex plant polysaccharides. We show, using proteomics, that carbon-starved cultures indeed release CAZymes with predicted activity on plant polysaccharides. Analysis of the enzymatic activity and the reaction products, indicates that these proteins are enzymes that can degrade various plant polysaccharides to generate both known, as well as potentially new, inducers of CAZymes. PMID:24792495
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van Munster, Jolanda M; Daly, Paul; Delmas, Stéphane; Pullan, Steven T; Blythe, Martin J; Malla, Sunir; Kokolski, Matthew; Noltorp, Emelie C M; Wennberg, Kristin; Fetherston, Richard; Beniston, Richard; Yu, Xiaolan; Dupree, Paul; Archer, David B
2014-11-01
Fungi are an important source of enzymes for saccharification of plant polysaccharides and production of biofuels. Understanding of the regulation and induction of expression of genes encoding these enzymes is still incomplete. To explore the induction mechanism, we analysed the response of the industrially important fungus Aspergillus niger to wheat straw, with a focus on events occurring shortly after exposure to the substrate. RNA sequencing showed that the transcriptional response after 6h of exposure to wheat straw was very different from the response at 24h of exposure to the same substrate. For example, less than half of the genes encoding carbohydrate active enzymes that were induced after 24h of exposure to wheat straw, were also induced after 6h exposure. Importantly, over a third of the genes induced after 6h of exposure to wheat straw were also induced during 6h of carbon starvation, indicating that carbon starvation is probably an important factor in the early response to wheat straw. The up-regulation of the expression of a high number of genes encoding CAZymes that are active on plant-derived carbohydrates during early carbon starvation suggests that these enzymes could be involved in a scouting role during starvation, releasing inducing sugars from complex plant polysaccharides. We show, using proteomics, that carbon-starved cultures indeed release CAZymes with predicted activity on plant polysaccharides. Analysis of the enzymatic activity and the reaction products, indicates that these proteins are enzymes that can degrade various plant polysaccharides to generate both known, as well as potentially new, inducers of CAZymes. Copyright © 2014 The Authors. Published by Elsevier Inc. All rights reserved.
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Dusza, Yann; Barot, Sébastien; Kraepiel, Yvan; Lata, Jean-Christophe; Abbadie, Luc; Raynaud, Xavier
2017-04-01
Green roofs provide ecosystem services through evapotranspiration and nutrient cycling that depend, among others, on plant species, substrate type, and substrate depth. However, no study has assessed thoroughly how interactions between these factors alter ecosystem functions and multifunctionality of green roofs. We simulated some green roof conditions in a pot experiment. We planted 20 plant species from 10 genera and five families (Asteraceae, Caryophyllaceae, Crassulaceae, Fabaceae, and Poaceae) on two substrate types (natural vs. artificial) and two substrate depths (10 cm vs. 30 cm). As indicators of major ecosystem functions, we measured aboveground and belowground biomasses, foliar nitrogen and carbon content, foliar transpiration, substrate water retention, and dissolved organic carbon and nitrates in leachates. Interactions between substrate type and depth strongly affected ecosystem functions. Biomass production was increased in the artificial substrate and deeper substrates, as was water retention in most cases. In contrast, dissolved organic carbon leaching was higher in the artificial substrates. Except for the Fabaceae species, nitrate leaching was reduced in deep, natural soils. The highest transpiration rates were associated with natural soils. All functions were modulated by plant families or species. Plant effects differed according to the observed function and the type and depth of the substrate. Fabaceae species grown on natural soils had the most noticeable patterns, allowing high biomass production and high water retention but also high nitrate leaching from deep pots. No single combination of factors enhanced simultaneously all studied ecosystem functions, highlighting that soil-plant interactions induce trade-offs between ecosystem functions. Substrate type and depth interactions are major drivers for green roof multifunctionality.
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Co-Consumption of Methanol and Succinate by Methylobacterium extorquens AM1
Peyraud, Rémi; Kiefer, Patrick; Christen, Philipp; Portais, Jean-Charles; Vorholt, Julia A.
2012-01-01
Methylobacterium extorquens AM1 is a facultative methylotrophic Alphaproteobacterium and has been subject to intense study under pure methylotrophic as well as pure heterotrophic growth conditions in the past. Here, we investigated the metabolism of M. extorquens AM1 under mixed substrate conditions, i.e., in the presence of methanol plus succinate. We found that both substrates were co-consumed, and the carbon conversion was two-thirds from succinate and one-third from methanol relative to mol carbon. 13C-methanol labeling and liquid chromatography mass spectrometry analyses revealed the different fates of the carbon from the two substrates. Methanol was primarily oxidized to CO2 for energy generation. However, a portion of the methanol entered biosynthetic reactions via reactions specific to the one-carbon carrier tetrahydrofolate. In contrast, succinate was primarily used to provide precursor metabolites for bulk biomass production. This work opens new perspectives on the role of methylotrophy when substrates are simultaneously available, a situation prevailing under environmental conditions. PMID:23133625
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Liu, Yuhao; Lü, Fan; Shao, Liming; He, Pinjing
2016-10-01
The objective of the study was to investigate whether the ratio of ethanol to acetate affects yield and product structure in chain elongation initiated by unacclimatized mixed cultures. The effect of varying the substrate concentration, while maintaining the same ratio of alcohol to acid, was also investigated. With a high substrate concentration, an alcohol to acid ratio >2:1 provided sufficient electron donor capacity for the chain elongation reaction. With an ethanol to acetate ratio of 3:1 (300mM total carbon), the highest n-caproate concentration (3033±98mg/L) was achieved during the stable phase of the reaction. A lower substrate concentration (150mM total carbon) gave a lower yield of products and led to reduced carbon transformation efficiency compared with other reaction conditions. The use of unacclimatized inoculum in chain elongation can produce significant amounts of odd-carbon-number carboxylates as a result of protein hydrolysis. Copyright © 2016 Elsevier Ltd. All rights reserved.
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Method for in-situ cleaning of carbon contaminated surfaces
Klebanoff, Leonard E.; Grunow, Philip; Graham, Jr., Samuel
2006-12-12
Activated gaseous species generated adjacent a carbon contaminated surface affords in-situ cleaning. A device for removing carbon contamination from a surface of the substrate includes (a) a housing defining a vacuum chamber in which the substrate is located; (b) a source of gaseous species; and (c) a source of electrons that are emitted to activate the gaseous species into activated gaseous species. The source of electrons preferably includes (i) a filament made of a material that generates thermionic electron emissions; (ii) a source of energy that is connected to the filament; and (iii) an electrode to which the emitted electrons are attracted. The device is particularly suited for photolithography systems with optic surfaces, e.g., mirrors, that are otherwise inaccessible unless the system is dismantled. A method of removing carbon contaminants from a substrate surface that is housed within a vacuum chamber is also disclosed. The method employs activated gaseous species that react with the carbon contaminants to form carbon containing gaseous byproducts.
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Proteolytic regulation of metabolic enzymes by E3 ubiquitin ligase complexes: lessons from yeast.
Nakatsukasa, Kunio; Okumura, Fumihiko; Kamura, Takumi
2015-01-01
Eukaryotic organisms use diverse mechanisms to control metabolic rates in response to changes in the internal and/or external environment. Fine metabolic control is a highly responsive, energy-saving process that is mediated by allosteric inhibition/activation and/or reversible modification of preexisting metabolic enzymes. In contrast, coarse metabolic control is a relatively long-term and expensive process that involves modulating the level of metabolic enzymes. Coarse metabolic control can be achieved through the degradation of metabolic enzymes by the ubiquitin-proteasome system (UPS), in which substrates are specifically ubiquitinated by an E3 ubiquitin ligase and targeted for proteasomal degradation. Here, we review select multi-protein E3 ligase complexes that directly regulate metabolic enzymes in Saccharomyces cerevisiae. The first part of the review focuses on the endoplasmic reticulum (ER) membrane-associated Hrd1 and Doa10 E3 ligase complexes. In addition to their primary roles in the ER-associated degradation pathway that eliminates misfolded proteins, recent quantitative proteomic analyses identified native substrates of Hrd1 and Doa10 in the sterol synthesis pathway. The second part focuses on the SCF (Skp1-Cul1-F-box protein) complex, an abundant prototypical multi-protein E3 ligase complex. While the best-known roles of the SCF complex are in the regulation of the cell cycle and transcription, accumulating evidence indicates that the SCF complex also modulates carbon metabolism pathways. The increasing number of metabolic enzymes whose stability is directly regulated by the UPS underscores the importance of the proteolytic regulation of metabolic processes for the acclimation of cells to environmental changes.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Zestos, Alexander G.; Yang, Cheng; Jacobs, Christopher B.
Carbon nanomaterials are advantageous as electrodes for neurotransmitter detection, but the difficulty of nanomaterials deposition on electrode substrates limits the reproducibility and future applications. In our study, we used plasma enhanced chemical vapor deposition (PECVD) to directly grow a thin layer of carbon nanospikes (CNS) on cylindrical metal substrates. No catalyst is required and the CNS surface coverage is uniform over the cylindrical metal substrate. We characterized the CNS growth on several metallic substrates including tantalum, niobium, palladium, and nickel wires. Using fast-scan cyclic voltammetry (FSCV), bare metal wires could not detect 1 mu M dopamine while carbon nanospike coatedmore » wires could. Moreover, the highest sensitivity and optimized S/N ratio was recorded from carbon nanospike-tantalum (CNS-Ta) microwires grown for 7.5 minutes, which had a LOD of 8 +/- 2 nM for dopamine with FSCV. CNS-Ta microelectrodes were more reversible and had a smaller Delta E-p for dopamine than carbon-fiber microelectrodes, suggesting faster electron transfer kinetics. The kinetics of dopamine redox were adsorption controlled at CNS-Ta microelectrodes and repeated electrochemical measurements displayed stability for up to ten hours in vitro and over a ten day period as well. The oxidation potential was significantly different for ascorbic acid and uric acid compared to dopamine. Finally, growing carbon nanospikes on metal wires is a promising method to produce uniformly-coated, carbon nanostructured cylindrical microelectrodes for sensitive dopamine detection.« less
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Iron(IV)hydroxide pK(a) and the role of thiolate ligation in C-H bond activation by cytochrome P450.
Yosca, Timothy H; Rittle, Jonathan; Krest, Courtney M; Onderko, Elizabeth L; Silakov, Alexey; Calixto, Julio C; Behan, Rachel K; Green, Michael T
2013-11-15
Cytochrome P450 enzymes activate oxygen at heme iron centers to oxidize relatively inert substrate carbon-hydrogen bonds. Cysteine thiolate coordination to iron is posited to increase the pK(a) (where K(a) is the acid dissociation constant) of compound II, an iron(IV)hydroxide complex, correspondingly lowering the one-electron reduction potential of compound I, the active catalytic intermediate, and decreasing the driving force for deleterious auto-oxidation of tyrosine and tryptophan residues in the enzyme's framework. Here, we report on the preparation of an iron(IV)hydroxide complex in a P450 enzyme (CYP158) in ≥90% yield. Using rapid mixing technologies in conjunction with Mössbauer, ultraviolet/visible, and x-ray absorption spectroscopies, we determine a pK(a) value for this compound of 11.9. Marcus theory analysis indicates that this elevated pK(a) results in a >10,000-fold reduction in the rate constant for oxidations of the protein framework, making these processes noncompetitive with substrate oxidation.
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Impacts of Enhanced Reductive Bioremediation on Post-Remediation Groundwater Quality
2015-11-15
and natural attenuation of SWQIs at ERB sites. Much of the organic carbon added to the aquifer is fermented to CH4. In coarse-grained sediments...for stimulating ERB involves addition of a fermentable organic substrate to the aquifer to serve as an electron donor and carbon source for microbial...composed of edible oils or solid substrates tend to stay in place for an extended treatment period. Soluble substrates or soluble fermentation
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Carbon nanospikes grown on metal wires as microelectrode sensors for dopamine
Zestos, Alexander G.; Yang, Cheng; Jacobs, Christopher B.; ...
2015-09-14
Carbon nanomaterials are advantageous as electrodes for neurotransmitter detection, but the difficulty of nanomaterials deposition on electrode substrates limits the reproducibility and future applications. In our study, we used plasma enhanced chemical vapor deposition (PECVD) to directly grow a thin layer of carbon nanospikes (CNS) on cylindrical metal substrates. No catalyst is required and the CNS surface coverage is uniform over the cylindrical metal substrate. We characterized the CNS growth on several metallic substrates including tantalum, niobium, palladium, and nickel wires. Using fast-scan cyclic voltammetry (FSCV), bare metal wires could not detect 1 mu M dopamine while carbon nanospike coatedmore » wires could. Moreover, the highest sensitivity and optimized S/N ratio was recorded from carbon nanospike-tantalum (CNS-Ta) microwires grown for 7.5 minutes, which had a LOD of 8 +/- 2 nM for dopamine with FSCV. CNS-Ta microelectrodes were more reversible and had a smaller Delta E-p for dopamine than carbon-fiber microelectrodes, suggesting faster electron transfer kinetics. The kinetics of dopamine redox were adsorption controlled at CNS-Ta microelectrodes and repeated electrochemical measurements displayed stability for up to ten hours in vitro and over a ten day period as well. The oxidation potential was significantly different for ascorbic acid and uric acid compared to dopamine. Finally, growing carbon nanospikes on metal wires is a promising method to produce uniformly-coated, carbon nanostructured cylindrical microelectrodes for sensitive dopamine detection.« less
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Halouzka, Vladimir; Halouzkova, Barbora; Jirovsky, David; Hemzal, Dusan; Ondra, Peter; Siranidi, Eirini; Kontos, Athanassios G; Falaras, Polycarpos; Hrbac, Jan
2017-04-01
Miniature Surface Enhanced Raman Scattering (SERS) sensors were fabricated by coating the carbon fiber microelectrodes with copper nanowires. The coating procedure, based on anodizing the copper wire in ultrapure water followed by cathodic deposition of the anode-derived material onto carbon fiber electrodes, provides a "clean" copper nanowire network. The developed miniature (10µm in diameter and 2mm in length) and nanoscopically rough SERS substrates are applicable in drug sensing, as shown by the detection and resolving of a range of seized designer drugs in trace amounts (microliter volumes of 10 -10 -10 -12 M solutions). The copper nanowire modified carbon microfiber substrates could also find further applications in biomedical and environmental sensing. Copyright © 2016 Elsevier B.V. All rights reserved.
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A model of extracellular enzymes in free-living microbes: which strategy pays off?
Traving, Sachia J; Thygesen, Uffe H; Riemann, Lasse; Stedmon, Colin A
2015-11-01
An initial modeling approach was applied to analyze how a single, nonmotile, free-living, heterotrophic bacterial cell may optimize the deployment of its extracellular enzymes. Free-living cells live in a dilute and complex substrate field, and to gain enough substrate, their extracellular enzymes must be utilized efficiently. The model revealed that surface-attached and free enzymes generate unique enzyme and substrate fields, and each deployment strategy has distinctive advantages. For a solitary cell, surface-attached enzymes are suggested to be the most cost-efficient strategy. This strategy entails potential substrates being reduced to very low concentrations. Free enzymes, on the other hand, generate a radically different substrate field, which suggests significant benefits for the strategy if free cells engage in social foraging or experience high substrate concentrations. Swimming has a slight positive effect for the attached-enzyme strategy, while the effect is negative for the free-enzyme strategy. The results of this study suggest that specific dissolved organic compounds in the ocean likely persist below a threshold concentration impervious to biological utilization. This could help explain the persistence and apparent refractory state of oceanic dissolved organic matter (DOM). Microbial extracellular enzyme strategies, therefore, have important implications for larger-scale processes, such as shaping the role of DOM in ocean carbon sequestration. Copyright © 2015, American Society for Microbiology. All Rights Reserved.
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Li, Huai; Chi, Zifang; Yan, Baixing; Cheng, Long; Li, Jianzheng
2017-01-01
Removal of nitrogen in wastewater before discharge into receiving water courses is an important consideration in treatment systems. However, nitrogen removal efficiency is usually limited due to the low carbon/nitrogen (C/N) ratio. A common solution is to add external carbon sources, but amount of liquid is difficult to determine. Therefore, a combined wood-chip-framework substrate (with wood, slag and gravel) as a slow-release carbon source was constructed in baffled subsurface-flow constructed wetlands to overcome the problem. Results show that the removal rate of ammonia nitrogen (NH 4 + -N), total nitrogen (TN) and chemical oxygen demand (COD) could reach 37.5%-85%, 57.4%-86%, 32.4%-78%, respectively, indicating the combined substrate could diffuse sufficient oxygen for the nitrification process (slag and gravel zone) and provide carbon source for denitrification process (wood-chip zone). The nitrification and denitrification were determined according to the location of slag/gravel and wood-chip, respectively. Nitrogen removal was efficient at the steady phase before a shock loading using slag-wood-gravel combined substrate because of nitrification-denitrification process, while nitrogen removal was efficient under a shock loading with wood-slag-gravel combined substrate because of ANAMMOX process. This study provides a new idea for wetland treatment of high-strength nitrogen wastewater. Copyright © 2016. Published by Elsevier B.V.
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NASA Astrophysics Data System (ADS)
Cyle, K. T.; Martinez, C. E.
2017-12-01
Recent experimental work has elevated the importance of microbial processing for the stabilization of fresh carbon inputs within the soil mineral matrix. Enhancing our understanding of soil carbon and nitrogen dynamics therefore requires a better understanding of how efficiently microbial metabolism can process low molecular weight carbon substrates (carbon use efficiency, CUE) under environmentally relevant conditions. One approach to better understanding microbial uptake rates and CUE is the ecophysiological study of soil isolates in liquid media culture consisting of soil-extracted solubilized organic matter (SESOM). We are using SESOM from an Oa horizon under hemlock hardwood vegetation in upstate New York as liquid media for the growth of 12 isolates from the Oa and B horizon of the same site. Here we seek to test the uptake rates as well as CUE of 5 different low molecular weight substrates spanning compound class and nominal oxidation state (glucose, acetate, formate, glycine, valine) by isolates differing in phylogeny and physiology. The use of a spike of each of the 13C-labeled substrates into SESOM, along with a 0.2 μm filtration step, allows accurate partitioning of labeled carbon between biomass, gaseous CO2 as well as the exometabolome. Coupled UHPLC-MS measurements are being used to identify and determine uptake rates of over 80 potential C substrates present in the extract as well as our labeled substrate of interest along the course of the isolate growth curve. This work seeks to utilize a gradient in substrate class as well as microbial physiologies to inform our understanding of C and N cycling under relevant soil solution conditions. Future experiments may also use labeled biomass from stationary phase to investigate the stabilization potential of anabolic products formed from each substrate with a clay fraction isolated from the same site.
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Reduction of CO2 using a Rhenium Bipyridine Complex Containing Ancillary BODIPY Redox Reservoirs
DOE Office of Scientific and Technical Information (OSTI.GOV)
Teesdale, Justin; Pistner, Allen; Yapp, Glenn P. A.
2014-01-01
The reduction of carbon dioxide to chemical fuels such as carbon monoxide is an important challenge in the field of renewable energy conversion. Given the thermodynamic stability of carbon dioxide, it is difficult to efficiently activate this substrate in a selective fashion and the development of new electrocatalysts for CO2 reduction is of prime importance. To this end, we have prepared and studied a new fac-ReI(CO)3 complex supported by a bipyridine ligand containing ancillary BODIPY moieties ([Re(BB2)(CO)3Cl]). Voltammetry experiments revealed that this system displays a rich redox chemistry under N2, as [Re(BB2)(CO)3Cl] can be reduced by up to four electronsmore » at modest potentials. These redox events have been characterized as the ReI/0 couple, and three ligand based reductions two of which are localized on the BODIPY units. The ability of the BB2 ligand to serve as a noninnocent redox reservoir is manifest in an enhanced electrocatalysis with CO2 as compared to an unsubstituted Re-bipyridine complex lacking BODIPY units ([Re(bpy)(CO)3Cl]). The second order rate constant for reduction of CO2 by [Re(BB2)(CO)3Cl] was measured to be k = 3400 M 1s 1 at an applied potential of 2.0 V versus SCE, which is roughly three times greater than the corresponding unsubstituted Re-bipyridine homologue. Photophysical and photochemical studies were also carried out to determine if [Re(BB2)(CO)3Cl] was a competent platform for CO2 reduction using visible light. These experiments showed that this complex supports unusual excited state dynamics that are not typically observed for fac- ReI(CO)3 complexes.« less
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Apparatus and process for deposition of hard carbon films
Nyaiesh, Ali R.; Garwin, Edward L.
1989-01-01
A process and an apparatus for depositing thin, amorphous carbon films having extreme hardness on a substrate is described. An enclosed chamber maintained at less than atmospheric pressure houses the substrate and plasma producing elements. A first electrode is comprised of a cavity enclosed within an RF coil which excites the plasma. A substrate located on a second electrode is excited by radio frequency power applied to the substrate. A magnetic field confines the plasma produced by the first electrode to the area away from the walls of the chamber and focuses the plasma onto the substrate thereby yielding film deposits having higher purity and having more rapid buildup than other methods of the prior art.
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Apparatus and process for deposition of hard carbon films
Nyaiesh, Ali R.; Garwin, Edward L.
1989-01-03
A process and an apparatus for depositing thin, amorphous carbon films having extreme hardness on a substrate is described. An enclosed chamber maintained at less than atmospheric pressure houses the substrate and plasma producing elements. A first electrode is comprised of a cavity enclosed within an RF coil which excites the plasma. A substrate located on a second electrode is excited by radio frequency power applied to the substrate. A magnetic field confines the plasma produced by the first electrode to the area away from the walls of the chamber and focuses the plasma onto the substrate thereby yielding film deposits having higher purity and having more rapid buildup than other methods of the prior art.
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Mechanisms of methylene blue stimulation of the hexose monophosphate shunt in erythrocytes.
Metz, E N; Balcerzak, P; Sagone, A L
1976-10-01
The response of the hexose monophosphate shunt in erythrocytes was studied with the ionization chamber-electrometer apparatus to measure continuously 14CO2 derived from 14C-labeled substrates. The effect of methylene blue at high (0.1 mM) and low (1 muM) concentrations was evaluated under different gas mixtures; air, carbon monoxide, and 6% carbon monoxide in air. The latter gas mixture results in nearly 100% carboxyhemoglobin but provides a physiologic partial pressure of oxygen. The extent to which pentose is recycled through the shunt in response to methylene blue stimulation was examined with radioactive glucose substrates labeled on the first, second, and third carbon positions. Generation of hydrogen peroxide after stimulation of erythrocytes with methylene blue was evaluated by the catalase-aminotriazole trapping technique, [14C]formate oxidation, and oxidation of reduced glutatione. Stimulation of the shunt with 1 muM methylene blue was markedly impaired in the absence of oxyhemoglobin, but stimulation with 0.1 mM methylene blue was only slightly impaired under the carbon monoxide-air mixture. The higher concentration of methylene blue produced evidence of hydrogen peroxide generation of all three techniques. Despite the evidence for the involvement of oxygen, oxyhemoglobin, and hydrogen peroxide in the response to methylene blue, cells containing methemoglobin induced by sodium nitrite or from a patient with congenital methemoglobinemia responded normally to methylene blue in the absence of oxygen. These experiments indicate that the reactions induced by methylene blue in erythrocytes are more complex than generally thought and that high concentrations are associated with production of peroxide.
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Micro and nanocrystalline diamond formation on reticulated vitreous carbon substrate
NASA Astrophysics Data System (ADS)
Diniz, A. V.; Trava-Airoldi, V. J.; Corat, E. J.; Ferreira, N. G.
2005-10-01
High diamond nucleation and a three-dimensional growth on reticulated vitreous carbon substrate are obtained by chemical vapor deposition. Scanning electron microscopy images show continuous films covering the whole substrate including the center of 3.5 mm thick porous samples. It is evident the nanocrystalline diamond (NCD) film formation on deeper substrate regions. The grain size can vary from nano to micro scale for deposition time of 20 h. Raman spectra of sample regions closer to filaments exhibit well-defined diamond line. For central regions of sample (depth between 1.0 and 2.0 mm) Raman spectra also confirm NCD film.
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Formation of graphene on BN substrate by vapor deposition method and size effects on its structure
NASA Astrophysics Data System (ADS)
Giang, Nguyen Hoang; Hanh, Tran Thi Thu; Ngoc, Le Nhu; Nga, Nguyen To; Van Hoang, Vo
2018-04-01
We report MD simulation of the growth of graphene by the vapor deposition on a two-dimensional hBN substrate. The systems (containing carbon vapor and hBN substrate) are relaxed at high temperature (1500 K), and then it is cooled down to room one (300 K). Carbon atoms interact with the substrate via the Lennard-Jones potential while the interaction between carbon atoms is computed via the Tersoff potential. Depending on the size of the model, different crystalline honeycomb structures have been found. Structural properties of the graphene obtained at 300 K are studied by analyzing radial distribution functions (RDFs), coordination numbers, ring statistics, interatomic distances, bond-angle distributions and 2D visualization of atomic configurations. We find that the models containing various numbers of atoms have a honeycomb structure. Besides, differences in structural properties of graphene formed by the vapor deposition on the substrate and free standing one are found. Moreover, the size effect on the structure is significant.
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Testing of some assumptions about biodegradability in soil as measured by carbon dioxide evolution
DOE Office of Scientific and Technical Information (OSTI.GOV)
El-Din Sharabi, N.; Bartha, R.
1993-04-01
The Toxic Substance Control Act calls for a premanufacturing review of novel chemical substances including their biodegradability. Carbon dioxide evolution, using non-labeled carbon or [sup 14]C, is a common method of testing. This study examines assumptions of carbon dioxide evolution testing. Test substances used included: glucose, adipic acid, benzoic acid, and n-hexadecane. Chemical composition other than carbon content appears to influence minimally the percentages conversion to CO[sub 2]. However, that although CO[sub 2] evolution seemed proportional to the carbon content and concentration of the test substance, at least one-half of the evolved net CO[sub 2] did not come directly frommore » the test substance. Conversion to CO[sub 2] in the soil appeared to depend on carbon content only. In experiments of 1 month or longer, the net CO[sub 2] evolution in response to substrate may be above 100% of the added substrate carbon. Whether this applies to all substrate additions remains to be studied. The authors conclude that net CO[sub 2] and [sup 14]CO[sub 2] evolution measurements are useful as a first-tier tests for assessing biodegradability in soil. 11 refs., 6 figs.« less
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Dermer, Juri; Fuchs, Georg
2012-01-01
Cholesterol is a ubiquitous hydrocarbon compound that can serve as substrate for microbial growth. This steroid and related cyclic compounds are recalcitrant due to their low solubility in water, complex ring structure, the presence of quaternary carbon atoms, and the low number of functional groups. Aerobic metabolism therefore makes use of reactive molecular oxygen as co-substrate of oxygenases to hydroxylate and cleave the sterane ring system. Consequently, anaerobic metabolism must substitute oxygenase-catalyzed steps by O2-independent hydroxylases. Here we show that one of the initial reactions of anaerobic cholesterol metabolism in the β-proteobacterium Sterolibacterium denitrificans is catalyzed by an unprecedented enzyme that hydroxylates the tertiary C25 atom of the side chain without molecular oxygen forming a tertiary alcohol. This steroid C25 dehydrogenase belongs to the dimethyl sulfoxide dehydrogenase molybdoenzyme family, the closest relative being ethylbenzene dehydrogenase. It is a heterotrimer, which is probably located at the periplasmic side of the membrane and contains one molybdenum cofactor, five [Fe-S] clusters, and one heme b. The draft genome of the organism contains several genes coding for related enzymes that probably replace oxygenases in steroid metabolism. PMID:22942275
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Methanol Metabolism in Pseudomonad C
Stieglitz, B.; Mateles, R. I.
1973-01-01
Cell suspensions of pseudomonad C, a bacterium capable of growth on methanol as sole carbon source, were able to oxidize methanol, formaldehyde, and formate, although the rates of oxidation for the latter two compounds were much slower. The latter compounds also could not serve as sole carbon sources. Through the use of labeled compounds, it was shown that in the presence of methanol, formaldehyde, formate, and bicarbonate were incorporated into trichloroacetic acid-precipitable material. Hexose phosphate synthetase activity was found, indicating the assimilation of methanol via an allulose pathway. No hydroxypyruvate reductase activity was found, nor was any complex membrane structure observed. Such a combination of characteristics has been observed in an obligate methylotroph (Pseudomonas W1), but pseudomonad C can utilize a variety of non-methyl substrates. Images PMID:4349032
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Homogeneously catalysed conversion of aqueous formaldehyde to H2 and carbonate.
Trincado, M; Sinha, Vivek; Rodriguez-Lugo, Rafael E; Pribanic, Bruno; de Bruin, Bas; Grützmacher, Hansjörg
2017-04-28
Small organic molecules provide a promising solution for the requirement to store large amounts of hydrogen in a future hydrogen-based energy system. Herein, we report that diolefin-ruthenium complexes containing the chemically and redox non-innocent ligand trop 2 dad catalyse the production of H 2 from formaldehyde and water in the presence of a base. The process involves the catalytic conversion to carbonate salt using aqueous solutions and is the fastest reported for acceptorless formalin dehydrogenation to date. A mechanism supported by density functional theory calculations postulates protonation of a ruthenium hydride to form a low-valent active species, the reversible uptake of dihydrogen by the ligand and active participation of both the ligand and the metal in substrate activation and dihydrogen bond formation.
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Synthetic substrates for enzyme analysis
Bissell, E.R.; Mitchell, A.R.; Pearson, K.W.; Smith, R.E.
1983-06-14
Synthetic substrates are provided which may be represented as A-D. The A moiety includes an amino acid, polypeptide, or derivative. The D moiety includes 7-amino coumarin derivatives having an electron withdrawing substituent group at the 3 position carbon or fused between the 3 and 4 position carbons. No Drawings
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Metabolic Profile of Wound-Induced Changes in Primary Carbon Metabolism in Sugarbeet Root
USDA-ARS?s Scientific Manuscript database
Injury to plant products induces respiration rate and increases the demand for respiratory substrates. Alterations in primary carbon metabolism are likely to support the elevated demand for respiratory substrates, although the nature of these alterations is unknown. To gain insight into the metabo...
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Synthetic substrates for enzyme analysis
Bissell, Eugene R.; Mitchell, Alexander R.; Pearson, Karen W.; Smith, Robert E.
1983-01-01
Synthetic substrates are provided which may be represented as A-D. The A moiety thereof includes an amino acid, polypeptide, or derivative thereof. The D moiety thereof includes 7-amino coumarin derivatives having an electron withdrawing substituent group at the 3 position carbon or fused between the 3 and 4 position carbons.
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Singamneni, Sarat; Ramos, Maximiano; Al-Jumaily, Ahmed M
2017-01-01
The conventional gas diffusion layer (GDL) of polymer electrolyte membrane (PEM) fuel cells incorporates a carbon-based substrate, which suffers from electrochemical oxidation as well as mechanical degradation, resulting in reduced durability and performance. In addition, it involves a complex manufacturing process to produce it. The proposed technique aims to resolve both these issues by an advanced 3D printing technique, namely selective laser sintering (SLS). In the proposed work, polyamide (PA) is used as the base powder and titanium metal powder is added at an optimised level to enhance the electrical conductivity, thermal, and mechanical properties. The application of selective laser sintering to fabricate a robust gas diffusion substrate for PEM fuel cell applications is quite novel and is attempted here for the first time. PMID:28773156
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Jayakumar, Arunkumar; Singamneni, Sarat; Ramos, Maximiano; Al-Jumaily, Ahmed M; Pethaiah, Sethu Sundar
2017-07-14
The conventional gas diffusion layer (GDL) of polymer electrolyte membrane (PEM) fuel cells incorporates a carbon-based substrate, which suffers from electrochemical oxidation as well as mechanical degradation, resulting in reduced durability and performance. In addition, it involves a complex manufacturing process to produce it. The proposed technique aims to resolve both these issues by an advanced 3D printing technique, namely selective laser sintering (SLS). In the proposed work, polyamide (PA) is used as the base powder and titanium metal powder is added at an optimised level to enhance the electrical conductivity, thermal, and mechanical properties. The application of selective laser sintering to fabricate a robust gas diffusion substrate for PEM fuel cell applications is quite novel and is attempted here for the first time.
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Structure of the Ergothioneine-Biosynthesis Amidohydrolase EgtC.
Vit, Allegra; Mashabela, Gabriel T; Blankenfeldt, Wulf; Seebeck, Florian P
2015-07-06
The ubiquitous sulfur metabolite ergothioneine is biosynthesized by oxidative attachment of a sulfur atom to the imidazole ring of Nα-trimethylhistidine. Most actinobacteria, including Mycobacterium tuberculosis, use γ-glutamyl cysteine as a sulfur donor. In subsequent steps the carbon scaffold of γ-glutamyl cysteine is removed by the glutamine amidohydrolase EgtC and the β-lyase EgtE. We determined the crystal structure of EgtC from Mycobacterium smegmatis in complex with its physiological substrate. The set of active site residues that define substrate specificity in EgtC are highly conserved, even in homologues that are not involved in ergothioneine production. This conservation is compounded by the phylogenetic distribution of EgtC-like enzymes indicates that their last common ancestor might have emerged for a purpose other than ergothioneine production. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Salmon, Melissa; Thimmappa, Ramesha B.; Minto, Robert E.; Melton, Rachel E.; O’Maille, Paul E.; Hemmings, Andrew M.; Osbourn, Anne
2016-01-01
Triterpenes are structurally complex plant natural products with numerous medicinal applications. They are synthesized through an origami-like process that involves cyclization of the linear 30 carbon precursor 2,3-oxidosqualene into different triterpene scaffolds. Here, through a forward genetic screen in planta, we identify a conserved amino acid residue that determines product specificity in triterpene synthases from diverse plant species. Mutation of this residue results in a major change in triterpene cyclization, with production of tetracyclic rather than pentacyclic products. The mutated enzymes also use the more highly oxygenated substrate dioxidosqualene in preference to 2,3-oxidosqualene when expressed in yeast. Our discoveries provide new insights into triterpene cyclization, revealing hidden functional diversity within triterpene synthases. They further open up opportunities to engineer novel oxygenated triterpene scaffolds by manipulating the precursor supply. PMID:27412861
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Lu, Wen-Tong P.; Garcia, Earl R.
1983-01-01
Disclosed is an improvement on a method of making an electrode wherein a suspension in a liquid is prepared of a powdered catalyst containing a noble metal, carbon powder and a binder, and the suspension is poured over a carbon substrate dried, compressed and sintered to form a solid catalyst layer bonded to the carbon substrate. The improvement is placing a carbon paper on the catalyst layer prior to compressing. The improved electrode can be used as either a cathode or an anode in a sulfur dioxide depolarized electrolyzer in a process for producing hydrogen from water.
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Fromm, Steffanie; Senkler, Jennifer; Eubel, Holger; Peterhänsel, Christoph; Braun, Hans-Peter
2016-01-01
The mitochondrial NADH dehydrogenase complex (complex I) is of particular importance for the respiratory chain in mitochondria. It is the major electron entry site for the mitochondrial electron transport chain (mETC) and therefore of great significance for mitochondrial ATP generation. We recently described an Arabidopsis thaliana double-mutant lacking the genes encoding the carbonic anhydrases CA1 and CA2, which both form part of a plant-specific ‘carbonic anhydrase domain’ of mitochondrial complex I. The mutant lacks complex I completely. Here we report extended analyses for systematically characterizing the proteome of the ca1ca2 mutant. Using various proteomic tools, we show that lack of complex I causes reorganization of the cellular respiration system. Reduced electron entry into the respiratory chain at the first segment of the mETC leads to induction of complexes II and IV as well as alternative oxidase. Increased electron entry at later segments of the mETC requires an increase in oxidation of organic substrates. This is reflected by higher abundance of proteins involved in glycolysis, the tricarboxylic acid cycle and branched-chain amino acid catabolism. Proteins involved in the light reaction of photosynthesis, the Calvin cycle, tetrapyrrole biosynthesis, and photorespiration are clearly reduced, contributing to the significant delay in growth and development of the double-mutant. Finally, enzymes involved in defense against reactive oxygen species and stress symptoms are much induced. These together with previously reported insights into the function of plant complex I, which were obtained by analysing other complex I mutants, are integrated in order to comprehensively describe ‘life without complex I’. PMID:27122571
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Van Humbeck, Jeffrey F; Simonovich, Scott P; Knowles, Robert R; MacMillan, David W C
2010-07-28
The mechanism of a recently reported aldehyde alpha-oxyamination reaction has been studied using a combination of kinetic, spectrometric, and spectrophotometric techniques. Most crucially, the use of a validated cyclopropane-based radical-clock substrate has demonstrated that carbon-oxygen bond formation occurs predominantly through an enamine activation manifold. The mechanistic details reported herein indicate that, as has been proposed for previously studied alcohol oxidations, complexation between TEMPO and a simple metal salt leads to electrophilic ionic reactivity.
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NASA Astrophysics Data System (ADS)
Kolo, K.; Claeys, Ph.
2005-10-01
This study investigates the in vitro formation of Ca-oxalates and glushinskite through fungal interaction with carbonate substrates and seawater as a process of biologically induced metal recycling and neo-mineral formation. The study also emphasizes the role of the substrates as metal donors. In the first experiment, thin sections prepared from dolomitic rock samples of Terwagne Formation (Carboniferous, Viséan, northern France) served as substrates. The thin sections placed in Petri dishes were exposed to fungi grown from naturally existing airborne spores. In the second experiment, fungal growth and mineral formation was monitored using only standard seawater (SSW) as a substrate. Fungal growth media consisted of a high protein/carbohydrates and sugar diet with demineralized water for irrigation. Fungal growth process reached completion under uncontrolled laboratory conditions. The newly formed minerals and textural changes caused by fungal attack on the carbonate substrates were investigated using light and scanning electron microscopy (SEM-EDX), x-ray diffraction (XRD) and Raman spectroscopy. The fungal interaction and attack on the dolomitic and seawater substrates resulted in the formation of Ca-oxalates (weddellite CaC2O4·2(H2O), whewellite (CaC2O4·(H2O)) and glushinskite MgC2O4·2(H2O) associated with the destruction of the original hard substrates and their replacement by the new minerals. Both of Ca and Mg were mobilized from the experimental substrates by fungi. This metal mobilization involved a recycling of substrate metals into newly formed minerals. The biochemical and diagenetic results of the interaction strongly marked the attacked substrates with a biological fingerprint. Such fingerprints are biomarkers of primitive life. The formation of glushinskite is of specific importance that is related, besides its importance as a biomineral bearing a recycled Mg, to the possibility of its transformation through diagenetic pathway into an Mg carbonate. This work is the first report on the in vitro formation of the mineral glushinskite through fungal interaction with carbonate and seawater substrates. Besides recording the detailed Raman signature of various crystal habits of Mg- and Ca-oxalates, the Raman spectroscopy proved two new crystal habits for glushinskite. The results of this work document the role of microorganisms as metal recyclers in biomineralization, neo-mineral formation, sediment diagenesis, bioweathering and in the production of mineral and diagenetic biomarkers. They also reveal the capacity of living fungi to interact with liquid substrates and precipitate new minerals.
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Haack, S.K.; Garchow, H.; Klug, M.J.; Forney, L.J.
1995-01-01
We determined factors that affect responses of bacterial isolates and model bacterial communities to the 95 carbon substrates in Biolog microliter plates. For isolates and communities of three to six bacterial strains, substrate oxidation rates were typically nonlinear and were delayed by dilution of the inoculum. When inoculum density was controlled, patterns of positive and negative responses exhibited by microbial communities to each of the carbon sources were reproducible. Rates and extents of substrate oxidation by the communities were also reproducible but were not simply the sum of those exhibited by community members when tested separately. Replicates of the same model community clustered when analyzed by principal- components analysis (PCA), and model communities with different compositions were clearly separated un the first PCA axis, which accounted for >60% of the dataset variation. PCA discrimination among different model communities depended on the extent to which specific substrates were oxidized. However, the substrates interpreted by PCA to be most significant in distinguishing the communities changed with reading time, reflecting the nonlinearity of substrate oxidation rates. Although whole-community substrate utilization profiles were reproducible signatures for a given community, the extent of oxidation of specific substrates and the numbers or activities of microorganisms using those substrates in a given community were not correlated. Replicate soil samples varied significantly in the rate and extent of oxidation of seven tested substrates, suggesting microscale heterogeneity in composition of the soil microbial community.
