Search NASA⌕ Search

SEARCH · Search NASA

Results for “organic substrate”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 307 records · Page 17

Pore-scale view of microbial turnover: combining 14 C imaging, μCT, and zymography after adding soluble carbon to soil pores of specific sizes

The location of microorganisms and substrates within soil pore networks plays a crucial role for organic carbon (C) processing, its microbial utilization and turnover, and has direct consequences for C and nutrient cycling. An optimal approach to quantify responses to new C inputs from microorganisms residing in specific pores is the addition of new C to pores of target sizes in undisturbed soil cores. We used the matric potential approach to add 14 C labeled glucose to small (< 40 μm, root free) or large (60-180 μm, potentially inhabited by roots) pores of undisturbed soil cores. Localization of glucose-derived C via 14 C imaging was related to pore size distributions and connectivity, characterized via X-ray computed micro-tomography (μCT), and to β-glucosidase activity, characterized via zymography. After two-week incubations, 1.3 times more glucose was mineralized ( 14 CO 2 ) when it was added to the large pores, however more 14 C remained in microbial biomass when glucose was added to the small pores. Consequently, while utilizing the same amounts of easily available C, the microorganisms localized in the large pores had faster turnover compared to microorganisms in small pores. Stronger associations between β-glucosidase activity and glucose-derived C were observed when glucose was added to the large pores. We conclude that 1) the matric potential approach allows placing, albeit not exactly, soluble substrates into pores of target diameter range, and 2) microorganisms localized in large pores respond to new C inputs with faster turnover, greater growth, and more intensive enzyme production compared to those inhabiting the small pores.

54 ENVIRONMENTAL SCIENCES↗

Guanidine Soaps As Vehicles For Coating Ceramic Fibers

Soaps made from strong organic base guanidine and organic fatty acids serve as vehicles and binders for coating ceramic fibers, various smooth substrates, and other problematic surfaces with thin precious-metal or metal-oxide films. Films needed to serve as barriers to diffusion in fiber/matrix ceramic composite materials. Guanidine soaps entirely organic and burn off, leaving no residues.

Philipp, Warren H.↗

Automated microbial metabolism laboratory

The design and rationale of an advanced labeled release experiment based on single addition of soil and multiple sequential additions of media into each of four test chambers are outlined. The feasibility for multiple addition tests was established and various details of the methodology were studied. The four chamber battery of tests include: (1) determination of the effect of various atmospheric gases and selection of that gas which produces an optimum response; (2) determination of the effect of incubation temperature and selection of the optimum temperature for performing Martian biochemical tests; (3) sterile soil is dosed with a battery of C-14 labeled substrates and subjected to experimental temperature range; and (4) determination of the possible inhibitory effects of water on Martian organisms is performed initially by dosing with 0.01 ml and 0.5 ml of medium, respectively. A series of specifically labeled substrates are then added to obtain patterns in metabolic 14CO2 (C-14)O2 evolution.

Source record↗

Metabolic Redox Coupling Controls Methane Production in Permafrost‐Affected Peatlands Through Organic Matter Quality‐Dependent Energy Allocation

ABSTRACT Permafrost thaw represents one of Earth's largest climate feedback risks, potentially releasing vast carbon (C) stores as greenhouse gases (GHG). However, our ability to predict emissions remains limited by poor understanding of how changing organic matter (OM) composition affects microbial carbon processing. We test a metabolism‐centered redox framework, which views microbial processes as coupled oxidative‐reductive reactions, to mechanistically explain how organic matter metabolite quality controls greenhouse gas production in permafrost‐affected peatland ecosystems. Rather than relying solely on geochemical redox measurements, our approach examines how microbes balance electron flow through metabolic pathways. Using active layer peat (9–19 cm) from contrasting environments (bog and fen), we employed multi‐omics approaches, including metabolomics, metagenomics, and metatranscriptomics, to link OM chemistry to microbial function. Our results reveal distinct dissolved organic matter metabolite composition, with fen systems enriched in compounds with higher substrate quality (low molecular weight (MW) sugars with high H:C ratios and low aromaticity) and bog systems dominated by compounds with lower substrate quality (high MW phenols with lower H:C ratios and higher aromaticity). In fen samples, these sugar‐like compounds correlated with higher oxidative metabolism and methanogenesis, supported by increased glycolysis gene expression. Initially, electrons from increased oxidative metabolism were balanced through nitrate and sulfate reduction, but as these electron acceptors were depleted, methanogenesis increased to maintain redox balance. Fen samples showed rapid degradation of both high‐ and low‐substrate‐quality compounds, suggesting sufficient energy for efficient C cycling. Conversely, bog samples exhibited more polyphenolic compounds, lower glycolysis activity, and higher stress‐related gene expression, suggesting energy was diverted towards cell maintenance under acidic conditions rather than C processing. This approach suggests that predicting greenhouse gas emissions requires an understanding of how organic matter quality shapes microbial energy allocation strategies, providing a mechanistic framework for improving emission predictions from permafrost‐affected peatlands and similar ecosystems.

