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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.

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At least 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Nonthermal Plasma-Stimulated C–N Coupling from CH 4 and N 2 Depends on the Presence of Surface CH x and Plasma-Phase CN Species

Formation of C–N containing compounds from plasma-catalytic coupling of CH 4 and N 2 over various transition metals (Ni, Pd, Cu, Ag, and Au) is investigated using a multimodal spectroscopic approach, combining polarization-modulation infrared reflection–absorption spectroscopy (PM-IRAS) and optical emission spectroscopy (OES). Through sequential experiments utilizing CH 4 and N 2 nonthermal plasmas, we minimize plasma-phase reactions and identify key intermediates for C–N coupling on metal surfaces. Results show that simultaneous CH 4 and N 2 exposure with plasma stimulation produces surface C–N species. However, N 2 –CH 4 sequential exposure does not lead to C–N species formation, while CH 4 –N 2 sequential exposure reveals the presence of CH x surface species and CN radical species as key precursors to C–N species formation. From further analysis using X-ray photoelectron spectroscopy and liquid chromatography–mass spectrometry, the influence of exposure conditions on the degree of nitrogen incorporation and the nature of C–N species formed were revealed. The work highlights the importance of surface chemistry and exposure conditions in surface C–N coupling with plasma stimulation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Advanced Diagnostics for High Pressure Spray Combustion.

The development of accurate predictive engine simulations requires experimental data to both inform and validate the models, but very limited information is presently available about the chemical structure of high pressure spray flames under engine- relevant conditions. Probing such flames for chemical information using non- intrusive optical methods or intrusive sampling techniques, however, is challenging because of the physical and optical harshness of the environment. This work details two new diagnostics that have been developed and deployed to obtain quantitative species concentrations and soot volume fractions from a high-pressure combusting spray. A high-speed, high-pressure sampling system was developed to extract gaseous species (including soot precursor species) from within the flame for offline analysis by time-of-flight mass spectrometry. A high-speed multi-wavelength optical extinction diagnostic was also developed to quantify transient and quasi-steady soot processes. High-pressure sampling and offline characterization of gas-phase species formed following the pre-burn event was accomplished as well as characterization of gas-phase species present in the lift-off region of a high-pressure n-dodecane spray flame. For the initial samples discussed in this work several species were identified, including polycyclic aromatic hydrocarbons (PAH); however, quantitative mole fractions were not determined. Nevertheless, the diagnostic developed here does have this capability. Quantitative, time-resolved measurements of soot extinction were also accomplished and the novel use of multiple incident wavelengths proved valuable toward characterizing changes in soot optical properties within different regions of the spray flame.

Skeen, Scott A.↗
DOE OSTI2021

The Pre-He White Dwarfs in Eclipsing Binaries. II. WASP 0843–11

We present the Transiting Exoplanet Survey Satellite (TESS) photometry and our high-resolution spectra of the EL CVn–type star 1SWASP J084356.46–113327.5 (WASP 0843–11), which consists of an F-type main-sequence (MS) star and a hotter low-mass helium white dwarf precursor (pre-He WD). In a spectral analysis, double-lined radial velocities (RVs) were obtained for the first time. From a simultaneous analysis of the TESS light and RV curves, the masses, radii, and temperatures of each component were determined to be M {sub 1} = 1.733 ± 0.031 M {sub ⊙}, M {sub 2} = 0.220 ± 0.008 M {sub ⊙}, R {sub 1} = 2.094 ± 0.013 R {sub ⊙}, R {sub 2} = 0.331 ± 0.003 R {sub ⊙}, T {sub 1} = 6960 ± 120 K, and T {sub 2} =9870 ± 310 K, respectively. According to their physical properties, the primary and secondary stars are located on the instability strips of δ Sct/γ Dor hybrids and extremely low-mass WDs, respectively. We applied multiple frequency analyses to the residual light curve after subtracting the binarity effects and detected a total of four independent frequencies. A frequency of f {sub 3} = 1.6356 day{sup −1} in the low-frequency region was reminiscent of γ Dor stars, while the other three frequencies of f {sub 2}, f {sub 15}, and f {sub 18} in the high-frequency region (150–196 day{sup −1}) are probably related to pre-He WD components. Our results demonstrate that the more massive MS primary star of WASP 0843–11 is a γ Dor pulsator, whereas the hotter secondary component is a pre-He WD with high-frequency pulsations.