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NASA Astrophysics Data System (ADS)
Luchinin, Viktor V.; Goloudina, Svetlana I.; Pasyuta, Vyacheslav M.; Panov, Mikhail F.; Smirnov, Alexander N.; Kirilenko, Demid A.; Semenova, Tatyana F.; Sklizkova, Valentina P.; Gofman, Iosif V.; Svetlichnyi, Valentin M.; Kudryavtsev, Vladislav V.
2017-06-01
High-quality crystalline nano-thin SiC films on Si substrates were prepared by carbonization of polyimide (PI) Langmuir-Blodgett (LB) films. The obtained films were characterized by Fourier transform-infrared (FTIR) spectroscopy, X-ray diffraction (XRD) analysis, Raman spectroscopy, transmission electon microscopy (TEM), transmission electron diffraction (TED), and scanning electron microscopy (SEM). We demonstrated that the carbonization of a PI film on a Si substrate at 1000 °C leads to the formation of a carbon film and SiC nanocrystals on the Si substrate. It was found that five planes in the 3C-SiC(111) film are aligned with four Si(111) planes. As a result of repeated annealing of PI films containing 121 layers at 1200 °C crystalline SiC films were formed on the Si substrate. It was shown that the SiC films (35 nm) grown on Si(111) at 1200 °C have a mainly cubic 3C-SiC structure with small amount of hexagonal polytypes. Only 3C-SiC films (30 nm) were formed on the Si(100) substrate at the same temperature. It was shown that the SiC films (30-35 nm) can cover the voids with size up to 10 µm in the Si substrate. The current-voltage (I-V) characteristics of the n-Si/n-SiC heterostructure were obtained by conductive atomic force microscopy.
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Dinasquet, Julie; Richert, Inga; Logares, Ramiro; Yager, Patricia; Bertilsson, Stefan; Riemann, Lasse
2017-06-01
The number of icebergs produced from ice-shelf disintegration has increased over the past decade in Antarctica. These drifting icebergs mix the water column, influence stratification and nutrient condition, and can affect local productivity and food web composition. Data on whether icebergs affect bacterioplankton function and composition are scarce, however. We assessed the influence of iceberg drift on bacterial community composition and on their ability to exploit carbon substrates during summer in the coastal Southern Ocean. An elevated bacterial production and a different community composition were observed in iceberg-influenced waters relative to the undisturbed water column nearby. These major differences were confirmed in short-term incubations with bromodeoxyuridine followed by CARD-FISH. Furthermore, one-week bottle incubations amended with inorganic nutrients and carbon substrates (a mix of substrates, glutamine, N-acetylglucosamine, or pyruvate) revealed contrasting capacity of bacterioplankton to utilize specific carbon substrates in the iceberg-influenced waters compared with the undisturbed site. Our study demonstrates that the hydrographical perturbations introduced by a drifting iceberg can affect activity, composition, and substrate utilization capability of marine bacterioplankton. Consequently, in a context of global warming, increased frequency of drifting icebergs in polar regions holds the potential to affect carbon and nutrient biogeochemistry at local and possibly regional scales. © 2017 Society for Applied Microbiology and John Wiley & Sons Ltd.
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Method of produce ultra-low friction carbon films
Erdemir, Ali; Fenske, George R.; Eryilmaz, Osman Levent; Lee, Richard H.
2003-04-15
A method and article of manufacture of amorphous diamond-like carbon. The method involves providing a substrate in a chamber, providing a mixture of a carbon containing gas and hydrogen gas with the mixture adjusted such that the atomic molar ratio of carbon to hydrogen is less than 0.3, including all carbon atoms and all hydrogen atoms in the mixture. A plasma is formed of the mixture and the amorphous diamond-like carbon film is deposited on the substrate. To achieve optimum bonding an intervening bonding layer, such as Si or SiO.sub.2, can be formed from SiH.sub.4 with or without oxidation of the layer formed.
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Extracellular enzyme kinetics scale with resource availability
Sinsabaugh, Robert L.; Belnap, Jayne; Findlay, Stuart G.; Follstad Shah, Jennifer J.; Hill, Brian H.; Kuehn, Kevin A.; Kuske, Cheryl; Litvak, Marcy E.; Martinez, Noelle G.; Moorhead, Daryl L.; Warnock, Daniel D.
2014-01-01
Microbial community metabolism relies on external digestion, mediated by extracellular enzymes that break down complex organic matter into molecules small enough for cells to assimilate. We analyzed the kinetics of 40 extracellular enzymes that mediate the degradation and assimilation of carbon, nitrogen and phosphorus by diverse aquatic and terrestrial microbial communities (1160 cases). Regression analyses were conducted by habitat (aquatic and terrestrial), enzyme class (hydrolases and oxidoreductases) and assay methodology (low affinity and high affinity substrates) to relate potential reaction rates to substrate availability. Across enzyme classes and habitats, the scaling relationships between apparent Vmax and apparent Km followed similar power laws with exponents of 0.44 to 0.67. These exponents, called elasticities, were not statistically distinct from a central value of 0.50, which occurs when the Km of an enzyme equals substrate concentration, a condition optimal for maintenance of steady state. We also conducted an ecosystem scale analysis of ten extracellular hydrolase activities in relation to soil and sediment organic carbon (2,000–5,000 cases/enzyme) that yielded elasticities near 1.0 (0.9 ± 0.2, n = 36). At the metabolomic scale, the elasticity of extracellular enzymatic reactions is the proportionality constant that connects the C:N:P stoichiometries of organic matter and ecoenzymatic activities. At the ecosystem scale, the elasticity of extracellular enzymatic reactions shows that organic matter ultimately limits effective enzyme binding sites. Our findings suggest that one mechanism by which microbial communities maintain homeostasis is regulating extracellular enzyme expression to optimize the short-term responsiveness of substrate acquisition. The analyses also show that, like elemental stoichiometry, the fundamental attributes of enzymatic reactions can be extrapolated from biochemical to community and ecosystem scales.
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Ashfaque, Mohammad; Solomon, Sushil; Pathak, Neelam
2014-01-01
Sugarcane bagasse (SCB), a lignocellulosic byproduct of juice extraction from sugarcane, is rich in cellulose (40-42%). This could be used as a substrate for the production of cellulase complex. Fermentation conditions were optimized for production of cellulase complex (CMCase, Cellulobiase and FPase) by wild type Trichoderma sp. using sugarcane bagasse as sole carbon source. Alkaline treatment (2% NaOH) of bagasse (AlSCB) was found suitable for the production of reducing sugar over the acidic pretreatment method. After 5 days of incubation period, 5% substrate concentration at pH 5.0 and 400C resulted in maximum production of CMCase (0.622 U), while maximum (3.388 U) production of cellulobiase was obtained at 300C. The CMCase was precipitated and purified to the extent of 59.06 fold by affinity chromatography with 49.09% recovery. On 12% SDS-PAGE, a single band corresponding to 33 kDa was observed. The Km and Vmax for CMCase from Trichoderma was found 507.04 mg/ml and 65.32 mM/min, respectively. The enzyme exhibited maximum activity at 300C at pH-5.0 (0.363 U) and was stable over range of 20-60°C and pH 5.0-7.5.
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Schotes, Christoph; Mezzetti, Antonio
2011-01-01
We report here dicationic ruthenium PNNP complexes that promote the enantioselective Diels-Alder reaction of alpha-methylene beta-ketoesters with various dienes. Complex [Ru(OEt2)2(PNNP)](PF6)2, formed in situ from [RuCl2,(PNNP)] and (Et3O)PF6 (2 equiv.), catalyzes the Diels-Alder reaction of such unsaturated beta-ketoesters to give novel alkoxycarbonyltetrahydro-1-indanone derivatives (nine examples) with up to 93% ee. The crystal structure of the substrate-catalyst adduct shows that the lower face of the substrate is shielded by a phenyl ring of the PNNP ligand, which accounts for the high enantioselectivity. The attack of the diene from the open re enantioface of the unsaturated beta-ketoester is consistent with the absolute configuration of the product. A useful application of this method is the reaction with Dane's diene to give estrone derivatives with up to 99% ee and an ester-exo:endo ratio of up to 145:1 (after recrystallization). Besides the enantioselective formation of all-carbon quaternary centers, this methodology is notable because unsaturated beta-ketoesters have been rarely used in Diels-Alder reactions. Furthermore, enantiomerically pure estrone derivatives are interesting in view of their potential applications, including the treatment of breast cancer.
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A Global Protein Kinase and Phosphatase Interaction Network in Yeast
Breitkreutz, Ashton; Choi, Hyungwon; Sharom, Jeffrey R.; Boucher, Lorrie; Neduva, Victor; Larsen, Brett; Lin, Zhen-Yuan; Breitkreutz, Bobby-Joe; Stark, Chris; Liu, Guomin; Ahn, Jessica; Dewar-Darch, Danielle; Reguly, Teresa; Tang, Xiaojing; Almeida, Ricardo; Qin, Zhaohui Steve; Pawson, Tony; Gingras, Anne-Claude; Nesvizhskii, Alexey I.; Tyers, Mike
2011-01-01
The interactions of protein kinases and phosphatases with their regulatory subunits and substrates underpin cellular regulation. We identified a kinase and phosphatase interaction (KPI) network of 1844 interactions in budding yeast by mass spectrometric analysis of protein complexes. The KPI network contained many dense local regions of interactions that suggested new functions. Notably, the cell cycle phosphatase Cdc14 associated with multiple kinases that revealed roles for Cdc14 in mitogen-activated protein kinase signaling, the DNA damage response, and metabolism, whereas interactions of the target of rapamycin complex 1 (TORC1) uncovered new effector kinases in nitrogen and carbon metabolism. An extensive backbone of kinase-kinase interactions cross-connects the proteome and may serve to coordinate diverse cellular responses. PMID:20489023
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A Forty Year Odyssey in Metallo-Organic Chemistry.
Nicholas, Kenneth M
2015-07-17
In this invited Perspective, I provide a personal account highlighting several of my group's research contributions in metallo-organic chemistry over the past 40 years. Our early work focused primarily in stoichiometric structure/reactivity of transition metal-organic compounds and their use in organic synthesis. More recent efforts have centered on the discovery and development of new metal-catalyzed organic reactions via reactive metal-organic intermediates. The major research findings that are described here include (1) propargyl-cobalt complexes as electrophilic agents for C-C and C-Nu coupling; (2) the activation of carbon dioxide by metal complexes; (3) metal-promoted C-H nitrogenation reactions; (4) oxo-metal catalyzed deoxygenation reactions; and (5) catalyst discovery via dynamic templating with substrate- and transition-state analogues.
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Rotational actuator of motor based on carbon nanotubes
Zettl, Alexander K.; Fennimore, Adam M.; Yuzvinsky, Thomas D.
2008-11-18
A rotational actuator/motor based on rotation of a carbon nanotube is disclosed. The carbon nanotube is provided with a rotor plate attached to an outer wall, which moves relative to an inner wall of the nanotube. After deposit of a nanotube on a silicon chip substrate, the entire structure may be fabricated by lithography using selected techniques adapted from silicon manufacturing technology. The structures to be fabricated may comprise a multiwall carbon nanotube (MWNT), two in plane stators S1, S2 and a gate stator S3 buried beneath the substrate surface. The MWNT is suspended between two anchor pads and comprises a rotator attached to an outer wall and arranged to move in response to electromagnetic inputs. The substrate is etched away to allow the rotor to freely rotate. Rotation may be either in a reciprocal or fully rotatable manner.
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Oxidation resistant slurry coating for carbon-based materials
NASA Technical Reports Server (NTRS)
Smialek, J. L.; Rybicki, G. C. (Inventor)
1985-01-01
An oxidation resistant coating is produced on carbon-base materials, and the same processing step effects an infiltration of the substrate with silicon containing material. The process comprises making a slurry of nickel and silicon powders in a nitrocellulose lacquer, spraying onto the graphite or carbon-carbon substrate, and sintering in vacuum to form a fused coating that wets and covers the surface as well as penetrates into the pores of the substrate. Optimum wetting and infiltration occurs in the range of Ni-60 w/o Si to Ni-90 w/o Si with deposited thicknesses of 25-100 mg/sq. cm. Sintering temperatures of about 1200 C to about 1400 C are used, depending on the melting point of the specific coating composition. The sintered coating results in Ni-Si intermetallic phases and SiC, both of which are highly oxidation resistant.
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Rotational actuator or motor based on carbon nanotubes
Zetti, Alexander K.; Fennimore, Adam M.; Yuzvinsky, Thomas D.
2006-05-30
A rotational actuator/motor based on rotation of a carbon nanotube is disclosed. The carbon nanotube is provided with a rotor plate attached to an outer wall, which moves relative to an inner wall of the nanotube. After deposit of a nanotube on a silicon chip substrate, the entire structure may be fabricated by lithography using selected techniques adapted from silicon manufacturing technology. The structures to be fabricated may comprise a multiwall carbon nanotube (MWNT), two in plane stators S1, S2 and a gate stator S3 buried beneath the substrate surface. The MWNT is suspended between two anchor pads and comprises a rotator attached to an outer wall and arranged to move in response to electromagnetic inputs. The substrate is etched away to allow the rotor to freely rotate. Rotation may be either in a reciprocal or fully rotatable manner.
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NASA Astrophysics Data System (ADS)
Christian, Bradley W.; Lind, Owen T.
2006-06-01
Bacterial heterotrophy in aquatic ecosystems is important in the overall carbon cycle. Biolog MicroPlates provide information into the metabolic potential of bacteria involved in carbon cycling. Specifically, Biolog EcoPlatesTM were developed with ecologically relevant carbon substrates to allow investigators to measure carbon substrate utilization patterns and develop community-level physiological profiles from natural bacterial assemblages. However, understanding of the functionality of these plates in freshwater research is limited. We explored several issues of EcoPlate use for freshwater bacterial assemblages including inoculum density, incubation temperature, non-bacterial color development, and substrate selectivity. Each of these has various effects on plate interpretation. We offer suggestions and techniques to resolve these interpretation issues. Lastly we propose a technique to allow EcoPlate use in anaerobic freshwater bacterial studies.
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High-yield growth of vertically aligned carbon nanotubes on a continuously moving substrate.
Guzmán de Villoria, R; Figueredo, S L; Hart, A J; Steiner, S A; Slocum, A H; Wardle, B L
2009-10-07
Vertically aligned carbon nanotube (CNT) arrays are grown on a moving substrate, demonstrating continuous growth of nanoscale materials with long-range order. A cold-wall chamber with an oscillating moving platform is used to locally heat a silicon growth substrate coated with an Fe/Al2O3 catalyst film for CNT growth via chemical vapor deposition. The reactant gases are introduced over the substrate through a directed nozzle to attain high-yield CNT growth. Aligned multi-wall carbon nanotube arrays (or 'forests') with heights of approximately 1 mm are achieved at substrate speeds up to 2.4 mm s(-1). Arrays grown on moving substrates at different velocities are studied in order to identify potential physical limitations of repeatable and fast growth on a continuous basis. No significant differences are noted between static and moving growth as characterized by scanning electron microscopy and Raman spectroscopy, although overall growth height is marginally reduced at the highest substrate velocity. CNT arrays produced on moving substrates are also found to be comparable to those produced through well-characterized batch processes consistent with a base-growth mechanism. Growth parameters required for the moving furnace are found to differ only slightly from those used in a comparable batch process; thermal uniformity appears to be the critical parameter for achieving large-area uniform array growth. If the continuous-growth technology is combined with a reaction zone isolation scheme common in other types of processing (e.g., in the manufacture of carbon fibers), large-scale dense and aligned CNT arrays may be efficiently grown and harvested for numerous applications including providing interlayers for advanced composite reinforcement and improved electrical and thermal transport.
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Saratale, Ganesh D; Kshirsagar, Siddheshwar D; Sampange, Vilas T; Saratale, Rijuta G; Oh, Sang-Eun; Govindwar, Sanjay P; Oh, Min-Kyu
2014-12-01
Phanerochaete chrysosporium was evaluated for cellulase and hemicellulase production using various agricultural wastes under solid state fermentation. Optimization of various environmental factors, type of substrate, and medium composition was systematically investigated to maximize the production of enzyme complex. Using grass powder as a carbon substrate, maximum activities of endoglucanase (188.66 U/gds), exoglucanase (24.22 U/gds), cellobiase (244.60 U/gds), filter paperase (FPU) (30.22 U/gds), glucoamylase (505.0 U/gds), and xylanase (427.0 U/gds) were produced under optimized conditions. The produced crude enzyme complex was employed for hydrolysis of untreated and mild acid pretreated rice husk. The maximum amount of reducing sugar released from enzyme treated rice husk was 485 mg/g of the substrate. Finally, the hydrolysates of rice husk were used for hydrogen production by Clostridium beijerinckii. The maximum cumulative H2 production and H2 yield were 237.97 mL and 2.93 mmoL H2/g of reducing sugar, (or 2.63 mmoL H2/g of cellulose), respectively. Biohydrogen production performance obtained from this work is better than most of the reported results from relevant studies. The present study revealed the cost-effective process combining cellulolytic enzymes production under solid state fermentation (SSF) and the conversion of agro-industrial residues into renewable energy resources.
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NASA Astrophysics Data System (ADS)
Roberts, Megan J.; Leach, Michelle K.; Bedewy, Mostafa; Meshot, Eric R.; Copic, Davor; Corey, Joseph M.; Hart, A. John
2014-06-01
Objective. Carbon nanotubes (CNTs) are attractive for use in peripheral nerve interfaces because of their unique combination of strength, flexibility, electrical conductivity and nanoscale surface texture. Here we investigated the growth of motor neurons on thin films of horizontally aligned CNTs (HACNTs). Approach. We cultured primary embryonic rat motor neurons on HACNTs and performed statistical analysis of the length and orientation of neurites. We next presented motor neurons with substrates of alternating stripes of HACNTs and SiO2. Main results. The neurons survived on HACNT substrates for up to eight days, which was the full duration of our experiments. Statistical analysis of the length and orientation of neurites indicated that the longest neurites on HACNTs tended to align with the CNT direction, although the average neurite length was similar between HACNTs and glass control substrates. We observed that when motor neurons were presented with alternating stripes of HACNTs and SiO2, the proportion of neurons on HACNTs increases over time, suggesting that neurons selectively migrate toward and adhere to the HACNT surface. Significance. The behavior of motor neurons on CNTs has not been previously investigated, and we show that aligned CNTs could provide a viable interface material to motor neurons. Combined with emerging techniques to build complex hierarchical structures of CNTs, our results suggest that organised CNTs could be incorporated into nerve grafts that use physical and electrical cues to guide regenerating axons.
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Leßmeier, Lennart; Pfeifenschneider, Johannes; Carnicer, Marc; Heux, Stephanie; Portais, Jean-Charles; Wendisch, Volker F
2015-12-01
Methanol, a one-carbon compound, can be utilized by a variety of bacteria and other organisms as carbon and energy source and is regarded as a promising substrate for biotechnological production. In this study, a strain of non-methylotrophic Corynebacterium glutamicum, which was able to produce the polyamide building block cadaverine as non-native product, was engineered for co-utilization of methanol. Expression of the gene encoding NAD+-dependent methanol dehydrogenase (Mdh) from the natural methylotroph Bacillus methanolicus increased methanol oxidation. Deletion of the endogenous aldehyde dehydrogenase genes ald and fadH prevented methanol oxidation to carbon dioxide and formaldehyde detoxification via the linear formaldehyde dissimilation pathway. Heterologous expression of genes for the key enzymes hexulose-6-phosphate synthase and 6-phospho-3-hexuloisomerase of the ribulose monophosphate (RuMP) pathway in this strain restored growth in the presence of methanol or formaldehyde, which suggested efficient formaldehyde detoxification involving RuMP key enzymes. While growth with methanol as sole carbon source was not observed, the fate of 13C-methanol added as co-substrate to sugars was followed and the isotopologue distribution indicated incorporation into central metabolites and in vivo activity of the RuMP pathway. In addition, 13C-label from methanol was traced to the secreted product cadaverine. Thus, this synthetic biology approach led to a C. glutamicum strain that converted the non-natural carbon substrate methanol at least partially to the non-native product cadaverine.
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Beatty, Joel W; Stephenson, Corey R J
2015-05-19
While the use of visible light to drive chemical reactivity is of high importance to the development of environmentally benign chemical transformations, the concomitant use of a stoichiometric electron donor or acceptor is often required to steer the desired redox behavior of these systems. The low-cost and ubiquity of tertiary amine bases has led to their widespread use as reductive additives in photoredox catalysis. Early use of trialkylamines in this context was focused on their role as reductive excited state quenchers of the photocatalyst, which in turn provides a more highly reducing catalytic intermediate. In this Account, we discuss some of the observations and thought processes that have led from our use of amines as reductive additives to their use as complex substrates and intermediates for natural product synthesis. Early attempts by our group to construct key carbon-carbon bonds via free-radical intermediates led to the observation that some trialkylamines readily behave as efficient hydrogen atom donors under redox-active photochemical conditions. In the wake of in-depth mechanistic studies published in the 1970s, 1980s and 1990s, this understanding has in turn allowed for a systematic approach to the design of a number of photochemical methodologies through rational tuning of the amine component. Minimization of the C-H donicity of the amine additive was found to promote desired C-C bond formation in a number of contexts, and subsequent elucidation of the amine's redox fate has sparked a reevaluation of the amine's role from that of reagent to that of substrate. The reactivity of tertiary amines in these photochemical systems is complex, and allows for a number of mechanistic possibilities that are not necessarily mutually exclusive. A variety of combinations of single-electron oxidation, C-H abstraction, deprotonation, and β-scission result in the formation of reactive intermediates such as α-amino radicals and iminium ions. These processes have been explored in depth in the photochemical literature and have resulted in a firm mechanistic grasp of the behavior of amine radical cations in fundamental systems. Harnessing the synthetic potential of these transient species represents an ongoing challenge for the controlled functionalization of amine substrates, because these mechanistic possibilities may result in undesired byproduct formation or substrate decomposition. The presence of tertiary amines in numerous alkaloids, pharmaceuticals, and agrochemicals lends credence to the potential utility of this chemistry in natural product synthesis, and herein we will discuss how these transformations might be controlled for synthetic purposes.
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Zou, Yuan; Li, Qunqing; Liu, Junku; Jin, Yuanhao; Qian, Qingkai; Jiang, Kaili; Fan, Shoushan
2013-11-13
SWNT thin films with different nanotube densities are fabricated by CVD while controlling the concentration of catalyst and growth time. Three layers of SWNT films are transferred to flexible substrates serving as electrodes and channel materials, respectively. All-carbon nanotube TFTs with an on/off ratio as high as 10(5) are obtained. Inverters are fabricated on top of the flexible substrates with symmetric input/output behavior. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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2006-11-01
gradient coatings with diamond like carbon (DLC) coating on 440C stainless steel substrate were assumed as a series of perfectly bonded layers with...resistance and low friction. Ti1-xCx (0≤ x ≤1) gradient coatings with diamond like carbon (DLC) coating on 440C stainless steel substrate were...indenter tip was used for the FEA model. Each coating sample consists of 1 μm thick coating and 440C stainless steel substrate. The area function for
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Remote carboxylation of halogenated aliphatic hydrocarbons with carbon dioxide
NASA Astrophysics Data System (ADS)
Juliá-Hernández, Francisco; Moragas, Toni; Cornella, Josep; Martin, Ruben
2017-05-01
Catalytic carbon-carbon bond formation has enabled the streamlining of synthetic routes when assembling complex molecules. It is particularly important when incorporating saturated hydrocarbons, which are common motifs in petrochemicals and biologically relevant molecules. However, cross-coupling methods that involve alkyl electrophiles result in catalytic bond formation only at specific and previously functionalized sites. Here we describe a catalytic method that is capable of promoting carboxylation reactions at remote and unfunctionalized aliphatic sites with carbon dioxide at atmospheric pressure. The reaction occurs via selective migration of the catalyst along the hydrocarbon side-chain with excellent regio- and chemoselectivity, representing a remarkable reactivity relay when compared with classical cross-coupling reactions. Our results demonstrate that site-selectivity can be switched and controlled, enabling the functionalization of less-reactive positions in the presence of a priori more reactive ones. Furthermore, we show that raw materials obtained in bulk from petroleum processing, such as alkanes and unrefined mixtures of olefins, can be used as substrates. This offers an opportunity to integrate a catalytic platform en route to valuable fatty acids by transforming petroleum-derived feedstocks directly.
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USDA-ARS?s Scientific Manuscript database
Rapid detection of shifts in substrate utilization and energy balance would provide a compelling biofeedback tool to enable individuals to lose weight. In a pilot study, we tested whether the natural abundance of exhaled carbon stable isotope ratios (breath d13C values) reflects shifts between negat...
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Decreased carbon limitation of litter respiration in a mortality-affected pinon-juniper woodland
Erin Berryman; John D. Marshall; Thom Rahn; Marcie Litvak; John Butnor
2013-01-01
Microbial respiration depends on microclimatic variables and carbon (C) substrate availability, all of which are altered when ecosystems experience major disturbance. Widespread tree mortality, currently affecting pinon-juniper ecosystems in southwestern North America, may affect C substrate availability in several ways, for example, via litterfall pulses and loss of...
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Shanklin, John; Cahoon, Edgar B.
2004-02-03
The present invention relates to a method for producing mutants of a fatty acid desaturase having a substantially increased activity towards fatty acid substrates with chains containing fewer than 18 carbons relative to an unmutagenized precursor desaturase having an 18 carbon atom chain length substrate specificity. The method involves inducing one or more mutations in the nucleic acid sequence encoding the precursor desaturase, transforming the mutated sequence into an unsaturated fatty acid auxotroph cell such as MH13 E. coli, culturing the cells in the absence of supplemental unsaturated fatty acids, thereby selecting for recipient cells which have received and which express a mutant fatty acid desaturase with an elevated specificity for fatty acid substrates having chain lengths of less than 18 carbon atoms. A variety of mutants having 16 or fewer carbon atom chain length substrate specificities are produced by this method. Mutant desaturases produced by this method can be introduced via expression vectors into prokaryotic and eukaryotic cells and can also be used in the production of transgenic plants which may be used to produce specific fatty acid products.
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Low substrate temperature deposition of diamond coatings derived from glassy carbon
Holcombe, C.E. Jr.; Seals, R.D.
1995-09-26
A process is disclosed for depositing a diamond coating on a substrate at temperatures less than about 550 C. A powder mixture of glassy carbon and diamond particles is passed through a high velocity oxy-flame apparatus whereupon the powders are heated prior to impingement at high velocity against the substrate. The powder mixture contains between 5 and 50 powder volume percent of the diamond particles, and preferably between 5 and 15 powder volume percent. The particles have a size from about 5 to about 100 micrometers, with the diamond particles being about 5 to about 30 micrometers. The flame of the apparatus provides a velocity of about 350 to about 1000 meters per second, with the result that upon impingement upon the substrate, the glassy carbon is phase transformed to diamond as coaxed by the diamond content of the powder mixture. 2 figs.
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Yang, Yi; Ling, Yichuan; Wang, Gongming; Lu, Xihong; Tong, Yexiang; Li, Yat
2013-03-07
We report a general strategy for synthesis of gallium nitride (GaN) and indium nitride (InN) nanowires on conductive and flexible carbon cloth substrates. GaN and InN nanowires were prepared via a nanocluster-mediated growth method using a home built chemical vapor deposition (CVD) system with Ga and In metals as group III precursors and ammonia as a group V precursor. Electron microscopy studies reveal that the group III-nitride nanowires are single crystalline wurtzite structures. The morphology, density and growth mechanism of these nanowires are determined by the growth temperature. Importantly, a photoelectrode fabricated by contacting the GaN nanowires through a carbon cloth substrate shows pronounced photoactivity for photoelectrochemical water oxidation. The ability to synthesize group III-nitride nanowires on conductive and flexible substrates should open up new opportunities for nanoscale photonic, electronic and electrochemical devices.
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Wang, Fan; Zuo, Zicheng; Shang, Hong; Zhao, Yingjie; Li, Yuliang
2018-03-08
A moderate method is first developed here for superfast (in seconds) growth of an ultrafine graphdiyne (GDY) nanochain on arbitrary substrates in the atmosphere. This is an environmentally friendly and metal-catalyst-free method, efficiently eliminating extraneous contaminations for the carbon materials. The seamless GDY coating on any substrates demonstrates that an all-carbon GDY possesses outstanding controllability and processability, perfectly compensating for the drawbacks of prevailing all-carbon materials. After the decoration of 3D GDY nanostructures, the substrates become superhydrophobic with contact angles high up to of 148° and can be used as outstanding frameworks for storing organic pollution. Because of the reasonable porous and 3D continuous features, the as-prepared samples can be applied as high-performance binder-free supercapacitor electrodes with high area capacitance of up to 53.66 mF cm -2 , prominent power performance, and robust long-term retention (99% after 1300 cycles).
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On-chip purification via liquid immersion of arc-discharge synthesized multiwalled carbon nanotubes
NASA Astrophysics Data System (ADS)
Hokkanen, Matti J.; Lautala, Saara; Shao, Dongkai; Turpeinen, Tuomas; Koivistoinen, Juha; Ahlskog, Markus
2016-07-01
Arc-discharge synthesized multiwalled carbon nanotubes (AD-MWNT) have been proven to be of high quality, but their use is very limited due to difficulties in obtaining them in a clean and undamaged form. Here, we present a simple method that purifies raw AD-MWNT material in laboratory scale without damage, and that in principle can be scaled up. The method consists of depositing raw AD-MWNT material on a flat substrate and immersing the substrate slowly in water, whereby the surface tension force of the liquid-substrate contact line selectively sweeps away the larger amorphous carbon debris and leaves relatively clean MWNTs on the substrate. We demonstrate the utility of the method by preparing clean individual MWNTs for measurement of their Raman spectra. The spectra exhibit the characteristics of high-quality tubes free from contaminants. We also show how one concomitantly with the purification process can obtain large numbers of clean suspended MWNTs.
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Low substrate temperature deposition of diamond coatings derived from glassy carbon
Holcombe, Jr., Cressie E.; Seals, Roland D.
1995-01-01
A process for depositing a diamond coating on a substrate at temperatures less than about 550.degree. C. A powder mixture of glassy carbon and diamond particles is passed through a high velocity oxy-flame apparatus whereupon the powders are heated prior to impingement at high velocity against the substrate. The powder mixture contains between 5 and 50 powder volume percent of the diamond particles, and preferably between 5 and 15 powder volume percent. The particles have a size from about 5 to about 100 micrometers, with the diamond particles being about 5 to about 30 micrometers. The flame of the apparatus provides a velocity of about 350 to about 1000 meters per second, with the result that upon impingement upon the substrate, the glassy carbon is phase transformed to diamond as coaxed by the diamond content of the powder mixture.
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NASA Astrophysics Data System (ADS)
Matyas, J.; Olejnik, R.; Slobodian, P.
2017-12-01
A most of portable devices, such as mobile phones, tablets, uses antennas made of cupper. In this paper we demonstrate possible use of electrically conductive polymer composite material for such antenna application. Here we describe the method of preparation and properties of the carbon nanotubes (CNTs)/(ethylene-octene copolymer) as flexible microstrip antenna. Carbon nanotubes dispersion in (ethylene-octene copolymer) toluene solution was prepared by ultrasound finally coating PET substrate by method of dip-coating. Main advantages of PET substrate are low weight and also flexibility. The final size of flexible microstrip antenna was 5 x 50 mm with thickness of 0.48 mm (PET substrate 0.25 mm) with the weight of only 0.402 g. Antenna operates at three frequencies 1.66 GHz (-6.51 dB), 2.3 GHz (-13 dB) and 2.98 GHz (-33.59 dB).
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NASA Technical Reports Server (NTRS)
Douglas, F. C.; Paradis, E. L.; Veltri, R. D.
1973-01-01
A radio frequency powered ion-plating system was used to plate protective layers of refractory oxides and carbide onto high strength fiber substrates. Subsequent overplating of these combinations with nickel and titanium was made to determine the effectiveness of such barrier layers in preventing diffusion of the overcoat metal into the fibers with consequent loss of fiber strength. Four substrates, five coatings, and two metal matrix materials were employed for a total of forty material combinations. The substrates were tungsten, niobium, NASA-Hough carbon, and Tyco sapphire. The diffusion-barrier coatings were aluminum oxide, yttrium oxide, titanium carbide, tungsten carbide with 14% cobalt addition, and zirconium carbide. The metal matrix materials were IN 600 nickel and Ti 6/4 titanium. Adhesion of the coatings to all substrates was good except for the NASA-Hough carbon, where flaking off of the oxide coatings in particular was observed.
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NASA Astrophysics Data System (ADS)
Balalykin, N. I.; Huran, J.; Nozdrin, M. A.; Feshchenko, A. A.; Kobzev, A. P.; Sasinková, V.; Boháček, P.; Arbet, J.
2018-03-01
N-doped carbon thin films were deposited on a silicon substrate and quartz glass by RF reactive magnetron sputtering using a carbon target and an Ar+N2 gas mixture. During the magnetron sputtering, the substrate holder temperatures was kept at 800 °C. The carbon film thickness on the silicon substrate was about 70 nm, while on the quartz glass it was in the range 15 nm – 60 nm. The elemental concentration in the films was determined by RBS and ERD. Raman spectroscopy was used to evaluate the intensity ratios I D/I G of the D and G peaks of the carbon films. The transmission photocathodes prepared were placed in the hollow-cathode assembly of a Pierce-structure DC gun to produce photoelectrons. The quantum efficiency (QE) was calculated from the laser energy and cathode charge measured. The properties of the transmission photocathodes based on semitransparent N-doped carbon thin films on quartz glass and their potential for application in DC gun technology are discussed.
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NASA Astrophysics Data System (ADS)
Onaka-Masada, Ayumi; Nakai, Toshiro; Okuyama, Ryosuke; Okuda, Hidehiko; Kadono, Takeshi; Hirose, Ryo; Koga, Yoshihiro; Kurita, Kazunari; Sueoka, Koji
2018-02-01
The effect of oxygen (O) concentration on the Fe gettering capability in a carbon-cluster (C3H5) ion-implanted region was investigated by comparing a Czochralski (CZ)-grown silicon substrate and an epitaxial growth layer. A high Fe gettering efficiency in a carbon-cluster ion-implanted epitaxial growth layer, which has a low oxygen region, was observed by deep-level transient spectroscopy (DLTS) and secondary ion mass spectroscopy (SIMS). It was demonstrated that the amount of gettered Fe in the epitaxial growth layer is approximately two times higher than that in the CZ-grown silicon substrate. Furthermore, by measuring the cathodeluminescence, the number of intrinsic point defects induced by carbon-cluster ion implantation was found to differ between the CZ-grown silicon substrate and the epitaxial growth layer. It is suggested that Fe gettering by carbon-cluster ion implantation comes through point defect clusters, and that O in the carbon-cluster ion-implanted region affects the formation of gettering sinks for Fe.
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Patterned growth of carbon nanotubes on Si substrates without predeposition of metal catalysts
NASA Astrophysics Data System (ADS)
Chen, Y.; Yu, J.
2005-07-01
Aligned carbon nanotubes (CNTs) can be readily synthesized on quartz or silicon-oxide-coated Si substrates using a chemical vapor deposition method, but it is difficult to grow them on pure Si substrates without predeposition of metal catalysts. We report that aligned CNTs were grown by pyrolysis of iron phthalocyanine at 1000°C on the templates created on Si substrates with simple mechanical scratching. Scanning electron microscopy and x-ray energy spectroscopy analysis revealed that the trenches and patterns created on the surface of Si substrates were preferred nucleation sites for nanotube growth due to a high surface energy, metastable surface structure, and possible capillarity effect. A two-step pyrolysis process maintained Fe as an active catalyst.
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Species and Media Effects on Soil Carbon Dynamics in the Landscape
Marble, S. Christopher; Prior, Stephen A.; Runion, G. Brett; Torbert, H. Allen; Gilliam, Charles H.; Fain, Glenn B.; Sibley, Jeff L.; Knight, Patricia R.
2016-01-01
Three woody shrub species [cleyera (Ternstroemia gymnanthera Thunb. ‘Conthery’), Indian hawthorn (Rhaphiolepis indica L.) and loropetalum (Loropetalum chinensis Oliv.‘Ruby’)] were container-grown for one growing season in 2008 using either pinebark (industry standard), clean chip residual or WholeTree (derived by-products from the forestry industry) as potting substrates and then transplanted into the landscape in 2008. An Automated Carbon Efflux System was used to continually monitor soil CO2 efflux from December 2010 through November 2011 in each species and substrate combination. Changes in soil carbon (C) levels as a result of potting substrate were assessed through soil sampling in 2009 and 2011 and plant biomass was determined at study conclusion. Results showed that soil CO2-C efflux was similar among all species and substrates, with few main effects of species or substrate observed throughout the study. Soil analysis showed that plots with pinebark contained higher levels of soil C in both 2009 and 2011, suggesting that pinebark decomposes slower than clean chip residual or WholeTree and consequently has greater C storage potential than the two alternative substrates. Results showed a net C gain for all species and substrate combinations; however, plants grown in pinebark had greater C sequestration potential. PMID:27140321
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Species and Media Effects on Soil Carbon Dynamics in the Landscape
NASA Astrophysics Data System (ADS)
Marble, S. Christopher; Prior, Stephen A.; Runion, G. Brett; Torbert, H. Allen; Gilliam, Charles H.; Fain, Glenn B.; Sibley, Jeff L.; Knight, Patricia R.
2016-05-01
Three woody shrub species [cleyera (Ternstroemia gymnanthera Thunb. ‘Conthery’), Indian hawthorn (Rhaphiolepis indica L.) and loropetalum (Loropetalum chinensis Oliv.‘Ruby’)] were container-grown for one growing season in 2008 using either pinebark (industry standard), clean chip residual or WholeTree (derived by-products from the forestry industry) as potting substrates and then transplanted into the landscape in 2008. An Automated Carbon Efflux System was used to continually monitor soil CO2 efflux from December 2010 through November 2011 in each species and substrate combination. Changes in soil carbon (C) levels as a result of potting substrate were assessed through soil sampling in 2009 and 2011 and plant biomass was determined at study conclusion. Results showed that soil CO2-C efflux was similar among all species and substrates, with few main effects of species or substrate observed throughout the study. Soil analysis showed that plots with pinebark contained higher levels of soil C in both 2009 and 2011, suggesting that pinebark decomposes slower than clean chip residual or WholeTree and consequently has greater C storage potential than the two alternative substrates. Results showed a net C gain for all species and substrate combinations; however, plants grown in pinebark had greater C sequestration potential.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Mayali, Xavier; Stewart, Benjamin; Mabery, Shalini
Here, we investigated bacterial carbon assimilation from stable isotope-labelled macromolecular substrates (proteins; lipids; and two types of polysaccharides, starch and cellobiose) while attached to killed diatom detrital particles during laboratory microcosms incubated for 17 days. Using Chip-SIP (secondary ion mass spectrometry analysis of RNA microarrays), we identified generalist operational taxonomic units (OTUs) from the Gammaproteobacteria, belonging to the genera Colwellia, Glaciecola, Pseudoalteromonas and Rheinheimera, and from the Bacteroidetes, genera Owenweeksia and Maribacter, that incorporated the four tested substrates throughout the incubation period. Many of these OTUs exhibited the highest isotope incorporation relative to the others, indicating that they were likelymore » the most active. Additional OTUs from the Gammaproteobacteria, Bacteroidetes and Alphaproteobacteria exhibited generally (but not always) lower activity and did not incorporate all tested substrates at all times, showing species succession in organic carbon incorporation. We also found evidence to suggest that both generalist and specialist OTUs changed their relative substrate incorporation over time, presumably in response to changing substrate availability as the particles aged. This pattern was demonstrated by temporal succession from relatively higher starch incorporation early in the incubations, eventually switching to higher cellobiose incorporation after 2 weeks.« less
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Rüdiger, Celine; Favaro, Marco; Valero-Vidal, Carlos; Calvillo, Laura; Bozzolo, Nathalie; Jacomet, Suzanne; Hejny, Clivia; Gregoratti, Luca; Amati, Matteo; Agnoli, Stefano; Granozzi, Gaetano; Kunze-Liebhäuser, Julia
2016-04-07
Composite materials of titania and graphitic carbon, and their optimized synthesis are highly interesting for application in sustainable energy conversion and storage. We report on planar C/TiO2 composite films that are prepared on a polycrystalline titanium substrate by carbothermal treatment of compact anodic TiO2 with acetylene. This thin film material allows for the study of functional properties of C/TiO2 as a function of chemical composition and structure. The chemical and structural properties of the composite on top of individual Ti substrate grains are examined by scanning photoelectron microscopy and micro-Raman spectroscopy. Through comparison of these data with electron backscatter diffraction, it is found that the amount of generated carbon and the grade of anodic film crystallinity correlate with the crystallographic orientation of the Ti substrate grains. On top of Ti grains with ∼(0001) orientations the anodic TiO2 exhibits the highest grade of crystallinity, and the composite contains the highest fraction of graphitic carbon compared to Ti grains with other orientations. This indirect effect of the Ti substrate grain orientation yields new insights into the activity of TiO2 towards the decomposition of carbon precursors.