Biodiversity & Conservation↗

Point-scale organic-matter decomposition in streambeds is weakly associated with reach-scale respiration

Stream and river ecosystems play a central role in the movement and decomposition of particulate organic matter, serving as a conduit between terrestrial hillslopes and coastal environments. Microbial-catalyzed decomposition generates simpler organic molecules that fuel respiration, often in the sediments of these ecosystems. However, the degree of connection between sediment-associated respiration (ER??d) and organic-matter decomposition remains poorly understood. How that relationship compares to decomposition’s relationship with whole ecosystem (ERtot) and water column (ERwc) respiration is also not clear. We examined the link between particulate organic matter decomposition—using cellulose-based cotton strips as a standardized substrate—and all three components of respiration across 48 sites in the environmentally diverse Yakima River Basin (Washington State, USA). We hypothesized that decomposition within sediments would be most strongly related to ERsed, but decomposition rates were more closely associated with ERtot, with little connection to ERsed or ERwc. This suggests that particulate organic matter decomposition within stream/river sediments reflects integrated system respiration rather than processes confined to sediments or the water column alone. Further, across the basin, decomposition rates nearly spanned the previously reported global range for streams and rivers and were best explained by total dissolved nitrogen (TDN), sediment grain size, and aridity of the upstream drainage area. These results highlight the strong influence of land cover and basin-scale biophysical variation on sediment-associated decomposition processes and indicate that mechanistic models of organic matter decomposition in streams/rivers should account for coupled sediment–water–land interactions.

Stegen, James C. (ORCID:0000000191357424)↗

Substrate-Driven Catalyst Reducibility for Oxygen Evolution and Its Effect on the Operation of Proton Exchange Membrane Water Electrolyzers

To increase the efficiency of hydrogen production by proton exchange membrane water electrolyzers (PEMWEs), the relationships between the specific activity and stability of the membrane–electrode assembly (MEA) must be clarified. Ir oxide electrodeposited on Ti substrate is used as an oxygen electrode, and its electronic properties and electrochemical behavior in PEMWE operation are observed. The electrode, fabricated through a facile strategy based on annealing in the air atmosphere, enhances the specific oxygen evolution reaction (OER) activity and stability in PEMWE operation. Furthermore, the electronic catalyst–substrate interactions associated with different reducibilities in the heteroatom system are studied. The morphology, electronic properties, and chemical state of the oxygen electrode are investigated through X-ray spectroscopy, microscopy techniques, and computational analyses. Thermal treatment of the catalyst-coated substrate decreases the bulk oxidation state of Ir and increases the surface oxidation state. According to the electrochemical and physical behavior analyses of PEMWEs, the oxygen content in the Ir oxide structure, which defines the OER activity and its stability, is influenced by the crystalline structure and formation of a stable interface between the catalyst and substrate. The outcomes can facilitate the development of strategies for enhancing the performance of PEMWEs and designing rational MEAs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Space Product Development of Commercial NLO Materials