47 OTHER INSTRUMENTATION↗
DOE OSTI2017

Surface defects on the Gd{sub 2}Zr{sub 2}O{sub 7} oxide films grown on textured NiW technical substrates by chemical solution method

Epitaxial growth of oxide thin films has attracted much interest because of their broad applications in various fields. In this study, we investigated the microstructure of textured Gd{sub 2}Zr{sub 2}O{sub 7} films grown on (001)〈100〉 orientated NiW alloy substrates by a chemical solution deposition (CSD) method. The aging effect of precursor solution on defect formation was thoroughly investigated. A slight difference was observed between the as-obtained and aged precursor solutions with respect to the phase purity and global texture of films prepared using these solutions. However, the surface morphologies are different, i.e., some regular-shaped regions (mainly hexagonal or dodecagonal) were observed on the film prepared using the as-obtained precursor, whereas the film prepared using the aged precursor exhibits a homogeneous structure. Electron backscatter diffraction and scanning electron microscopy analyses showed that the Gd{sub 2}Zr{sub 2}O{sub 7} grains present within the regular-shaped regions are polycrystalline, whereas those present in the surrounding are epitaxial. Some polycrystalline regions ranging from several micrometers to several tens of micrometers grew across the NiW grain boundaries underneath. To understand this phenomenon, the properties of the precursors and corresponding xerogel were studied by Fourier transform infrared spectroscopy and coupled thermogravimetry/differential thermal analysis. The results showed that both the solutions mainly contain small Gd−Zr−O clusters obtained by the reaction of zirconium acetylacetonate with propionic acid during the precursor synthesis. The regular-shaped regions were probably formed by large Gd−Zr−O frameworks with a metastable structure in the solution with limited aging time. This study demonstrates the importance of the precise control of chemical reaction path to enhance the stability and homogeneity of the precursors of the CSD route. - Highlights: •We investigate microstructure of Gd{sub 2}Zr{sub 2}O{sub 7} films grown by a chemical solution route. •The aging effect of precursor solution on formation of surface defect was thoroughly studied. •Gd−Zr−O clusters are present in the precursor solutions.

36 MATERIALS SCIENCE↗
DOE OSTI2016

New Ir Bis-Carbonyl Precursor for Water Oxidation Catalysis

This paper introduces Ir I (CO) 2 (pyalc) (pyalc = (2-pyridyl)-2-propanoate) as an atom-efficient precursor for Ir-based homogeneous oxidation catalysis. This compound was chosen to simplify analysis of the water oxidation catalyst species formed by the previously reported Cp*Ir III (pyalc)OH water oxidation precatalyst. Here, we present a comparative study on the chemical and catalytic properties of these two precursors. Previous studies show that oxidative activation of Cp*Ir-based precursors with NaIO 4 results in formation of a blue Ir IV species. This activation is concomitant with the loss of the placeholder Cp* ligand which oxidatively degrades to form acetic acid, iodate, and other obligatory byproducts. The activation process requires substantial amounts of primary oxidant, and the degradation products complicate analysis of the resulting Ir IV species. The species formed from oxidation of the Ir(CO) 2 (pyalc) precursor, on the other hand, lacks these degradation products (the CO ligands are easily lost upon oxidation) which allows for more detailed examination of the resulting Ir(pyalc) active species both catalytically and spectroscopically, although complete structural analysis is still elusive. Once Ir(CO) 2 (pyalc) is activated, the system requires acetic acid or acetate to prevent the formation of nanoparticles. Investigation of the activated bis-carbonyl complex also suggests several Ir(pyalc) isomers may exist in solution. By 1 H NMR, activated Ir(CO) 2 (pyalc) has fewer isomers than activated Cp*Ir complexes, allowing for advanced characterization. Future research in this direction is expected to contribute to a better structural understanding of the active species. A diol crystallization agent was needed for the structure determination of 3.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Obtaining aluminas from the thermal decomposition of their different precursors: An {sup 27}Al MAS NMR and X-ray powder diffraction studies