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Phosphoketolase pathway engineering for carbon-efficient biocatalysis
DOE Office of Scientific and Technical Information (OSTI.GOV)
Henard, Calvin Andrew; Freed, Emily Frances; Guarnieri, Michael Thomas
2015-12-01
Recent advances in metabolic engineering have facilitated the development of microbial biocatalysts capable of producing an array of bio-products, ranging from fuels to drug molecules. These bio-products are commonly generated through an acetyl-CoA intermediate, which serves as a key precursor in the biological conversion of carbon substrates. Moreover, conventional biocatalytic upgrading strategies proceeding through this route are limited by low carbon efficiencies, in large part due to carbon losses associated with pyruvate decarboxylation to acetyl-CoA. Bypass of pyruvate decarboxylation offers a means to dramatically enhance carbon yields and, in turn, bioprocess economics. Here, we discuss recent advances and prospects formore » employing the phosphoketolase pathway for direct biosynthesis of acetyl-CoA from carbon substrates, and phosphoketolase-based metabolic engineering strategies for carbon efficient biocatalysis.« less
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High rates of organic carbon processing in the hyporheic zone of intermittent streams.
Burrows, Ryan M; Rutlidge, Helen; Bond, Nick R; Eberhard, Stefan M; Auhl, Alexandra; Andersen, Martin S; Valdez, Dominic G; Kennard, Mark J
2017-10-16
Organic carbon cycling is a fundamental process that underpins energy transfer through the biosphere. However, little is known about the rates of particulate organic carbon processing in the hyporheic zone of intermittent streams, which is often the only wetted environment remaining when surface flows cease. We used leaf litter and cotton decomposition assays, as well as rates of microbial respiration, to quantify rates of organic carbon processing in surface and hyporheic environments of intermittent and perennial streams under a range of substrate saturation conditions. Leaf litter processing was 48% greater, and cotton processing 124% greater, in the hyporheic zone compared to surface environments when calculated over multiple substrate saturation conditions. Processing was also greater in more saturated surface environments (i.e. pools). Further, rates of microbial respiration on incubated substrates in the hyporheic zone were similar to, or greater than, rates in surface environments. Our results highlight that intermittent streams are important locations for particulate organic carbon processing and that the hyporheic zone sustains this fundamental process even without surface flow. Not accounting for carbon processing in the hyporheic zone of intermittent streams may lead to an underestimation of its local ecological significance and collective contribution to landscape carbon processes.
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NASA Astrophysics Data System (ADS)
Riley, W. J.; Tang, J.
2014-12-01
We hypothesize that the large observed variability in decomposition temperature sensitivity and carbon use efficiency arises from interactions between temperature, microbial biogeochemistry, and mineral surface sorptive reactions. To test this hypothesis, we developed a numerical model that integrates the Dynamic Energy Budget concept for microbial physiology, microbial trait-based community structure and competition, process-specific thermodynamically based temperature sensitivity, a non-linear mineral sorption isotherm, and enzyme dynamics. We show, because mineral surfaces interact with substrates, enzymes, and microbes, both temperature sensitivity and microbial carbon use efficiency are hysteretic and highly variable. Further, by mimicking the traditional approach to interpreting soil incubation observations, we demonstrate that the conventional labile and recalcitrant substrate characterization for temperature sensitivity is flawed. In a 4 K temperature perturbation experiment, our fully dynamic model predicted more variable but weaker carbon-climate feedbacks than did the static temperature sensitivity and carbon use efficiency model when forced with yearly, daily, and hourly variable temperatures. These results imply that current earth system models likely over-estimate the response of soil carbon stocks to global warming.
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Weaker soil carbon-climate feedbacks resulting from microbial and abiotic interactions
NASA Astrophysics Data System (ADS)
Tang, Jinyun; Riley, William J.
2015-01-01
The large uncertainty in soil carbon-climate feedback predictions has been attributed to the incorrect parameterization of decomposition temperature sensitivity (Q10; ref. ) and microbial carbon use efficiency. Empirical experiments have found that these parameters vary spatiotemporally, but such variability is not included in current ecosystem models. Here we use a thermodynamically based decomposition model to test the hypothesis that this observed variability arises from interactions between temperature, microbial biogeochemistry, and mineral surface sorptive reactions. We show that because mineral surfaces interact with substrates, enzymes and microbes, both Q10 and microbial carbon use efficiency are hysteretic (so that neither can be represented by a single static function) and the conventional labile and recalcitrant substrate characterization with static temperature sensitivity is flawed. In a 4-K temperature perturbation experiment, our fully dynamic model predicted more variable but weaker soil carbon-climate feedbacks than did the static Q10 and static carbon use efficiency model when forced with yearly, daily and hourly variable temperatures. These results imply that current Earth system models probably overestimate the response of soil carbon stocks to global warming. Future ecosystem models should therefore consider the dynamic interactions between sorptive mineral surfaces, substrates and microbial processes.
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Stable carbon isotope fractionation by sulfate-reducing bacteria
NASA Technical Reports Server (NTRS)
Londry, Kathleen L.; Des Marais, David J.
2003-01-01
Biogeochemical transformations occurring in the anoxic zones of stratified sedimentary microbial communities can profoundly influence the isotopic and organic signatures preserved in the fossil record. Accordingly, we have determined carbon isotope discrimination that is associated with both heterotrophic and lithotrophic growth of pure cultures of sulfate-reducing bacteria (SRB). For heterotrophic-growth experiments, substrate consumption was monitored to completion. Sealed vessels containing SRB cultures were harvested at different time intervals, and delta(13)C values were determined for gaseous CO(2), organic substrates, and products such as biomass. For three of the four SRB, carbon isotope effects between the substrates, acetate or lactate and CO(2), and the cell biomass were small, ranging from 0 to 2 per thousand. However, for Desulfotomaculum acetoxidans, the carbon incorporated into biomass was isotopically heavier than the available substrates by 8 to 9 per thousand. SRB grown lithoautotrophically consumed less than 3% of the available CO(2) and exhibited substantial discrimination (calculated as isotope fractionation factors [alpha]), as follows: for Desulfobacterium autotrophicum, alpha values ranged from 1.0100 to 1.0123; for Desulfobacter hydrogenophilus, the alpha value was 0.0138, and for Desulfotomaculum acetoxidans, the alpha value was 1.0310. Mixotrophic growth of Desulfovibrio desulfuricans on acetate and CO(2) resulted in biomass with a delta(13)C composition intermediate to that of the substrates. The extent of fractionation depended on which enzymatic pathways were used, the direction in which the pathways operated, and the growth rate, but fractionation was not dependent on the growth phase. To the extent that environmental conditions affect the availability of organic substrates (e.g., acetate) and reducing power (e.g., H(2)), ecological forces can also influence carbon isotope discrimination by SRB.
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Chemically attached gold nanoparticle-carbon nanotube hybrids for highly sensitive SERS substrate
NASA Astrophysics Data System (ADS)
Beqa, Lule; Singh, Anant Kumar; Fan, Zheng; Senapati, Dulal; Ray, Paresh Chandra
2011-08-01
Surface-enhanced Raman spectroscopy (SERS) has been shown as one of the most powerful analytical tool with high sensitivity. In this manuscript, we report the chemical design of SERS substrate, based on gold nanoparticles of different shapes-decorated with carbon nanotube with an enhancement factor of 7.5 × 1010. Shape dependent result shows that popcorn shape gold nanoparticle decorated SWCNT is the best choice for SERS substrate due to the existence of 'lightning rod effect' through several sharp edges or corners. Our results provide a good approach to develop highly sensitive SERS substrates and can help to improve the fundamental understanding of SERS phenomena.
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High-performance carbon nanotube thin-film transistors on flexible paper substrates
DOE Office of Scientific and Technical Information (OSTI.GOV)
Liu, Na; Yun, Ki Nam; Yu, Hyun-Yong
Single-walled carbon nanotubes (SWCNTs) are promising materials as active channels for flexible transistors owing to their excellent electrical and mechanical properties. However, flexible SWCNT transistors have never been realized on paper substrates, which are widely used, inexpensive, and recyclable. In this study, we fabricated SWCNT thin-film transistors on photo paper substrates. The devices exhibited a high on/off current ratio of more than 10{sup 6} and a field-effect mobility of approximately 3 cm{sup 2}/V·s. The proof-of-concept demonstration indicates that SWCNT transistors on flexible paper substrates could be applied as low-cost and recyclable flexible electronics.
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NASA Astrophysics Data System (ADS)
Wang, Yongfu; Wang, Yan; Zhang, Xingkai; Shi, Jing; Gao, Kaixiong; Zhang, Bin; Zhang, Junyan
2017-10-01
In this study, we prepared hydrogenated amorphous carbon films on steel balls and Si substrates (steel ball- and Si substrate-films) with different deposition time, and discussed their carbon nanostructural evolutions and tribological behaviors. The steel ball-film structure started to be graphite-like structure and then gradually transformed into fullerene-like (FL) structure. The Si substrate-film structure began in FL structure and kept it through the thickness. The difference may be result from the competition between high starting substrate temperature after additional nitriding applied on the steel balls (its supply power is higher than that in the film deposition), and relaxation of compressive stress from energized ion bombardment in film deposition process. The FL structural film friction couples could achieve ultra-low friction in open air. In particular, the Si substrate-film with 3 h, against the steel ball-film with 2 h and 3 h, exhibited super-low friction (∼0.009) and superlong wear life (∼5.5 × 105 cycles). Our result could widen the superlubricity scope from previously high load and velocity, to middle load and velocity.
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Carbon nanotube nanoelectrode arrays
Ren, Zhifeng; Lin, Yuehe; Yantasee, Wassana; Liu, Guodong; Lu, Fang; Tu, Yi
2008-11-18
The present invention relates to microelectode arrays (MEAs), and more particularly to carbon nanotube nanoelectrode arrays (CNT-NEAs) for chemical and biological sensing, and methods of use. A nanoelectrode array includes a carbon nanotube material comprising an array of substantially linear carbon nanotubes each having a proximal end and a distal end, the proximal end of the carbon nanotubes are attached to a catalyst substrate material so as to form the array with a pre-determined site density, wherein the carbon nanotubes are aligned with respect to one another within the array; an electrically insulating layer on the surface of the carbon nanotube material, whereby the distal end of the carbon nanotubes extend beyond the electrically insulating layer; a second adhesive electrically insulating layer on the surface of the electrically insulating layer, whereby the distal end of the carbon nanotubes extend beyond the second adhesive electrically insulating layer; and a metal wire attached to the catalyst substrate material.
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Organic nanowire hierarchy over fabric platform for flexible cold cathode
NASA Astrophysics Data System (ADS)
Maiti, Soumen; Narayan Maiti, Uday; Pal, Shreyasi; Chattopadhyay, Kalyan Kumar
2013-11-01
Organic charge transfer (CT) complexes initiated a growing interest in modern electronic devices owing to their easy processability and unique characteristics. In this work, three-dimensional field emitters comprising metal-organic charge transfer complex nanostructures of AgTCNQ and CuTCNQ (TCNQ, 7,7,8,8-tetracyanoquinodimethane) over flexible fabric substrate are realized. Deliberate control over the reaction parameter during organic solid phase reaction leads to modification in structural parameters of the nanowires (i.e. length, diameter) as well as their arrangement atop the carbon fibers. The optimized arrays of AgTCNQ and CuTCNQ nanowires exhibit excellent field electron emission performance with very low turn-on (1.72 and 2.56 V μm-1) and threshold fields (4.21 and 6.33 V μm-1) respectively, which are comparable to those of the best organic field emitters reported to date. The underlying conducting carbon cloth with special woven-like geometry not only offers a flexible platform for nanowire growth, but also provides an additional field enhancement to ease the electron emission.
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Beyond Vmax and Km: How details of enzyme function influence geochemical cycles
NASA Astrophysics Data System (ADS)
Steen, A. D.
2015-12-01
Enzymes catalyze the vast majority of chemical reactions relevant to geomicrobiology. Studies of the activities of enzymes in environmental systems often report Vmax (the maximum possible rate of reaction; often proportional to the concentration of enzymes in the system) and sometimes Km (a measure of the affinity between enzymes and their substrates). However, enzyme studies - particularly those related to enzymes involved in organic carbon oxidation - are often limited to only those parameters, and a relatively limited and mixed set of enzymes. Here I will discuss some novel methods to assay and characterize the specific sets of enzymes that may be important to the carbon cycle in aquatic environments. First, kinetic experiments revealed the collective properties of the complex mixtures of extracellular peptidases that occur where microbial communities are diverse. Crystal structures combined with biochemical characterization of specific enzymes can yield more detailed information about key steps in organic carbon transformations. These new techniques have the potential to provide mechanistic grounding to geomicrobiological models.
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Szabó, Anna; Kecsenovity, Egon; Pápa, Zsuzsanna; Gyulavári, Tamás; Németh, Krisztián; Horvath, Endre; Hernadi, Klara
2017-08-25
In the past two decades, important results have been achieved in the field of carbon nanotube (CNT) research, which revealed that carbon nanotubes have extremely good electrical and mechanical properties The range of applications widens more, if CNTs form a forest-like, vertically aligned structure (VACNT) Although, VACNT-conductive substrate structure could be very advantageous for various applications, to produce proper system without barrier films i.e. with good electrical contact is still a challenge. The aim of the current work is to develop a cheap and easy method for growing carbon nanotubes forests on conductive substrate with the CCVD (Catalytic Chemical Vapor Deposition) technique at 640 °C. The applied catalyst contained Fe and Co and was deposited via dip coating onto an aluminum substrate. In order to control the height of CNT forest several parameters were varied during the both catalyst layer fabrication (e.g. ink concentration, ink composition, dipping speed) and the CCVD synthesis (e.g. gas feeds, reaction time). As-prepared CNT forests were investigated with various methods such as scanning electron microscopy, Raman spectroscopy, and cyclic voltammetry. With such an easy process it was possible to tune both the height and the quality of carbon nanotube forests.
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Postils, Verònica; Company, Anna; Solà, Miquel; Costas, Miquel; Luis, Josep M
2015-09-08
The reaction mechanisms for alkane hydroxylation catalyzed by non-heme Fe(V)O complexes presented in the literature vary from rebound stepwise to concerted highly asynchronous processes. The origin of these important differences is still not completely understood. Herein, in order to clarify this apparent inconsistency, the hydroxylation of a series of alkanes (methane and substrates bearing primary, secondary, and tertiary C-H bonds) through a Fe(V)O species, [Fe(V)(O)(OH)(PyTACN)](2+) (PyTACN = 1-(2'-pyridylmethyl)-4,7-dimethyl-1,4,7-triazacyclononane), has been computationally examined at the gas phase and in acetonitrile solution. The initial breaking of the C-H bond can occur via hydrogen atom transfer (HAT), leading to an intermediate where there is an interaction between the radical substrate and [Fe(IV)(OH)2(PyTACN)](2+), or through hydride transfer to form a cationic substrate interacting with the [Fe(III)(OH)2(PyTACN)](+) species. Our calculations show the following: (i) except for methane in the rest of the alkanes studied, the intermediate formed by R(+) and [Fe(III)(OH)2(PyTACN)](+) is more stable than that involving the alkyl radical and the [Fe(IV)(OH)2(PyTACN)](2+) complex; (ii) in spite of (i), the first step of the reaction mechanism for all substrates is a HAT instead of hydride abstraction; (iii) the HAT is the rate-determining step for all analyzed cases; and (iv) the barrier for the HAT decreases along methane → primary → secondary → tertiary carbon. The second part of the reaction mechanism corresponds to the rebound process. Therefore, the stereospecific hydroxylation of alkane C-H bonds by non-heme Fe(V)(O) species occurs through a rebound stepwise mechanism that resembles that taking place at heme analogues. Finally, our study also shows that, to properly describe alkane hydroxylation processes mediated by Fe(V)O species, it is essential to consider the solvent effects during geometry optimizations. The use of gas-phase geometries explains the variety of mechanisms for the hydroxylation of alkanes reported in the literature.
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Structure of Mandelate Racemase with Bound Intermediate Analogues Benzohydroxamate and Cupferron†
Lietzan, Adam D.; Nagar, Mitesh; Pellmann, Elise A.; Bourque, Jennifer R.; Bearne, Stephen L.; St Maurice, Martin
2012-01-01
Mandelate racemase (MR, EC 5.1.2.2) from Pseudomonas putida catalyzes the Mg2+-dependent interconversion of the enantiomers of mandelate, stabilizing the altered substrate in the transition state by 26 kcal/mol relative to the substrate in the ground state. To understand the origins of this binding discrimination, we solved the X-ray crystal structures of wild-type MR complexed with two analogues of the putative aci-carboxylate intermediate, benzohydroxamate and cupferron, to 2.2-Å resolution. Benzohydroxamate is shown to be a reasonable mimic of the transition state/intermediate since its binding affinity to 21 MR variants correlates well with changes in the free energy of transition state stabilization afforded by these variants. Both benzohydroxamate and cupferron chelate the active site divalent metal ion and are bound in a conformation with the phenyl ring coplanar with the hydroxamate and diazeniumdiolate moieties, respectively. Structural overlays of MR complexed with benzohydroxamate, cupferron, and the ground state analogue (S)-atrolacatate reveal that the para-carbon of the substrate phenyl ring moves by 0.8–1.2 Å between the ground state and intermediate state, consistent with the proposal that the phenyl ring moves during MR catalysis while the polar groups remain relatively fixed. Although the overall protein structure of MR with bound intermediate analogues is very similar to MR with bound (S)-atrolactate, the intermediate-Mg2+ distance shortens, suggesting a tighter complex with the catalytic Mg2+. In addition, Tyr 54 moves nearer to the phenyl ring of the bound intermediate analogues, contributing to an overall constriction of the active site cavity. However, site-directed mutagenesis experiments revealed that the role of Tyr 54 in MR catalysis is relatively minor, suggesting that alterations in enzyme structure that contribute to discrimination between the altered substrate in the transition state and the ground state by this proficient enzyme are extremely subtle. PMID:22264153
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Probes of the catalytic site of cysteine dioxygenase.
Chai, Sergio C; Bruyere, John R; Maroney, Michael J
2006-06-09
The first major step of cysteine catabolism, the oxidation of cysteine to cysteine sulfinic acid, is catalyzed by cysteine dioxygenase (CDO). In the present work, we utilize recombinant rat liver CDO and cysteine derivatives to elucidate structural parameters involved in substrate recognition and x-ray absorption spectroscopy to probe the interaction of the active site iron center with cysteine. Kinetic studies using cysteine structural analogs show that most are inhibitors and that a terminal functional group bearing a negative charge (e.g. a carboxylate) is required for binding. The substrate-binding site has no stringent restrictions with respect to the size of the amino acid. Lack of the amino or carboxyl groups at the alpha-carbon does not prevent the molecules from interacting with the active site. In fact, cysteamine is shown to be a potent activator of the enzyme without being a substrate. CDO was also rendered inactive upon complexation with the metal-binding inhibitors azide and cyanide. Unlike many non-heme iron dioxygenases that employ alpha-keto acids as cofactors, CDO was shown to be the only dioxygenase known to be inhibited by alpha-ketoglutarate.
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Controlled Deposition and Alignment of Carbon Nanotubes
NASA Technical Reports Server (NTRS)
Smits, Jan M. (Inventor); Wincheski, Russell A. (Inventor); Ingram, JoAnne L. (Inventor); Watkins, Anthony Neal (Inventor); Jordan, Jeffrey D. (Inventor)
2009-01-01
A carbon nanotube (CNT) attraction material is deposited on a substrate in the gap region between two electrodes on the . substrate. An electric potential is applied to the two electrodes. The CNT attraction material is wetted with a solution defined by a carver liquid having carbon nanotubes (CNTs) suspended therein. A portion of the CNTs align with the electric field and adhere to The CNT attraction material. The carrier liquid and any CNTs not adhered to the CNT attraction material are then removed.
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Controlled Deposition and Alignment of Carbon Nanotubes
NASA Technical Reports Server (NTRS)
Patry, JoAnne L. (Inventor); Smits, Jan M. (Inventor); Watkins, Anthony Neal (Inventor); Jordan, Jeffrey D. (Inventor); Wincheski, Russell A. (Inventor)
2012-01-01
A carbon nanotube (CNT) attraction material is deposited on a substrate in the gap region between two electrodes on the substrate. An electric potential is applied to the two electrodes. The CNT attraction material is wetted with a solution defined by a carrier liquid having carbon nanotubes (CNTs) suspended therein. A portion of the CNTs align with the electric field and adhere to the CNT attraction material. The carrier liquid and any CNTs not adhered to the CNT attraction material are then removed.
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Decomposition of heterogeneous organic matterand its long-term stabilization in soils
Sierra, Carlos A.; Harmon, Mark E.; Perakis, Steven S.
2011-01-01
Soil organic matter is a complex mixture of material with heterogeneous biological, physical, and chemical properties. Decomposition models represent this heterogeneity either as a set of discrete pools with different residence times or as a continuum of qualities. It is unclear though, whether these two different approaches yield comparable predictions of organic matter dynamics. Here, we compare predictions from these two different approaches and propose an intermediate approach to study organic matter decomposition based on concepts from continuous models implemented numerically. We found that the disagreement between discrete and continuous approaches can be considerable depending on the degree of nonlinearity of the model and simulation time. The two approaches can diverge substantially for predicting long-term processes in soils. Based on our alternative approach, which is a modification of the continuous quality theory, we explored the temporal patterns that emerge by treating substrate heterogeneity explicitly. The analysis suggests that the pattern of carbon mineralization over time is highly dependent on the degree and form of nonlinearity in the model, mostly expressed as differences in microbial growth and efficiency for different substrates. Moreover, short-term stabilization and destabilization mechanisms operating simultaneously result in long-term accumulation of carbon characterized by low decomposition rates, independent of the characteristics of the incoming litter. We show that representation of heterogeneity in the decomposition process can lead to substantial improvements in our understanding of carbon mineralization and its long-term stability in soils.
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Kubis, Christoph; Sawall, Mathias; Block, Axel; Neymeyr, Klaus; Ludwig, Ralf; Börner, Armin; Selent, Detlef
2014-09-08
The influence of carbon monoxide concentration on the kinetics of the hydroformylation of 3,3-dimethyl-1-butene with a phosphite-modified rhodium catalyst has been studied for the pressure range p(CO)=0.20-3.83 MPa. Highly resolved time-dependent concentration profiles of the organometallic intermediates were derived from IR spectroscopic data collected in situ for the entire olefin-conversion range. The dynamics of the catalyst and organic components are described by enzyme-type kinetics with competitive and uncompetitive inhibition reactions involving carbon monoxide taken into account. Saturation of the alkyl-rhodium intermediates with carbon monoxide as a cosubstrate occurs between 1.5 and 2 MPa of carbon monoxide pressure, which brings about a convergence of aldehyde regioselectivity. Hydrogenolysis of the acyl intermediate is fast at 30 °C and low pressure of p(CO)=0.2 MPa, but is of minus first order with respect to the solution concentration of carbon monoxide. Resting 18-electron hydrido and acyl complexes that correspond to early and late rate-determining states, respectively, coexist as long as the conversion of the substrate is not complete. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Reduced substrate supply limits the temperature response of soil organic carbon decomposition
Cinzia Fissore; Christian P. Giardina; Randall K. Kolka
2013-01-01
Controls on the decomposition rate of soil organic carbon (SOC), especially the more stable fraction of SOC, remain poorly understood, with implications for confidence in efforts to model terrestrial C balance under future climate. We investigated the role of substrate supply in the temperature sensitivity of SOC decomposition in laboratory incubations of coarse-...
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The effects of substrate supply on the temperature sensitivity of soil carbon decomposition
Cinzia Fissore; Christian P. Giardina; Randall K. Kolka
2013-01-01
Controls on the decomposition rate of soil organic carbon (SOC), especially the more stable fraction of SOC, remain poorly understood, with implications for confidence in efforts to model terrestrial C balance under future climate. We investigated the role of substrate supply in the temperature sensitivity of SOC decomposition in laboratory incubations of coarse-...
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Synthesis of Diamond Nanoplatelets/Carbon Nanowalls on Graphite Substrate by MPCVD
NASA Astrophysics Data System (ADS)
Zhang, Wei; Lyu, Jilei; Lin, Xiaoqi; Zhu, Jinfeng; Man, Weidong; Jiang, Nan
2015-07-01
The films composed of carbon nanowalls and diamond nanoplatelets, respectively, can be simultaneously formed on graphite substrate by controlling the hydrogen etching rate during microwave plasma chemical vapor deposition. To modulate the etching rate, two kinds of substrate design were used: a bare graphite plate and a graphite groove covered with a single crystal diamond sheet. After deposition at 1200°C for 3 hours, we find that dense diamond nanoplatelets were grown on the bare graphite, whereas carbon nanowalls were formed on the grooved surface, indicating that not only reaction temperature but also etching behavior is a key factor for nanostructure formation. supported by the Public Welfare Technology Application Projects of Zhejiang Province, China (No. 2013C33G3220012)
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NASA Astrophysics Data System (ADS)
Dou, X. Y.; Zhou, Z. P.; Tan, P. H.; Song, L.; Liu, L. F.; Zhao, X. W.; Luo, S. D.; Yan, X. Q.; Liu, D. F.; Wang, J. X.; Gao, Y.; Zhang, Z. X.; Yuan, H. J.; Zhou, W. Y.; Xie, S. S.
2005-05-01
In this paper, we developed a new kind of substrate, the silver-coated anodic aluminum oxide (AAO), to investigate the characters of surface-enhanced resonant Raman scattering (SERRS) of the dilute single-walled carbon nanotubes. Homogeneous Ag-coated AAO substrate was obtained by decomposing the AgNO 3 on the surface of AAO. single-walled carbon nanotubes (SWNTs) were directly grown onto this substrate through floating catalyst chemical vapor deposition method (CVD). SERRS of SWNTs was carried out using several different wavelength lasers. The bands coming from metallic SWNTs were significantly enhanced. The two SERRS mechanisms, the “electromagnetic” and “chemical” mechanism, were mainly responsible for the experiment results.
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Directed-Assembly of Carbon Nanotubes on Soft Substrates for Flexible Biosensor Array
NASA Astrophysics Data System (ADS)
Lee, Hyoung Woo; Koh, Juntae; Lee, Byung Yang; Kim, Tae Hyun; Lee, Joohyung; Hong, Seunghun; Yi, Mihye; Jhon, Young Min
2009-03-01
We developed a method to selectively assemble and align carbon nanotubes (CNTs) on soft substrates for flexible biosensors. In this strategy, thin oxide layer was deposited on soft substrates via low temperature plasma enhanced chemical vapor deposition, and linker-free assembly process was applied onto the oxide surface where the assembly of carbon nanotubes was guided by methyl-terminated molecular patterns on the oxide surface. The electrical characterization of the fabricated CNT devices exhibited typical p-type gating effect and 1/f noise behavior. The bare oxide regions near CNTs were functionalized with glutamate oxidase to fabricate selective biosensors to detect two forms of glutamate substances existing in different situations: L-glutamic acid, a neuro-transmitting material, and monosodium glutamate, a food additive.
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Huang, Xiaoqiang; Webster, Richard D; Harms, Klaus; Meggers, Eric
2016-09-28
Electron-acceptor-substituted aryl azides and α-diazo carboxylic esters are used as substrates for visible-light-activated asymmetric α-amination and α-alkylation, respectively, of 2-acyl imidazoles catalyzed by a chiral-at-metal rhodium-based Lewis acid in combination with a photoredox sensitizer. This novel proton- and redox-neutral method provides yields of up to 99% and excellent enantioselectivities of up to >99% ee with broad functional group compatibility. Mechanistic investigations suggest that an intermediate rhodium enolate complex acts as a reductive quencher to initiate a radical process with the aryl azides and α-diazo carboxylic esters serving as precursors for nitrogen and carbon-centered radicals, respectively. This is the first report on using aryl azides and α-diazo carboxylic esters as substrates for asymmetric catalysis under photoredox conditions. These reagents have the advantage that molecular nitrogen is the leaving group and sole byproduct in this reaction.
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Ashikawa, Yuji; Fujimoto, Zui; Usami, Yusuke; Inoue, Kengo; Noguchi, Haruko; Yamane, Hisakazu; Nojiri, Hideaki
2012-06-24
Dihydroxylation of tandemly linked aromatic carbons in a cis-configuration, catalyzed by multicomponent oxygenase systems known as Rieske nonheme iron oxygenase systems (ROs), often constitute the initial step of aerobic degradation pathways for various aromatic compounds. Because such RO reactions inherently govern whether downstream degradation processes occur, novel oxygenation mechanisms involving oxygenase components of ROs (RO-Os) is of great interest. Despite substantial progress in structural and physicochemical analyses, no consensus exists on the chemical steps in the catalytic cycles of ROs. Thus, determining whether conformational changes at the active site of RO-O occur by substrate and/or oxygen binding is important. Carbazole 1,9a-dioxygenase (CARDO), a RO member consists of catalytic terminal oxygenase (CARDO-O), ferredoxin (CARDO-F), and ferredoxin reductase. We have succeeded in determining the crystal structures of oxidized CARDO-O, oxidized CARDO-F, and both oxidized and reduced forms of the CARDO-O: CARDO-F binary complex. In the present study, we determined the crystal structures of the reduced carbazole (CAR)-bound, dioxygen-bound, and both CAR- and dioxygen-bound CARDO-O: CARDO-F binary complex structures at 1.95, 1.85, and 2.00 Å resolution. These structures revealed the conformational changes that occur in the catalytic cycle. Structural comparison between complex structures in each step of the catalytic mechanism provides several implications, such as the order of substrate and dioxygen bindings, the iron-dioxygen species likely being Fe(III)-(hydro)peroxo, and the creation of room for dioxygen binding and the promotion of dioxygen binding in desirable fashion by preceding substrate binding. The RO catalytic mechanism is proposed as follows: When the Rieske cluster is reduced, substrate binding induces several conformational changes (e.g., movements of the nonheme iron and the ligand residue) that create room for oxygen binding. Dioxygen bound in a side-on fashion onto nonheme iron is activated by reduction to the peroxo state [Fe(III)-(hydro)peroxo]. This state may react directly with the bound substrate, or O-O bond cleavage may occur to generate Fe(V)-oxo-hydroxo species prior to the reaction. After producing a cis-dihydrodiol, the product is released by reducing the nonheme iron. This proposed scheme describes the catalytic cycle of ROs and provides important information for a better understanding of the mechanism.
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Development of reproducible assays for polygalacturonase and pectinase.
Li, Qian; Coffman, Anthony M; Ju, Lu-Kwang
2015-05-01
Polygalacturonase and pectinase activities reported in the literature were measured by several different procedures. These procedures do not give comparable results, partly owing to the complexity of the substrates involved. This work was aimed at developing consistent and efficient assays for polygalacturonase and pectinase activities, using polygalacturonic acid and citrus pectin, respectively, as the substrate. Different enzyme mixtures produced by Aspergillus niger and Trichoderma reesei with different inducing carbon sources were used for the method development. A series of experiments were conducted to evaluate the incubation time, substrate concentration, and enzyme dilution. Accordingly, for both assays the recommended (optimal) hydrolysis time is 30min and substrate concentration is 5g/L. For polygalacturonase, the sample should be adjusted to have 0.3-0.8U/mL polygalacturonase activity, because in this range the assay outcomes were consistent (independent of dilution factors). Such a range did not exist for the pectinase assay. The recommended procedure is to assay the sample at multiple (at least 2) dilution factors and determine, by linear interpolation, the dilution factor that would release reducing sugar equivalent to 0.4g/L d-galacturonic acid, and then calculate the activity of the sample accordingly (dilution factor×0.687U/mL). Validation experiments showed consistent results using these assays. Effects of substrate preparation methods were also examined. Copyright © 2015 Elsevier Inc. All rights reserved.
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Hard carbon nitride and method for preparing same
Haller, Eugene E.; Cohen, Marvin L.; Hansen, William L.
1992-01-01
Novel crystalline .alpha. (silicon nitride-like)-carbon nitride and .beta. (silicon nitride-like)-carbon nitride are formed by sputtering carbon in the presence of a nitrogen atmosphere onto a single crystal germanium or silicon, respectively, substrate.
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Pint, Cary; Pheasant, Sean; Nicholas, Nolan; Horton, Charles; Hauge, Robert
2008-11-01
Growth of high quality, vertically aligned single-walled carbon nanotubes (carpets) is achieved using a rapid insertion hot filament chemical vapor deposition (HF-CVD) technique. The effect of the substrate morphology on growth is explored by comparing carpets grown on epitaxially polished MgO substrates to those grown on "as-cut", macroscopically rough MgO substrates. Depending on the substrate morphology, we observe differences in both the overall carpet morphology as well as the diameter distribution of nanotubes grown in the carpet based on optical measurements. In addition, we explore the role of water in the growth of carpets on MgO and the conventional Al2O3 coated Si substrates. We find that the addition of a small amount of water is beneficial to the growth rates of the SWNT carpets, enhancing the growth rates by up to eight times.
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Weak coordination as a powerful means for developing broadly useful C-H functionalization reactions.
Engle, Keary M; Mei, Tian-Sheng; Wasa, Masayuki; Yu, Jin-Quan
2012-06-19
Reactions that convert carbon-hydrogen (C-H) bonds into carbon-carbon (C-C) or carbon-heteroatom (C-Y) bonds are attractive tools for organic chemists, potentially expediting the synthesis of target molecules through new disconnections in retrosynthetic analysis. Despite extensive inorganic and organometallic study of the insertion of homogeneous metal species into unactivated C-H bonds, practical applications of this technology in organic chemistry are still rare. Only in the past decade have metal-catalyzed C-H functionalization reactions become more widely utilized in organic synthesis. Research in the area of homogeneous transition metal-catalyzed C-H functionalization can be broadly grouped into two subfields. They reflect different approaches and goals and thus have different challenges and opportunities. One approach involves reactions of completely unfunctionalized aromatic and aliphatic hydrocarbons, which we refer to as "first functionalization". Here the substrates are nonpolar and hydrophobic and thus interact very weakly with polar metal species. To overcome this weak affinity and drive metal-mediated C-H cleavage, chemists often use hydrocarbon substrates in large excess (for example, as solvent). Because highly reactive metal species are needed in first functionalization, controlling the chemoselectivity to avoid overfunctionalization is often difficult. Additionally, because both substrates and products are comparatively low-value chemicals, developing cost-effective catalysts with exceptionally high turnover numbers that are competitive with alternatives (including heterogeneous catalysts) is challenging. Although an exciting field, first functionalization is beyond the scope of this Account. The second subfield of C-H functionalization involves substrates containing one or more pre-existing functional groups, termed "further functionalization". One advantage of this approach is that the existing functional group (or groups) can be used to chelate the metal catalyst and position it for selective C-H cleavage. Precoordination can overcome the paraffin nature of C-H bonds by increasing the effective concentration of the substrate so that it need not be used as solvent. From a synthetic perspective, it is desirable to use a functional group that is an intrinsic part of the substrate so that extra steps for installation and removal of an external directing group can be avoided. In this way, dramatic increases in molecular complexity can be accomplished in a single stroke through stereo- and site-selective introduction of a new functional group. Although reactivity is a major challenge (as with first functionalization), the philosophy in further functionalization differs; the major challenge is developing reactions that work with predictable selectivity in intricately functionalized contexts on commonly occurring structural motifs. In this Account, we focus on an emergent theme within the further functionalization literature: the use of commonly occurring functional groups to direct C-H cleavage through weak coordination. We discuss our motivation for studying Pd-catalyzed C-H functionalization assisted by weakly coordinating functional groups and chronicle our endeavors to bring reactions of this type to fruition. Through this approach, we have developed reactions with a diverse range of substrates and coupling partners, with the broad scope likely stemming from the high reactivity of the cyclopalladated intermediates, which are held together through weak interactions.
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Dalcin Martins, Paula; Hoyt, David W; Bansal, Sheel; Mills, Christopher T; Tfaily, Malak; Tangen, Brian A; Finocchiaro, Raymond G; Johnston, Michael D; McAdams, Brandon C; Solensky, Matthew J; Smith, Garrett J; Chin, Yu-Ping; Wilkins, Michael J
2017-08-01
Inland waters are increasingly recognized as critical sites of methane emissions to the atmosphere, but the biogeochemical reactions driving such fluxes are less well understood. The Prairie Pothole Region (PPR) of North America is one of the largest wetland complexes in the world, containing millions of small, shallow wetlands. The sediment pore waters of PPR wetlands contain some of the highest concentrations of dissolved organic carbon (DOC) and sulfur species ever recorded in terrestrial aquatic environments. Using a suite of geochemical and microbiological analyses, we measured the impact of sedimentary carbon and sulfur transformations in these wetlands on methane fluxes to the atmosphere. This research represents the first study of coupled geochemistry and microbiology within the PPR and demonstrates how the conversion of abundant labile DOC pools into methane results in some of the highest fluxes of this greenhouse gas to the atmosphere ever reported. Abundant DOC and sulfate additionally supported some of the highest sulfate reduction rates ever measured in terrestrial aquatic environments, which we infer to account for a large fraction of carbon mineralization in this system. Methane accumulations in zones of active sulfate reduction may be due to either the transport of free methane gas from deeper locations or the co-occurrence of methanogenesis and sulfate reduction. If both respiratory processes are concurrent, any competitive inhibition of methanogenesis by sulfate-reducing bacteria may be lessened by the presence of large labile DOC pools that yield noncompetitive substrates such as methanol. Our results reveal some of the underlying mechanisms that make PPR wetlands biogeochemical hotspots, which ultimately leads to their critical, but poorly recognized role in regional greenhouse gas emissions. © 2017 John Wiley & Sons Ltd.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Dalcin Martins, Paula; Hoyt, David W.; Bansal, Sheel
Inland waters are increasingly recognized as critical sites of methane emissions to the atmosphere, but the biogeochemical reactions driving such fluxes are less well understood. The Prairie Pothole Region (PPR) of North America is one of the largest wetland complexes in the world, containing millions of small, shallow wetlands. The sediment pore waters of PPR wetlands contain some of the highest concentrations of dissolved organic carbon (DOC) and sulfur species ever recorded in terrestrial aquatic environments. Using a suite of geochemical and microbiological analyses we measured the impact of sedimentary carbon and sulfur transformations in these wetlands on methane fluxesmore » to the atmosphere. This research represents the first study of coupled geochemistry and microbiology within the PPR, and demonstrates how the conversion of abundant labile DOC pools into methane results in some of the highest fluxes of this greenhouse gas to the atmosphere ever reported. Abundant DOC and sulfate additionally supported some of the highest sulfate reduction rates ever measured in terrestrial aquatic environments, which we infer to account for a large fraction of carbon mineralization in this system. Methane accumulations in zones of active sulfate reduction may be due to either the transport of free methane gas from deeper locations, or the co-occurrence of methanogenesis and sulfate reduction. If both respiratory processes are concurrent, any competitive inhibition of methanogenesis by sulfate-reducing bacteria may be lessened by the presence of large labile DOC pools that yield non-competitive substrates such as methanol. Our results reveal some of the underlying mechanisms that make PPR wetlands biogeochemical hotspots, which ultimately leads to their critical, but poorly recognized role in regional greenhouse gas emissions.« less
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Martins, Paula; Hoyt, David W.; Bansal, Sheel; Mills, Christopher T.; Tfaily, Malak; Tangen, Brian; Finocchiaro, Raymond; Johnston, Michael D.; McAdams, Brandon C.; Solensky, Matthew J.; Smith, Garrett J.; Chin, Yu-Ping; Wilkins, Michael J.