Growth on selected substrates under various processing conditions have been useful for preparing highly oriented and otherwise promising films of organic compounds for optical thin films and waveguides. The significance of processing conditions to uniformity in thickness, degree of orientation, film quality, and optical properties for a specific processing technique is the general focus of work in this area. A study on the effect of processing conditions relevant to thin-film deposition by various techniques is particularly difficult because of the possibility that convection may play a major role in some cases. It is a goal of some researchers to produce good quality anisotropic films, therefore, an important, yet understudied, requirement should be to assess the role of gravity during certain processing methods. This may be particularly true for the vapor deposition of diacetylenes where subsequent polymerization in the crystal is topochemical and occurs readily only when neighboring monomer molecules are sufficiently close and suitably oriented. Likewise, this requirement is equally viable for the vapor deposition of certain materials such as Pcs in view of the results of microgravity experiments by 3M Corporation involving the preparation of thin films of copper Pc (CuPc). Microgravity-grown CuPc had several desirable features which indicate that the vapor growth of organic films in low-g may result in better quality films for optical and electrical applications. Indeed, other materials vapor deposited onto specific substrates in microgravity produce films potentially beneficial for electro-optic applications. A novel technique, recently discovered, for growing polydiacetylene thin films involves exposing a transparent substrate, in contact with diacetylene monomer solution, to ultraviolet (LTV) light. A polymer film deposits on the side of the substrate in contact with monomer in solution, and there are distinct gravitational effects, which influence film quality. Good quality thin films elude growth from solutions absent of uniform flow fields and homogeneous temperature distributions near the substrate surfaces. The flow fields and temperature distributions during the polymerization process by exposure to UV light details the nature of gravitational influences on this process.

Frazier, Donald O.↗

Structural insights into hydrolytic defluorination of difluoroacetate by microbial fluoroacetate dehalogenases

Fluorine forms the strongest single bond to carbon with the highest bond dissociation energy among natural products. However, fluoroacetate dehalogenases (FADs) have been shown to hydrolyze this bond in fluoroacetate under mild reaction conditions. Furthermore, two recent studies demonstrated that the FAD RPA1163 fromRhodopseudomonas palustriscan also accept bulkier substrates. In this study, we explored the substrate promiscuity of microbial FADs and their ability to defluorinate polyfluorinated organic acids. Enzymatic screening of eight purified dehalogenases with reported fluoroacetate defluorination activity revealed significant hydrolytic activity against difluoroacetate in three proteins. Product analysis using liquid chromatography‐mass spectrometry identified glyoxylic acid as the final product of enzymatic DFA defluorination. The crystal structures of DAR3835 fromDechloromonas aromaticaand NOS0089 fromNostocsp. were determined in the apo‐state along with the DAR3835 H274N glycolyl intermediate. Structure‐based site‐directed mutagenesis of DAR3835 demonstrated a key role for the catalytic triad and other active site residues in the defluorination of both fluoroacetate and difluoroacetate. Computational analysis of the dimer structures of DAR3835, NOS0089, and RPA1163 indicated the presence of one substrate access tunnel in each protomer. Moreover, protein‐ligand docking simulations suggested similar catalytic mechanisms for the defluorination of both fluoroacetate and difluoroacetate, with difluoroacetate being defluorinated via two consecutive defluorination reactions producing glyoxylate as the final product. Thus, our findings provide molecular insights into substrate promiscuity and catalytic mechanism of FADs, which are promising biocatalysts for applications in synthetic chemistry and bioremediation of fluorochemicals.

Biochemistry & Molecular Biology↗

The Multiphasic Teeth of Chiton Articulatus , an Abrasion‐Resistant and Self‐Sharpening Tool for Hard Algae Collection

Abstract Chiton articulatus is a species of mollusk living in the tropical Pacific intertidal rocky shores of Mexico. This species feeds on solid waste organic sources, including hard crustose algae that grow on rocky substrates, by grazing on them with its radula, a flexible chitinous membrane lined with mineralized major lateral teeth. In this study, the composition, morphology, and resulting mechanics of the mature teeth of this species, which have yet to be examined, are revealed. The results show the presence of multiphasic mature teeth, each consisting of aligned hard magnetite nanoparticles on the leading edge of the tooth underneath which are magnetite lamellae, followed by goethite, lepidocrocite, and eventually hydroxyapatite near the trailing edge. This multiregional structure demonstrates a gradation in hardness as well as different microstructural features integrated with tough interfaces. The combination of these microstructural and phase arrangements results in an abrasion‐resistant tough structure with a self‐sharpening ability. The results of this work will help contribute to developing new bioinspired designs while also helping to understand the evolution and feeding habits of these intriguing invertebrates.