Graphical abstract: - Highlights: • We synthesized three precursors of alumina from different methods. • The calcination of the precursors generated several alumina polymorphs. • XRD and NMR were used for structural investigation of the polymorphs. • The synthesis route determines the structural and textural properties of the solids. - Abstract: A commercial sample of Boehmite was used as precursor of alumina polymorphs. For comparison, three other precursors were synthesized from different methods. Particularly, the use of excess of urea promoted a very crystalline form of basic aluminum carbonate. The characteristics of the four precursors were investigated by thermal, vibrational and X-ray powder diffraction (XRD) analysis. Additionally, the nuclear magnetic resonance, with magic angle spinning ({sup 27}Al MAS NMR), was used to verify the coordination of aluminum cations. Each precursor was calcined at various temperatures generating alumina polymorphs, which were structurally analyzed by XRD and {sup 27}Al MAS NMR. Due to interest in catalysis supports, special attention was given to the γ-Al{sub 2}O{sub 3} phase, which in addition to structural investigation was subjected to textural analysis. The results showed that, from different synthesis procedures and common route of calcination, one can obtain materials with the same composition but with different structural and textural properties, which in turn can significantly influence the performance of a supported catalyst.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Templated synthesis of nickel nanoparticles: Toward heterostructured nanocomposites for efficient hydrogen storage

The world is currently facing an energy and environmental crisis for which new technologies are needed. Development of cost-competitive materials for catalysis and hydrogen storage on-board motor vehicles is crucial to lead subsequent generations into a more sustainable and energy independent future. This thesis presents work toward the scalable synthesis of bimetallic heterostructures that can enable hydrogen to compete with carbonaceous fuels by meeting the necessary gravimetric and volumetric energy densities and by enhancing hydrogen sorption/desorption kinetics near ambient temperatures and pressures. Utilizing the well-known phenomenon of hydrogen spillover, these bimetallic heterostructures could work by lowering the activation energy for hydrogenation and dehydrogenation of metals. Herein, we report a novel method for the scalable synthesis of silica templated zero-valent nickel particles (Ni$\subset$ SiO 2 ) that hold promise for the synthesis of nickel nanorods for use in bimetallic heterostructures for hydrogen storage. Our synthesis proceeds by chemical reduction of a nickel-hydrazine complex with sodium borohydride followed by calcination under hydrogen gas to yield silica encapsulated nickel particles. Transmission electron microscopy and powder X-ray diffraction were used to characterize the general morphology of the resultant nanocapsules as well as the crystalline phases of the incorporated Ni 0 nanocrystals. The structures display strong magnetic behavior at room temperature and preliminary data suggests nickel particle size can be controlled by varying the amount of nickel precursor used in the synthesis. Calcination under different environments and TEM analysis provides evidence for an atomic migration mechanism of particle formation. Ni$\subset$SiO 2 nanocapsules were used as seeds to induce heterogeneous nucleation and subsequent growth within the nanocapsule via electroless nickel plating. Nickel nanoparticle growth occurs under high temperature alkaline conditions, however silica nanocapsule integrity is not maintained due to the incompatibility of silica with the growth conditions. Silica nanocapsule integrity is maintained under low temperature neutral conditions, but nickel particle growth is not observed. Through FTIR and UV/Vis analysis, we show the degree of crosslinking and condensation increases in calcined silica compared to as-synthesized silica. We propose the increased density of the silica nanocapsule hinders mass transfer of the bulky nickel precursor complex from solution and onto the surface of the “catalytic” zero-valent nickel seed within the nanocapsule cavity. Decreasing the density of the silica nanocapsule can be achieved through co-condensation of tetraethylorthosilicate with an alkyl functionalized silane followed by calcination to remove the organic component or by chemical etching in alkaline solution, but will not be addressed in this thesis.