2017-01-01
Inland waters are increasingly recognized as critical sites of methane emissions to the atmosphere, but the biogeochemical reactions driving such fluxes are less well understood. The Prairie Pothole Region (PPR) of North America is one of the largest wetland complexes in the world, containing millions of small, shallow wetlands. The sediment pore waters of PPR wetlands contain some of the highest concentrations of dissolved organic carbon (DOC) and sulfur species ever recorded in terrestrial aquatic environments. Using a suite of geochemical and microbiological analyses, we measured the impact of sedimentary carbon and sulfur transformations in these wetlands on methane fluxes to the atmosphere. This research represents the first study of coupled geochemistry and microbiology within the PPR and demonstrates how the conversion of abundant labile DOC pools into methane results in some of the highest fluxes of this greenhouse gas to the atmosphere ever reported. Abundant DOC and sulfate additionally supported some of the highest sulfate reduction rates ever measured in terrestrial aquatic environments, which we infer to account for a large fraction of carbon mineralization in this system. Methane accumulations in zones of active sulfate reduction may be due to either the transport of free methane gas from deeper locations or the co-occurrence of methanogenesis and sulfate reduction. If both respiratory processes are concurrent, any competitive inhibition of methanogenesis by sulfate-reducing bacteria may be lessened by the presence of large labile DOC pools that yield noncompetitive substrates such as methanol. Our results reveal some of the underlying mechanisms that make PPR wetlands biogeochemical hotspots, which ultimately leads to their critical, but poorly recognized role in regional greenhouse gas emissions.
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Improvement of carbon nanotube field emission properties by ultrasonic nanowelding
NASA Astrophysics Data System (ADS)
Zhao, Bo; Yadian, Boluo; Chen, Da; Xu, Dong; Zhang, Yafei
2008-12-01
Ultrasonic nanowelding was used to improve the field emission properties of carbon nanotube (CNT) cathodes. The CNTs were deposited on the Ti-coated glass substrate by electrophoretic deposition. By pressing CNTs against metal (Ti) substrate under a vibrating force at ultrasonic frequency, a reliable and low resistance contact was obtained between CNTs and Ti. The scanning electron microscopy results show that CNTs are embedded into the metal substrate and act as stable field emitters. The welded cathode demonstrates an excellent field emission with high emission current density and good current stability.
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Carbon nanotube growth density control
NASA Technical Reports Server (NTRS)
Delzeit, Lance D. (Inventor); Schipper, John F. (Inventor)
2010-01-01
Method and system for combined coarse scale control and fine scale control of growth density of a carbon nanotube (CNT) array on a substrate, using a selected electrical field adjacent to a substrate surface for coarse scale density control (by one or more orders of magnitude) and a selected CNT growth temperature range for fine scale density control (by multiplicative factors of less than an order of magnitude) of CNT growth density. Two spaced apart regions on a substrate may have different CNT growth densities and/or may use different feed gases for CNT growth.
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Conversion of fullerenes to diamonds
Gruen, Dieter M.
1995-01-01
A method of forming synthetic diamond or diamond-like films on a substrate surface. The method involves the steps of providing a vapor selected from the group of fullerene molecules or an inert gas/fullerene molecule mixture, providing energy to the fullerene molecules consisting of carbon-carbon bonds, the energized fullerene molecules breaking down to form fragments of fullerene molecules including C.sub.2 molecules and depositing the energized fullerene molecules with C.sub.2 fragments onto the substrate with farther fragmentation occurring and forming a thickness of diamond or diamond-like films on the substrate surface.
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Pugh, David; Bloor, Leanne G; Parkin, Ivan P; Carmalt, Claire J
2012-05-07
The donor-functionalised alkoxides {Me(3-x)N(CH(2)CH(2)O)(x)} (L(x); x = 1, 2) have been used to form gallium hydride complexes [{GaH(2)(L(1))}(2)] and [{GaH(L(2))}(2)] that are stable and isolable at room temperature. Along with a heteroleptic gallium tris(alkoxide) complex [Ga(L(1))(3)] and the dimeric complex [{GaMe(L(2))}(2)], these compounds have been used as single-source precursors for the deposition of Ga(2)O(3) by aerosol-assisted chemical vapour deposition (AACVD) with toluene as solvent. The resulting films were mostly transparent, indicating low levels of carbon contamination, and they were also mainly amorphous. However, [Ga(L(1))(3)] did contain visibly crystalline material deposited at a substrate temperature of 450 °C, by far the lowest ever observed for the CVD of gallium oxide. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Growth of carbon nanotubes by Fe-catalyzed chemical vapor processes on silicon-based substrates
NASA Astrophysics Data System (ADS)
Angelucci, Renato; Rizzoli, Rita; Vinciguerra, Vincenzo; Fortuna Bevilacqua, Maria; Guerri, Sergio; Corticelli, Franco; Passini, Mara
2007-03-01
In this paper, a site-selective catalytic chemical vapor deposition synthesis of carbon nanotubes on silicon-based substrates has been developed in order to get horizontally oriented nanotubes for field effect transistors and other electronic devices. Properly micro-fabricated silicon oxide and polysilicon structures have been used as substrates. Iron nanoparticles have been obtained both from a thin Fe film evaporated by e-gun and from iron nitrate solutions accurately dispersed on the substrates. Single-walled nanotubes with diameters as small as 1 nm, bridging polysilicon and silicon dioxide “pillars”, have been grown. The morphology and structure of CNTs have been characterized by SEM, AFM and Raman spectroscopy.
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Multiple binding modes of substrate to the catalytic RNA subunit of RNase P from Escherichia coli.
Pomeranz Krummel, D A; Altman, S
1999-01-01
M1 RNA that contained 4'-thiouridine was photochemically cross-linked to different substrates and to a product of the reaction it governs. The locations of the cross-links in these photochemically induced complexes were identified. The cross-links indicated that different substrates share some contacts but have distinct binding modes to M1 RNA. The binding of some substrates also results in a substrate-dependent conformational change in the enzymatic RNA, as evidenced by the appearance of an M1 RNA intramolecular cross-link. The identification of the cross-links between M1 RNA and product indicate that they are shared with only one of the three cross-linked E-S complexes that were identified, an indication of noncompetitive inhibition by the product. We also examined whether the cross-linked complexes between M1 RNA and substrate(s) or product are altered in the presence of the enzyme's protein cofactor (C5 protein) and in the presence of different concentrations of divalent metal ions. C5 protein enhanced the yield of certain M1 RNA-substrate cross-linked complexes for both wild-type M1 RNA and a deletion mutant of M1 RNA (delta[273-281]), but not for the M1 RNA-product complex. High concentrations of Mg2+ increased the yield of all M1 RNA-substrate complexes but not the M1 RNA-product complex. PMID:10445877
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Novel Determination of the Orientation of Calcite on Mineral Substrates
NASA Astrophysics Data System (ADS)
Zhao, L.; Ji, X.; Teng, H.
2016-12-01
In the threat of global warming, the transformation from CO2 to stable carbonate minerals is significant to geological CO2 sequestration in the long term.Previous efforts have found that when carbonate minerals nucleate on some mineral substrates ,the time of carbon capture can be shorted .Many efforts have been focused on the dynamics when carbonate minerals nucleate on mineral substrates, but few have studied the orientation of carbonate minerals on mineral substrates. In our experiment, we mainly focused on the orientation of calcite on mineral substrates.We mixed NaHCO3 and CaCl2 to nucleate when mineral substrates were added and a multi-parameter analyzer was used to monitor in real time to determine the induction time for nucleation. On the basis of classical nucleation theory, we got a brand new formula to decide the orientation of calcite on mineral substrates. lntind=(2-cosθ+cos3θ)*16πγ3vm2(12*(kBT)3*(lnS)2)+ln(1/N0v)+ ΔEa/(kBT)where θ is the angle between the substrate and the nuclei, tind is the induction time for nucleation, γ is he average surface free energy, N0 is the total number of particles per unit volume of solution, ΔEa is the activation energy for molecular motion across the embryo-matrix interface, S is the supersaturation index ,kB is the Boltzmann constant. Using the new formula above , when biotite was used as substrate mineral ,we found that the angle between the biotite and the nuclei was 119°. Angle measured on SEM images also supported our conclusion above. Combined with SEM and Debye ring analysed by Rigaku 2D data processing software, we only found one point of (006) in Debye ring, unlike (104)(many points in one ring and it meant that the orientation of (104) is random ). That meant (001) of calcite was first formed on biotite (001). In that case we inferred that 119° was formed by (001) of botite and (012) of calcite for the intersection angle of (001) and (012) was 120°. Future research will focus on the orientation of calcite on muscovite and feldspar to find out the main influence factor of the contact relationship.
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Steinbacher, Stefan; Schiffmann, Susanne; Bacher, Adelbert; Fischer, Markus
2004-07-01
The crystal structure of Methanococcus jannaschii 3,4-dihydroxy-2-butanone 4-phosphate synthase in complex with the substrate ribulose 5-phosphate at a dimetal centre has recently been determined at 1.7 A resolution. The enzyme converts ribulose 5-phosphate into 3,4-dihydroxy-2-butanone 4-phosphate, while its C4 atom is released as formate. The resulting four-carbon body supplies all eight C atoms for the xylene moiety of riboflavin. Three of the four hydroxyl groups of ribulose 5-phosphate were coordinated by the metal ions. Based on crystallographic refinement, the metals were assigned as zinc and calcium, which were present in the crystallization buffer. Neither metal supports the enzymatic reaction. In the present study, the correctness of this assignment is assessed using anomalous diffraction data collected at the high-energy side of the zinc absorption edge (lambda = 1.2823 A). Only the three tentative zinc ions give strong peaks in an anomalous difference Fourier map (>20sigma), whereas the four tentative calcium ions do not show anomalous signals above the noise level. These results confirm the initial assignment. In addition, the resolution was improved to 1.55 A.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Hast, Michael A.; Beese, Lorena S.
2008-11-21
Protein geranylgeranyltransferase-I (GGTase-I) catalyzes the transfer of a 20-carbon isoprenoid lipid to the sulfur of a cysteine residue located near the C terminus of numerous cellular proteins, including members of the Rho superfamily of small GTPases and other essential signal transduction proteins. In humans, GGTase-I and the homologous protein farnesyltransferase (FTase) are targets of anticancer therapeutics because of the role small GTPases play in oncogenesis. Protein prenyltransferases are also essential for many fungal and protozoan pathogens that infect humans, and have therefore become important targets for treating infectious diseases. Candida albicans, a causative agent of systemic fungal infections in immunocompromisedmore » individuals, is one pathogen for which protein prenylation is essential for survival. Here we present the crystal structure of GGTase-I from C. albicans (CaGGTase-I) in complex with its cognate lipid substrate, geranylgeranylpyrophosphate. This structure provides a high-resolution picture of a non-mammalian protein prenyltransferase. There are significant variations between species in critical areas of the active site, including the isoprenoid-binding pocket, as well as the putative product exit groove. These differences indicate the regions where specific protein prenyltransferase inhibitors with antifungal activity can be designed.« less
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Disassembling Iron Availability to Phytoplankton
Shaked, Yeala; Lis, Hagar
2012-01-01
The bioavailability of iron to microorganisms and its underlying mechanisms have far reaching repercussions to many natural systems and diverse fields of research, including ocean biogeochemistry, carbon cycling and climate, harmful algal blooms, soil and plant research, bioremediation, pathogenesis, and medicine. Within the framework of ocean sciences, short supply and restricted bioavailability of Fe to phytoplankton is thought to limit primary production and curtail atmospheric CO2 drawdown in vast ocean regions. Yet a clear-cut definition of bioavailability remains elusive, with elements of iron speciation and kinetics, phytoplankton physiology, light, temperature, and microbial interactions, to name a few, all intricately intertwined into this concept. Here, in a synthesis of published and new data, we attempt to disassemble the complex concept of iron bioavailability to phytoplankton by individually exploring some of its facets. We distinguish between the fundamentals of bioavailability – the acquisition of Fe-substrate by phytoplankton – and added levels of complexity involving interactions among organisms, iron, and ecosystem processes. We first examine how phytoplankton acquire free and organically bound iron, drawing attention to the pervasiveness of the reductive uptake pathway in both prokaryotic and eukaryotic autotrophs. Turning to acquisition rates, we propose to view the availability of various Fe-substrates to phytoplankton as a spectrum rather than an absolute “all or nothing.” We then demonstrate the use of uptake rate constants to make comparisons across different studies, organisms, Fe-compounds, and environments, and for gaging the contribution of various Fe-substrates to phytoplankton growth in situ. Last, we describe the influence of aquatic microorganisms on iron chemistry and fate by way of organic complexation and bio-mediated redox transformations and examine the bioavailability of these bio-modified Fe species. PMID:22529839
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Fraser, F C; Todman, L C; Corstanje, R; Deeks, L K; Harris, J A; Pawlett, M; Whitmore, A P; Ritz, K
2016-12-01
Factors governing the turnover of organic matter (OM) added to soils, including substrate quality, climate, environment and biology, are well known, but their relative importance has been difficult to ascertain due to the interconnected nature of the soil system. This has made their inclusion in mechanistic models of OM turnover or nutrient cycling difficult despite the potential power of these models to unravel complex interactions. Using high temporal-resolution respirometery (6 min measurement intervals), we monitored the respiratory response of 67 soils sampled from across England and Wales over a 5 day period following the addition of a complex organic substrate (green barley powder). Four respiratory response archetypes were observed, characterised by different rates of respiration as well as different time-dependent patterns. We also found that it was possible to predict, with 95% accuracy, which type of respiratory behaviour a soil would exhibit based on certain physical and chemical soil properties combined with the size and phenotypic structure of the microbial community. Bulk density, microbial biomass carbon, water holding capacity and microbial community phenotype were identified as the four most important factors in predicting the soils' respiratory responses using a Bayesian belief network. These results show that the size and constitution of the microbial community are as important as physico-chemical properties of a soil in governing the respiratory response to OM addition. Such a combination suggests that the 'architecture' of the soil, i.e. the integration of the spatial organisation of the environment and the interactions between the communities living and functioning within the pore networks, is fundamentally important in regulating such processes.
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Hard carbon nitride and method for preparing same
Haller, E.E.; Cohen, M.L.; Hansen, W.L.
1992-05-05
Novel crystalline [alpha](silicon nitride-like)-carbon nitride and [beta](silicon nitride-like)-carbon nitride are formed by sputtering carbon in the presence of a nitrogen atmosphere onto a single crystal germanium or silicon, respectively, substrate. 1 figure.
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Computational design of an enzyme catalyst for a stereoselective bimolecular Diels-Alder reaction
Siegel, Justin B.; Zanghellini, Alexandre; Lovick, Helena M.; Kiss, Gert; Lambert, Abigail R.; St.Clair, Jennifer L.; Gallaher, Jasmine L.; Hilvert, Donald; Gelb, Michael H.; Stoddard, Barry L.; Houk, Kendall N.; Michael, Forrest E.; Baker, David
2011-01-01
The Diels-Alder reaction is a cornerstone in organic synthesis, forming two carbon-carbon bonds and up to four new stereogenic centers in one step. No naturally occurring enzymes have been shown to catalyze bimolecular Diels-Alder reactions. We describe the de novo computational design and experimental characterization of enzymes catalyzing a bimolecular Diels-Alder reaction with high stereoselectivity and substrate specificity. X-ray crystallography confirms that the structure matches the design for the most active of the enzymes, and binding site substitutions reprogram the substrate specificity. Designed stereoselective catalysts for carbon-carbon bond forming reactions should be broadly useful in synthetic chemistry. PMID:20647463
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Computational design of an enzyme catalyst for a stereoselective bimolecular Diels-Alder reaction.
Siegel, Justin B; Zanghellini, Alexandre; Lovick, Helena M; Kiss, Gert; Lambert, Abigail R; St Clair, Jennifer L; Gallaher, Jasmine L; Hilvert, Donald; Gelb, Michael H; Stoddard, Barry L; Houk, Kendall N; Michael, Forrest E; Baker, David
2010-07-16
The Diels-Alder reaction is a cornerstone in organic synthesis, forming two carbon-carbon bonds and up to four new stereogenic centers in one step. No naturally occurring enzymes have been shown to catalyze bimolecular Diels-Alder reactions. We describe the de novo computational design and experimental characterization of enzymes catalyzing a bimolecular Diels-Alder reaction with high stereoselectivity and substrate specificity. X-ray crystallography confirms that the structure matches the design for the most active of the enzymes, and binding site substitutions reprogram the substrate specificity. Designed stereoselective catalysts for carbon-carbon bond-forming reactions should be broadly useful in synthetic chemistry.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Pooth, Alexander, E-mail: a.pooth@bristol.ac.uk; IQE; Uren, Michael J.
2015-12-07
Charge trapping and transport in the carbon doped GaN buffer of a GaN-based hetero-structure field effect transistor (HFET) has been investigated under both positive and negative substrate bias. Clear evidence of redistribution of charges in the carbon doped region by thermally generated holes is seen, with electron injection and capture observed during positive bias. Excellent agreement is found with simulations. It is shown that these effects are intrinsic to the carbon doped GaN and need to be controlled to provide reliable and efficient GaN-based power HFETs.
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Nanostructured carbon films with oriented graphitic planes
DOE Office of Scientific and Technical Information (OSTI.GOV)
Teo, E. H. T.; Kalish, R.; Kulik, J.
2011-03-21
Nanostructured carbon films with oriented graphitic planes can be deposited by applying energetic carbon bombardment. The present work shows the possibility of structuring graphitic planes perpendicular to the substrate in following two distinct ways: (i) applying sufficiently large carbon energies for deposition at room temperature (E>10 keV), (ii) utilizing much lower energies for deposition at elevated substrate temperatures (T>200 deg. C). High resolution transmission electron microscopy is used to probe the graphitic planes. The alignment achieved at elevated temperatures does not depend on the deposition angle. The data provides insight into the mechanisms leading to the growth of oriented graphiticmore » planes under different conditions.« less
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Utilization of carbon sources by clinical isolates of Aeromonas.
Prediger, Karoline C; Surek, Monica; Dallagassa, Cibelle B; Assis, Flávia E A; Piantavini, Mario S; Souza, Emanuel M; Pedrosa, Fábio O; Farah, Sônia M S S; Alberton, Dayane; Fadel-Picheth, Cyntia M T
2017-04-01
Bacteria in the genus Aeromonas are primarily aquatic organisms; however, some species can cause diseases in humans, ranging from wound infections to septicemia, of which diarrhea is the most common condition. The ability to use a variety of carbon substrates is advantageous for pathogenic bacteria. Therefore, we used Biolog GN2 microplates to analyze the ability of 103 clinical, predominantly diarrheal, isolates of Aeromonas to use various carbon sources, and we verified whether, among the substrates metabolized by these strains, there were some endogenous to the human intestine. The results indicate that Aeromonas present great diversity in the utilization of carbon sources, and that they preferentially use carbohydrates and amino acids as carbon sources. Among the carbon sources metabolized by Aeromonas in vitro, some were found to be components of intestinal mucin, including aspartic acid, glutamic acid, l-serine, galactose, N-acetyl-glucosamine, and glucose, which were used by all strains tested. Additionally, mannose, d-serine, proline, threonine, and N-acetyl-galactosamine were used by several strains. The potential to metabolize substrates endogenous to the intestine may contribute to Aeromonas' capacity to grow in and colonize the intestine. We speculate that this may help explain the ability of Aeromonas to cause diarrhea.
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Photoredox Catalysis in Organic Chemistry
2016-01-01
In recent years, photoredox catalysis has come to the forefront in organic chemistry as a powerful strategy for the activation of small molecules. In a general sense, these approaches rely on the ability of metal complexes and organic dyes to convert visible light into chemical energy by engaging in single-electron transfer with organic substrates, thereby generating reactive intermediates. In this Perspective, we highlight the unique ability of photoredox catalysis to expedite the development of completely new reaction mechanisms, with particular emphasis placed on multicatalytic strategies that enable the construction of challenging carbon–carbon and carbon–heteroatom bonds. PMID:27477076
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Method of synthesizing small-diameter carbon nanotubes with electron field emission properties
NASA Technical Reports Server (NTRS)
Liu, Jie (Inventor); Du, Chunsheng (Inventor); Qian, Cheng (Inventor); Gao, Bo (Inventor); Qiu, Qi (Inventor); Zhou, Otto Z. (Inventor)
2009-01-01
Carbon nanotube material having an outer diameter less than 10 nm and a number of walls less than ten are disclosed. Also disclosed are an electron field emission device including a substrate, an optionally layer of adhesion-promoting layer, and a layer of electron field emission material. The electron field emission material includes a carbon nanotube having a number of concentric graphene shells per tube of from two to ten, an outer diameter from 2 to 8 nm, and a nanotube length greater than 0.1 microns. One method to fabricate carbon nanotubes includes the steps of (a) producing a catalyst containing Fe and Mo supported on MgO powder, (b) using a mixture of hydrogen and carbon containing gas as precursors, and (c) heating the catalyst to a temperature above 950.degree. C. to produce a carbon nanotube. Another method of fabricating an electron field emission cathode includes the steps of (a) synthesizing electron field emission materials containing carbon nanotubes with a number of concentric graphene shells per tube from two to ten, an outer diameter of from 2 to 8 nm, and a length greater than 0.1 microns, (b) dispersing the electron field emission material in a suitable solvent, (c) depositing the electron field emission materials onto a substrate, and (d) annealing the substrate.
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Oliveira, Catarina S S; Silva, Carlos E; Carvalho, Gilda; Reis, Maria A
2017-07-25
Production of polyhydroxyalkanoates (PHAs) by open mixed microbial cultures (MMCs) has been attracting increasing interest as an alternative technology to PHA production by pure cultures, due to the potential for lower costs associated with the use of open systems (eliminating the requirement for sterile conditions) and the utilisation of cheap feedstock (industrial and agricultural wastes). Such technology relies on the efficient selection of an MMC enriched in PHA-accumulating organisms. Fermented cheese whey, a protein-rich complex feedstock, has been used previously to produce PHA using the feast and famine regime for selection of PHA accumulating cultures. While this selection strategy was found efficient when operated at relatively low organic loading rate (OLR, 2g-CODL -1 d -1 ), great instability and low selection efficiency of PHA accumulating organisms were observed when higher OLR (ca. 6g-CODL -1 d -1 ) was applied. High organic loading is desirable as a means to enhance PHA productivity. In the present study, a new selection strategy was tested with the aim of improving selection for high OLR. It was based on uncoupling carbon and nitrogen supply and was implemented and compared with the conventional feast and famine strategy. For this, two selection reactors were fed with fermented cheese whey applying an OLR of ca. 8.5g-CODL -1 (with 3.8g-CODL -1 resulting from organic acids and ethanol), and operated in parallel under similar conditions, except for the timing of nitrogen supplementation. Whereas in the conventional strategy nitrogen and carbon substrates were added simultaneously at the beginning of the cycle, in the uncoupled substrates strategy, nitrogen addition was delayed to the end of the feast phase (i.e. after exogenous carbon was exhausted). The two different strategies selected different PHA-storing microbial communities, dominated by Corynebacterium and a Xantomonadaceae, respectively with the conventional and the new approaches. The new strategy originated a more efficient PHA-production process than the conventional one (global PHA productivity of 6.09g-PHAL -1 d -1 and storage yield of 0.96 versus 2.55g-PHAL -1 d -1 and 0.86, respectively). Dissociation between the feast to famine length ratio (F/F) and storage efficiency was shown to be possible with the new strategy, allowing selection of an efficient PHA-storing culture with complex feedstock under high organic loading rates. Copyright © 2016 Elsevier B.V. All rights reserved.
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Effect of substrate RNA sequence on the cleavage reaction by a short ribozyme.
Ohmichi, T; Okumoto, Y; Sugimoto, N
1998-01-01
Leadzyme is a ribozyme that requires Pb2+. The catalytic sequence, CUGGGAGUCC, binds to an RNA substrate, GGACC downward arrowGAGCCAG, cleaving the RNA substrate at one site. We have investigated the effect of the substrate sequence on the cleavage activity of leadzyme using mutant substrates in order to structurally understand the RNA catalysis. The results showed that leadzyme acted as a catalyst for single site cleavage of a C5 deletion mutant substrate, GGAC downward arrowGAGCCAG, as well as the wild-type substrate. However, a mutant substrate GGACCGACCAG, which had G8 deleted from the wild-type substrate, was not cleaved. Kinetic studies by surface plasmon resonance indicated that the difference between active and inactive structures reflected the slow association and dissociation rate constants of complex formation induced by Pb2+rather than differences in complex stability. CD spectra showed that the active form of the substrate-leadzyme complex was rearranged by Pb2+binding. The G8 of the wild-type substrate, which was absent in the inactive complex, is not near the cleavage site. Thus, these results show that the active substrate-leadzyme complex has a Pb2+binding site at the junction between the unpaired region (asymmetric internal loop) and the stem region, which is distal to the cleavage site. Pb2+may play a role in rearranging the bases in the asymmetric internal loop to the correct position for catalysis. PMID:9837996
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Bradford, M A; Melillo, J M; Reynolds, J F
2010-06-10
The central objective of the proposed work was to develop a genomic approach (nucleic acid-based) that elucidates the mechanistic basis for the observed impacts of experimental soil warming on forest soil respiration. The need to understand the mechanistic basis arises from the importance of such information for developing effective adaptation strategies for dealing with projected climate change. Specifically, robust predictions of future climate will permit the tailoring of the most effective adaptation efforts. And one of the greatest uncertainties in current global climate models is whether there will be a net loss of carbon from soils to the atmosphere asmore » climate warms. Given that soils contain approximately 2.5 times as much carbon as the atmosphere, a net loss could lead to runaway climate warming. Indeed, most ecosystem models predict that climate warming will stimulate microbial decomposition of soil carbon, producing such a positive feedback to rising global temperatures. Yet the IPCC highlights the uncertainty regarding this projected feedback. The uncertainty arises because although warming-experiments document an initial increase in the loss of carbon from soils, the increase in respiration is short-lived, declining to control levels in a few years. This attenuation could result from changes in microbial physiology with temperature. We explored possible microbial responses to warming using experiments and modeling. Our work advances our understanding of how soil microbial communities and their activities are structured, generating insight into how soil carbon might respond to warming. We show the importance of resource partitioning in structuring microbial communities. Specifically, we quantified the relative abundance of fungal taxa that proliferated following the addition of organic substrates to soil. We added glycine, sucrose, cellulose, lignin, or tannin-protein to soils in conjunction with 3-bromo-deoxyuridine (BrdU), a nucleotide analog. Active microbes absorb BrdU from the soil solution; if they multiply in response to substrate additions, they incorporate the BrdU into their DNA. After allowing soils to incubate, we extracted BrdU-labeled DNA and sequenced the ITS regions of fungal rDNA. Fungal taxa that proliferated following substrate addition were likely using the substrate as a resource for growth. We found that the structure of active fungal communities varied significantly among substrates. The active fungal community under glycine was significantly different from those under other conditions, while the active communities under sucrose and cellulose were marginally different from each other and the control. These results indicate that the overall community structure of active fungi was altered by the addition of glycine, sucrose, and cellulose and implies that some fungal taxa respond to changes in resource availability. The community composition of active fungi is also altered by experimental warming. We found that glycine-users tended to increase under warming, while lignin-, tannin/protein-, and sucrose-users declined. The latter group of substrates requires extracellular enzymes for use, but glycine does not. It is possible that warming selects for fungal species that target, in particular, labile substrates. Linking these changes in microbial communities and resource partitioning to soil carbon dynamics, we find that substrate mineralization rates are, in general, significantly lower in soils exposed to long-term warming. This suggests that microbial use of organic substrates is impaired by warming. Yet effects are dependent on substrate identity. There are fundamental differences in the metabolic capabilities of the communities in the control and warmed soils. These differences might relate to the changes in microbial community composition, which appeared to be associated with groups specialized on different resources. We also find that functional responses indicate temperature acclimation of the microbial community. There are distinct seasonal patterns and to long-term soil warming, with higher-temperature optima for soils exposed to warmer temperatures. To relate these changes within the microbial community to potential positive feedbacks between climate warming and soil respiration, we develop a microbial-enzyme model to simulate the responses of soil carbon to warming. We find that declines in microbial biomass and degradative enzymes can explain the observed attenuation of soil-carbon emissions in response to warming. Specifically, reduced carbon-use efficiency limits the biomass of microbial decomposers and mitigates loss of soil carbon. However, microbial adaptation or a change in microbial communities could lead to an upward adjustment of the efficiency of carbon use, counteracting the decline in microbial biomass and accelerating soil-carbon loss. We conclude that the soil-carbon response to climate warming depends on the efficiency of soil microbes in using carbon.« less
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NASA Astrophysics Data System (ADS)
Zhang, Rui; Chen, Fenghua; Wang, Jinbin; Fu, Dejun
2018-03-01
Here we demonstrate the synthesis of graphene directly on SiC substrates at 900 °C using ion beam mixing technique with energetic carbon cluster ions on Ni/SiC structures. The thickness of 7-8 nm Ni films was evaporated on the SiC substrates, followed by C cluster ion bombarding. Carbon cluster ions C4 were bombarded at 16 keV with the dosage of 4 × 1016 atoms/cm2. After thermal annealing process Ni silicides were formed, whereas C atoms either from the decomposition of the SiC substrates or the implanted contributes to the graphene synthesis by segregating and precipitating process. The limited solubility of carbon atoms in silicides, involving SiC, Ni2Si, Ni5Si2, Ni3Si, resulted in diffusion and precipitation of carbon atoms to form graphene on top of Ni and the interface of Ni/SiC. The ion beam mixing technique provides an attractive production method of a transfer-free graphene growth on SiC and be compatible with current device fabrication.
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Development of Advanced Conformal Ablative TPS Fabricated from Rayon- and PAN-Based Carbon Felts
NASA Technical Reports Server (NTRS)
Gasch, Matthew; Stackpoole, Margaret; White, Susan; Boghozian, Tane
2016-01-01
The conformal ablative TPS first developed under NASA's Hypersonics Project in the early 2000's demonstrated very low through the thickness conductivity compared to state-ofthe- art PICA. However, in initial arcjet testing of Conformal-1, surface recession rates were 2x higher than PICA. Because commercial carbon felts are currently available as very thin substrates, this was a concern if conformal TPS were to be considered for a mission that required thicker material. Discussed in this paper are the results of the development of an Advanced Conformal TPS derived from thicker, higher density carbon felt. Two substrate systems were evaluated, the first material was a needled rayon-based carbon felt and the other a needled PAN-based carbon felt. Both substrates were impregnated with phenolic resin following the PICA/CPICA process to add a low density phenolic matrix to the system prior to aerothermal screening at the LaRC HyMETS facility and larger scale testing in the NASA ARC Interaction Heating Facility (IHF) at heating fluxes ranging from 250-1700 W/cm2.
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NASA Astrophysics Data System (ADS)
Boi, Filippo S.; Medranda, Daniel; Ivaturi, Sameera; Wang, Jiayu; Guo, Jian; Lan, Mu; Wen, Jiqiu; Wang, Shanling; He, Yi; Mountjoy, Gavin; Willis, Maureen A. C.; Xiang, Gang
2017-06-01
We report the observation of an unusual self-peeling effect which allows the synthesis of free standing vertically aligned carbon nanotube films filled with large quantities of Fe3C and small quantities of γ-Fe crystals. We demonstrate that this effect depends on the interplay of three main factors: (1) the physical interactions between the chosen substrate surface and grown carbon nanotubes (CNTs), which is fixed by the composition of the used substrate (111 SiO2/Si or quartz), (2) the CNT-CNT Van der Waals interactions, and (3) the differential thermal contraction between the grown CNT film and the used substrate, which is fixed by the cooling rate differences between the grown film and the used quartz or Si/SiO2 substrates. The width and stability of these films are then further increased to cm-scale by addition of small quantities of toluene to the ferrocene precursor.
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NASA Astrophysics Data System (ADS)
Yamagiwa, Kiyofumi
2018-02-01
Carbon nanotubes (CNTs) and related nanocarbons were selectively synthesized on commercially available alloy substrates by a simple liquid-phase technique. Fe- and Ni-rich stainless-steel (JIS SUS316L and Inconel®600, respectively) and Ni-Cu alloy (Monel®400) substrates were used for the synthesis, and each substrate was preheated in air to promote the self-formation of catalyst nanolayers on the surface. The substrates were resistance heated in ethanol without any addition of catalysts to grow CNTs. The yield of the CNTs effectively increased when the preheating process was employed. Highly aligned CNT arrays grew on the SUS316L substrate, while non-aligned CNTs and distinctive twisted fibers were observed on the other substrates. An Fe oxide layer was selectively formed on the preheated SUS316L substrate promoting the growth of the CNT arrays. Characterizations including cyclic voltammetry for the arrays revealed that the CNTs possess a comparatively defect-rich surface, which is a desirable characteristic for its application such as electrode materials for capacitors.
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Remote site-selective C-H activation directed by a catalytic bifunctional template
NASA Astrophysics Data System (ADS)
Zhang, Zhipeng; Tanaka, Keita; Yu, Jin-Quan
2017-03-01
In chemical syntheses, the activation of carbon-hydrogen (C-H) bonds converts them directly into carbon-carbon or carbon-heteroatom bonds without requiring any prior functionalization. C-H activation can thus substantially reduce the number of steps involved in a synthesis. A single specific C-H bond in a substrate can be activated by using a ‘directing’ (usually a functional) group to obtain the desired product selectively. The applicability of such a C-H activation reaction can be severely curtailed by the distance of the C-H bond in question from the directing group, and by the shape of the substrate, but several approaches have been developed to overcome these limitations. In one such approach, an understanding of the distal and geometric relationships between the functional groups and C-H bonds of a substrate has been exploited to achieve meta-selective C-H activation by using a covalently attached, U-shaped template. However, stoichiometric installation of this template has not been feasible in the absence of an appropriate functional group on which to attach it. Here we report the design of a catalytic, bifunctional nitrile template that binds a heterocyclic substrate via a reversible coordination instead of a covalent linkage. The two metal centres coordinated to this template have different roles: one reversibly anchors substrates near the catalyst, and the other cleaves remote C-H bonds. Using this strategy, we demonstrate remote, site-selective C-H olefination of heterocyclic substrates that do not have the necessary functional groups for covalently attaching templates.
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Remote site-selective C-H activation directed by a catalytic bifunctional template.
Zhang, Zhipeng; Tanaka, Keita; Yu, Jin-Quan
2017-03-23
In chemical syntheses, the activation of carbon-hydrogen (C-H) bonds converts them directly into carbon-carbon or carbon-heteroatom bonds without requiring any prior functionalization. C-H activation can thus substantially reduce the number of steps involved in a synthesis. A single specific C-H bond in a substrate can be activated by using a 'directing' (usually a functional) group to obtain the desired product selectively. The applicability of such a C-H activation reaction can be severely curtailed by the distance of the C-H bond in question from the directing group, and by the shape of the substrate, but several approaches have been developed to overcome these limitations. In one such approach, an understanding of the distal and geometric relationships between the functional groups and C-H bonds of a substrate has been exploited to achieve meta-selective C-H activation by using a covalently attached, U-shaped template. However, stoichiometric installation of this template has not been feasible in the absence of an appropriate functional group on which to attach it. Here we report the design of a catalytic, bifunctional nitrile template that binds a heterocyclic substrate via a reversible coordination instead of a covalent linkage. The two metal centres coordinated to this template have different roles: one reversibly anchors substrates near the catalyst, and the other cleaves remote C-H bonds. Using this strategy, we demonstrate remote, site-selective C-H olefination of heterocyclic substrates that do not have the necessary functional groups for covalently attaching templates.
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Beckers, Veronique; Poblete-Castro, Ignacio; Tomasch, Jürgen; Wittmann, Christoph
2016-05-03
Given its high surplus and low cost, glycerol has emerged as interesting carbon substrate for the synthesis of value-added chemicals. The soil bacterium Pseudomonas putida KT2440 can use glycerol to synthesize medium-chain-length poly(3-hydroxyalkanoates) (mcl-PHA), a class of biopolymers of industrial interest. Here, glycerol metabolism in P. putida KT2440 was studied on the level of gene expression (transcriptome) and metabolic fluxes (fluxome), using precisely adjusted chemostat cultures, growth kinetics and stoichiometry, to gain a systematic understanding of the underlying metabolic and regulatory network. Glycerol-grown P. putida KT2440 has a maintenance energy requirement [0.039 (mmolglycerol (gCDW h)(-1))] that is about sixteen times lower than that of other bacteria, such as Escherichia coli, which provides a great advantage to use this substrate commercially. The shift from carbon (glycerol) to nitrogen (ammonium) limitation drives the modulation of specific genes involved in glycerol metabolism, transport electron chain, sensors to assess the energy level of the cell, and PHA synthesis, as well as changes in flux distribution to increase the precursor availability for PHA synthesis (Entner-Doudoroff pathway and pyruvate metabolism) and to reduce respiration (glyoxylate shunt). Under PHA-producing conditions (N-limitation), a higher PHA yield was achieved at low dilution rate (29.7 wt% of CDW) as compared to a high rate (12.8 wt% of CDW). By-product formation (succinate, malate) was specifically modulated under these regimes. On top of experimental data, elementary flux mode analysis revealed the metabolic potential of P. putida KT2440 to synthesize PHA and identified metabolic engineering targets towards improved production performance on glycerol. This study revealed the complex interplay of gene expression levels and metabolic fluxes under PHA- and non-PHA producing conditions using the attractive raw material glycerol as carbon substrate. This knowledge will form the basis for the development of future metabolically engineered hyper-PHA-producing strains derived from the versatile bacterium P. putida KT2440.
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Feng, Wenting; Liang, Junyi; Hale, Lauren E; Jung, Chang Gyo; Chen, Ji; Zhou, Jizhong; Xu, Minggang; Yuan, Mengting; Wu, Liyou; Bracho, Rosvel; Pegoraro, Elaine; Schuur, Edward A G; Luo, Yiqi
2017-11-01
Quantifying soil organic carbon (SOC) decomposition under warming is critical to predict carbon-climate feedbacks. According to the substrate regulating principle, SOC decomposition would decrease as labile SOC declines under field warming, but observations of SOC decomposition under warming do not always support this prediction. This discrepancy could result from varying changes in SOC components and soil microbial communities under warming. This study aimed to determine the decomposition of SOC components with different turnover times after subjected to long-term field warming and/or root exclusion to limit C input, and to test whether SOC decomposition is driven by substrate lability under warming. Taking advantage of a 12-year field warming experiment in a prairie, we assessed the decomposition of SOC components by incubating soils from control and warmed plots, with and without root exclusion for 3 years. We assayed SOC decomposition from these incubations by combining inverse modeling and microbial functional genes during decomposition with a metagenomic technique (GeoChip). The decomposition of SOC components with turnover times of years and decades, which contributed to 95% of total cumulative CO 2 respiration, was greater in soils from warmed plots. But the decomposition of labile SOC was similar in warmed plots compared to the control. The diversity of C-degradation microbial genes generally declined with time during the incubation in all treatments, suggesting shifts of microbial functional groups as substrate composition was changing. Compared to the control, soils from warmed plots showed significant increase in the signal intensities of microbial genes involved in degrading complex organic compounds, implying enhanced potential abilities of microbial catabolism. These are likely responsible for accelerated decomposition of SOC components with slow turnover rates. Overall, the shifted microbial community induced by long-term warming accelerates the decomposition of SOC components with slow turnover rates and thus amplify the positive feedback to climate change. © 2017 John Wiley & Sons Ltd.