36 MATERIALS SCIENCE↗

Kinetic Control via Binding Sites within the Confined Space of Metal Metalloporphyrin‐Frameworks for Enhanced Shape‐Selectivity Catalysis

Abstract One striking feature of enzyme is its controllable ability to trap substrates via synergistic or cooperative binding in the enzymatic pocket, which renders the shape‐selectivity of product by the confined spatial environment. The success of shape‐selective catalysis relies on the ability of enzyme to tune the thermodynamics and kinetics for chemical reactions. In emulation of enzyme's ability, we showcase herein a targeting strategy with the substrate being anchored on the internal pore wall of metal‐organic frameworks (MOFs), taking full advantage of the sterically kinetic control to achieve shape‐selectivity for the reactions. For this purpose, a series of binding site‐accessible metal metalloporphyrin‐frameworks (MMPFs) have been investigated to shed light on the nature of enzyme‐mimic catalysis. They exhibit a different density of binding sites that are well arranged into the nanospace with corresponding distances of opposite binding sites. Such a structural specificity results in a facile switch in selectivity from an exclusive formation of the thermodynamically stable product to the kinetic product. Thus, the proposed targeting strategy, based on the combination of porous materials and binding events, paves a new way to develop highly efficient heterogeneous catalysts for shifting selectivity.

Zhang, Weijie↗

Efficient and stable perovskite solar cells based on blade-coated CH 3 NH 3 PbI 3 thin films fabricated using “green” solvents under ambient conditions

Metal halide perovskites are considered the most promising candidates for solar cells of the decade due to their exceptional optical and electronic properties. The power conversion efficiency of metal halide perovskites, when incorporated as the active layer of solar cells, has become comparable to that observed for conventional silicon solar cells. However, the stability, scaleup, green solvent usage, and fabrication in ambient conditions of metal halide perovskites need to be solved for commercial applications. Here, in this work, we report the fabrication of blade-coated methylammonium lead iodide (MAPbI 3 ) perovskite thin films using methylamine and acetonitrile as “green” solvents under ambient conditions. Our perovskite films are initially prepared from low purity PbI2 (99%) and are blade-coated in dry air at relative humidity (RH) levels above 30%. A significant advantage of fabricating our perovskite thin films via blade-coating protocols is that there is a minimal amount of precursors (5 μL) used compared to spin-coating methods (50μL–60μL) for a 4 cm 2 substrate. With the addition of a small amount of an organic halide salt, namely, phenethylammonium chloride, the film crystallinity is improved and non-radiative recombination is suppressed, resulting in power conversion efficiencies over 20%. In addition, the device maintains more than 95% of its initial efficiency after 500 h under continuous light illumination of 1-sun at open circuit conditions, 50 °C and 60% RH. The above method leads a path towards the commercial fabrication of perovskite solar cells.

14 SOLAR ENERGY↗

A detailed genome-scale metabolic model of Clostridium thermocellum investigates sources of pyrophosphate for driving glycolysis

Lignocellulosic biomass is an abundant and renewable source of carbon for chemical manufacturing, yet it is cumbersome in conventional processes. A promising, and increasingly studied, candidate for lignocellulose bioprocessing is the thermophilic anaerobe Clostridium thermocellum given its potential to produce ethanol, organic acids, and hydrogen gas from lignocellulosic biomass under high substrate loading. Possessing an atypical glycolytic pathway which substitutes GTP or pyrophosphate (PP i ) for ATP in some steps, including in the energy-investment phase, identification, and manipulation of PP i sources are key to engineering its metabolism. Previous efforts to identify the primary pyrophosphate have been unsuccessful. Here, we explore pyrophosphate metabolism through reconstructing, updating, and analyzing a new genome-scale stoichiometric model for C. thermocellum, iCTH669. Hundreds of changes to the former GEM, iCBI655, including correcting cofactor usages, addressing charge and elemental balance, standardizing biomass composition, and incorporating the latest experimental evidence led to a MEMOTE score improvement to 94%. We found agreement of iCTH669 model predictions across all available fermentation and biomass yield datasets. The feasibility of hundreds of PP i synthesis routes, newly identified and previously proposed, were assessed through the lens of the iCTH669 model including biomass synthesis, tRNA synthesis, newly identified sources, and previously proposed PP i -generating cycles. In all cases, the metabolic cost of PP i synthesis is at best equivalent to investment of one ATP suggesting no direct energetic advantage for the cofactor substitution in C. thermocellum. Even though no unique source of PP i could be gleaned by the model, by combining with gene expression data two most likely scenarios emerge. First, previously investigated PP i sources likely account for most PP i production in wild-type strains. Second, alternate metabolic routes as encoded by iCTH669 can collectively maintain PP i levels even when previously investigated synthesis cycles are disrupted. Model iCTH669 is available at github.com/maranasgroup/iCTH669.