08 HYDROGEN↗
DOE OSTI2014

Conversion of 4-Hydroxybutyrate to Acetyl Coenzyme A and Its Anapleurosis in the Metallosphaera sedula 3-Hydroxypropionate/4-Hydroxybutyrate Carbon Fixation Pathway

The extremely thermoacidophilic archaeon Metallosphaera sedula (optimum growth temperature, 73 degrees C, pH 2.0) grows chemolithoautotrophically on metal sulfides or molecular hydrogen by employing the 3-hydroxypropionate/4-hydroxybutyrate (3HP/4HB) carbon fixation cycle. This cycle adds two CO2 molecules to acetyl coenzyme A (acetyl-CoA) to generate 4HB, which is then rearranged and cleaved to form two acetyl-CoA molecules. Previous metabolic flux analysis showed that two-thirds of central carbon precursor molecules are derived from succinyl-CoA, which is oxidized to malate and oxaloacetate. The remaining one-third is apparently derived from acetyl-CoA. As such, the steps beyond succinyl-CoA are essential for completing the carbon fixation cycle and for anapleurosis of acetyl-CoA. Here, the final four enzymes of the 3HP/4HB cycle, 4-hydroxybutyrate-CoA ligase (AMP forming) (Msed_0406), 4-hydroxybutyryl-CoA dehydratase (Msed_1321), crotonyl-CoA hydratase/(S)-3-hydroxybutyryl-CoA dehydrogenase (Msed_0399), and acetoacetyl-CoA beta-ketothiolase (Msed_0656), were produced recombinantly in Escherichia coli, combined in vitro, and shown to convert 4HB to acetyl-CoA. Metabolic pathways connecting CO2 fixation and central metabolism were examined using a gas-intensive bioreactor system in which M. sedula was grown under autotrophic (CO2-limited) and heterotrophic conditions. Transcriptomic analysis revealed the importance of the 3HP/4HB pathway in supplying acetyl-CoA to anabolic pathways generating intermediates in M. sedula metabolism. The results indicated that flux between the succinate and acetyl-CoA branches in the 3HP/4HB pathway is governed by 4-hydroxybutyrate-CoA ligase, possibly regulated posttranslationally by the protein acetyltransferase (Pat)/Sir2-dependent system. Taken together, this work confirms the final four steps of the 3HP/4HB pathway, thereby providing the framework for examining connections between CO2 fixation and central metabolism in M. sedula.

Hawkins, AB↗
DOE OSTI2018

Adverse Event Prediction Using Graph-Augmented Temporal Analysis (Final Report)

This report summarizes the work performed under the Sandia LDRD project "Adverse Event Prediction Using Graph-Augmented Temporal Analysis." The goal of the project was to develop a method for analyzing multiple time-series data streams to identify precursors providing advance warning of the potential occurrence of events of interest. The proposed approach combined temporal analysis of each data stream with reasoning about relationships between data streams using a geospatial-temporal semantic graph. This class of problems is relevant to several important topics of national interest. In the course of this work we developed new temporal analysis techniques, including temporal analysis using Markov Chain Monte Carlo techniques, temporal shift algorithms to refine forecasts, and a version of Ripley's K-function extended to support temporal precursor identification. This report summarizes the project's major accomplishments, and gathers the abstracts and references for the publication submissions and reports that were prepared as part of this work. We then describe work in progress that is not yet ready for publication.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2018

Adverse Event Prediction Using Graph-Augmented Temporal Analysis (Final Report)

This report summarizes the work performed under the Sandia LDRD project "Adverse Event Prediction Using Graph-Augmented Temporal Analysis." The goal of the project was to develop a method for analyzing multiple time-series data streams to identify precursors providing advance warning of the potential occurrence of events of interest. The proposed approach combined temporal analysis of each data stream with reasoning about relationships between data streams using a geospatial-temporal semantic graph. This class of problems is relevant to several important topics of national interest. In the course of this work we developed new temporal analysis techniques, including temporal analysis using Markov Chain Monte Carlo techniques, temporal shift algorithms to refine forecasts, and a version of Ripley's K-function extended to support temporal precursor identification. This report summarizes the project's major accomplishments, and gathers the abstracts and references for the publication sub-missions and reports that were prepared as part of this work. We then describe work in progress that is not yet ready for publication.