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Directed assembly of carbon nanotubes on soft substrates for use as a flexible biosensor array.
Koh, Juntae; Yi, Mihye; Yang Lee, Byung; Kim, Tae Hyun; Lee, Joohyung; Jhon, Young Min; Hong, Seunghun
2008-12-17
We have developed a method to selectively assemble and align carbon nanotubes (CNTs) on soft substrates for use as flexible biosensors. In this strategy, a thin oxide layer was deposited on soft substrates via low temperature plasma enhanced chemical vapor deposition, and a linker-free assembly process was applied on the oxide surface where the assembly of carbon nanotubes was guided by methyl-terminated molecular patterns on the oxide surface. The electrical characterization of the fabricated CNT devices exhibited a typical p-type gating effect and 1/f noise behavior. The bare oxide regions near CNTs were functionalized with glutamate oxidase to fabricate selective biosensors to detect two forms of glutamate substances existing in different situations: L-glutamic acid, a neurotransmitting material, and monosodium glutamate, a food additive.
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Influence of oxidation temperature on the oxide scale formation of NiCoCrAl coatings
NASA Astrophysics Data System (ADS)
Sugiarti, E.; Zaini, K. A.; Sundawa, R.; Wang, Y.; Ohnuki, S.; Hayashi, S.
2017-04-01
Intermetalic coatings of NiCoCrAl have been successfully developed on low carbon steel substrate to improve oxidation resistance in extreme environments. The influence of oxidation temperature on the oxide scale formation was studied in the temperature range of 600-1000 °C. The measurements were made in air under isothermal oxidation test for 100 h. The surface morphology showed that a cauliflower like structure developed entire the oxide scale of sample oxidized at 800 °C and 1000 °C, while partly distributed on the surface of sample oxidized at 600 °C. The XRD analysis identified Cr2O3 phase predominantly formed on the oxidized sample at 600 °C and meta-stable Al2O3 with several polymorphs crystalline structures: η, δ, θ, κ, and α-Al2O3 at relatively high temperatures, i.e. 800 °C and 1000 °C. A Cross-sectional microstructure showed that complex and porous structures formed on the top surface of 600 °C and 1000 °C samples. In contrast, a very thin oxide scale formed on 800 °C oxidized samples and it appeared to act as a diffusion barrier of oxygen to diffuse inward, hence could increase in the service life of carbon steel substrate.
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Tuck, Laura R.; Altenbach, Kirsten; Ang, Thiau Fu; Crawshaw, Adam D.; Campopiano, Dominic J.; Clarke, David J.; Marles-Wright, Jon
2016-01-01
The breakdown of fucose and rhamnose released from plant cell walls by the cellulolytic soil bacterium Clostridium phytofermentans produces toxic aldehyde intermediates. To enable growth on these carbon sources, the pathway for the breakdown of fucose and rhamnose is encapsulated within a bacterial microcompartment (BMC). These proteinaceous organelles sequester the toxic aldehyde intermediates and allow the efficient action of acylating aldehyde dehydrogenase enzymes to produce an acyl-CoA that is ultimately used in substrate-level phosphorylation to produce ATP. Here we analyse the kinetics of the aldehyde dehydrogenase enzyme from the fucose/rhamnose utilisation BMC with different short-chain fatty aldehydes and show that it has activity against substrates with up to six carbon atoms, with optimal activity against propionaldehyde. We have also determined the X-ray crystal structure of this enzyme in complex with CoA and show that the adenine nucleotide of this cofactor is bound in a distinct pocket to the same group in NAD+. This work is the first report of the structure of CoA bound to an aldehyde dehydrogenase enzyme and our crystallographic model provides important insight into the differences within the active site that distinguish the acylating from non-acylating aldehyde dehydrogenase enzymes. PMID:26899032
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Tuck, Laura R; Altenbach, Kirsten; Ang, Thiau Fu; Crawshaw, Adam D; Campopiano, Dominic J; Clarke, David J; Marles-Wright, Jon
2016-02-22
The breakdown of fucose and rhamnose released from plant cell walls by the cellulolytic soil bacterium Clostridium phytofermentans produces toxic aldehyde intermediates. To enable growth on these carbon sources, the pathway for the breakdown of fucose and rhamnose is encapsulated within a bacterial microcompartment (BMC). These proteinaceous organelles sequester the toxic aldehyde intermediates and allow the efficient action of acylating aldehyde dehydrogenase enzymes to produce an acyl-CoA that is ultimately used in substrate-level phosphorylation to produce ATP. Here we analyse the kinetics of the aldehyde dehydrogenase enzyme from the fucose/rhamnose utilisation BMC with different short-chain fatty aldehydes and show that it has activity against substrates with up to six carbon atoms, with optimal activity against propionaldehyde. We have also determined the X-ray crystal structure of this enzyme in complex with CoA and show that the adenine nucleotide of this cofactor is bound in a distinct pocket to the same group in NAD(+). This work is the first report of the structure of CoA bound to an aldehyde dehydrogenase enzyme and our crystallographic model provides important insight into the differences within the active site that distinguish the acylating from non-acylating aldehyde dehydrogenase enzymes.
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Muhammadi; Afzal, Muhammad
2014-01-01
Optimum culture conditions, and carbon and nitrogen sources for production of water absorbing exopolysaccharide by Bacillus strain CMG1403 on local cheap substrates were determined using one variable at a time approach. Carbon source was found to be sole substrate for EPS biosynthesis in the presence of yeast extract that supported the growth only and hence, indirectly enhanced the EPS yield. Whereas, urea only coupled with carbon source could enhance the EPS production but no effect on growth. The maximum yield of EPS was obtained when Bacillus strain CMG1403 was grown statically in neutral minimal medium with 25% volumetric aeration at 30°C for 10 days. Under these optimum conditions, a maximum yield of 2.71±0.024, 3.82±0.005, 4.33±0.021, 4.73±0.021, 4.85±0.024, and 5.52±0.016 g/L culture medium was obtained with 20 g (sugar) of sweet whey, glucose, fructose, sucrose, cane molasses and sugar beet the most efficient one respectively as carbon sources. Thus, the present study showed that under optimum culture conditions, the local cheap substrates could be superior and efficient alternatives to synthetic carbon sources providing way for an economical production of water absorbing EPS by indigenous soil bacterium Bacillus strain CMG1403.
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Carbon-containing cathodes for enhanced electron emission
Cao, Renyu; Pan, Lawrence; Vergara, German; Fox, Ciaran
2000-01-01
A cathode has electropositive atoms directly bonded to a carbon-containing substrate. Preferably, the substrate comprises diamond or diamond-like (sp.sup.3) carbon, and the electropositive atoms are Cs. The cathode displays superior efficiency and durability. In one embodiment, the cathode has a negative electron affinity (NEA). The cathode can be used for field emission, thermionic emission, or photoemission. Upon exposure to air or oxygen, the cathode performance can be restored by annealing or other methods. Applications include detectors, electron multipliers, sensors, imaging systems, and displays, particularly flat panel displays.
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Arntzen, Magnus Ø; Várnai, Anikó; Mackie, Roderick I; Eijsink, Vincent G H; Pope, Phillip B
2017-07-01
Fibrobacter succinogenes is an anaerobic bacterium naturally colonising the rumen and cecum of herbivores where it utilizes an enigmatic mechanism to deconstruct cellulose into cellobiose and glucose, which serve as carbon sources for growth. Here, we illustrate that outer membrane vesicles (OMVs) released by F. succinogenes are enriched with carbohydrate-active enzymes and that intact OMVs were able to depolymerize a broad range of linear and branched hemicelluloses and pectin, despite the inability of F. succinogenes to utilize non-cellulosic (pentose) sugars for growth. We hypothesize that the degradative versatility of F. succinogenes OMVs is used to prime hydrolysis by destabilising the tight networks of polysaccharides intertwining cellulose in the plant cell wall, thus increasing accessibility of the target substrate for the host cell. This is supported by observations that OMV-pretreatment of the natural complex substrate switchgrass increased the catalytic efficiency of a commercial cellulose-degrading enzyme cocktail by 2.4-fold. We also show that the OMVs contain a putative multiprotein complex, including the fibro-slime protein previously found to be important in binding to crystalline cellulose. We hypothesize that this complex has a function in plant cell wall degradation, either by catalysing polysaccharide degradation itself, or by targeting the vesicles to plant biomass. © 2017 Society for Applied Microbiology and John Wiley & Sons Ltd.
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NASA Astrophysics Data System (ADS)
Ogée, J.; Barbour, M. M.; Wingate, L.; Bert, D.; Bosc, A.; Stievenard, M.; Lambrot, C.; Pierre, M.; Bariac, T.; Dewar, R. C.
2009-04-01
High-resolution intra-annual measurements of the carbon and oxygen stable isotope composition of cellulose in annual tree rings (δ13Ccellulose and δ18Ocellulose, respectively) reveal well-defined seasonal patterns that could contain valuable records of past climate and tree function. Interpreting these signals is nonetheless complex because they not only record the signature of current assimilates, but also depend on carbon allocation dynamics within the trees. Here, we present a simple, single-substrate model for wood growth containing only 12 main parameters. The model is used to interpret an isotopic intra-annual chronology collected in an even-aged maritime pine plantation growing in the South-West of France, where climate, soil and flux variables were also monitored. The empirical δ13Ccellulose and δ18Ocellulose exhibit dynamic seasonal patterns, with clear differences between years and individuals, that are mostly captured by the model. In particular, the amplitude of both signals is reproduced satisfactorily as well as the sharp 18O enrichment at the beginning of 1997 and the less pronounced 13C and 18O depletion observed at the end of the latewood. Our results suggest that the single-substrate hypothesis is a good approximation for tree ring studies on Pinus pinaster, at least for the environmental conditions covered by this study. A sensitivity analysis revealed that, in the early wood, the model was particularly sensitive to the date when cell wall thickening begins (twt). We therefore propose to use the model to reconstruct time series of twt and explore how climate influences this key parameter of xylogenesis.
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Germination and seedling establishment in orchids: a complex of requirements.
Rasmussen, Hanne N; Dixon, Kingsley W; Jersáková, Jana; Těšitelová, Tamara
2015-09-01
Seedling recruitment is essential to the sustainability of any plant population. Due to the minute nature of seeds and early-stage seedlings, orchid germination in situ was for a long time practically impossible to observe, creating an obstacle towards understanding seedling site requirements and fluctuations in orchid populations. The introduction of seed packet techniques for sowing and retrieval in natural sites has brought with it important insights, but many aspects of orchid seed and germination biology remain largely unexplored. The germination niche for orchids is extremely complex, because it is defined by requirements not only for seed lodging and germination, but also for presence of a fungal host and its substrate. A mycobiont that the seedling can parasitize is considered an essential element, and a great diversity of Basidiomycota and Ascomycota have now been identified for their role in orchid seed germination, with fungi identifiable as imperfect Rhizoctonia species predominating. Specificity patterns vary from orchid species employing a single fungal lineage to species associating individually with a limited selection of distantly related fungi. A suitable organic carbon source for the mycobiont constitutes another key requirement. Orchid germination also relies on factors that generally influence the success of plant seeds, both abiotic, such as light/shade, moisture, substrate chemistry and texture, and biotic, such as competitors and antagonists. Complexity is furthermore increased when these factors influence seeds/seedling, fungi and fungal substrate differentially. A better understanding of germination and seedling establishment is needed for conservation of orchid populations. Due to the obligate association with a mycobiont, the germination niches in orchid species are extremely complex and varied. Microsites suitable for germination can be small and transient, and direct observation is difficult. An experimental approach using several levels of environmental manipulation/control is recommended. © The Author 2015. Published by Oxford University Press on behalf of the Annals of Botany Company. All rights reserved. For Permissions, please email: journals.permissions@oup.com.
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Wang, Hancheng; Wang, Jin; Chen, Qingyuan; Wang, Maosheng; Hsiang, Tom; Shang, Shenghua; Yu, Zhihe
2016-06-01
Azoxystrobin and kresoxim-methyl are strobilurin fungicides, and are effective in controlling many plant diseases, including Fusarium wilt. The mode of action of this kind of chemical is inhibition of respiration. This research investigated the sensitivities of Fusarium kyushuense to azoxystrobin and kresoxim-methyl, and to the alternative oxidase inhibitor salicylhydroxamic acid (SHAM). The Biolog FF MicroPlate is designed to examine substrate utilization and metabolic profiling of micro-organisms, and was used here to study the activity of azoxystrobin, kresoxim-methyl and SHAM against F. kyushuense. Results presented that azoxystrobin and kresoxim-methyl strongly inhibited conidial germination and mycelial growth of F. kyushuense, with EC50 values of 1.60 and 1.79μgml(-1), and 6.25 and 11.43μgml(-1), respectively; while not for SHAM. In the absence of fungicide, F. kyushuense was able to metabolize 91.6% of the tested carbon substrates, including 69 effectively and 18 moderately. SHAM did not inhibit carbon substrate utilization. Under the selective pressure of azoxystrobin and kresoxim-methyl during mycelial growth (up to 100μgml(-1)) and conidial germination (up to 10μgml(-1)), F. kyushuense was unable to metabolize many substrates in the Biolog FF MicroPlate; while especially for carbon substrates in glycolysis and tricarboxylic acid cycle, with notable exceptions such as β-hydroxybutyric acid, y-hydroxybutyric acid, α-ketoglutaric acid, α-d-glucose-1-phosphate, d-saccharic acid and succinic acid in the mycelial growth stage, and β-hydroxybutyric acid, y-hydroxybutyric acid, α-ketoglutaric acid, tween-80, arbutin, dextrin, glycerol and glycogen in the conidial germination stage. This is a new finding for some effect of azoxystrobin and kresoxim-methyl on carbon substrate utilization related to glycolysis and tricarboxylic acid cycle and other carbons, and may lead to future applications of Biolog FF MicroPlate for metabolic effects of other fungicides and other fungi, as well as providing a carbon metabolic fingerprint of F. kyushuense that could be useful for identification. Copyright © 2015 Elsevier Inc. All rights reserved.
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Observation of a photoinduced, resonant tunneling effect in a carbon nanotube–silicon heterojunction
Ambrosio, Antonio; Boscardin, Maurizio; Castrucci, Paola; Crivellari, Michele; Cilmo, Marco; De Crescenzi, Maurizio; De Nicola, Francesco; Fiandrini, Emanuele; Grossi, Valentina; Maddalena, Pasqualino; Passacantando, Maurizio; Santucci, Sandro; Scarselli, Manuela; Valentini, Antonio
2015-01-01
Summary A significant resonant tunneling effect has been observed under the 2.4 V junction threshold in a large area, carbon nanotube–silicon (CNT–Si) heterojunction obtained by growing a continuous layer of multiwall carbon nanotubes on an n-doped silicon substrate. The multiwall carbon nanostructures were grown by a chemical vapor deposition (CVD) technique on a 60 nm thick, silicon nitride layer, deposited on an n-type Si substrate. The heterojunction characteristics were intensively studied on different substrates, resulting in high photoresponsivity with a large reverse photocurrent plateau. In this paper, we report on the photoresponsivity characteristics of the device, the heterojunction threshold and the tunnel-like effect observed as a function of applied voltage and excitation wavelength. The experiments are performed in the near-ultraviolet to near-infrared wavelength range. The high conversion efficiency of light radiation into photoelectrons observed with the presented layout allows the device to be used as a large area photodetector with very low, intrinsic dark current and noise. PMID:25821710
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Aramo, Carla; Ambrosio, Antonio; Ambrosio, Michelangelo; Boscardin, Maurizio; Castrucci, Paola; Crivellari, Michele; Cilmo, Marco; De Crescenzi, Maurizio; De Nicola, Francesco; Fiandrini, Emanuele; Grossi, Valentina; Maddalena, Pasqualino; Passacantando, Maurizio; Santucci, Sandro; Scarselli, Manuela; Valentini, Antonio
2015-01-01
A significant resonant tunneling effect has been observed under the 2.4 V junction threshold in a large area, carbon nanotube-silicon (CNT-Si) heterojunction obtained by growing a continuous layer of multiwall carbon nanotubes on an n-doped silicon substrate. The multiwall carbon nanostructures were grown by a chemical vapor deposition (CVD) technique on a 60 nm thick, silicon nitride layer, deposited on an n-type Si substrate. The heterojunction characteristics were intensively studied on different substrates, resulting in high photoresponsivity with a large reverse photocurrent plateau. In this paper, we report on the photoresponsivity characteristics of the device, the heterojunction threshold and the tunnel-like effect observed as a function of applied voltage and excitation wavelength. The experiments are performed in the near-ultraviolet to near-infrared wavelength range. The high conversion efficiency of light radiation into photoelectrons observed with the presented layout allows the device to be used as a large area photodetector with very low, intrinsic dark current and noise.
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Process for forming a metal compound coating on a substrate
Sharp, D.J.; Vernon, M.E.; Wright, S.A.
1988-06-29
A method of coating a substrate with a thin layer of a metal compound by forming a dispersion of an electrophoretically active organic colloid and a precursor of the metal compound in an electrolytic cell in which the substrate is an electrode. Upon application of an electric potential, the electrode is coated with a mixture of the organic colloid and the precursor to the metal compound, and the coated substrate is then heated in the presence of an atmosphere or vacuum to decompose the organic colloid and form a coating of either a combination of metal compound and carbon, or optionally forming a porous metal compound coating by heating to a temperature high enough to chemically react the carbon.
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Solar-induced chemical vapor deposition of diamond-type carbon films
Pitts, J.R.; Tracy, C.E.; King, D.E.; Stanley, J.T.
1994-09-13
An improved chemical vapor deposition method for depositing transparent continuous coatings of sp[sup 3]-bonded diamond-type carbon films, comprises: (a) providing a volatile hydrocarbon gas/H[sub 2] reactant mixture in a cold wall vacuum/chemical vapor deposition chamber containing a suitable substrate for said films, at pressure of about 1 to 50 Torr; and (b) directing a concentrated solar flux of from about 40 to about 60 watts/cm[sup 2] through said reactant mixture to produce substrate temperatures of about 750 C to about 950 C to activate deposition of the film on said substrate. 11 figs.
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Solar-induced chemical vapor deposition of diamond-type carbon films
Pitts, J. Roland; Tracy, C. Edwin; King, David E.; Stanley, James T.
1994-01-01
An improved chemical vapor deposition method for depositing transparent continuous coatings of sp.sup.3 -bonded diamond-type carbon films, comprising: a) providing a volatile hydrocarbon gas/H.sub.2 reactant mixture in a cold wall vacuum/chemical vapor deposition chamber containing a suitable substrate for said films, at pressure of about 1 to 50 Torr; and b) directing a concentrated solar flux of from about 40 to about 60 watts/cm.sup.2 through said reactant mixture to produce substrate temperatures of about 750.degree. C. to about 950.degree. C. to activate deposition of the film on said substrate.
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Homogeneous catalytic hydrogenations of complex carbonaceous substrates. [16 references
DOE Office of Scientific and Technical Information (OSTI.GOV)
Cox, J L; Wilcox, W A; Roberts, G L
1976-11-05
Results of homogeneous catalytic hydrogenation of complex unsaturated substrates including coal and coal-derived materials are reported, with organic soluble molecular complexes as catalysts. Among the substrates used were Hvab coal, solvent-refined coal, and COED pyrolysate. The hydrogenations were carried out in an autoclave. The results are summarized in tables.
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Liu, Hui; Chen, Yinguang; Wu, Jiang
2017-11-01
Carbon substrate is required by biological nutrient removal (BNR) microorganism, but it is usually insufficient in the influent of many municipal wastewater treatment plants. In this study the use of ethanol-enriched fermentation liquid, which was derived from dairy wastewater, as the preferred carbon substrate of BNR was reported. First, the application of dairy wastewater and food processing wastewater and their fermentation liquid as the carbon substrate of BNR was compared in the short-term tests. The fermented wastewater showed higher BNR performance than the unfermented one, and the fermentation liquid of dairy wastewater (FL-DW), which was obtained under pH 8 and fermentation time of 6 day, exhibited the highest phosphorus (95.5%) and total nitrogen (97.6%) removal efficiencies due to its high ethanol content (57.9%). Then, the long-term performance of FL-DW acting as the carbon substrate of BNR was compared with that of acetate and ethanol, and the FL-DW showed the greatest phosphorus and total nitrogen removal. Further investigation showed that the use of FL-DW caused the highest polyhydroxyalkanoates (PHAs) synthesis in BNR microbial cells, and more PHAs were used for phosphorus uptake and denitrification rather than glycogen synthesis and microbial growth. The FL-DW can be used as a preferred carbon substrate for BNR microbes. AB: aerobic end sludge active biomass; BNR: biological nutrient removal; DW: dairy wastewater; FL-DW: fermentation liquid of dairy wastewater; FPW: food processing wastewater; FL-FPW: fermentation liquid of food processing wastewater; PHAs: polyhydroxyalkanoates; PHB: poly-3-hydroxybutyrate; PHV: poly-3-hydroxyvalerate; PH2MV: poly-3-hydroxy-2- methylvalerate; PAOs: phosphorus accumulating organisms; SBR: sequencing batch reactor; SOP: soluble ortho-phosphorus; TN: total nitrogen; TSS: total suspended solids; VSS: volatile suspended solids; VFAs: volatile fatty acids; WWTPs: wastewater treatment plants.
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NASA Astrophysics Data System (ADS)
D'Arcy, Julio M.; Tran, Henry D.; Stieg, Adam Z.; Gimzewski, James K.; Kaner, Richard B.
2012-05-01
A procedure for depositing thin films of carbon nanostructures is described that overcomes the limitations typically associated with solution based methods. Transparent and conductively continuous carbon coatings can be grown on virtually any type of substrate within seconds. Interfacial surface tension gradients result in directional fluid flow and film spreading at the water/oil interface. Transparent films of carbon nanostructures are produced including aligned ropes of single-walled carbon nanotubes and assemblies of single sheets of chemically converted graphene and graphite oxide. Process scale-up, layer-by-layer deposition, and a simple method for coating non-activated hydrophobic surfaces are demonstrated.A procedure for depositing thin films of carbon nanostructures is described that overcomes the limitations typically associated with solution based methods. Transparent and conductively continuous carbon coatings can be grown on virtually any type of substrate within seconds. Interfacial surface tension gradients result in directional fluid flow and film spreading at the water/oil interface. Transparent films of carbon nanostructures are produced including aligned ropes of single-walled carbon nanotubes and assemblies of single sheets of chemically converted graphene and graphite oxide. Process scale-up, layer-by-layer deposition, and a simple method for coating non-activated hydrophobic surfaces are demonstrated. Electronic supplementary information (ESI) available: Droplet coalescence, catenoid formation, mechanism of film growth, scanning electron micrographs showing carbon nanotube alignment, flexible transparent films of SWCNTs, AFM images of a chemically converted graphene film, and SEM images of SWCNT free-standing thin films. See DOI: 10.1039/c2nr00010e
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Maskless writing of a flexible nanoscale transistor with Au-contacted carbon nanotube electrodes
NASA Astrophysics Data System (ADS)
Dockendorf, Cedric P. R.; Poulikakos, Dimos; Hwang, Gilgueng; Nelson, Bradley J.; Grigoropoulos, Costas P.
2007-12-01
A flexible polymer field effect transistor with a nanoscale carbon nanotube channel is conceptualized and realized herein. Carbon nanotubes (CNTs) were dispersed on a polyimide substrate and marked in an scanning electron microscope with focused ion beam such that they could be contacted with gold nanoink. The CNTs were divided into two parts forming the source and drain of the transistor. A micropipette writing method was used to contact the carbon nanotube electrodes with gold nanoink and to deposit the poly(3-hexylthiophene) as an active layer. The mobility of the transistors is of the order of 10-5cm/Vs. After fabrication, the flexible transistors can be peeled off the substrate.
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Influence of substrate surface loading on the kinetic behaviour of aerobic granules.
Liu, Yu; Liu, Yong-Qiang; Wang, Zhi-Wu; Yang, Shu-Fang; Tay, Joo-Hwa
2005-06-01
In the aerobic granular sludge reactor, the substrate loading is related to the size of the aerobic granules cultivated. This study investigated the influence of substrate surface loading on the growth and substrate-utilization kinetics of aerobic granules. Results showed that microbial surface growth rate and surface biodegradation rate are fairly related to the substrate surface loading by the Monod-type equation. In this study, both the theoretical maximum growth yield and the Pirt maintenance coefficient were determined. It was found that the estimated theoretical maximum growth yield of aerobic granules was as low as 0.2 g biomass g(-1) chemical oxygen demand (COD) and 10-40% of input substrate-COD was consumed through the maintenance metabolism, while experimental results further showed that the unit oxygen uptake by aerobic granules was 0.68 g oxygen g(-1) COD, which was much higher than that reported in activated sludge processes. Based on the growth yield and unit oxygen uptake determined, an oxidative assimilation equation of acetate-fed aerobic granules was derived; and this was confirmed by respirometric tests. In aerobic granular culture, about 74% of the input substrate-carbon was converted to carbon dioxide. The growth yield of aerobic granules was three times lower than that of activated sludge. It is likely that high carbon dioxide production is the main cause of the low growth yield of aerobic granules, indicating a possible energy uncoupling in aerobic granular culture.
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Vertically, interconnected carbon nanowalls as biocompatible scaffolds for osteoblast cells
NASA Astrophysics Data System (ADS)
Ion, Raluca; Vizireanu, Sorin; Luculescu, Catalin; Cimpean, Anisoara; Dinescu, Gheorghe
2016-07-01
The response of MC3T3-E1 pre-osteoblasts to vertically aligned, interconnected carbon nanowalls prepared by plasma enhanced chemical vapor deposition on silicon substrate has been evaluated in terms of cell adhesion, viability and cell proliferation. The behavior of osteoblasts seeded on carbon nanowalls was analyzed in parallel and compared with the behavior of the cells maintained in contact with tissue culture polystyrene (TCPS). The results demonstrate that osteoblasts adhere and remain viable in the long term on carbon nanowalls. Moreover, on the investigated scaffold cell proliferation was significantly promoted, although to a lower extent than on TCPS. Overall, the successful culture of osteoblasts on carbon nanowalls coated substrate confirms the biocompatibility of this scaffold, which could have potential applications in the development of orthopedic biomaterials.
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Tuning the Slide-Roll Motion Mode of Carbon Nanotubes via Hydroxyl Groups
NASA Astrophysics Data System (ADS)
Li, Rui; Wang, Shiwei; Peng, Qing
2018-05-01
Controlling the motion of carbon nanotubes is critical in manipulating nanodevices, including nanorobots. Herein, we investigate the motion behavior of SWCNT (10,10) on Si substrate utilizing molecular dynamics simulations. We show that hydroxyl groups have sensitive effect on the carbon nanotube's motion mode. When the hydroxyl groups' ratio on carbon nanotube and silicon substrate surfaces is larger than 10 and 20%, respectively, the motion of carbon nanotube transforms from sliding to rolling. When the hydroxyl groups' ratio is smaller, the slide or roll mode can be controlled by the speed of carbon nanotube, which is ultimately determined by the competition between the interface potential energy and kinetic energy. The change of motion mode holds true for different carbon nanotubes with hydroxyl groups. The chirality has little effect on the motion behavior, as opposed to the diameter, attributed to the hydroxyl groups' ratio. Our study suggests a new route to control the motion behavior of carbon nanotube via hydroxyl groups.
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Tuning the Slide-Roll Motion Mode of Carbon Nanotubes via Hydroxyl Groups.
Li, Rui; Wang, Shiwei; Peng, Qing
2018-05-08
Controlling the motion of carbon nanotubes is critical in manipulating nanodevices, including nanorobots. Herein, we investigate the motion behavior of SWCNT (10,10) on Si substrate utilizing molecular dynamics simulations. We show that hydroxyl groups have sensitive effect on the carbon nanotube's motion mode. When the hydroxyl groups' ratio on carbon nanotube and silicon substrate surfaces is larger than 10 and 20%, respectively, the motion of carbon nanotube transforms from sliding to rolling. When the hydroxyl groups' ratio is smaller, the slide or roll mode can be controlled by the speed of carbon nanotube, which is ultimately determined by the competition between the interface potential energy and kinetic energy. The change of motion mode holds true for different carbon nanotubes with hydroxyl groups. The chirality has little effect on the motion behavior, as opposed to the diameter, attributed to the hydroxyl groups' ratio. Our study suggests a new route to control the motion behavior of carbon nanotube via hydroxyl groups.
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Liu, Fanxin; Cao, Zhishen; Tang, Chaojun; Chen, Ling; Wang, Zhenlin
2010-05-25
We have demonstrated that by coating with a thin dielectric layer of tetrahedral amorphous carbon (ta-C), a biocompatible and optical transparent material in the visible range, the Ag nanoparticle-based substrate becomes extremely suitable for surface-enhanced Raman spectroscopy (SERS). Our measurements show that a 10 A or thicker ta-C layer becomes efficient to protect the oxygen-free Ag in air and prevent Ag ionizing in aqueous solutions. Furthermore, the Ag nanoparticles substrate coated with a 10 A ta-C film shows a higher enhancement of Raman signals than the uncoated substrate. These observations are further supported by our numerical simulations. We suggest that biomolecule detections in analytic assays could be easily realized using ta-C-coated Ag-based substrate for SERS especially in the visible range. The coated substrate also has higher mechanical stability, chemical inertness, and technological compliance, and may be useful, for example, to enhance TiO(2) photocatalysis and solar-cell efficiency by the surface plasmons.
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Applying a biodeposition layer to increase the bond of a repair mortar on a mortar substrate.
Snoeck, D; Wang, J; Bentz, D P; De Belie, N
2018-02-01
One of the major concerns in infrastructure repair is a sufficient bond between the substrate and the repair material, especially for the long-term performance and durability of the repaired structure. In this study, the bond of the repair material on the mortar substrate is promoted via the biodeposition of a calcium carbonate layer by a ureolytic bacterium. X-ray diffraction and scanning electron microscopy were used to examine the interfaces between the repair material and the substrate, as well as the polymorph of the deposited calcium carbonate. The approximately 50 μm thick biodeposition film on the mortar surface mostly consisted of calcite and vaterite. Both the repair material and the substrate tended to show a good adherence to that layer. The bond, as assessed by slant shear specimen testing, was improved by the presence of the biodeposition layer. A further increase was found when engineering the substrate surface using a structured pattern layer of biodeposition.
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Improved Wear Resistance of Low Carbon Steel with Plasma Melt Injection of WC Particles
NASA Astrophysics Data System (ADS)
Liu, Aiguo; Guo, Mianhuan; Hu, Hailong
2010-08-01
Surface of a low carbon steel Q235 substrate was melted by a plasma torch, and tungsten carbide (WC) particles were injected into the melt pool. WC reinforced surface metal matrix composite (MMC) was synthesized. Dry sliding wear behavior of the surface MMC was studied and compared with the substrate. The results show that dry sliding wear resistance of low carbon steel can be greatly improved by plasma melt injection of WC particles. Hardness of the surface MMC is much higher than that of the substrate. The high hardness lowers the adhesion and abrasion of the surface MMC, and also the friction coefficient of it. The oxides formed in the sliding process also help to lower the friction coefficient. In this way, the dry sliding wear resistance of the surface MMC is greatly improved.
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NASA Astrophysics Data System (ADS)
Arora, Sweety; Rekha, M. Y.; Gupta, Abhay; Srivastava, Chandan
2018-02-01
The inert and hydrophobic nature of carbon nanotubes (CNTs) makes them a potential material for corrosion protection coatings. In this work, a uniform coating of multi-walled CNTs (MWCNTs) was formed over a mild steel substrate by direct decomposition of a ferrocene-benzene mixture over the substrate which was kept inside a chemical vapor deposition setup at a temperature of 800°C. The MWCNTs formed over the substrate were characterized using x-ray diffraction, Raman spectroscopy and transmission electron microscopy techniques. Corrosion behavior of the bare and MWCNT-coated mild steel substrate was examined through potentiodynamic polarization and electrochemical impedance spectroscopy methods. A significant improvement in the corrosion resistance in terms of the reduction in corrosion current and corrosion rate and increase in polarization resistance was noted in the case of the MWCNT-coated mild steel plate. Corrosion resistance increased due to MWCNT coating.
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Sun, Yinghui; Liu, Kai; Miao, Jiao; Wang, Zheyao; Tian, Baozhong; Zhang, Lina; Li, Qunqing; Fan, Shoushan; Jiang, Kaili
2010-05-12
Surface-enhanced Raman scattering (SERS) has attracted wide attention because it can enhance normally weak Raman signal by several orders of magnitude and facilitate the sensitive detection of molecules. Conventional SERS substrates are constructed by placing metal nanoparticles on a planar surface. Here we show that, if the planar surface was substituted by a unique nanoporous surface, the enhancement effect can be dramatically improved. The nanoporous surface can be easily fabricated in batches and at low costs by cross stacking superaligned carbon nanotube films. The as-prepared transparent and freestanding SERS substrate is capable of detecting ambient trinitrotoluene vapor, showing much higher Raman enhancement than ordinary planar substrates because of the extremely large surface area and the unique zero-dimensional at one-dimensional nanostructure. These results not only provide a new approach to ultrasensitive SERS substrates, but also are helpful for improving the fundamental understanding of SERS phenomena.
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Substrate morphology induced self-organization into carbon nanotube arrays, ropes, and agglomerates.
Huang, Jia-Qi; Zhang, Qiang; Xu, Guang-Hui; Qian, Wei-Zhong; Wei, Fei
2008-10-29
In this paper, hydrophobic carbon nanotube (CNT) arrays, ropes, and agglomerates were synthesized through self-organization on quartz substrates with different micro-structures under the same growth condition. On a flat substrate, a uniform woven structure was formed which resulted in a synchronous growth into an array. When the substrate with 10 µm round concaves distributed on the surface was adopted, the woven structure was sporadic and a CNT cluster was grown in the concave. With further growth, CNT ropes were self-organized. Subsequently, when the substrate consisting of irregular ∼100 nm gaps was used, the initial woven structure was high density, thus resulting in the formation of CNT agglomerates. Study results showed that CNT arrays grown on the flat substrate were of the highest purity and had a contact angle of 153.8 ± 0.9°. Thus, the self-organization behavior among CNTs was in situ modulated by different substrate morphology without further treatments. This provides us with an additional understanding of the self-organization of CNTs during growth, as well as strategies for the controllable synthesis of CNTs with fixed properties.
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Wong, Ming-Show; Chu, Wen-Chen; Sun, Der-Shan; Huang, Hsuan-Shun; Chen, Jiann-Hwa; Tsai, Pei-Jane; Lin, Nien-Tsung; Yu, Mei-Shiuan; Hsu, Shang-Feng; Wang, Shih-Lien; Chang, Hsin-Hou
2006-01-01
The antibacterial activity of photocatalytic titanium dioxide (TiO2) substrates is induced primarily by UV light irradiation. Recently, nitrogen- and carbon-doped TiO2 substrates were shown to exhibit photocatalytic activities under visible-light illumination. Their antibacterial activity, however, remains to be quantified. In this study, we demonstrated that nitrogen-doped TiO2 substrates have superior visible-light-induced bactericidal activity against Escherichia coli compared to pure TiO2 and carbon-doped TiO2 substrates. We also found that protein- and light-absorbing contaminants partially reduce the bactericidal activity of nitrogen-doped TiO2 substrates due to their light-shielding effects. In the pathogen-killing experiment, a significantly higher proportion of all tested pathogens, including Shigella flexneri, Listeria monocytogenes, Vibrio parahaemolyticus, Staphylococcus aureus, Streptococcus pyogenes, and Acinetobacter baumannii, were killed by visible-light-illuminated nitrogen-doped TiO2 substrates than by pure TiO2 substrates. These findings suggest that nitrogen-doped TiO2 has potential application in the development of alternative disinfectants for environmental and medical usages. PMID:16957236
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Time dependence of carbon film deposition on SnO{sub 2}/Si using DC unbalanced magnetron sputtering
DOE Office of Scientific and Technical Information (OSTI.GOV)
Alfiadi, H., E-mail: yudi@fi.itb.ac.id; Aji, A. S., E-mail: yudi@fi.itb.ac.id; Darma, Y., E-mail: yudi@fi.itb.ac.id
Carbon deposition on SnO{sub 2} layer has been demonstrated at low temperature using DC unbalanced magnetron-sputtering technique for various time depositions. Before carbon sputtering process, SnO{sub 2} thin layer is grown on silicon substrate by thermal evaporation method using high purity Sn wire and then fully oxidizes by dry O{sub 2} at 225°C. Carbon sputtering process was carried out at pressure of 4.6×10{sup −2} Torr by keeping the substrate temperature of 300 °C for sputtering deposition time of 1 to 4 hours. The properties of SnO{sub 2}/Si structure and carbon thin film on SnO{sub 2} is characterized using SEM, EDAX,more » XRD, FTIR, and Raman Spectra. SEM images and XRD spectra show that SnO2 thin film has uniformly growth on Si substrate and affected by annealing temperature. Raman and FTIR results confirm the formation of carbon-rich thin film on SnO{sub 2}. In addition, XRD spectra indicate that some structural change occur by increasing sputtering deposition time. Furthermore, the change of atomic structure due to the thermal annealing is analized by XRD spectra and Raman spectroscopy.« less
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Raman studied of undoped amorphous carbon thin film deposited by bias assisted-CVD
NASA Astrophysics Data System (ADS)
Ishak, A.; Fadzilah, A. N.; Dayana, K.; Saurdi, I.; Malek, M. F.; Nurbaya, Z.; Shafura, A. K.; Rusop, M.
2018-05-01
The undoped amorphous carbon thin film carbon was deposited at 200°C-350°C by bias assisted-CVD using palm oil as a precursor material. The effect of different substrate deposition temperatures on structural and electrical properties of undoped doped amorphous carbon film was discussed. The structural of undoped amorphous carbon films were correlated with Raman analysis through the evolution of D and G bands, Fourier spectra, and conductivity measurement. The spectral evolution observed showed the increase of upward shift of D and G peaks as substrate deposition temperatures increased. The spectral evolution observed at different substrate deposition temperatures show progressive formation of crystallites. It was predicted that small number of hydrogen is terminated with carbon at surface of thin film as shown by FTIR spectra since palm oil has high number of hydrogen (C67H127O8). These structural changes were further correlated with conductivity and the results obtained are discussed and compared. The conductivity is found in the range of 10-8 Scm-1. The increase of conductivity is correlated by the change of structural properties as correlated with characteristic parameters of Raman spectra including the position of G peak, full width at half maximum of G peak, and ID/IG and FTIR result.
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NASA Astrophysics Data System (ADS)
Yan, Zheng
Graphene, a two-dimensional sp2-bonded carbon material, has attracted enormous attention due to its excellent electrical, optical and mechanical properties. Recently developed chemical vapor deposition (CVD) methods could produce large-size and uniform polycrystalline graphene films, limited to gas carbon sources, metal catalyst substrates and degraded properties induced by grain boundaries. Meanwhile, pristine monolayer graphene exhibits a standard ambipolar behavior with a zero neutrality point in field-effect transistors (FETs), limiting its future electronic applications. This thesis starts with the investigation of CVD synthesis of pristine and N-doped graphene with controlled thickness using solid carbon sources on metal catalyst substrates (chapter 1), and then discusses the direct growth of bilayer graphene on insulating substrates, including SiO2, h-BN, Si3N4 and Al2O3, without needing further transfer-process (chapter 2). Chapter 3 discusses the synthesis of high-quality graphene single crystals and hexagonal onion-ring-like graphene domains, and also explores the basic growth mechanism of graphene on Cu substrates. To extend graphene's potential applications, both vertical and planar graphene-carbon nanotube hybrids are fabricated using CVD method and their interesting properties are investigated (chapter 4). Chapter 5 discusses how to use chemical methods to modulate graphene's electronic behaviors.