59 BASIC BIOLOGICAL SCIENCES↗

Metabolic engineering of Caldicellulosiruptor bescii for 2,3-butanediol production from unpretreated lignocellulosic biomass and metabolic strategies for improving yields and titers

ABSTRACT The platform chemical 2,3-butanediol (2,3-BDO) is used to derive products, such as 1,3-butadiene and methyl ethyl ketone, for the chemical and fuel production industries. Efficient microbial 2,3-BDO production at industrial scales has not been achieved yet for various reasons, including product inhibition to host organisms, mixed stereospecificity in product formation, and dependence on expensive substrates (i.e., glucose). In this study, we explore engineering of a 2,3-BDO pathway inCaldicellulosiruptor bescii, an extremely thermophilic (optimal growth temperature = 78°C) and anaerobic bacterium that can break down crystalline cellulose and hemicellulose into fermentable C 5 and C 6 sugars. In addition, C. besciigrows on unpretreated plant biomass, such as switchgrass. Biosynthesis of 2,3-BDO involves three steps: two molecules of pyruvate are condensed into acetolactate; acetolactate is decarboxylated to acetoin, and finally, acetoin is reduced to 2,3-BDO.C. besciinatively produces acetoin; therefore, in order to complete the 2,3-BDO biosynthetic pathway,C. besciiwas engineered to produce a secondary alcohol dehydrogenase (sADH) to catalyze the final step. Two previously characterized, thermostable sADH enzymes with high affinity for acetoin, one from a bacterium and one from an archaeon, were tested independently. When either sADH was present inC. bescii,the recombinant strains were able to produce up to 2.5-mM 2,3-BDO from crystalline cellulose and xylan and 0.2-mM 2,3-BDO directly from unpretreated switchgrass. This serves as the basis for higher yields and productivities, and to this end, limiting factors and potential genetic targets for further optimization were assessed using the genome-scale metabolic model ofC. bescii. IMPORTANCE Lignocellulosic plant biomass as the substrate for microbial synthesis of 2,3-butanediol is one of the major keys toward cost-effective bio-based production of this chemical at an industrial scale. However, deconstruction of biomass to release the sugars for microbial growth currently requires expensive thermochemical and enzymatic pretreatments. In this study, the thermo-cellulolytic bacteriumCaldicellulosiruptor besciiwas successfully engineered to produce 2,3-butanediol from cellulose, xylan, and directly from unpretreated switchgrass. Genome-scale metabolic modeling ofC. besciiwas applied to adjust carbon and redox fluxes to maximize productivity of 2,3-butanediol, thereby revealing bottlenecks that require genetic modifications.

Biotechnology & Applied Microbiology↗

w19_OMEC Scientific Highlight [Slides]

Scientific Achievement: Revealed the effect of graphite substrate on H binding / hydrogen evolution reaction (HER) activity of organic molecular electrocatalysts (OMECs); and demonstrated the effect of molecular modification on calculated HER activity descriptor. Significance and Impact: Understanding of HER processes is important for discovering low-cost OMECs for hydrogen production and energy application; design of OMEC structures remains challenging due to the unexplored redox properties of organic molecules; and density functional theory (DFT) has been proposed to provide needed insights into HER activity for improved materials design. Research Details: DFT calculations on the binding energy of HER intermediates are used for predicting reduction potentials and and calculated H adsorption energy as activity descriptor; and LANL Institutional Computing (IC) resources are essential for successful project execution given the size of structures involved in modeling molecule-support interaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structure and function of an inorganic-organic separator for electrochemical cells: Preliminary study