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NASA Astrophysics Data System (ADS)
Ciaravella, A.; Jiménez-Escobar, A.; Cosentino, G.; Cecchi-Pestellini, C.; Peres, G.; Candia, R.; Collura, A.; Barbera, M.; Di Cicca, G.; Varisco, S.; Venezia, A. M.
2018-05-01
An important issue in the chemistry of interstellar ices is the role of dust materials. In this work, we study the effect of an amorphous water-rich magnesium silicate deposited onto ZnSe windows on the chemical evolution of ultraviolet-irradiated methanol ices. For comparison, we also irradiate similar ices deposited onto bare ZnSe windows. Silicates are produced at relatively low temperatures exploiting a sol–gel technique. The chemical composition of the synthesized material reflects the forsterite stoichiometry. Si–OH groups and magnesium carbonates are incorporated during the process. The results show that the substrate material does affect the chemical evolution of the ice. In particular, the CO2/CO ratio within the ice is larger for methanol ices deposited onto the silicate substrate as a result of concurrent effects: the photolysis of carbonates present in the adopted substrate as a source of CO2, CO, and carbon and oxygen atoms; reactions of water molecules and hydroxyl radicals released from the substrate with the CO formed in the ice by the photolysis of the methanol ice; and changes in the structure and energy of the silicate surface by ultraviolet irradiation, leading to more favorable conditions for chemical reactions or catalysis at the grain surface. The results of our experiments allow such chemical effects contributed by the various substrate material components to be disentangled.
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Growth of Graphene by Catalytic Dissociation of Ethylene on CuNi(111)
NASA Astrophysics Data System (ADS)
Tyagi, Parul; Mowll, Tyler; Robinson, Zachary; Ventrice, Carl
2013-03-01
Copper foil is one of the most common substrates for growing large area graphene films. The main reason for this is that Cu has a very low carbon solubility, which results in the self-termination of a single layer of graphene when grown using hydrocarbon precursors at low pressure. Our previous results on Cu(111) substrates has found that temperatures of at least 900 °C are needed to form single domain epitaxial films. By using a CuNi alloy, the catalytic activity of the substrate is expected to increase, which will allow the catalytic decomposition of the hydrocarbon precursor at lower temperatures. In this study, the growth of graphene by the catalytic decomposition of ethylene on a 90:10 CuNi(111) substrate was attempted. The growths were done in an ultra-high vacuum system by either heating the substrate to the growth temperature followed by introducing the ethylene precursor or by introducing the ethylene precursor and subsequently heating it to the growth temperature. The growth using the former method results in a two-domain epitaxial graphene overlayer. However, introducing the ethylene before heating the substrate resulted in considerable rotational disorder within the graphene film. This has been attributed to the deposition of carbon atoms on the surface at temperatures too low for the carbon to crystallize into graphene. This research was supported by the NSF (DMR-1006411).
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NASA Astrophysics Data System (ADS)
Özbek, Neslihan; Alyar, Saliha; Memmi, Burcu Koçak; Gündüzalp, Ayla Balaban; Bahçeci, Zafer; Alyar, Hamit
2017-01-01
2-Hydroxyacetophenone-N-methyl p-toluenesulfonylhydrazone (afptsmh) derived from p-toluenesulfonicacid-1-methylhydrazide (ptsmh) and its Co(II), Pd(II), Pt(II) complexes were synthesized for the first time. Synthesized compounds were characterized by spectroscopic methods (FT-IR, 1Hsbnd 13C NMR, LC-MS, UV-vis), magnetic susceptibility and conductivity measurements. 1H and 13C shielding tensors for crystal structure of ligand were calculated with GIAO/DFT/B3LYP/6-311++G(d,p) methods in CDCl3. The vibrational band assignments were performed at B3LYP/6-311++G(d,p) theory level combined with scaled quantum mechanics force field (SQMFF) methodology. The antibacterial activities of synthesized compounds were studied against some Gram positive and Gram negative bacteria by using microdilution and disc diffusion methods. In vitro enzyme inhibitory effects of the compounds were measured by UV-vis spectrophotometer. The enzyme activities against human carbonic anhydrase II (hCA II) were evaluated as IC50 (the half maximal inhibitory concentration) values. It was found that afptsmh and its metal complexes have inhibitory effects on hCA II isoenzyme. General esterase activities were determined using alpha and beta naphtyl acetate substrates (α- and β-NAs) of Drosophila melanogaster (D. melanogaster). Activity results show that afptsmh does not strongly affect the bacteria strains and also shows poor inhibitory activity against hCAII isoenzyme whereas all complexes posses higher biological activities.
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Kim, H; Lipscomb, W N
1990-06-12
O-[[(1R)-[[N-(Phenylmethoxycarbonyl)-L-alanyl]amino]ethyl] hydroxyphosphinyl]-L-3-phenyllacetate [ZAAP(O)F], an analogue of (benzyloxycarbonyl)-Ala-Ala-Phe or (benzyloxycarbonyl)-Ala-Ala-phenyllactate, binds to carboxypeptidase A with great affinity (Ki = 3 pM). Similar phosphonates have been shown to be transition-state analogues of the CPA-catalyzed hydrolysis [Hanson, J. E., Kaplan, A. P., & Bartlett, P. A. (1989) Biochemistry 28, 6294-6305]. In the present study, the structure of the complex of this phosphonate with carboxypeptidase A has been determined by X-ray crystallography to a resolution of 2.0 A. The complex crystallizes in the space group P2(1)2(1)2(1) with cell dimensions a = 61.9 A, b = 67.2 A, and c = 76.2 A. The structure of the complex was solved by molecular replacement. Refinement of the structure against 20,776 unique reflections between 10.0 and 2.0 A yields a crystallographic residual of 0.193, including 140 water molecules. The two phosphinyl oxygens of the inhibitor bind to the active-site zinc at 2.2 A on the electrophilic (Arg-127) side and 3.1 A on the nucleophilic (Glu-270) side. Various features of the binding mode of this phosphonate inhibitor are consistent with the hypothesis that carboxypeptidase A catalyzed hydrolysis proceeds through a general-base mechanism in which the carbonyl carbon of the substrate is attacked by Zn-hydroxyl (or Zn-water). An unexpected feature of the bound inhibitor, the cis carbamoyl ester bond at the benzyloxycarbonyl linkage to alanine, allows the benzyloxycarbonyl phenyl ring of the inhibitor to interact favorably with Tyr-198. This complex structure is compared with previous structures of carboxypeptidase A, including the complexes with the potato inhibitor, a hydrated keto methylene substrate analogue, and a phosphonamidate inhibitor. Comparisons are also made with the complexes of thermolysin with some phosphonamidate inhibitors.
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Nanostructured Electrocatalysts for All-Vanadium Redox Flow Batteries.
Park, Minjoon; Ryu, Jaechan; Cho, Jaephil
2015-10-01
Vanadium redox reactions have been considered as a key factor affecting the energy efficiency of the all-vanadium redox flow batteries (VRFBs). This redox reaction determines the reaction kinetics of whole cells. However, poor kinetic reversibility and catalytic activity towards the V(2+)/V(3+) and VO(2+)/VO2(+) redox couples on the commonly used carbon substrate limit broader applications of VRFBs. Consequently, modified carbon substrates have been extensively investigated to improve vanadium redox reactions. In this Focus Review, recent progress on metal- and carbon-based nanomaterials as an electrocatalyst for VRFBs is discussed in detail, without the intention to provide a comprehensive review on the whole components of the system. Instead, the focus is mainly placed on the redox chemistry of vanadium ions at a surface of various metals, different dimensional carbons, nitrogen-doped carbon nanostructures, and metal-carbon composites. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Morrow, William P; Sardar, Sinjinee; Thapa, Pawan; Hossain, Mohammad S; Foss, Frank W; Pierce, Brad S
2017-10-01
Thiol dioxygenases are non-heme mononuclear iron enzymes that catalyze the O 2 -dependent oxidation of free thiols (-SH) to produce the corresponding sulfinic acid (-SO 2 - ). Previous chemical rescue studies identified a putative Fe III -O 2 - intermediate that precedes substrate oxidation in Mus musculus cysteine dioxygenase (Mm CDO). Given that a similar reactive intermediate has been identified in the extradiol dioxygenase 2, 3-HCPD, it is conceivable that these enzymes share other mechanistic features with regard to substrate oxidation. To explore this possibility, enzymatic reactions with Mm CDO (as well as the bacterial 3-mercaptopropionic acid dioxygenase, Av MDO) were performed using a substrate analogue (2-mercaptoaniline, 2ma). This aromatic thiol closely approximates the catecholic substrate of homoprotocatechuate of 2, 3-HPCD while maintaining the 2-carbon thiol-amine separation preferred by Mm CDO. Remarkably, both enzymes exhibit 2ma-gated O 2 -consumption; however, none of the expected products for thiol dioxygenase or intra/extradiol dioxygenase reactions were observed. Instead, benzothiazoles are produced by the condensation of 2ma with aldehydes formed by an off-pathway oxidation of primary alcohols added to aqueous reactions to solubilize the substrate. The observed oxidation of 1º-alcohols in 2ma-reactions is consistent with the formation of a high-valent intermediate similar to what has been reported for cytochrome P450 and mononuclear iron model complexes. Copyright © 2017 Elsevier Inc. All rights reserved.
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Schmidt, Yvonne; Lam, Jonathan K.; Pham, Hung V.; Houk, K. N.; Vanderwal, Christopher D.
2013-01-01
The unusual intramolecular arene/allene cycloaddition described thirty years ago by Himbert permits rapid access to strained polycyclic compounds that offer great potential for the synthesis of complex scaffolds. To more fully understand the mechanism of this cycloaddition reaction, and to guide efforts to extend its scope to new substrates, quantum mechanical computational methods were employed in concert with laboratory experiments. These studies indicated that the cycloadditions likely proceed via concerted processes; a stepwise biradical mechanism was shown to be higher in energy in the cases studied. The original Himbert cycloaddition chemistry is also extended from heterocyclic to carbocyclic systems, with computational guidance used to predict thermodynamically favorable cases. Complex polycyclic scaffolds result from the combination of the cycloaddition and subsequent ring-rearrangement metathesis reactions. PMID:23634642
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Hug, Laura A.; Thomas, Brian C.; Sharon, Itai
Nitrogen, sulfur and carbon fluxes in the terrestrial subsurface are determined by the intersecting activities of microbial community members, yet the organisms responsible are largely unknown. Metagenomic methods can identify organisms and functions, but genome recovery is often precluded by data complexity. To address this limitation, we developed subsampling assembly methods to re-construct high-quality draft genomes from complex samples. Here, we applied these methods to evaluate the interlinked roles of the most abundant organisms in biogeochemical cycling in the aquifer sediment. Community proteomics confirmed these activities. The eight most abundant organisms belong to novel lineages, and two represent phyla withmore » no previously sequenced genome. Four organisms are predicted to fix carbon via the Calvin Benson Bassham, Wood Ljungdahl or 3-hydroxyproprionate/4-hydroxybutarate pathways. The profiled organisms are involved in the network of denitrification, dissimilatory nitrate reduction to ammonia, ammonia oxidation and sulfate reduction/oxidation, and require substrates supplied by other community members. An ammonium-oxidizing Thaumarchaeote is the most abundant community member, despite low ammonium concentrations in the groundwater. Finally, this organism likely benefits from two other relatively abundant organisms capable of producing ammonium from nitrate, which is abundant in the groundwater. Overall, dominant members of the microbial community are interconnected through exchange of geochemical resources.« less
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Nickel-based anodic electrocatalysts for fuel cells and water splitting
NASA Astrophysics Data System (ADS)
Chen, Dayi
Our world is facing an energy crisis, so people are trying to harvest and utilize energy more efficiently. One of the promising ways to harvest energy is via solar water splitting to convert solar energy to chemical energy stored in hydrogen. Another of the options to utilize energy more efficiently is to use fuel cells as power sources instead of combustion engines. Catalysts are needed to reduce the energy barriers of the reactions happening at the electrode surfaces of the water-splitting cells and fuel cells. Nickel-based catalysts happen to be important nonprecious electrocatalysts for both of the anodic reactions in alkaline media. In alcohol fuel cells, nickel-based catalysts catalyze alcohol oxidation. In water splitting cells, they catalyze water oxidation, i.e., oxygen evolution. The two reactions occur in a similar potential range when catalyzed by nickel-based catalysts. Higher output current density, lower oxidation potential, and complete substrate oxidation are preferred for the anode in the applications. In this dissertation, the catalytic properties of nickel-based electrocatalysts in alkaline medium for fuel oxidation and oxygen evolution are explored. By changing the nickel precursor solubility, nickel complex nanoparticles with tunable sizes on electrode surfaces were synthesized. Higher methanol oxidation current density is achieved with smaller nickel complex nanoparticles. DNA aggregates were used as a polymer scaffold to load nickel ion centers and thus can oxidize methanol completely at a potential about 0.1 V lower than simple nickel electrodes, and the methanol oxidation pathway is changed. Nickel-based catalysts also have electrocatalytic activity towards a wide range of substrates. Experiments show that methanol, ethanol, glycerol and glucose can be deeply oxidized and carbon-carbon bonds can be broken during the oxidation. However, when comparing methanol oxidation reaction to oxygen evolution reaction catalyzed by current nickel-based catalysts, methanol oxidation suffers from high overpotential and catalyst poisoning by high concentration of substrates, so current nickel-based catalysts are more suitable to be used as oxygen evolution catalysts. A photoanode design that applies nickel oxides to a semiconductor that is incorporated with surface-plasmonic metal electrodes to do solar water oxidation with visible light is proposed.
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NASA Astrophysics Data System (ADS)
Kohl, L.; Cummings, E.; Cox, A.; Suzuki, S.; Morrrissey, L.; Lang, S. Q.; Richter, A.; Nealson, K. H.; Morrill, P. L.
2015-12-01
The Cedars is a complex of ultra-basic, reducing springs located in the Coastal Range Ophiolite (CA, USA), a site of present day serpentinization. Similar to other serpentinization-associated fluids, the groundwaters discharging at The Cedars contain elevated concentrations of C1-C6 alkanes and volatile organic acids (VOAs) which may originate from abiotic or thermogenic processes but can also be produced, consumed, or transformed by microbial activity. In contrast to other continental sites of serpentinization, geochemical indicators (δ13CCH4, δ2HCH4, CH4/C2-C6 alkanes) are consistent with a partial microbial origin of methane at The Cedars. These indicators, however, can provide only indirect evidence of microbial methanogenesis. To further explore the metabolic potential of the indigenous microbial communities at The Cedars, we conducted a series of microcosm experiments in which fluids and sediments collected at The Cedars were incubated with 13C labeled substrates (formate, acetate, bicarbonate, methanol) under anaerobic conditions. 13C from all amended substrates was incorporated into CH4 demonstrating that these microbial communities can convert both organic and inorganic substrates to CH4. The apparent fractionation of 13C between methane and potential substrates indicated that carbonate reduction was the dominant pathway of methanogenesis, and 16S rDNA based community profiling revealed the presence of an OTU closest related to Methanobacterium sp., an autotrophic (CO2/H2) methanogen. Concentrations of C1-C4 VOAs increased 5-fold over the course of the experiment indicating the microbial production of VOAs. This acetogenesis occurred heterotrophically as autotrophic acetogenesis can be excluded because (a) δ13C values of acetate were similar to those of inorganic carbon (inconsistent with the strong discrimination against 13C observed in autotrophic acetogenesis) and (b) no incorporation of 13C from labeled bicarbonate was into acetate was observed.
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Structure and Reaction Mechanism of Basil Eugenol Synthase
Louie, Gordon V.; Baiga, Thomas J.; Bowman, Marianne E.; Koeduka, Takao; Taylor, John H.; Spassova, Snejina M.; Pichersky, Eran; Noel, Joseph P.
2007-01-01
Phenylpropenes, a large group of plant volatile compounds that serve in multiple roles in defense and pollinator attraction, contain a propenyl side chain. Eugenol synthase (EGS) catalyzes the reductive displacement of acetate from the propenyl side chain of the substrate coniferyl acetate to produce the allyl-phenylpropene eugenol. We report here the structure determination of EGS from basil (Ocimum basilicum) by protein x-ray crystallography. EGS is structurally related to the short-chain dehydrogenase/reductases (SDRs), and in particular, enzymes in the isoflavone-reductase-like subfamily. The structure of a ternary complex of EGS bound to the cofactor NADP(H) and a mixed competitive inhibitor EMDF ((7S,8S)-ethyl (7,8-methylene)-dihydroferulate) provides a detailed view of the binding interactions within the EGS active site and a starting point for mutagenic examination of the unusual reductive mechanism of EGS. The key interactions between EMDF and the EGS-holoenzyme include stacking of the phenyl ring of EMDF against the cofactor's nicotinamide ring and a water-mediated hydrogen-bonding interaction between the EMDF 4-hydroxy group and the side-chain amino moiety of a conserved lysine residue, Lys132. The C4 carbon of nicotinamide resides immediately adjacent to the site of hydride addition, the C7 carbon of cinnamyl acetate substrates. The inhibitor-bound EGS structure suggests a two-step reaction mechanism involving the formation of a quinone-methide prior to reduction. The formation of this intermediate is promoted by a hydrogen-bonding network that favors deprotonation of the substrate's 4-hydroxyl group and disfavors binding of the acetate moiety, akin to a push-pull catalytic mechanism. Notably, the catalytic involvement in EGS of the conserved Lys132 in preparing the phenolic substrate for quinone methide formation through the proton-relay network appears to be an adaptation of the analogous role in hydrogen bonding played by the equivalent lysine residue in other enzymes of the SDR family. PMID:17912370
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Freese, Heike M; Eggert, Anja; Garland, Jay L; Schumann, Rhena
2010-01-01
Bacteria are very important degraders of organic substances in aquatic environments. Despite their influential role in the carbon (and many other element) cycle(s), the specific genetic identity of active bacteria is mostly unknown, although contributing phylogenetic groups had been investigated. Moreover, the degree to which phenotypic potential (i. e., utilization of environmentally relevant carbon substrates) is related to the genomic identity of bacteria or bacterial groups is unclear. The present study compared the genomic fingerprints of 27 bacterial isolates from the humic River Warnow with their ability to utilize 14 environmentally relevant substrates. Acetate was the only substrate utilized by all bacterial strains. Only 60% of the strains respired glucose, but this substrate always stimulated the highest bacterial activity (respiration and growth). Two isolates, both closely related to the same Pseudomonas sp., also had very similar substrate utilization patterns. However, similar substrate utilization profiles commonly belonged to genetically different strains (e.g., the substrate profile of Janthinobacterium lividum OW6/RT-3 and Flavobacterium sp. OW3/15-5 differed by only three substrates). Substrate consumption was sometimes totally different for genetically related isolates. Thus, the genomic profiles of bacterial strains were not congruent with their different substrate utilization profiles. Additionally, changes in pre-incubation conditions strongly influenced substrate utilization. Therefore, it is problematic to infer substrate utilization and especially microbial dissolved organic matter transformation in aquatic systems from bacterial molecular taxonomy.
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Schiebel, Johannes; Kapilashrami, Kanishk; Fekete, Agnes; Bommineni, Gopal R.; Schaefer, Christin M.; Mueller, Martin J.; Tonge, Peter J.; Kisker, Caroline
2013-01-01
The survival of Mycobacterium tuberculosis depends on mycolic acids, very long α-alkyl-β-hydroxy fatty acids comprising 60–90 carbon atoms. However, despite considerable efforts, little is known about how enzymes involved in mycolic acid biosynthesis recognize and bind their hydrophobic fatty acyl substrates. The condensing enzyme KasA is pivotal for the synthesis of very long (C38–42) fatty acids, the precursors of mycolic acids. To probe the mechanism of substrate and inhibitor recognition by KasA, we determined the structure of this protein in complex with a mycobacterial phospholipid and with several thiolactomycin derivatives that were designed as substrate analogs. Our structures provide consecutive snapshots along the reaction coordinate for the enzyme-catalyzed reaction and support an induced fit mechanism in which a wide cavity is established through the concerted opening of three gatekeeping residues and several α-helices. The stepwise characterization of the binding process provides mechanistic insights into the induced fit recognition in this system and serves as an excellent foundation for the development of high affinity KasA inhibitors. PMID:24108128
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Selective Growth of Metallic and Semiconducting Single Walled Carbon Nanotubes on Textured Silicon.
Jang, Mira; Lee, Jongtaek; Park, Teahee; Lee, Junyoung; Yang, Jonghee; Yi, Whikun
2016-03-01
We fabricated the etched Si substrate having the pyramidal pattern size from 0.5 to 4.2 μm by changing the texturing process parameters, i.e., KOH concentration, etching time, and temperature. Single walled carbon nanotubes (SWNTs) were then synthesized on the etched Si substrates with different pyramidal pattern by chemical vapor deposition. We investigated the optical and electronic properties of SWNT film grown on the etched Si substrates of different morphology by using scanning electron microscopy, Raman spectroscopy and conducting probe atomic force microscopy. We confirmed that the morphology of substrate strongly affected the selective growth of the SWNT film. Semiconducting SWNTs were formed on larger pyramidal sized Si wafer with higher ratio compared with SWNTs on smaller pyramidal sized Si.
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Feliu, Sebastián; Samaniego, Alejandro; Bermudez, Elkin Alejandro; El-Hadad, Amir Abdelsami; Llorente, Irene; Galván, Juan Carlos
2014-01-01
Possible relations between the native oxide film formed spontaneously on the AZ31 and AZ61 magnesium alloy substrates with different surface finish, the chemistry of the outer surface of the conversion coatings that grows after their subsequent immersion on saturated aqueous NaHCO3 solution treatment and the enhancement of corrosion resistance have been studied. The significant increase in the amount of aluminum and carbonate compounds on the surface of the conversion coating formed on the AZ61 substrate in polished condition seems to improve the corrosion resistance in low chloride ion concentration solutions. In contrast, the conversion coatings formed on the AZ31 substrates in polished condition has little effect on their protective properties compared to the respective as-received surface. PMID:28788582
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Feliu, Sebastián; Samaniego, Alejandro; Bermudez, Elkin Alejandro; El-Hadad, Amir Abdelsami; Llorente, Irene; Galván, Juan Carlos
2014-03-28
Possible relations between the native oxide film formed spontaneously on the AZ31 and AZ61 magnesium alloy substrates with different surface finish, the chemistry of the outer surface of the conversion coatings that grows after their subsequent immersion on saturated aqueous NaHCO₃ solution treatment and the enhancement of corrosion resistance have been studied. The significant increase in the amount of aluminum and carbonate compounds on the surface of the conversion coating formed on the AZ61 substrate in polished condition seems to improve the corrosion resistance in low chloride ion concentration solutions. In contrast, the conversion coatings formed on the AZ31 substrates in polished condition has little effect on their protective properties compared to the respective as-received surface.
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Synthesis of layer-tunable graphene: A combined kinetic implantation and thermal ejection approach
Wang, Gang; Zhang, Miao; Liu, Su; ...
2015-05-04
Layer-tunable graphene has attracted broad interest for its potentials in nanoelectronics applications. However, synthesis of layer-tunable graphene by using traditional chemical vapor deposition (CVD) method still remains a great challenge due to the complex experimental parameters and the carbon precipitation process. Herein, by performing ion implantation into a Ni/Cu bilayer substrate, the number of graphene layers, especially single or double layer, can be controlled precisely by adjusting the carbon ion implant fluence. The growth mechanism of the layer-tunable graphene is revealed by monitoring the growth process is observed that the entire implanted carbon atoms can be expelled towards the substratemore » surface and thus graphene with designed layer number can be obtained. Such a growth mechanism is further confirmed by theoretical calculations. The proposed approach for the synthesis of layer-tunable graphene offers more flexibility in the experimental conditions. Being a core technology in microelectronics processing, ion implantation can be readily implemented in production lines and is expected to expedite the application of graphene to nanoelectronics.« less
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Fuentes, Marcelo E; Quiñones, Renato A
Facultative marine filamentous fungi have recently emerged as a functional component in coastal marine systems. However, little is known about their ecological role and functions in biogeochemical cycles. Penicillium decumbens, S. strictum, and F. fujikuroi were isolated from the coastal upwelling zone off south-central Chile. Their carbon profiles were characterized using Biolog FF MicroPlates. These species used a wide range of carbon sources, mainly carbohydrates, but also amino acids, suggesting the use of metabolic routes that include glycolysis/gluconeogenesis. Substrate richness revealed a great capacity for the utilization of nutritional sources, reflected by the following Shannon Indices of utilization of specific substrates: 4.02 for S. strictum, 4.01 for P. decumbes, and 3.91 for F. fujikuroi, which reveals a high physiological capacity for oxidizing different substrates. Significant differences were found between 18 substrates utilized by all three species. Results suggest that filamentous fungi should be considered an integral part of the marine microbial community and included in biogeochemical cycling models of upwelling ecosystems.
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Investigation of different anode materials for aluminium rechargeable batteries
NASA Astrophysics Data System (ADS)
Muñoz-Torrero, David; Leung, Puiki; García-Quismondo, Enrique; Ventosa, Edgar; Anderson, Marc; Palma, Jesús; Marcilla, Rebeca
2018-01-01
In order to shed some light into the importance of the anodic reaction in reversible aluminium batteries, we investigate here the electrodeposition of aluminium in an ionic liquid electrolyte (BMImCl-AlCl3) using different substrates. We explore the influence of the type of anodic material (aluminium, stainless steel and carbon) and its 3D geometry on the reversibility of the anodic reaction by cyclic voltammetry (CV) and galvanostatic charge-discharge. The shape of the CVs confirms that electrodeposition of aluminium was feasible in the three materials but the highest peak currents and smallest peak separation in the CV of the aluminium anode suggested that this material was the most promising. Interestingly, carbon-based substrates appeared as an interesting alternative due to the high peak currents in CV, moderate overpotentials and dual role as anode and cathode. 3D substrates such as fiber-based carbon paper and aluminium mesh showed significantly smaller overpotentials and higher efficiencies for Al reaction suggesting that the use of 3D substrates in full batteries might result in enhanced power. This is corroborated by polarization testing of full Al-batteries.
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Bacsi, Attila; Woodberry, Mitchell; Widger, William; Papaconstantinou, John; Mitra, Sankar; Peterson, Johnny W.; Boldogh, Istvan
2011-01-01
3-Nitropropionic acid (3-NPA), an inhibitor of succinate dehydrogenase (SDH) at complex II of the mitochondrial electron transport chain induces cellular energy deficit and oxidative stress-related neurotoxicity. In the present study, we identified the site of reactive oxygen species production in mitochondria. 3-NPA increased O2•− generation in mitochondria respiring on the complex I substrates pyruvate + malate, an effect fully inhibited by rotenone. Antimycin A increased O2•− production in the presence of complex I and/or II substrates. Addition of 3-NPA markedly increased antimycin A-induced O2•− production by mitochondria incubated with complex I substrates, but 3-NPA inhibited O2•− formation driven with the complex II substrate succinate. At 0.6 μM, myxothiazol inhibits complex III, but only partially decreases complex I activity, and allowed 3-NPA-induced O2•− formation; however, at 40 μM myxothiazol (which completely inhibits both complexes I and III) eliminated O2•− production from mitochondria respiring via complex I substrates. These results indicate that in the presence of 3-NPA, mitochondria generate O2•− from a site between the ubiquinol pool and the 3-NPA block in the respiratory complex II. PMID:17011837
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NASA Astrophysics Data System (ADS)
Perry, C. T.; Beavington-Penney, S. J.
2005-02-01
Seagrass beds have been widely recognised as playing an important role in influencing carbonate sediment facies development. This reflects their role not only as facilitators of fine sediment settling and stabilisation, but also as substrates for epiphytic organisms that, after death, contribute skeletal carbonate to the sediment substrate. In low latitude (reef-related) settings, epiphytic carbonate production rates are often high and this, in combination with the trapping of carbonate mud produced by a range of associated calcareous algal species, typically results in the development of carbonate mud-rich facies. Whilst such environments, and their associated sediment substrates, have been widely documented, studies of seagrass facies in marginal (sub-tropical/warm temperate) marine settings have not been conducted from a sedimentological perspective. This study determines rates of epiphytic carbonate production on two seagrass species Thalassodendron ciliatum and Thalassia hemprichii, and examines seagrass sediment facies from a sub-tropical reef-related environment in southern Mozambique. Dense seagrass beds colonise primarily siliciclastic sediment substrates and are characterised by low rates of epiphytic carbonate production (mean: 43.9 g CaCO 3 m -2 year -1 for T. ciliatum, and 33.4 g CaCO 3 m -2 year -1 for T. hemprichii). Epiphytic encrusters are dominated by thin, monostromatic layers of the crustose coralline red algae Hydrolithon farinosum, along with rotaliid smaller benthic foraminifera (including Asterorotalia cf. gaimardi and Spirillina sp.) and the soritid Peneroplis sp., as well as rare encrusting acervulinid foraminifera, serpulids and bryozoans. Epiphytic calcium carbonate production rates are therefore low and this is reflected in the low (<15%) carbonate content of the seagrass sediments, as well as the low (<1%) sediment fine (<63 μm size fraction) content. This study suggests that mud-rich sediment facies do not necessarily develop in conjunction with seagrass beds and that mud-poor facies may develop in some seagrass-colonised environments. At these sites (sub-tropical and siliciclastic-sediment dominated) this is suggested to reflect both the low levels of epiphytic and benthic algal carbonate mud production as well as a net outflux of fine-grained sediment due to tidal current-induced sediment resuspension. In keeping with carbonate facies generally there are thus likely to be latitude and environment-related shifts in the composition and character of seagrass related sediment facies.
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Singh, Ravi; Pantarotto, Davide; McCarthy, David; Chaloin, Olivier; Hoebeke, Johan; Partidos, Charalambos D; Briand, Jean-Paul; Prato, Maurizio; Bianco, Alberto; Kostarelos, Kostas
2005-03-30
Carbon nanotubes (CNTs) constitute a class of nanomaterials that possess characteristics suitable for a variety of possible applications. Their compatibility with aqueous environments has been made possible by the chemical functionalization of their surface, allowing for exploration of their interactions with biological components including mammalian cells. Functionalized CNTs (f-CNTs) are being intensively explored in advanced biotechnological applications ranging from molecular biosensors to cellular growth substrates. We have been exploring the potential of f-CNTs as delivery vehicles of biologically active molecules in view of possible biomedical applications, including vaccination and gene delivery. Recently we reported the capability of ammonium-functionalized single-walled CNTs to penetrate human and murine cells and facilitate the delivery of plasmid DNA leading to expression of marker genes. To optimize f-CNTs as gene delivery vehicles, it is essential to characterize their interactions with DNA. In the present report, we study the interactions of three types of f-CNTs, ammonium-functionalized single-walled and multiwalled carbon nanotubes (SWNT-NH3+; MWNT-NH3+), and lysine-functionalized single-walled carbon nanotubes (SWNT-Lys-NH3+), with plasmid DNA. Nanotube-DNA complexes were analyzed by scanning electron microscopy, surface plasmon resonance, PicoGreen dye exclusion, and agarose gel shift assay. The results indicate that all three types of cationic carbon nanotubes are able to condense DNA to varying degrees, indicating that both nanotube surface area and charge density are critical parameters that determine the interaction and electrostatic complex formation between f-CNTs with DNA. All three different f-CNT types in this study exhibited upregulation of marker gene expression over naked DNA using a mammalian (human) cell line. Differences in the levels of gene expression were correlated with the structural and biophysical data obtained for the f-CNT:DNA complexes to suggest that large surface area leading to very efficient DNA condensation is not necessary for effective gene transfer. However, it will require further investigation to determine whether the degree of binding and tight association between DNA and nanotubes is a desirable trait to increase gene expression efficiency in vitro or in vivo. This study constitutes the first thorough investigation into the physicochemical interactions between cationic functionalized carbon nanotubes and DNA toward construction of carbon nanotube-based gene transfer vector systems.
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Robust forests of vertically aligned carbon nanotubes chemically assembled on carbon substrates.
Garrett, David J; Flavel, Benjamin S; Shapter, Joseph G; Baronian, Keith H R; Downard, Alison J
2010-02-02
Forests of vertically aligned carbon nanotubes (VACNTs) have been chemically assembled on carbon surfaces. The structures show excellent stability over a wide potential range and are resistant to degradation from sonication in acid, base, and organic solvent. Acid-treated single-walled carbon nanotubes (SWCNTs) were assembled on amine-terminated tether layers covalently attached to pyrolyzed photoresist films. Tether layers were electrografted to the carbon substrate by reduction of the p-aminobenzenediazonium cation and oxidation of ethylenediamine. The amine-modified surfaces were incubated with cut SWCNTs in the presence of N,N'-dicyclohexylcarbodiimide (DCC), giving forests of vertically aligned carbon nanotubes (VACNTs). The SWCNT assemblies were characterized by scanning electron microscopy, atomic force microscopy, and electrochemistry. Under conditions where the tether layers slow electron transfer between solution-based redox probes and the underlying electrode, the assembly of VACNTs on the tether layer dramatically increases the electron-transfer rate at the surface. The grafting procedure, and hence the preparation of VACNTs, is applicable to a wide range of materials including metals and semiconductors.
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Arendse, C J; Malgas, G F; Scriba, M R; Cummings, F R; Knoesen, D
2007-10-01
Hot-filament chemical vapor deposition has developed into an attractive method for the synthesis of various carbon nanostructures, including carbon nanotubes. This is primarily due to its versatility, low cost, repeatability, up-scalability, and ease of production. The resulting nano-material synthesized by this technique is dependent on the deposition conditions which can be easily controlled. In this paper we report on the effect of the deposition pressure on the structural properties and morphology of carbon nanotubes synthesized by hot-filament chemical vapor deposition, using Raman spectroscopy and high-resolution scanning electron microscopy, respectively. A 10 nm-thick Ni layer, deposited on a SiO2/Si substrate, was used as catalyst for carbon nanotube growth. Multi-walled carbon nanotubes with diameters ranging from 20-100 nm were synthesized at 500 degrees C with high structural perfection at deposition pressures between 150 and 200 Torr. Raman spectroscopy measurements confirm that the carbon nanotube deposit is homogeneous across the entire substrate area.
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NASA Technical Reports Server (NTRS)
Lee, S. S.; Shuler, M. L.
1986-01-01
An experimental system was developed to study the microbial growth kinetic of an undefined mixed culture in an erobic biological waste treatment process. The experimental results were used to develop a mathematical model that can predict the performance of a bioreactor. The bioreactor will be used to regeneratively treat waste material which is expected to be generated during a long term manned space mission. Since the presence of insoluble particles in the chemically undefined complex media made estimating biomass very difficult in the real system, a clean system was devised to study the microbial growth from the soluble substrate.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Intrator, Miranda Huang
Many industrial catalysts used for homogeneous hydrogenation and dehydrogenation of unsaturated substrates are derived from metal complexes that include (air-sensitive) ligands that are often expensive and difficult to synthesize. In particular, catalysts used for many hydrogenations are based on phosphorus containing ligands (in particular PNP pincer systems). These ligands are often difficult to make, are costly, are constrained to having two carbon atoms in the ligand backbone and are susceptible to oxidation at phosphorus, making their use somewhat complicated. Los Alamos researchers have recently developed a new and novel set of ligands that are based on a NNS (ENENES) skeletonmore » (i.e. no phosphorus donors, just nitrogen and sulfur).« less
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NASA Astrophysics Data System (ADS)
Chan, Y. C.; Vowles, P. D.; McTainsh, G. H.; Simpson, R. W.; Cohen, D. D.; Bailey, G. M.; McOrist, G. D.
This paper describes a method for the simultaneous collection of size-fractionated aerosol samples on several collection substrates, including glass-fibre filter, carbon tape and silver tape, with a commercially available high-volume cascade impactor. This permitted various chemical analysis procedures, including ion beam analysis (IBA), instrumental neutron activation analysis (INAA), carbon analysis and scanning electron microscopy (SEM), to be carried out on the samples.
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Carbon mineralization in acidic, xeric forest soils: induction of new activities.
Tate, R L
1985-08-01
Carbon mineralization was examined in Lakehurst and Atsion sands collected from the New Jersey Pinelands and in Pahokee muck from the Everglades Agricultural Area. Objectives were (i) to estimate the carbon mineralization capacities of acidic, xeric Pinelands soils in the absence of exogenously supplied carbon substrate (nonamended carbon mineralization rate) and to compare these activities with those of agriculturally developed pahokee muck, and (ii) to measure the capacity for increased carbon mineralization in the soils after carbon amendment. In most cases, nonamended carbon mineralization rates were greater in samples of the acid- and moisture-stressed Pinelands soils than in Pahokee muck collected from a fallow (bare) field. Carbon amendment resulted in augmented catabolic activity in Pahokee muck samples, suggesting that the microbial community was carbon limited in this soil. With many of the substrates, no stimulation of the catabolic rate was detected after amendment of Pinelands soils. This was documented by the observation that amendment of Pahokee muck with an amino acid mixture, glucose, or acetate resulted in a 3.0-, 3.9-, or 10.5-fold stimulation of catabolic activity, respectively, for the added substrate. In contrast, amendment of the Pinelands soils resulted in increased amino acid and acetate catabolic rates in Lakehurst sand and increased acetate metabolism only in Atsion sand. Other activities were unchanged. The increased glucose respiration rates resulted from stimulation of existing microbial activity rather than from microbial proliferation since no change in the microbial growth rate, as estimated by the rate of incorporation of C-labeled acetate into cell membranes, occurred after glucose amendment of the soils. A stimulation of microbial growth rate was recorded with glucose-amended Lakehurst sand collected from the B horizon.
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Carbon Mineralization in Acidic, Xeric Forest Soils: Induction of New Activities †
Tate, Robert L.
1985-01-01
Carbon mineralization was examined in Lakehurst and Atsion sands collected from the New Jersey Pinelands and in Pahokee muck from the Everglades Agricultural Area. Objectives were (i) to estimate the carbon mineralization capacities of acidic, xeric Pinelands soils in the absence of exogenously supplied carbon substrate (nonamended carbon mineralization rate) and to compare these activities with those of agriculturally developed pahokee muck, and (ii) to measure the capacity for increased carbon mineralization in the soils after carbon amendment. In most cases, nonamended carbon mineralization rates were greater in samples of the acid- and moisture-stressed Pinelands soils than in Pahokee muck collected from a fallow (bare) field. Carbon amendment resulted in augmented catabolic activity in Pahokee muck samples, suggesting that the microbial community was carbon limited in this soil. With many of the substrates, no stimulation of the catabolic rate was detected after amendment of Pinelands soils. This was documented by the observation that amendment of Pahokee muck with an amino acid mixture, glucose, or acetate resulted in a 3.0-, 3.9-, or 10.5-fold stimulation of catabolic activity, respectively, for the added substrate. In contrast, amendment of the Pinelands soils resulted in increased amino acid and acetate catabolic rates in Lakehurst sand and increased acetate metabolism only in Atsion sand. Other activities were unchanged. The increased glucose respiration rates resulted from stimulation of existing microbial activity rather than from microbial proliferation since no change in the microbial growth rate, as estimated by the rate of incorporation of 14C-labeled acetate into cell membranes, occurred after glucose amendment of the soils. A stimulation of microbial growth rate was recorded with glucose-amended Lakehurst sand collected from the B horizon. PMID:16346862
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Kang, Dongseok; Kim, Won-Jun; Lim, Jung Ah; Song, Yong-Won
2012-07-25
Using only a simple tube furnace, we demonstrate the synthesis of patterned graphene directly on a designed substrate without the need for an external carbon source. Carbon atoms are absorbed onto Ni evaporator sources as impurities, and incorporated into catalyst layers during the deposition. Heat treatment conditions were optimized so that the atoms diffused out along the grain boundaries to form nanocrystals at the catalyst-substrate interfaces. Graphene patterns were obtained under patterned catalysts, which restricted graphene formation to within patterned areas. The resultant multilayer graphene was characterized by Raman spectroscopy and transmission electron microscopy to verify the high crystallinity and two-dimensional nanomorphology. Finally, a metal-semiconductor diode with a catalyst-graphene contact structure were fabricated and characterized to assess the semiconducting properties of the graphene sheets with respect to the display of asymmetric current-voltage behavior.
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Wang, Xueshen; Li, Qunqing; Xie, Jing; Jin, Zhong; Wang, Jinyong; Li, Yan; Jiang, Kaili; Fan, Shoushan
2009-09-01
We report the controlled growth of ultralong single-wall carbon nanotube (SWNT) arrays using an improved chemical vapor deposition strategy. Using ethanol or methane as the feed gas, monodispersed Fe-Mo as the catalyst, and a superaligned carbon nanotube (CNT) film as the catalyst supporting frame, ultralong CNTs over 18.5 cm long were grown on Si substrates. The growth rate of the CNTs was more than 40 mum/s. No catalyst-related residual material was found on the substrates due to the use of a CNT film as the catalyst supporting frame, facilitating any subsequent fabrication of SWNT-based devices. Electrical transport measurements indicated that the electrical characteristics along a single ultralong SWNT were uniform. We also found that maintaining a spatially homogeneous temperature during the growth process was a critical factor for obtaining constant electrical characteristics along the length of the ultralong SWNTs.
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Carbon nanotube-lipase hybrid nanoflowers with enhanced enzyme activity and enantioselectivity.
Li, Kai; Wang, Jianhua; He, Yaojia; Abdulrazaq, Miaad Adnan; Yan, Yunjun
2018-06-19
Various nanoflowers are synthesized as supports for different methods of enzyme immobilization; however, the activities of these immobilized enzymes are limited because of their confinement in the nanoflowers. In order to increase the performance of nanoflowers, in this study, different protein-phosphate hybrid nanostructures were successfully synthesized and further enhanced by carbon nanotubes (CNTs) under the same conditions. Only Cu 3 (PO 4 ) 2 complex nanostructures exhibited flower-like structures and showed excellent results after enhancement with CNTs in this framework. An esterification reaction between lauric acid and 1-dodecanol was used to test enzyme activity during immobilization, revealing that the Cu 3 (PO 4 ) 2 /CNT/protein complex exhibited 68-fold higher activity relative to free lipase and 51-fold higher than that of Cu 3 (PO 4 ) 2 /Burkholderia cepacia lipase hybrid nanoflowers in the absence of CNTs. All three hybrid nanostructures showed good performance and exhibited excellent reusability in resolution reactions between 1-phenylethanol and vinyl acetate. Additionally, the substrate enantiomeric excess (ee s ) reached 98% in only 10 min, and the corresponding Cu 3 (PO 4 ) 2 /CNT/protein complex could be recycled eight times without obvious loss of activity. This approach involving nanoflowers enhanced with CNTs will be highly beneficial for decreasing mass-transfer resistance and providing enhanced enzyme loading along with promising potential for industrial application. Copyright © 2018 Elsevier B.V. All rights reserved.
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Naumann, Robert; Lehmann, Florian; Goez, Martin
2018-05-16
We have explored alkyl substitution of the ligands as a means to improve the performance of the title complexes in photoredox catalytic systems that produce synthetically useable amounts of hydrated electrons through photon pooling. Despite generating a superreductant, these electron sources only consume the bioavailable ascorbate and are driven by a green light-emitting diode (LED). The substitutions influence the catalyst activity through the quenching and recombination rates across the micelle-water interface, and the photoionization quantum yield. Laser flash photolysis yields comprehensive information on all these processes and allows quantitative predictions of the activity observed in LED kinetics, but the latter provides the only access to the catalyst stability under illumination on the timescale of the syntheses. The homoleptic complex with dimethylbipyridine ligands emerges as the optimum that combines an activity twice as high with an undiminished stability in relation to the parent compound. With this complex, we have effected dehalogenations of alkyl and aryl chlorides and fluorides, hydrogenations of carbon-carbon double bonds, and self- as well as cross-couplings. All the substrates employed are impervious to ordinary photoredox catalysts but present no problems to the hydrated electron as a super-reductant. A particularly attractive application is selective deuteration with high isotopic purity, which is achieved simply by using heavy water as the solvent. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Liu, Yuanyue; Wang, Y. Morris; Yakobson, Boris I.; ...
2014-07-11
Many key performance characteristics of carbon-based lithium-ion battery anodes are largely determined by the strength of binding between lithium (Li) and sp 2 carbon (C), which can vary significantly with subtle changes in substrate structure, chemistry, and morphology. We use density functional theory calculations to investigate the interactions of Li with a wide variety of sp 2 C substrates, including pristine, defective, and strained graphene, planar C clusters, nanotubes, C edges, and multilayer stacks. In almost all cases, we find a universal linear relation between the Li-C binding energy and the work required to fill previously unoccupied electronic states withinmore » the substrate. This suggests that Li capacity is predominantly determined by two key factors—namely, intrinsic quantum capacitance limitations and the absolute placement of the Fermi level. This simple descriptor allows for straightforward prediction of the Li-C binding energy and related battery characteristics in candidate C materials based solely on the substrate electronic structure. It further suggests specific guidelines for designing more effective C-based anodes. Furthermore, this method should be broadly applicable to charge-transfer adsorption on planar substrates, and provides a phenomenological connection to established principles in supercapacitor and catalyst design.« less
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Djukic, Ika; Zehetner, Franz; Watzinger, Andrea; Horacek, Micha; Gerzabek, Martin H
2013-01-01
Litter decomposition represents one of the largest fluxes in the global terrestrial carbon cycle. The aim of this study was to improve our understanding of the factors governing decomposition in alpine ecosystems and how their responses to changing environmental conditions change over time. Our study area stretches over an elevation gradient of 1000 m on the Hochschwab massif in the Northern Limestone Alps of Austria. We used high-to-low elevation soil translocation to simulate the combined effects of changing climatic conditions, shifting vegetation zones, and altered snow cover regimes. In original and translocated soils, we conducted in situ decomposition experiments with maize litter and studied carbon turnover dynamics as well as temporal response patterns of the pathways of carbon during microbial decomposition over a 2-year incubation period. A simulated mean annual soil warming (through down-slope translocation) of 1.5 and 2.7 °C, respectively, resulted in a significantly accelerated turnover of added maize carbon. Changes in substrate quantity and quality in the course of the decomposition appeared to have less influence on the microbial community composition and its substrate utilization than the prevailing environmental/site conditions, to which the microbial community adapted quickly upon change. In general, microbial community composition and function significantly affected substrate decomposition rates only in the later stage of decomposition when the differentiation in substrate use among the microbial groups became more evident. Our study demonstrated that rising temperatures in alpine ecosystems may accelerate decomposition of litter carbon and also lead to a rapid adaptation of the microbial communities to the new environmental conditions. © 2012 Federation of European Microbiological Societies. Published by Blackwell Publishing Ltd. All rights reserved.
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Self-Assembled Carbon-Polyoxometalate Composites for Electrochemical Capacitors
NASA Astrophysics Data System (ADS)
Genovese, Matthew
The development of high performance yet cost effective energy storage devices is critical for enabling the growth of important emerging sectors from the internet of things to grid integration of renewable energy. Material costs are by far the largest contributor to the overall cost of energy storage devices and thus research into cost effective energy storage materials will play an important role in developing technology to meet real world storage demands. In this thesis, low cost high performance composite electrode materials for supercapacitors (SCs) have been developed through the surface modification of electrochemically double layer capacitive (EDLC) carbon substrates with pseudocapacitive Polyoxometalates (POMs). Significant fundamental contributions have been made to the understanding of all components of the composite electrode including the POM active layer, cation linker, and carbon substrate. The interaction of different POM chemistries in solution has been studied to elucidate the novel ways in which these molecules combine and the mechanism underlying this combination. A more thorough understanding regarding the cation linker's role in electrode fabrication has been developed through examining the linker properties which most strongly affect electrode performance. The development of porosity in biomass derived carbon materials has also been examined leading to important insights regarding the effect of substrate porosity on POM modification and electrochemical properties. These fundamental contributions enabled the design and performance optimization of POM-carbon composite SC electrodes. Understanding how POMs combine in solution, allowed for the development of mixed POM molecular coatings with tunable electrochemical properties. These molecular coatings were used to modify low cost biomass derived carbon substrates that had been structurally optimized to accommodate POM molecules. The resulting electrode composites utilizing low cost materials fabricated through simple scalable techniques demonstrated (i) high capacitance (361 F g-1), (ii) close to ideal pseudocapacitive behavior, (iii) stable cycling, and (iv) good rate performance.
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Rapid kinetics of dehalogenation promoted by iodotyrosine deiodinase from human thyroid.
Bobyk, Kostyantyn D; Ballou, David P; Rokita, Steven E
2015-07-28
Reductive dehalogenation such as that catalyzed by iodotyrosine deiodinase (IYD) is highly unusual in aerobic organisms but necessary for iodide salvage from iodotyrosine generated during thyroxine biosynthesis. Equally unusual is the dependence of this process on flavin. Rapid kinetics have now been used to define the basic processes involved in IYD catalysis. Time-dependent quenching of flavin fluorescence was used to monitor halotyrosine association to IYD. The substrates chloro-, bromo-, and iodotyrosine bound with similar rate constants (kon) ranging from 1.3 × 10(6) to 1.9 × 10(6) M(-1) s(-1). Only the inert substrate analogue fluorotyrosine exhibited a significantly (5-fold) slower kon (0.3 × 10(6) M(-1) s(-1)). All data fit a standard two-state model and indicated that no intermediate complex accumulated during closure of the active site lid induced by substrate. Subsequent halide elimination does not appear to limit reactions of bromo- and iodotyrosine since both fully oxidized the reduced enzyme with nearly equivalent second-order rate constants (7.3 × 10(3) and 8.6 × 10(3) M(-1) s(-1), respectively) despite the differing strength of their carbon-halogen bonds. In contrast to these substrates, chlorotyrosine reacted with the reduced enzyme approximately 20-fold more slowly and revealed a spectral intermediate that formed at approximately the same rate as the bromo- and iodotyrosine reactions.
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van den Brink, Joost; Maitan-Alfenas, Gabriela Piccolo; Zou, Gen; Wang, Chengshu; Zhou, Zhihua; Guimarães, Valéria Monteze; de Vries, Ronald P
2014-10-01
Plant-degrading enzymes can be produced by fungi on abundantly available low-cost plant biomass. However, enzymes sets after growth on complex substrates need to be better understood, especially with emphasis on differences between fungal species and the influence of inhibitory compounds in plant substrates, such as monosaccharides. In this study, Aspergillus niger and Trichoderma reesei were evaluated for the production of enzyme sets after growth on two "second generation" substrates: wheat straw (WS) and sugarcane bagasse (SCB). A. niger and T. reesei produced different sets of (hemi-)cellulolytic enzymes after growth on WS and SCB. This was reflected in an overall strong synergistic effect in releasing sugars during saccharification using A. niger and T. reesei enzyme sets. T. reesei produced less hydrolytic enzymes after growth on non-washed SCB. The sensitivity to non-washed plant substrates was not reduced by using CreA/Cre1 mutants of T. reesei and A. niger with a defective carbon catabolite repression. The importance of removing monosaccharides for producing enzymes was further underlined by the decrease in hydrolytic activities with increased glucose concentrations in WS media. This study showed the importance of removing monosaccharides from the enzyme production media and combining T. reesei and A. niger enzyme sets to improve plant biomass saccharification. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Duan, Zhi-Qiang; Liu, Yi-Tao; Xie, Xu-Ming; Ye, Xiong-Ying; Zhu, Xiao-Dong
2016-03-18
h-BN, as an isoelectronic analogue of graphene, has improved thermal mechanical properties. Moreover, the liquid-phase production of h-BN is greener since harmful oxidants/reductants are unnecessary. Here we report a novel hybrid architecture by employing h-BN nanosheets as 2D substrates to load 0D Fe3O4 nanoparticles, followed by phenol/formol carbonization to form a carbon coating. The resulting carbon-encapsulated h-BN@Fe3O4 hybrid architecture exhibits synergistic interactions: 1) The h-BN nanosheets act as flexible 2D substrates to accommodate the volume change of the Fe3O4 nanoparticles; 2) The Fe3O4 nanoparticles serve as active materials to contribute to a high specific capacity; and 3) The carbon coating not only protects the hybrid architecture from deformation but also keeps the whole electrode highly conductive. The synergistic interactions translate into significantly enhanced electrochemical performances, laying a basis for the development of superior hybrid anode materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Liu, Ximeng; Guan, Cao; Hu, Yating; Zhang, Lei; Elshahawy, Abdelnaby M; Wang, John
2017-10-27
Direct assembling of active materials on carbon cloth (CC) is a promising way to achieve flexible electrodes for energy storage. However, the overall surface area and electrical conductivity of such electrodes are usually limited. Herein, 2D metal-organic framework derived nanocarbon nanowall (MOFC) arrays are successfully developed on carbon cloth by a facile solution + carbonization process. Upon growth of the MOFC arrays, the sites for growth of the active materials are greatly increased, and the equivalent series resistance is decreased, which contribute to the enhancement of the bare CC substrate. After decorating ultrathin flakes of MnO 2 and Bi 2 O 3 on the flexible CC/MOFC substrate, the hierarchical electrode materials show an abrupt improvement of areal capacitances by around 50% and 100%, respectively, compared to those of the active materials on pristine carbon cloth. A flexible supercapacitor can be further assembled using two hierarchical electrodes, which demonstrates an energy density of 124.8 µWh cm -2 at the power density of 2.55 mW cm -2 . © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Growth of the extremophilic Deinococcus geothermalis DSM 11302 using co-substrate fed-batch culture.
Bornot, Julie; Molina-Jouve, Carole; Uribelarrea, Jean-Louis; Gorret, Nathalie
2014-02-01
Deinococcus geothermalis metabolism has been scarcely studied to date, although new developments on its utilization for bioremediation have been carried out. So, large-scale production of this strain and a better understanding of its physiology are required. A fed-batch experiment was conducted to achieve a high cell density non-limiting culture of D. geothermalis DSM 11302. A co-substrate nutritional strategy using glucose and yeast extract was carried out in a 20-L bioreactor in order to maintain a non-limited growth at a maximal growth rate of 1 h(-1) at 45 °C. Substrate supplies were adjusted by monitoring online culture parameters and physiological data (dissolved oxygen, gas analyses, respiratory quotient, biomass concentration). The results showed that yeast extract could serve as both carbon and nitrogen sources, although glucose and ammonia were consumed too. Yeast extract carbon-specific uptake rate reached a value 4.5 times higher than glucose carbon-specific uptake rate. Cell concentration of 9.6 g L(-1) dry cell weight corresponding to 99 g of biomass was obtained using glucose and yeast extract as carbon and nitrogen sources.
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NASA Astrophysics Data System (ADS)
Kang, Sukill; Lowndes, Douglas H.; Ellis, Darren
2001-03-01
Nanostructured carbon films have been grown on uncatalysed n-type Si using a modified HF-CVD process and catalytic decomposition of ethylene (C_2H_4). Various metal catalyst wires such as Ni, Co, Fe and a NiFe composite were placed within the windings of a tungsten filament and the assembly was placed in close proximity ( ~7 mm) to the unheated substrate. Radiative heating of the substrate by the filament results in a substrate temperature of ~ 500^oC after 7 min. Films grown using the Ni catalyst showed a field emission turn-on field that varied from 9 to 15 V/μm and was stable for 30-50 hours (1-10 A/cm^2 emission current density), a result that is comparable to carbon nanotube- and carbon nanofiber-based structures. In this contribution, we present results from field emission scanning electron microscopy, transmission electron microscopy, and electron field emission measurements that elucidate the relationship between field emission properties, film morphology, and type of catalyst.
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NASA Astrophysics Data System (ADS)
Bowen, G. J.; Abels, H.
2015-12-01
Abrupt changes in the isotope composition of exogenic carbon pools accompany many major episodes of global change in the geologic record. The global expression of this change in substrates that reflect multiple carbon pools provides important evidence that many events reflect persistent, global redistribution of carbon between reduced and oxidized stocks. As the diversity of records documenting any event grows, however, discrepancies in the expression of carbon isotope change among substrates are almost always revealed. These differences in magnitude, pace, and pattern of change can complicate interpretations of global carbon redistribution, but under ideal circumstances can also provide additional information on changes in specific environmental and biogeochemical systems that accompanied the global events. Here we evaluate possible environmental influences on new terrestrial records of the negative carbon isotope excursions (CIEs) associated with multiple hyperthermals of the Early Eocene, which show a common pattern of amplified carbon isotope change in terrestrial paleosol carbonate records relative to that recorded in marine substrates. Scaling relationships between climate and carbon-cycle proxies suggest that that the climatic (temperature) impact of each event scaled proportionally with the magnitude of its marine CIE, likely implying that all events involved release of reduced carbon with a similar isotopic composition. Amplification of the terrestrial CIEs, however, does not scale with event magnitude, being proportionally less for the first, largest event (the PETM). We conduct a sensitivity test of a coupled plant-soil carbon isotope model to identify conditions that could account for the observed CIE scaling. At least two possibilities consistent with independent lines of evidence emerge: first, varying effects of pCO2 change on photosynthetic carbon isotope discrimination under changing background pCO2, and second, contrasting changes in regional hydroclimate during the PETM and subsequent hyperthermals. These mechanisms have very different implications for the reconstruction of environmental conditions, and resolving the correct interpretation will require new, complimentary records of plant and soil conditions associated with the Early Eocene hyperthermals.
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Self-assembly of InAs ring complexes on InP substrates by droplet epitaxy
DOE Office of Scientific and Technical Information (OSTI.GOV)
Noda, T.; Mano, T.; Jo, M.
We report the self-assembly of InAs ring complexes on InP (100) substrates by droplet epitaxy. Single-ring, ring-disk complex, and concentric double-ring structures were formed by controlling the As beam flux and substrate temperature. A clear photoluminescence signal was detected in a sample where InAs rings were embedded in InGaAs.
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Purification of carbon nanotubes via selective heating
DOE Office of Scientific and Technical Information (OSTI.GOV)
Rogers, John A.; Wilson, William L.; Jin, Sung Hun
The present invention provides methods for purifying a layer of carbon nanotubes comprising providing a precursor layer of substantially aligned carbon nanotubes supported by a substrate, wherein the precursor layer comprises a mixture of first carbon nanotubes and second carbon nanotubes; selectively heating the first carbon nanotubes; and separating the first carbon nanotubes from the second carbon nanotubes, thereby generating a purified layer of carbon nanotubes. Devices benefiting from enhanced electrical properties enabled by the purified layer of carbon nanotubes are also described.
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Control of stain geometry by drop evaporation of surfactant containing dispersions.
Erbil, H Yildirim
2015-08-01
Control of stain geometry by drop evaporation of surfactant containing dispersions is an important topic of interest because it plays a crucial role in many applications such as forming templates on solid surfaces, in ink-jet printing, spraying of pesticides, micro/nano material fabrication, thin film coatings, biochemical assays, deposition of DNA/RNA micro-arrays, and manufacture of novel optical and electronic materials. This paper presents a review of the published articles on the diffusive drop evaporation of pure liquids (water), the surfactant stains obtained from evaporating drops that do not contain dispersed particles and deposits obtained from drops containing polymer colloids and carbon based particles such as carbon nanotubes, graphite and fullerenes. Experimental results of specific systems and modeling attempts are discussed. This review also has some special subtopics such as suppression of coffee-rings by surfactant addition and "stick-slip" behavior of evaporating nanosuspension drops. In general, the drop evaporation process of a surfactant/particle/substrate system is very complex since dissolved surfactants adsorb on both the insoluble organic/inorganic micro/nanoparticles in the drop, on the air/solution interface and on the substrate surface in different extends. Meanwhile, surfactant adsorbed particles interact with the substrate giving a specific contact angle, and free surfactants create a solutal Marangoni flow in the drop which controls the location of the particle deposition together with the rate of evaporation. In some cases, the presence of a surfactant monolayer at the air/solution interface alters the rate of evaporation. At present, the magnitude of each effect cannot be predicted adequately in advance and consequently they should be carefully studied for any system in order to control the shape and size of the final deposit. Copyright © 2014 Elsevier B.V. All rights reserved.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Hua, Tian; Wu, Dong; Ding, Wei
2012-10-15
Peroxisomes play an essential role in maintaining fatty acid homeostasis. Although mitochondria are also known to participate in the catabolism of fatty acids via β-oxidation, differences exist between the peroxisomal and mitochondrial β-oxidation. Only peroxisomes, but not mitochondrion, can shorten very long chain fatty acids. Here, we describe the crystal structure of a ternary complex of peroxisomal 2,4-dienoyl CoA reductases (pDCR) with hexadienoyl CoA and NADP, as a prototype for comparison with the mitochondrial 2,4-dienoyl CoA reductase (mDCR) to shed light on the differences between the enzymes from the two organelles at the molecular level. Unexpectedly, the structure of pDCRmore » refined to 1.84 Å resolution reveals the absence of the tyrosine-serine pair seen in the active site of mDCR, which together with a lysine and an asparagine have been deemed a hallmark of the SDR family of enzymes. Instead, aspartate hydrogen-bonded to the Cα hydroxyl via a water molecule seems to perturb the water molecule for protonation of the substrate. Our studies provide the first structural evidence for participation of water in the DCR-catalyzed reactions. Biochemical studies and structural analysis suggest that pDCRs can catalyze the shortening of six-carbon-long substrates in vitro. However, the Km values of pDCR for short chain acyl CoAs are at least 6-fold higher than those for substrates with 10 or more aliphatic carbons. Unlike mDCR, hinge movements permit pDCR to process very long chain polyunsaturated fatty acids.« less
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Multivariate regulation of soil CO2 and N2 O pulse emissions from agricultural soils.
Liang, Liyin L; Grantz, David A; Jenerette, G Darrel
2016-03-01
Climate and land-use models project increasing occurrence of high temperature and water deficit in both agricultural production systems and terrestrial ecosystems. Episodic soil wetting and subsequent drying may increase the occurrence and magnitude of pulsed biogeochemical activity, affecting carbon (C) and nitrogen (N) cycles and influencing greenhouse gas (GHG) emissions. In this study, we provide the first data to explore the responses of carbon dioxide (CO2 ) and nitrous oxide (N2 O) fluxes to (i) temperature, (ii) soil water content as percent water holding capacity (%WHC), (iii) substrate availability throughout, and (iv) multiple soil drying and rewetting (DW) events. Each of these factors and their interactions exerted effects on GHG emissions over a range of four (CO2 ) and six (N2 O) orders of magnitude. Maximal CO2 and N2 O fluxes were observed in environments combining intermediate %WHC, elevated temperature, and sufficient substrate availability. Amendments of C and N and their interactions significantly affected CO2 and N2 O fluxes and altered their temperature sensitivities (Q10 ) over successive DW cycles. C amendments significantly enhanced CO2 flux, reduced N2 O flux, and decreased the Q10 of both. N amendments had no effect on CO2 flux and increased N2 O flux, while significantly depressing the Q10 for CO2 , and having no effect on the Q10 for N2 O. The dynamics across DW cycles could be attributed to changes in soil microbial communities as the different responses to wetting events in specific group of microorganisms, to the altered substrate availabilities, or to both. The complex interactions among parameters influencing trace gas fluxes should be incorporated into next generation earth system models to improve estimation of GHG emissions. © 2015 John Wiley & Sons Ltd.
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NASA Astrophysics Data System (ADS)
Li, Detian; Cheng, Yongjun; Wang, Yongjun; Zhang, Huzhong; Dong, Changkun; Li, Da
2016-03-01
Vertically aligned carbon nanotube (CNT) arrays were fabricated by chemical vapor deposition (CVD) technique on different substrates. Microstructures and field emission characteristics of the as-grown CNT arrays were investigated systematically, and its application in ionization gauge was also evaluated preliminarily. The results indicate that the as-grown CNT arrays are vertically well-aligned relating to the substrate surfaces, but the CNTs grown on stainless steel substrate are longer and more crystalline than the ones grown on silicon wafer substrate. The field emission behaviors of the as-grown CNT arrays are strongly dependent upon substrate properties. Namely, the CNT array grown on stainless steel substrate has better field emission properties, including lower turn on and threshold fields, better emission stability and repeatability, compared with the one grown on silicon wafer substrate. The superior field emission properties of the CNT array grown on stainless steel substrate are mainly attributed to low contact resistance, high thermal conductivity, good adhesion strength, etc. In addition, the metrological behaviors of ionization gauge with the CNT array grown on stainless steel substrate as an electron source were investigated, and this novel cathode ionization gauge extends the lower limit of linear pressure measurement to 10-8 Pa, which is one order of magnitude lower than the result reported for the same of gauge with CNT cathode.
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NASA Astrophysics Data System (ADS)
Schmidt, Frauke; Koch, Boris P.; Witt, Matthias; Hinrichs, Kai-Uwe
2014-09-01
Dissolved organic matter (DOM) in marine sediments is a complex mixture of thousands of individual constituents that participate in biogeochemical reactions and serve as substrates for benthic microbes. Knowledge of the molecular composition of DOM is a prerequisite for a comprehensive understanding of the biogeochemical processes in sediments. In this study, interstitial water DOM was extracted with Rhizon samplers from a sediment core from the Black Sea and compared to the corresponding water-extractable organic matter fraction (<0.4 μm) obtained by Soxhlet extraction, which mobilizes labile particulate organic matter and DOM. After solid phase extraction (SPE) of DOM, samples were analyzed for the molecular composition by Fourier Transform Ion-Cyclotron Resonance Mass Spectrometry (FT-ICR MS) with electrospray ionization in negative ion mode. The average SPE extraction yield of the dissolved organic carbon (DOC) in interstitial water was 63%, whereas less than 30% of the DOC in Soxhlet-extracted organic matter was recovered. Nevertheless, Soxhlet extraction yielded up to 4.35% of the total sedimentary organic carbon, which is more than 30-times the organic carbon content of the interstitial water. While interstitial water DOM consisted primarily of carbon-, hydrogen- and oxygen-bearing compounds, Soxhlet extracts yielded more complex FT-ICR mass spectra with more peaks and higher abundances of nitrogen- and sulfur-bearing compounds. The molecular composition of both sample types was affected by the geochemical conditions in the sediment; elevated concentrations of HS- promoted the early diagenetic sulfurization of organic matter. The Soxhlet extracts from shallow sediment contained specific three- and four-nitrogen-bearing molecular formulas that were also detected in bacterial cell extracts and presumably represent proteinaceous molecules. These compounds decreased with increasing sediment depth while one- and two-nitrogen-bearing molecules increased, resulting in a higher similarity of both sample types in the deep sediment. In summary, Soxhlet extraction of sediments accessed a larger and more complex pool of organic matter than present in interstitial water DOM.
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Zarzycki, Jan; Fuchs, Georg
2011-01-01
Chloroflexus aurantiacus is a facultative autotrophic green nonsulfur bacterium that grows phototrophically in thermal springs and forms microbial mats with cyanobacteria. Cyanobacteria produce glycolate during the day (photorespiration) and excrete fermentation products at night. C. aurantiacus uses the 3-hydroxypropionate bi-cycle for autotrophic carbon fixation. This pathway was thought to be also suited for the coassimilation of various organic substrates such as glycolate, acetate, propionate, 3-hydroxypropionate, lactate, butyrate, or succinate. To test this possibility, we added these compounds at a 5 mM concentration to autotrophically pregrown cells. Although the provided amounts of H2 and CO2 allowed continuing photoautotrophic growth, cells immediately consumed most substrates at rates equaling the rate of autotrophic carbon fixation. Using [14C]acetate, half of the labeled organic carbon was incorporated into cell mass. Our data suggest that C. aurantiacus uses the 3-hydroxypropionate bi-cycle, together with the glyoxylate cycle, to channel organic substrates into the central carbon metabolism. Enzyme activities of the 3-hydroxypropionate bi-cycle were marginally affected when cells were grown heterotrophically with such organic substrates. The 3-hydroxypropionate bi-cycle in Chloroflexi is unique and was likely fostered in an environment in which traces of organic compounds can be coassimilated. Other bacteria living under oligotrophic conditions acquired genes of a rudimentary 3-hydroxypropionate bi-cycle, possibly for the same purpose. Examples are Chloroherpeton thalassium, Erythrobacter sp. strain NAP-1, Nitrococcus mobilis, and marine gammaproteobacteria of the OM60/NOR5 clade such as Congregibacter litoralis. PMID:21764971
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Enzymatic catalysis of anti-Baldwin ring closure in polyether biosynthesis.
Hotta, Kinya; Chen, Xi; Paton, Robert S; Minami, Atsushi; Li, Hao; Swaminathan, Kunchithapadam; Mathews, Irimpan I; Watanabe, Kenji; Oikawa, Hideaki; Houk, Kendall N; Kim, Chu-Young
2012-03-04
Polycyclic polyether natural products have fascinated chemists and biologists alike owing to their useful biological activity, highly complex structure and intriguing biosynthetic mechanisms. Following the original proposal for the polyepoxide origin of lasalocid and isolasalocid and the experimental determination of the origins of the oxygen and carbon atoms of both lasalocid and monensin, a unified stereochemical model for the biosynthesis of polyether ionophore antibiotics was proposed. The model was based on a cascade of nucleophilic ring closures of postulated polyepoxide substrates generated by stereospecific oxidation of all-trans polyene polyketide intermediates. Shortly thereafter, a related model was proposed for the biogenesis of marine ladder toxins, involving a series of nominally disfavoured anti-Baldwin, endo-tet epoxide-ring-opening reactions. Recently, we identified Lsd19 from the Streptomyces lasaliensis gene cluster as the epoxide hydrolase responsible for the epoxide-opening cyclization of bisepoxyprelasalocid A to form lasalocid A. Here we report the X-ray crystal structure of Lsd19 in complex with its substrate and product analogue to provide the first atomic structure-to our knowledge-of a natural enzyme capable of catalysing the disfavoured epoxide-opening cyclic ether formation. On the basis of our structural and computational studies, we propose a general mechanism for the enzymatic catalysis of polyether natural product biosynthesis. © 2012 Macmillan Publishers Limited. All rights reserved
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Okamoto, Ken; Matsumoto, Koji; Hille, Russ; Eger, Bryan T.; Pai, Emil F.; Nishino, Takeshi
2004-01-01
Molybdenum is widely distributed in biology and is usually found as a mononuclear metal center in the active sites of many enzymes catalyzing oxygen atom transfer. The molybdenum hydroxylases are distinct from other biological systems catalyzing hydroxylation reactions in that the oxygen atom incorporated into the product is derived from water rather than molecular oxygen. Here, we present the crystal structure of the key intermediate in the hydroxylation reaction of xanthine oxidoreductase with a slow substrate, in which the carbon–oxygen bond of the product is formed, yet the product remains complexed to the molybdenum. This intermediate displays a stable broad charge–transfer band at ≈640 nm. The crystal structure of the complex indicates that the catalytically labile Mo—OH oxygen has formed a bond with a carbon atom of the substrate. In addition, the Mo⋕S group of the oxidized enzyme has become protonated to afford Mo—SH on reduction of the molybdenum center. In contrast to previous assignments, we find this last ligand at an equatorial position in the square-pyramidal metal coordination sphere, not the apical position. A water molecule usually seen in the active site of the enzyme is absent in the present structure, which probably accounts for the stability of this intermediate toward ligand displacement by hydroxide. PMID:15148401
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Zhang, Jing; Zhang, Baogang; Tian, Caixing; Ye, Zhengfang; Liu, Ye; Lei, Zhongfang; Huang, Wenli; Feng, Chuanping
2013-06-01
Microbial fuel cells (MFCs), representing a promising method to treat combined pollutants with energy recovery, were utilized to remove sulfide and recover power with corn stover filtrate (CSF) as the co-substrate in present study. A maximum power density of 744 mW/m(2) was achieved with sulfide removal of 91% during 72 h operation when the CSF concentrations (mg-COD/l) and the electrolyte conductivity were set at 800 mg/l and 10.06 mS/cm, respectively, while almost 52% COD was removed due to the microbial degradation of CSF to the volatile organic carbons. CSF concentrations and electrolyte conductivities had significant effects on the performance of the MFCs. Simultaneous removals of inorganic pollutant and complex organic compounds with electricity generation in MFCs are reported for the first time. These results provide a good reference for multiple contaminations treatment especially sulfide containing wastewaters based on the MFC technology. Copyright © 2013 Elsevier Ltd. All rights reserved.
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Prenafeta-Boldú, F. X.; Vervoort, J.; Grotenhuis, J. T. C.; van Groenestijn, J. W.
2002-01-01
The soil fungus Cladophialophora sp. strain T1 (= ATCC MYA-2335) was capable of growth on a model water-soluble fraction of gasoline that contained all six BTEX components (benzene, toluene, ethylbenzene, and the xylene isomers). Benzene was not metabolized, but the alkylated benzenes (toluene, ethylbenzene, and xylenes) were degraded by a combination of assimilation and cometabolism. Toluene and ethylbenzene were used as sources of carbon and energy, whereas the xylenes were cometabolized to different extents. o-Xylene and m-xylene were converted to phthalates as end metabolites; p-xylene was not degraded in complex BTEX mixtures but, in combination with toluene, appeared to be mineralized. The metabolic profiles and the inhibitory nature of the substrate interactions indicated that toluene, ethylbenzene, and xylene were degraded at the side chain by the same monooxygenase enzyme. Our findings suggest that soil fungi could contribute significantly to bioremediation of BTEX pollution. PMID:12039717
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Orotidine 5'-Monophosphate Decarboxylase: Probing the Limits of the Possible for Enzyme Catalysis.
Richard, John P; Amyes, Tina L; Reyes, Archie C
2018-04-17
The mystery associated with catalysis by what were once regarded as protein black boxes, diminished with the X-ray crystallographic determination of the three-dimensional structures of enzyme-substrate complexes. The report that several high-resolution X-ray crystal structures of orotidine 5'-monophosphate decarboxylase (OMPDC) failed to provide a consensus mechanism for enzyme-catalyzed decarboxylation of OMP to form uridine 5'-monophosphate, therefore, provoked a flurry of controversy. This controversy was fueled by the enormous 10 23 -fold rate acceleration for this enzyme, which had " jolted many biochemists' assumptions about the catalytic potential of enzymes." Our studies on the mechanism of action of OMPDC provide strong evidence that catalysis by this enzyme is not fundamentally different from less proficient catalysts, while highlighting important architectural elements that enable a peak level of performance. Many enzymes undergo substrate-induced protein conformational changes that trap their substrates in solvent occluded protein cages, but the conformational change induced by ligand binding to OMPDC is incredibly complex, as required to enable the development of 22 kcal/mol of stabilizing binding interactions with the phosphodianion and ribosyl substrate fragments of OMP. The binding energy from these fragments is utilized to activate OMPDC for catalysis of decarboxylation at the orotate fragment of OMP, through the creation of a tight, catalytically active, protein cage from the floppy, open, unliganded form of OMPDC. Such utilization of binding energy for ligand-driven conformational changes provides a general mechanism to obtain specificity in transition state binding. The rate enhancement that results from the binding of carbon acid substrates to enzymes is partly due to a reduction in the carbon acid p K a that is associated with ligand binding. The binding of UMP to OMPDC results in an unusually large >12 unit decrease in the p K a = 29 for abstraction of the C-6 substrate hydrogen, due to stabilization of an enzyme-bound vinyl carbanion, which is also an intermediate of OMPDC-catalyzed decarboxylation. The protein-ligand interactions operate to stabilize the vinyl carbanion at the enzyme active site compared to aqueous solution, rather than to stabilize the transition state for the concerted electrophilic displacement of CO 2 by H + that avoids formation of this reaction intermediate. There is evidence that OMPDC induces strain into the bound substrate. The interaction between the amide side chain of Gln-215 from the phosphodianion gripper loop and the hydroxymethylene side chain of Ser-154 from the pyrimidine umbrella of ScOMPDC position the amide side chain to interact with the phosphodianion of OMP. There are no direct stabilizing interactions between dianion gripper protein side chains Gln-215, Tyr-217, and Arg-235 and the pyrimidine ring at the decarboxylation transition state. Rather these side chains function solely to hold OMPDC in the catalytically active closed conformation. The hydrophobic side chains that line the active site of OMPDC in the region of the departing CO 2 product may function to stabilize the decarboxylation transition state by providing hydrophobic solvation of this product.
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Conductive Carbon Nanotube Inks for Use with Desktop Inkjet Printing Technology
NASA Technical Reports Server (NTRS)
Roberson, Luke; Williams, Martha; Tate, LaNetra; Fortier, Craig; Smith, David; Davia, Kyle; Gibson, Tracy; Snyder, Sarah
2013-01-01
Inkjet printing is a common commercial process. In addition to the familiar use in printing documents from computers, it is also used in some industrial applications. For example, wire manufacturers are required by law to print the wire type, gauge, and safety information on the exterior of each foot of manufactured wire, and this is typically done with inkjet or laser printers. The goal of this work was the creation of conductive inks that can be applied to a wire or flexible substrates via inkjet printing methods. The use of inkjet printing technology to print conductive inks has been in testing for several years. While researchers have been able to get the printing system to mechanically work, the application of conductive inks on substrates has not consistently produced adequate low resistances in the kilohm range. Conductive materials can be applied using a printer in single or multiple passes onto a substrate including textiles, polymer films, and paper. The conductive materials are composed of electrical conductors such as carbon nanotubes (including functionalized carbon nanotubes and metal-coated carbon nanotubes); graphene, a polycyclic aromatic hydrocarbon (e.g., pentacene and bisperipentacene); metal nanoparticles; inherently conductive polymers (ICP); and combinations thereof. Once the conductive materials are applied, the materials are dried and sintered to form adherent conductive materials on the substrate. For certain formulations, increased conductivity can be achieved by printing on substrates supported by low levels of magnetic field alignment. The adherent conductive materials can be used in applications such as damage detection, dust particle removal, smart coating systems, and flexible electronic circuitry. By applying alternating layers of different electrical conductors to form a layered composite material, a single homogeneous layer can be produced with improved electrical properties. It is believed that patterning alternate layers of different conductors may improve electrical pathways through alignment of the conductors and band gap optimization. One feature of this innovation is that flexible conductive traces could be accomplished with a conductive ink having a surface resistivity of less than 10 ohms/square. Another result was that a composite material comprising a mixture of carbon nanotubes and metallic nanoparticles could be applied by inkjet printing to flexible substrates, and the resulting applied material was one to two orders of magnitude more conductive than a material made by printing inks containing carbon nanotubes alone.
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NASA Astrophysics Data System (ADS)
Pape, Ellen; van Oevelen, Dick; Moodley, Leon; Soetaert, Karline; Vanreusel, Ann
2013-10-01
Sediments sampled from the Galicia Bank seamount and the adjacent slope (northeast Atlantic), and from a western Mediterranean slope site, were injected onboard with 13C-enriched dissolved organic matter (DOM) to evaluate nematode feeding strategies and the fate of DOM carbon in different benthic environments. We hypothesized that nematode 13C label assimilation resulted from either direct DOM uptake or feeding on 13C labeled bacteria. Slope sediments were injected with glucose ("simple" DOM) or "complex" diatom-derived DOM to investigate the influence of DOM composition on carbon assimilation. The time-series (1, 7 and 14 days) experiment at the seamount site was the first study to reveal a higher 13C enrichment of nematodes than bacteria and sediments after 7 days. Although isotope dynamics indicated that both DOM and bacteria were plausible candidate food sources, the contribution to nematode secondary production and metabolic requirements (estimated from biomass-dependent respiration rates) was higher for bacteria than for DOM at all sites. The seamount nematode community showed higher carbon assimilation rates than the slope assemblages, which may reflect an adaptation to the food-poor environment. Our results suggested that the trophic importance of bacteria did not depend on the amount of labile sedimentary organic matter. Furthermore, there was a discrepancy between carbon assimilation rates observed in the experiments and the feeding type classification, based on buccal morphology. Sites with a similar feeding type composition (i.e. the northeast Atlantic sites) showed large differences in uptake, whilst the nematode assemblages at the two slope sites, which had a differing trophic structure, took up similar amounts of the DOM associated carbon. Our results did not indicate substantial differences in carbon processing related to the complexity of the DOM substrate. The quantity of processed carbon (5-42% of added DOM) was determined by the bacteria, and was primarily respired. The bulk of the added 13C-DOM was not ingested by the benthic biota under study, and a considerable fraction was possibly adsorbed onto the sediment grains.