The structure of a new separator material for electrochemical cells has been investigated. Investigation into details of the separator structure showed it to be multilayered and to consist mainly of a quasi-impervious organic skin, a porous region of mixed organic and inorganic material, and an area of nonuniformly treated substrate. The essential feature of the coating (slurry) is believed to be interconnected pores which allow ionic conductivity. The interconnected pores are believed to be formed by the interaction of the plasticizer and inorganic fibers. The major failure mode of silver zinc cells using such a separator (zinc nodules shorting adjacent plates) was investigated.

Bozek, J. M.↗

Microbial trace fossils in Antarctica and the search for evidence of early life on Mars

It is possible to hypothesize that, if microbial life evolved on early Mars, fossil remnants of these organisms may be preserved on the surface. However, the cooling and drying of Mars probably resembled a cold desert and such an environment is not suitable for the process of fossilization. The frigid Ross Desert of Antarctica is probably the closest terrestrial analog to conditions that may have prevailed on the surface of the cooling and drying Mars. In this desert, cryptoendolithic microbial communities live in the airspaces of porous rocks, the last habitable niche in a hostile outside environment. The organisms produce characteristic chemical and physical changes in the rock substrate. Environmental changes (deterioration of conditions) may result in the death of the community. Although no cellular structures are fossilized, the conspicuous changes in the rock substrate are preserved as trace fossils. Likewise, microbial trace fossils (without cellular structures) may also be preserved on Mars: Discontinuities in structure or chemistry of the rock that are independent of physical or chemical gradients may be of biological origin. Ross Desert trace fossils can be used as a model for planning search strategies and for instrument design to find evidence of past Martian life.

Friedmann, E. Imre↗

Method of fabricating germanium and gallium arsenide devices

A method of semiconductor diode fabrication is disclosed which relies on the epitaxial growth of a precisely doped thickness layer of gallium arsenide or germanium on a semi-insulating or intrinsic substrate, respectively, of gallium arsenide or germanium by either molecular beam epitaxy (MBE) or by metal-organic chemical vapor deposition (MOCVD). The method involves: depositing a layer of doped or undoped silicon dioxide on a germanium or gallium arsenide wafer or substrate, selectively removing the silicon dioxide layer to define one or more surface regions for a device to be fabricated thereon, growing a matched epitaxial layer of doped germanium or gallium arsenide of an appropriate thickness using MBE or MOCVD techniques on both the silicon dioxide layer and the defined one or more regions; and etching the silicon dioxide and the epitaxial material on top of the silicon dioxide to leave a matched epitaxial layer of germanium or gallium arsenide on the germanium or gallium arsenide substrate, respectively, and upon which a field effect device can thereafter be formed.

Jhabvala, Murzban↗

Mg and Al-induced phase transformation and stabilization of Ga 2 O 3 -based $\gamma$-phase spinels

Ga 2 O 3 films were deposited on (100) MgAl 2 O 4 spinel substrates at 550, 650, 750, and 850 °C using metal-organic chemical vapor deposition and investigated using x-ray diffraction and transmission electron microscopy. A phase-pure γ-Ga 2 O 3 -based material having an inverse spinel structure was formed at 850 °C; a mixture of the γ-phase and β-Ga 2 O 3 was detected in films grown at 750 °C. Only β-Ga 2 O 3 was determined in the films deposited at 650 and 550 °C. A β- to γ-phase transition occurred from the substrate/film interface during growth at 750 °C. The growth and stabilization of the γ-phase at the outset of film growth at 850 °C was affected by the substantial Mg and Al chemical interdiffusion from the MgAl 2 O 4 substrate observed in the energy-dispersive x-ray spectrum. Further, atomic-scale investigations via scanning transmission electron microscopy of the films grown at 750 and 850 °C revealed a strong tetrahedral site preference for Ga and an octahedral site preference for Mg and Al. It is postulated that the occupation of these atoms in these particular sites drives the β-Ga 2 O 3 to γ-phase transition and markedly enhances the thermal stability of the latter phase at elevated temperatures.

42 ENGINEERING↗