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Enzyme microheterogeneous hydration and stabilization in supercritical carbon dioxide.
Silveira, Rodrigo L; Martínez, Julian; Skaf, Munir S; Martínez, Leandro
2012-05-17
Supercritical carbon dioxide is a promising green-chemistry solvent for many enzyme-catalyzed chemical reactions, yet the striking stability of some enzymes in such unconventional environments is not well understood. Here, we investigate the stabilization of the Candida antarctica Lipase B (CALB) in supercritical carbon dioxide-water biphasic systems using molecular dynamics simulations. The preservation of the enzyme structure and optimal activity depend on the presence of small amounts of water in the supercritical dispersing medium. When the protein is at least partially hydrated, water molecules bind to specific sites on the enzyme surface and prevent carbon dioxide from penetrating its catalytic core. Strikingly, water and supercritical carbon dioxide cover the protein surface quite heterogeneously. In the first solvation layer, the hydrophilic residues at the surface of the protein are able to pin down patches of water, whereas carbon dioxide solvates preferentially hydrophobic surface residues. In the outer solvation shells, water molecules tend to cluster predominantly on top of the larger water patches of the first solvation layer instead of spreading evenly around the remainder of the protein surface. For CALB, this exposes the substrate-binding region of the enzyme to carbon dioxide, possibly facilitating diffusion of nonpolar substrates into the catalytic funnel. Therefore, by means of microheterogeneous solvation, enhanced accessibility of hydrophobic substrates to the active site can be achieved, while preserving the functional structure of the enzyme. Our results provide a molecular picture on the nature of the stability of proteins in nonaqueous media.
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21 CFR 520.1802a - Piperazine-carbon disulfide complex suspension.
Code of Federal Regulations, 2010 CFR
2010-04-01
... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Piperazine-carbon disulfide complex suspension... § 520.1802a Piperazine-carbon disulfide complex suspension. (a) Specifications. Each fluid ounce of suspension contains 7.5 grams of piperazine-carbon disulfide complex. The piperazine-carbon disulfide complex...
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21 CFR 520.1802a - Piperazine-carbon disulfide complex suspension.
Code of Federal Regulations, 2011 CFR
2011-04-01
... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Piperazine-carbon disulfide complex suspension... § 520.1802a Piperazine-carbon disulfide complex suspension. (a) Specifications. Each fluid ounce of suspension contains 7.5 grams of piperazine-carbon disulfide complex. The piperazine-carbon disulfide complex...
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NASA Astrophysics Data System (ADS)
Winchester, Andrew; Ghosh, Sujoy; Turner, Ben; Zhang, X. F.; Talapatra, Saikat
2012-02-01
In this work we will present the use of Multi Walled Carbon Nanotubes (MWNT) directly grown on inconel substrates via chemical vapor deposition, as electrode materials for electrochemical double layer capacitors (EDLC). The performance of the MWNT EDLC electrodes were investigated using two electrolytes, an organic electrolyte, tetraethylammonium tetrafluoroborate in propylene carbonate (Et4NBF4 in PC), and a room temperature ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM-PF6). Cyclic voltammetry, galvanostatic charge-discharge, and electrochemical impedance spectroscopy measurements to obtain values for the capacitance and internal resistance of these devices will be presented and compared.
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Density controlled carbon nanotube array electrodes
Ren, Zhifeng F [Newton, MA; Tu, Yi [Belmont, MA
2008-12-16
CNT materials comprising aligned carbon nanotubes (CNTs) with pre-determined site densities, catalyst substrate materials for obtaining them and methods for forming aligned CNTs with controllable densities on such catalyst substrate materials are described. The fabrication of films comprising site-density controlled vertically aligned CNT arrays of the invention with variable field emission characteristics, whereby the field emission properties of the films are controlled by independently varying the length of CNTs in the aligned array within the film or by independently varying inter-tubule spacing of the CNTs within the array (site density) are disclosed. The fabrication of microelectrode arrays (MEAs) formed utilizing the carbon nanotube material of the invention is also described.
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Rapid Annealing Of Amorphous Hydrogenated Carbon
NASA Technical Reports Server (NTRS)
Alterovitz, Samuel A.; Pouch, John J.; Warner, Joseph D.
1989-01-01
Report describes experiments to determine effects of rapid annealing on films of amorphous hydrogenated carbon. Study represents first efforts to provide information for applications of a-C:H films where rapid thermal processing required. Major finding, annealing causes abrupt increase in absorption and concomitant decrease in optical band gap. Most of change occurs during first 20 s, continues during longer annealing times. Extend of change increases with annealing temperature. Researchers hypothesize abrupt initial change caused by loss of hydrogen, while gradual subsequent change due to polymerization of remaining carbon into crystallites or sheets of graphite. Optical band gaps of unannealed specimens on silicon substrates lower than those of specimens on quartz substrates.
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NASA Astrophysics Data System (ADS)
Murata, H.; Toko, K.; Saitoh, N.; Yoshizawa, N.; Suemasu, T.
2017-01-01
Multilayer graphene (MLG) growth on arbitrary substrates is desired for incorporating carbon wiring and heat spreaders into electronic devices. We investigated the metal-induced layer exchange growth of a sputtered amorphous C layer using Ni as a catalyst. A MLG layer uniformly formed on a SiO2 substrate at 600 °C by layer exchange between the C and Ni layers. Raman spectroscopy and electron microscopy showed that the resulting MLG layer was highly oriented and contained relatively few defects. The present investigation will pave the way for advanced electronic devices integrated with carbon materials.
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2007-02-21
dependent upon the carbon gross growth efficiency ( GGE ) and the C:N:P ratio of the organic substrate. This calculation and its structural...product of the temperature adjusted maximum gross carbon assimilation rate, the carbon gross growth efficiency ( GGE ), and the uptake kinetics for DOC...substrate: max T 4 [ ]( ) [ ]Cb b DOCg g GGE n DOC ⎛ ⎞ = ⎜ ⎟+⎝ ⎠ (21) and ( )( 30)max T m30 m30min[ , ]Kt Tb b bg g g e −= (22) To
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Enhancing the Properties of Carbon and Gold Substrates by Surface Modification
DOE Office of Scientific and Technical Information (OSTI.GOV)
Harnisch, Jennifer Anne
2001-01-01
The properties of both carbon and gold substrates are easily affected by the judicious choice of a surface modification protocol. Several such processes for altering surface composition have been published in literature. The research presented in this thesis primarily focuses on the development of on-column methods to modify carbon stationary phases used in electrochemically modulated liquid chromatography (EMLC). To this end, both porous graphitic carbon (PGC) and glassy carbon (GC) particles have been modified on-column by the electroreduction of arenediazonium salts and the oxidation of arylacetate anions (the Kolbe reaction). Once modified, the carbon stationary phases show enhanced chromatographic performancemore » both in conventional liquid chromatographic columns and EMLC columns. Additionally, one may also exploit the creation of aryl films to by electroreduction of arenediazonium salts in the creation of nanostructured materials. The formation of mercaptobenzene film on the surface of a GC electrode provides a linking platform for the chemisorption of gold nanoparticles. After deposition of nanoparticles, the surface chemistry of the gold can be further altered by self-assembled monolayer (SAM) formation via the chemisorption of a second thiol species. Finally, the properties of gold films can be altered such that they display carbon-like behavior through the formation of benzenehexathiol (BHT) SAMs. BHT chemisorbs to the gold surface in a previously unprecedented planar fashion. Carbon and gold substrates can be chemically altered by several methodologies resulting in new surface properties. The development of modification protocols and their application in the analytical arena is considered herein.« less
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Oxidation-Resistant Coating For Bipolar Lead/Acid Battery
NASA Technical Reports Server (NTRS)
Bolstad, James J.
1993-01-01
Cathode side of bipolar substrate coated with nonoxidizable conductive layer. Coating prepared as water slurry of aqueous dispersion of polyethylene copolymer plus such conductive fillers as tin oxide, titanium, tantalum, or tungsten oxide. Applied easily to substrate of polyethylene carbon plastic. As slurry dries, conductive, oxidation-resistant coating forms on positive side of substrate.
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NASA Technical Reports Server (NTRS)
Biegert, L. L.
2001-01-01
Because of the 1990 Clean Air Act Amendment (CAAA) many chlorinated solvents used in the aerospace industry are being phased out. Replacement of the ODC (ozone-depleting chemicals) with less volatile, non-ozone depleting cleaners has been extensively studied over the past seven years at Thiokol Propulsion, a Division of Cordant Technologies, Inc. The down selection of ODC replacement cleaners has been based on several factors including the diffusion evaporation of the cleaners in selected substrates. Methodologies were developed to evaluate the cleaner content in substrates. Methods of cutting thin slices of material (microtoming) were combined with GC/MS (gas chromatography/mass spectroscopy) analysis. Substrates evaluated in this study include potential solid rocket motor materials: ASNBR (asbestos-filled nitrile butadiene rubber) and CFEPDM (carbon-filled ethylene propylene dimonomer) insulation and glass (GCP), carbon (CCP) and silica (SCP) cloth phenolic substrates with fibers either parallel (0 deg) or perpendicular (90 deg) to the surface. Residue profiles indicate both cleaner and substrate composition affect the diffusion and subsequent evaporation of the cleaner from the substrate surface.
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Impact of substrate off-angle on the m-plane GaN Schottky diodes
NASA Astrophysics Data System (ADS)
Yamada, Hisashi; Chonan, Hiroshi; Takahashi, Tokio; Shimizu, Mitsuaki
2018-04-01
We investigated the effects of the substrate off-angle on the m-plane GaN Schottky diodes. GaN epitaxial layers were grown by metal-organic chemical vapor deposition on m-plane GaN substrates having an off-angle of 0.1, 1.1, 1.7, or 5.1° toward [000\\bar{1}]. The surface of the GaN epitaxial layers on the 0.1°-off substrate consisted of pyramidal hillocks and contained oxygen (>1017 cm-3) and carbon (>1016 cm-3) impurities. The residual carbon and oxygen impurities decreased to <1016 cm-3 when the off-angle of the m-plane GaN substrate was increased. The leakage current of the 0.1°-off m-plane GaN Schottky diodes originated from the +c facet of the pyramidal hillocks. The leakage current was efficiently suppressed through the use of an off-angle that was observed to be greater than 1.1°. The off-angle of the m-plane GaN substrate is critical in obtaining high-performance Schottky diodes.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Blaszczyk, Jaroslaw; Lu, Zhenwei; Li, Yue
2014-09-01
To understand the structural basis for the biochemical differences and further investigate the catalytic mechanism of DHNA, we have determined the structure of EcDHNA complexed with NP at 1.07-Å resolution [PDB:2O90], built an atomic model of EcDHNA complexed with the substrate DHNP, and performed molecular dynamics (MD) simulation analysis of the substrate complex. EcDHNA has the same fold as SaDHNA and also forms an octamer that consists of two tetramers, but the packing of one tetramer with the other is significantly different between the two enzymes. Furthermore, the structures reveal significant differences in the vicinity of the active site, particularlymore » in the loop that connects strands β3 and β4, mainly due to the substitution of nearby residues. The building of an atomic model of the complex of EcDHNA and the substrate DHNP and the MD simulation of the complex show that some of the hydrogen bonds between the substrate and the enzyme are persistent, whereas others are transient. The substrate binding model and MD simulation provide the molecular basis for the biochemical behaviors of the enzyme, including noncooperative substrate binding, indiscrimination of a pair of epimers as the substrates, proton wire switching during catalysis, and formation of epimerization product.« less
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Microspheres and their methods of preparation
Bose, Anima B; Yang, Junbing
2015-03-24
Carbon microspheres are doped with boron to enhance the electrical and physical properties of the microspheres. The boron-doped carbon microspheres are formed by a CVD process in which a catalyst, carbon source and boron source are evaporated, heated and deposited onto an inert substrate.
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Local electric and electro-chemical investigations of cyanobacteria films
NASA Astrophysics Data System (ADS)
Marlière, C.; Ramonda, M.; de Wit, R.
2009-12-01
Carbonate reservoirs are submitted to microbial metabolic processes promoting either the precipitation or the dissolution of calcium carbonate, especially in network of fractures and fault zones. Such phenomena may act as a seal during fault zone evolution and, later, reservoir production, modifying greatly the connectivity of fractures, permeability structure and drainage in the vicinity of otherwise major fluid conduits. Several laboratory studies have demonstrated the utility of geophysical methods such as complex electrical conductivity ones for the investigation of microbial-induced changes in porous geologic media. The primary suggestion of these studies was that temporal variations in the geophysical signatures corresponded with microbial-induced changes in the geologic media. However these variations of electric signal could be due to the combined effects of surface and volume contributions in the studied geologic medium. Surface effects such as attachment of the bacteria on substrate surface or reactions of carbonate precipitation/dissolution are crucial for concerns about local seal or opening or, more generally, modification in connectivity of fracture or porosity network in reservoirs. That is why we have launched a new study in order to clearly distinguish surface effects from volume one in electrical responses mediated by biogenic material. The surface processes of cell growth, attachment onto substrate surfaces and the reactions of carbonate precipitation/dissolution are studied by local (at sub-micrometric scales) methods such as atomic force microscopy (AFM) and scanning electrochemical potential microscopy (SECM) probing. These methods are carried out with living biological specimen under in situ conditions. Our first studies have been done by AFM in tunnelling mode on cyanobacteria (from CaCO3 rich sediments from a hyper saline lake). The immobilized bacteria have been scanned in ambient gaseous atmosphere by the nanometric AFM tip. In these conditions the cyanobacteria are recovered by a micrometric film of water. Both the roughness signal and electric current flowing from the tip to the substrate through the sample have simultaneously been measured for different values of electrical voltage. The measured electrical signals are weak but well above the noise level. Our observations of the local variations of the electro-chemical signal at a high spatial resolution (at sub-micrometer level) and at short acquisition times will be presented and discussed in detail.
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Surface segregation on Fe3%Si0.04%VC(100) single crystal surfaces
NASA Astrophysics Data System (ADS)
Uebing, C.; Viefhaus, H.
1990-10-01
Surface segregation phenomena on (100) oriented single crystal surfaces of the ferritic Fe-3%Si-0.04%V-C alloy were investigated by AES and LEED. At temperatures below 635 °C vanadium and carbon cosegregation is observed after prolonged heating. At thermodynamic equilibrium the substrate surface is saturated with the binary surface compound VC. The two-dimensional VC is epitaxially arranged on the substrate surface as indicated by LEED investigations. Its structure corresponds to the (100) plane of the three-dimensional VC with rocksalt structure. Sharp above 635 °C the surface compound VC is dissolved into the bulk. At higher temperatures the substrate surface is covered with segregated silicon forming a c(2 × 2) structure. This surface phase transition is reversible. Because of the low concentration and slow diffusion of vanadium, non-equilibrium surface states are formed as intermediates upon segregation of silicon and carbon. Below 500 °C a disordered graphite layer with a characteristical asymmetrical C Auger peak is observed on the substrate surface. Above 500 °C carbon segregation leads to the formation of an ordered c(2 × 2) structure with a symmetrical C Auger peak being characteristic for carbidic or atomically adsorbed species. At increasing temperatures silicon segregation takes place leading to a c(2 × 2) structure. Between silicon and carbon site competition is effective.
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Dioxygen in Polyoxometalate Mediated Reactions.
Weinstock, Ira A; Schreiber, Roy E; Neumann, Ronny
2018-03-14
In this review article, we consider the use of molecular oxygen in reactions mediated by polyoxometalates. Polyoxometalates are anionic metal oxide clusters of a variety of structures that are soluble in liquid phases and therefore amenable to homogeneous catalytic transformations. Often, they are active for electron transfer oxidations of a myriad of substrates and upon reduction can be reoxidized by molecular oxygen. For example, the phosphovanadomolybdate, H 5 PV 2 Mo 10 O 40 , can oxidize Pd(0) thereby enabling aerobic reactions catalyzed by Pd and H 5 PV 2 Mo 10 O 40 . In a similar vein, polyoxometalates can stabilize metal nanoparticles, leading to additional transformations. Furthermore, electron transfer oxidation of other substrates such as halides and sulfur-containing compounds is possible. More uniquely, H 5 PV 2 Mo 10 O 40 and its analogues can mediate electron transfer-oxygen transfer reactions where oxygen atoms are transferred from the polyoxometalate to the substrate. This unique property has enabled correspondingly unique transformations involving carbon-carbon, carbon-hydrogen, and carbon-metal bond activation. The pathway for the reoxidation of vanadomolybdates with O 2 appears to be an inner-sphere reaction, but the oxidation of one-electron reduced polyoxotungstates has been shown through intensive research to be an outer-sphere reaction. Beyond electron transfer and electron transfer-oxygen transfer aerobic transformations, there a few examples of apparent dioxygenase activity where both oxygen atoms are donated to a substrate.
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Modeling of substrate and inhibitor binding to phospholipase A2.
Sessions, R B; Dauber-Osguthorpe, P; Campbell, M M; Osguthorpe, D J
1992-09-01
Molecular graphics and molecular mechanics techniques have been used to study the mode of ligand binding and mechanism of action of the enzyme phospholipase A2. A substrate-enzyme complex was constructed based on the crystal structure of the apoenzyme. The complex was minimized to relieve initial strain, and the structural and energetic features of the resultant complex analyzed in detail, at the molecular and residue level. The minimized complex was then used as a basis for examining the action of the enzyme on modified substrates, binding of inhibitors to the enzyme, and possible reaction intermediate complexes. The model is compatible with the suggested mechanism of hydrolysis and with experimental data about stereoselectivity, efficiency of hydrolysis of modified substrates, and inhibitor potency. In conclusion, the model can be used as a tool in evaluating new ligands as possible substrates and in the rational design of inhibitors, for the therapeutic treatment of diseases such as rheumatoid arthritis, atherosclerosis, and asthma.
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NASA Astrophysics Data System (ADS)
Dieterich, Axel; Mörtl, Martin; Eckmann, Reiner
2004-07-01
Complex habitat structures can influence the foraging success of fish. Competition for food between fish species can therefore depend on the competitors' abilities to cope with structural complexity. In laboratory experiments, we comparatively assessed effects of zebra mussels (Dreissena polymorpha Pall.) on the foraging success of Eurasian perch (Perca fluviatilis L.) and ruffe (Gymnocephalus cernuus (L.)). In single-species and mixed-species experiments, the fish were fed caddisfly larvae (Tinodes waeneri (L.)) over complex (mussel-covered stones) and less-complex (bare stones) substrates. With intraspecific competition, food consumption by perch and ruffe decreased significantly when the complex substrate was used. With interspecific competition, food consumption by perch and ruffe did not change with substrate complexity, but perch clearly out-competed ruffe on both substrates. Zebra mussel beds provide a refuge for macrozoobenthos against predation by ruffe and probably also by perch. (
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Activation of the DnaK-ClpB Complex is Regulated by the Properties of the Bound Substrate.
Fernández-Higuero, Jose Angel; Aguado, Alejandra; Perales-Calvo, Judit; Moro, Fernando; Muga, Arturo
2018-04-11
The chaperone ClpB in bacteria is responsible for the reactivation of aggregated proteins in collaboration with the DnaK system. Association of these chaperones at the aggregate surface stimulates ATP hydrolysis, which mediates substrate remodeling. However, a question that remains unanswered is whether the bichaperone complex can be selectively activated by substrates that require remodeling. We find that large aggregates or bulky, native-like substrates activates the complex, whereas a smaller, permanently unfolded protein or extended, short peptides fail to stimulate it. Our data also indicate that ClpB interacts differently with DnaK in the presence of aggregates or small peptides, displaying a higher affinity for aggregate-bound DnaK, and that DnaK-ClpB collaboration requires the coupled ATPase-dependent remodeling activities of both chaperones. Complex stimulation is mediated by residues at the β subdomain of DnaK substrate binding domain, which become accessible to the disaggregase when the lid is allosterically detached from the β subdomain. Complex activation also requires an active NBD2 and the integrity of the M domain-ring of ClpB. Disruption of the M-domain ring allows the unproductive stimulation of the DnaK-ClpB complex in solution. The ability of the DnaK-ClpB complex to discrimínate different substrate proteins might allow its activation when client proteins require remodeling.
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Microbial community changes as a possible factor controlling carbon sequestration in subsoil
NASA Astrophysics Data System (ADS)
Strücker, Juliane; Jörgensen, Rainer Georg
2015-04-01
In order to gain more knowledge regarding the microbial community and their influence on carbon sequestration in subsoil two depth profiles with different soil organic carbon (SOC) concentrations were sampled. The SOC concentrations developed naturally due to deposition and erosion. This experiment offers the opportunity to investigate to which extend natural SOC availability or other subsoil specific conditions influence the composition and the functional diversity of the microbial community and in return if there is any evidence how the microbial community composition affects carbon sequestration under these conditions. Soil samples were taken at four different depths on two neighbouring arable sites; one Kolluvisol with high SOC concentrations (8-12 g/kg) throughout the profile and one Luvisol with low SOC concentrations (3-4 g/kg) below 30 cm depth. The multi substrate induced respiration (MSIR) method was used to identify shifts in the functional diversity of the microbial community along the depth profiles. Amino sugars Muramic Acid and Glucosamine were measured as indicators for bacterial and fungal residues and ergosterol was determined as marker for saprotrophic fungi. The results of the discriminant analysis of the respiration values obtained from the 17 substrates used in the MSIR show that the substrate use in subsoil is different from the substrate use in topsoil. The amino sugar analysis and the ratio of ergosterol to microbial biomass C indicate that the fungal dominance of the microbial community decreases with depth. The results from this study support previous findings, which also observed decreasing fungal dominance with depth. Furthermore the MSIR approach shows clearly that not only the composition of the microbial community but also their substrate use changes with depth. Thus, a different microbial community with altered substrate requirements could be an important reason for enhanced carbon sequestration in subsoil. The fact that the MSIR was also able to differentiate between the two sites proves the assumption that resources are an important factor controlling the functional diversity of the microbial community, as abiotic factors are very similar for the two profiles, but the sites show a different depth gradient for SOC.
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NASA Technical Reports Server (NTRS)
Curren, A. N.; Jensen, K. A.
1985-01-01
Experimentally determined values of true secondary electron emission and relative values of reflected primary electron yield for a range of primary electron beam energies and beam impingement angles are presented for a series of novel textured carbon surfaces on copper substrates. (All copper surfaces used in this study were oxygen-free, high-conductivity grade). The purpose of this investigation is to provide information necessary to develop high-efficiency multistage depressed collectors (MDC's) for microwave amplifier traveling-wave tubes (TWT's) for communications and aircraft applications. To attain the highest TWT signal quality and overall efficiency, the MDC electrode surface must have low secondary electron emission characteristics. While copper is the material most commonly used for MDC electrodes, it exhibits relatively high levels of secondary electron emission unless its surface is treated for emission control. The textured carbon surface on copper substrate described in this report is a particularly promising candidate for the MDC electrode application. Samples of textured carbon surfaces on copper substrates typical of three different levels of treatment are prepared and tested for this study. The materials are tested at primary electron beam energies of 200 to 2000 eV and at direct (0 deg) to near-grazing (85 deg) beam impingement angles. True secondary electron emission and relative reflected primary electron yield characteristics of the textured surfaces are compared with each other and with those of untreated copper. All the textured carbon surfaces on copper substrate tested exhibited sharply lower secondary electron emission characteristics than those of an untreated copper surface.
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Form and Function of Clostridium thermocellum Biofilms
Dumitrache, Alexandru; Allen, Grant; Liss, Steven N.; Lynd, Lee R.
2013-01-01
The importance of bacterial adherence has been acknowledged in microbial lignocellulose conversion studies; however, few reports have described the function and structure of biofilms supported by cellulosic substrates. We investigated the organization, dynamic formation, and carbon flow associated with biofilms of the obligately anaerobic cellulolytic bacterium Clostridium thermocellum 27405. Using noninvasive, in situ fluorescence imaging, we showed biofilms capable of near complete substrate conversion with a characteristic monolayered cell structure without an extracellular polymeric matrix typically seen in biofilms. Cell division at the interface and terminal endospores appeared throughout all stages of biofilm growth. Using continuous-flow reactors with a rate of dilution (2 h−1) 12-fold higher than the bacterium's maximum growth rate, we compared biofilm activity under low (44 g/liter) and high (202 g/liter) initial cellulose loading. The average hydrolysis rate was over 3-fold higher in the latter case, while the proportions of oligomeric cellulose hydrolysis products lost from the biofilm were 13.7% and 29.1% of the total substrate carbon hydrolyzed, respectively. Fermentative catabolism was comparable between the two cellulose loadings, with ca. 4% of metabolized sugar carbon being utilized for cell production, while 75.4% and 66.7% of the two cellulose loadings, respectively, were converted to primary carbon metabolites (ethanol, acetic acid, lactic acid, carbon dioxide). However, there was a notable difference in the ethanol-to-acetic acid ratio (g/g), measured to be 0.91 for the low cellulose loading and 0.41 for the high cellulose loading. The results suggest that substrate availability for cell attachment rather than biofilm colonization rates govern the efficiency of cellulose conversion. PMID:23087042
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Form and function of Clostridium thermocellum biofilms.
Dumitrache, Alexandru; Wolfaardt, Gideon; Allen, Grant; Liss, Steven N; Lynd, Lee R
2013-01-01
The importance of bacterial adherence has been acknowledged in microbial lignocellulose conversion studies; however, few reports have described the function and structure of biofilms supported by cellulosic substrates. We investigated the organization, dynamic formation, and carbon flow associated with biofilms of the obligately anaerobic cellulolytic bacterium Clostridium thermocellum 27405. Using noninvasive, in situ fluorescence imaging, we showed biofilms capable of near complete substrate conversion with a characteristic monolayered cell structure without an extracellular polymeric matrix typically seen in biofilms. Cell division at the interface and terminal endospores appeared throughout all stages of biofilm growth. Using continuous-flow reactors with a rate of dilution (2 h(-1)) 12-fold higher than the bacterium's maximum growth rate, we compared biofilm activity under low (44 g/liter) and high (202 g/liter) initial cellulose loading. The average hydrolysis rate was over 3-fold higher in the latter case, while the proportions of oligomeric cellulose hydrolysis products lost from the biofilm were 13.7% and 29.1% of the total substrate carbon hydrolyzed, respectively. Fermentative catabolism was comparable between the two cellulose loadings, with ca. 4% of metabolized sugar carbon being utilized for cell production, while 75.4% and 66.7% of the two cellulose loadings, respectively, were converted to primary carbon metabolites (ethanol, acetic acid, lactic acid, carbon dioxide). However, there was a notable difference in the ethanol-to-acetic acid ratio (g/g), measured to be 0.91 for the low cellulose loading and 0.41 for the high cellulose loading. The results suggest that substrate availability for cell attachment rather than biofilm colonization rates govern the efficiency of cellulose conversion.
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Wettability of eutectic NaLiCO3 salt on magnesium oxide substrates at 778 K
NASA Astrophysics Data System (ADS)
Li, Chuan; Li, Qi; Cao, Hui; Leng, Guanghui; Li, Yongliang; Wang, Li; Zheng, Lifang; Ding, Yulong
2018-06-01
We investigated the wetting behavior of a eutectic carbonate salt of NaLiCO3 on MgO substrates at an elevated temperature of 778 K by measuring contact angle with a sessile drop method. Both sintered and non-sintered MgO were prepared and used as the substrates. The sintered substrates were obtained by sintering compacted MgO powders at 500-1300 °C. For comparison purposes, a single crystal MgO substrate was also used in the work. The different sintering temperatures provided MgO substrates with different structures, allowing their effects on salt penetration and hence wettability and surface energy to be investigated. A scanning electron microscope equipped with energy dispersive spectrometry and an atomic force microscope were used to observe the morphology and structures of the MgO substrates as well as the salt penetration. The results showed a good wettability of the carbonate salt on both the sintered and non-sintered MgO substrates and the wettability depended strongly on the structure of the substrates. The non-sintered MgO substrate has a loose surface particle packing with large pores and crevices, leading to significant salt infiltration, and the corresponding contact angle was measured to be ∼25°. The contact angle of the salt on the sintered MgO substrates increased with an increase in the sintering temperature of the MgO substrate, and the contact angle of the salt on the single crystal substrate was the highest at ∼40°. The effect of the sintering temperature for making the MgO substrate could be linked to the surface energy, and the linkage is validated by the AFM measurements of the adhesion forces of the MgO substrates.
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Strange, Richard W; Hough, Michael A; Antonyuk, Svetlana V; Hasnain, S Samar
2012-01-01
Copper-zinc superoxide dismutase (SOD) is of fundamental importance to our understanding of oxidative damage. Its primary function is catalysing the dismutation of superoxide to O(2) and H(2)O(2). SOD also reacts with H(2)O(2), leading to the formation of a strong copper-bound oxidant species that can either inactivate the enzyme or oxidise other substrates. In the presence of bicarbonate (or CO(2)) and H(2)O(2), this peroxidase activity is enhanced and produces the carbonate radical. This freely diffusible reactive oxygen species is proposed as the agent for oxidation of large substrates that are too bulky to enter the active site. Here, we provide direct structural evidence, from a 2.15 Å resolution crystal structure, of (bi)carbonate captured at the active site of reduced SOD, consistent with the view that a bound carbonate intermediate could be formed, producing a diffusible carbonate radical upon reoxidation of copper. The bound carbonate blocks direct access of substrates to Cu(I), suggesting that an adjunct to the accepted mechanism of SOD catalysed dismutation of superoxide operates, with Cu(I) oxidation by superoxide being driven via a proton-coupled electron transfer mechanism involving the bound carbonate rather than the solvent. Carbonate is captured in a different site when SOD is oxidised, being located in the active site channel adjacent to the catalytically important Arg143. This is the probable route of diffusion from the active site following reoxidation of the copper. In this position, the carbonate is poised for re-entry into the active site and binding to the reduced copper.
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Strange, Richard W.; Hough, Michael A.; Antonyuk, Svetlana V.; Hasnain, S. Samar
2012-01-01
Copper-zinc superoxide dismutase (SOD) is of fundamental importance to our understanding of oxidative damage. Its primary function is catalysing the dismutation of superoxide to O2 and H2O2. SOD also reacts with H2O2, leading to the formation of a strong copper-bound oxidant species that can either inactivate the enzyme or oxidise other substrates. In the presence of bicarbonate (or CO2) and H2O2, this peroxidase activity is enhanced and produces the carbonate radical. This freely diffusible reactive oxygen species is proposed as the agent for oxidation of large substrates that are too bulky to enter the active site. Here, we provide direct structural evidence, from a 2.15 Å resolution crystal structure, of (bi)carbonate captured at the active site of reduced SOD, consistent with the view that a bound carbonate intermediate could be formed, producing a diffusible carbonate radical upon reoxidation of copper. The bound carbonate blocks direct access of substrates to Cu(I), suggesting that an adjunct to the accepted mechanism of SOD catalysed dismutation of superoxide operates, with Cu(I) oxidation by superoxide being driven via a proton-coupled electron transfer mechanism involving the bound carbonate rather than the solvent. Carbonate is captured in a different site when SOD is oxidised, being located in the active site channel adjacent to the catalytically important Arg143. This is the probable route of diffusion from the active site following reoxidation of the copper. In this position, the carbonate is poised for re-entry into the active site and binding to the reduced copper. PMID:22984565
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Composite catalysts supported on modified carbon substrates and methods of making the same
Popov, Branko N [Columbia, SC; Subramanian, Nalini [Kennesaw, GA; Colon-Mercado, Hector R [Columbia, SC
2009-11-17
A method of producing a composite carbon catalyst is generally disclosed. The method includes oxidizing a carbon precursor (e.g., carbon black). Optionally, nitrogen functional groups can be added to the oxidized carbon precursor. Then, the oxidized carbon precursor is refluxed with a non-platinum transitional metal precursor in a solution. Finally, the solution is pyrolyzed at a temperature of at least about 500.degree. C.
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Transfer and alignment of random single-walled carbon nanotube films by contact printing.
Liu, Huaping; Takagi, Daisuke; Chiashi, Shohei; Homma, Yoshikazu
2010-02-23
We present a simple method to transfer large-area random single-walled carbon nanotube (SWCNT) films grown on SiO(2) substrates onto another surface through a simple contact printing process. The transferred random SWCNT films can be assembled into highly ordered, dense regular arrays with high uniformity and reproducibility by sliding the growth substrate during the transfer process. The position of the transferred SWCNT film can be controlled by predefined patterns on the receiver substrates. The process is compatible with a variety of substrates, and even metal meshes for transmission electron microscopy (TEM) can be used as receiver substrates. Thus, suspended web-like SWCNT networks and aligned SWCNT arrays can be formed over the grids of TEM meshes, so that the structures of the transferred SWCNTs can be directly observed by TEM. This simple technique can be used to controllably transfer SWCNTs for property studies, for the fabrication of devices, or even as support films for TEM meshes.
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NASA Astrophysics Data System (ADS)
Torvinen, Katariina; Lehtimäki, Suvi; Keränen, Janne T.; Sievänen, Jenni; Vartiainen, Jari; Hellén, Erkki; Lupo, Donald; Tuukkanen, Sampo
2015-11-01
Pigment-cellulose nanofibril (PCN) composites were manufactured in a pilot line and used as a separator-substrate in printed graphene and carbon nanotube supercapacitors. The composites consisted typically of 80% pigment and 20% cellulose nanofibrils (CNF). This composition makes them a cost-effective alternative as a substrate for printed electronics at high temperatures that only very special plastic films can nowadays stand. The properties of these substrates can be varied within a relatively large range by the selection of raw materials and their relative proportions. A semi-industrial scale pilot line was successfully used to produce smooth, flexible, and nanoporous composites, and their performance was tested in a double functional separator-substrate element in supercapacitors. The nanostructural carbon films printed on the composite worked simultaneously as high surface area active electrodes and current collectors. Low-cost supercapacitors made from environmentally friendly materials have significant potential for use in flexible, wearable, and disposable low-end products. [Figure not available: see fulltext.
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Substrate independent approach for synthesis of graphene platelet networks.
Shashurin, A; Fang, X; Zemlyanov, D; Keidar, M
2017-06-23
Graphene platelet networks (GPNs) comprised of randomly oriented graphene flakes two to three atomic layers thick are synthesized using a novel plasma-based approach. The approach uses a substrate capable of withstanding synthesis temperatures around 800 °C, but is fully independent of the substrate material. The synthesis occurs directly on the substrate surface without the necessity of any additional steps. GPNs were synthesized on various substrate materials including silicon (Si), thermally oxidized Si (SiO 2 ), molybdenum (Mo), nickel (Ni) and copper (Cu), nickel-chromium (NiCr) alloy and alumina ceramics (Al 2 O 3 ). The mismatch between the atomic structures of sp 2 honeycomb carbon networks and the substrate material is fully eliminated shortly after the synthesis initiation, namely when about 100 nm thick deposits are formed on the substrate. GPN structures synthesized on a substrate at a temperature of about 800 °C are significantly more porous in comparison to the much denser packed amorphous carbon deposits synthesized at lower temperatures. The method proposed here can potentially revolutionize the area of electrochemical energy storage by offering a single-step direct approach for the manufacture of graphene-based electrodes for non-Faradaic supercapacitors. Mass production can be achieved using this method if a roll-to-roll system is utilized.
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Substrate independent approach for synthesis of graphene platelet networks
NASA Astrophysics Data System (ADS)
Shashurin, A.; Fang, X.; Zemlyanov, D.; Keidar, M.
2017-06-01
Graphene platelet networks (GPNs) comprised of randomly oriented graphene flakes two to three atomic layers thick are synthesized using a novel plasma-based approach. The approach uses a substrate capable of withstanding synthesis temperatures around 800 °C, but is fully independent of the substrate material. The synthesis occurs directly on the substrate surface without the necessity of any additional steps. GPNs were synthesized on various substrate materials including silicon (Si), thermally oxidized Si (SiO2), molybdenum (Mo), nickel (Ni) and copper (Cu), nickel-chromium (NiCr) alloy and alumina ceramics (Al2O3). The mismatch between the atomic structures of sp2 honeycomb carbon networks and the substrate material is fully eliminated shortly after the synthesis initiation, namely when about 100 nm thick deposits are formed on the substrate. GPN structures synthesized on a substrate at a temperature of about 800 °C are significantly more porous in comparison to the much denser packed amorphous carbon deposits synthesized at lower temperatures. The method proposed here can potentially revolutionize the area of electrochemical energy storage by offering a single-step direct approach for the manufacture of graphene-based electrodes for non-Faradaic supercapacitors. Mass production can be achieved using this method if a roll-to-roll system is utilized.
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Growing Aligned Carbon Nanotubes for Interconnections in ICs
NASA Technical Reports Server (NTRS)
Li, Jun; Ye, Qi; Cassell, Alan; Ng, Hou Tee; Stevens, Ramsey; Han, Jie; Meyyappan, M.
2005-01-01
A process for growing multiwalled carbon nanotubes anchored at specified locations and aligned along specified directions has been invented. Typically, one would grow a number of the nanotubes oriented perpendicularly to a silicon integrated-circuit (IC) substrate, starting from (and anchored on) patterned catalytic spots on the substrate. Such arrays of perpendicular carbon nanotubes could be used as electrical interconnections between levels of multilevel ICs. The process (see Figure 1) begins with the formation of a layer, a few hundred nanometers thick, of a compatible electrically insulating material (e.g., SiO(x) or Si(y)N(z) on the silicon substrate. A patterned film of a suitable electrical conductor (Al, Mo, Cr, Ti, Ta, Pt, Ir, or doped Si), having a thickness between 1 nm and 2 m, is deposited on the insulating layer to form the IC conductor pattern. Next, a catalytic material (usually, Ni, Fe, or Co) is deposited to a thickness between 1 and 30 nm on the spots from which it is desired to grow carbon nanotubes. The carbon nanotubes are grown by plasma-enhanced chemical vapor deposition (PECVD). Unlike the matted and tangled carbon nanotubes grown by thermal CVD, the carbon nanotubes grown by PECVD are perpendicular and freestanding because an electric field perpendicular to the substrate is used in PECVD. Next, the free space between the carbon nanotubes is filled with SiO2 by means of CVD from tetraethylorthosilicate (TEOS), thereby forming an array of carbon nanotubes embedded in SiO2. Chemical mechanical polishing (CMP) is then performed to remove excess SiO2 and form a flat-top surface in which the outer ends of the carbon nanotubes are exposed. Optionally, depending on the application, metal lines to connect selected ends of carbon nanotubes may be deposited on the top surface. The top part of Figure 2 is a scanning electron micrograph (SEM) of carbon nanotubes grown, as described above, on catalytic spots of about 100 nm diameter patterned by electron-beam lithography. These and other nanotubes were found to have lengths ranging from 2 to 10 m and diameters ranging from 30 to 200 nm, the exact values of length depending on growth times and conditions and the exact values of diameter depending on the diameters and thicknesses of the catalyst spots. The bottom part of Figure 2 is an SEM of an embedded array of carbon nanotubes after CMP.
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A facile method to align carbon nanotubes on polymeric membrane substrate
Zhao, Haiyang; Zhou, Zhijun; Dong, Hang; Zhang, Lin; Chen, Huanlin; Hou, Lian
2013-01-01
The alignment of carbon nanotubes (CNT) is the fundamental requirement to ensure their excellent functions but seems to be desolated in recent years. A facile method, hot-press combined with peel-off (HPPO), is introduced here, through which CNT can be successfully vertically aligned on the polymeric membrane substrate. Shear force and mechanical stretch are proposed to be the main forces to align the tubes perpendicular to the substrate surface during the peel-off process. The alignment of CNT keeps its orientation in a thin hybrid membrane by dip-coating cellulose acetate dope solution. It is expected that the stable alignment of CNT by HPPO would contribute to the realization of its potential applications. PMID:24326297