42 ENGINEERING↗
DOE OSTI2015

Direct comparison of defect ensembles extracted from damage probability and raster scan measurements

The presented study addresses the characterization of nanometer sized defects acting as damage precursors in nanosecond laser pulse duration regime. Two approaches are used to extract distributions of localized damage precursors, namely, damage probability and damage density measurements. Testing is performed on uncoated and SiO{sub 2} monolayer film deposited fused silica substrate exposed with pulsed UV irradiation (355 nm, 4.8 ns). Then, a direct comparison of damage precursor ensembles obtained from both methods is carried out. Our analysis indicates apparent differences between both methods that are discussed in detail. Contamination by ablation products is identified as one of the key factors that influence damage density measurements.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2016

Deep eutectic solvent approach towards nickel/nickel nitride nanocomposites

Nickel nitride is an attractive material for a broad range of applications including catalysis. However preparations and especially those targeting nanoscale particles remain a major challenge. Herein, we report a wet-chemical approach to produce nickel/nickel nitride nanocomposites using deep eutectic solvents. A choline chloride/urea deep eutectic solvent was used as a reaction medium to form gels containing nickel acetate tetrahydrate. Heat treatment of the gel in inert atmosphere forms nanoparticles embedded within a nitrogen-doped carbon matrix. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) were used to understand the decomposition profile of the precursors and to select pyrolysis temperatures located in regions of thermal stability. X-ray diffraction (XRD) confirmed the presence of metallic nickel, whereas X-ray photoelectron spectroscopy (XPS) suggested the existence of a nickel nitride surface layer. According to transmission electron microscopy (TEM) analysis these mixed phase, possibly core-shell type nanoparticles, have very defined facets. Furthermore, these materials represent a unique opportunity to tune catalytic properties of nickel-based catalysts through control of their composition, surface structure, and morphology; in addition to employing potential benefits of a nitrogen-doped carbon support.

36 MATERIALS SCIENCE↗
DOE OSTI2013

CuAl{sub x}Ga{sub 1−x}Se{sub 2} thin films for photovoltaic applications: Optical and compositional analysis

Highlights: ► Wide band gap CAGS thin films have been obtained by selenization of evaporated metallic precursors. ► Direct nonlinear dependence of the band gap energy with the Al/(Al + Ga) ratio is found. ► The bowing parameter decreases when the CAGS film thickness increases. ► The Cu at% remains constant in depth, together with some Al, Ga and Se gradients. ► Surface is strongly oxidized but the oxidation is relatively low in bulk. - Abstract: Wide-band gap chalcopyrite semiconductors have a great interest due to their potential application in multi-junction thin film solar cells or as window layers. Polycrystalline CuAl{sub x}Ga{sub 1−x}Se{sub 2} (CAGS) thin films have been prepared by selenization of evaporated metallic precursor layers on bare and Mo-coated soda lime glass substrates. The optical properties of CAGS films of 2 thicknesses have been analyzed by spectrophotometry in the visible-infrared (VIS-IR) and the compositional characteristics have been studied by energy dispersive analysis of X-rays (EDAX) and X-ray photoelectron spectroscopy (XPS). The optical transmission increases and the band gap energy shifts toward higher values as the Al content increases, which indicates the partial substitution of Ga by Al. The dependence of the band gap with the composition has resulted to be nonlinear and a bowing parameter of b = 0.62 and b = 0.54 for 0.6 μm and 1.1 μm-CAGS samples, respectively, has been obtained. XPS data have shown an Al, Ga and Se composition gradient in depth and a surface strongly oxidized. However, XPS reveals that the Cu composition remains constant in depth and the oxidation is relatively low in bulk increasing slightly in the interface with Mo/SLG. Moreover, samples with high Al content reveal a higher contribution of CuO in depth.

36 MATERIALS SCIENCE↗
DOE OSTI2014

TiO{sub 2} flower-like nanostructures decorated with CdS/PbS nanoparticles

Highlights: • TiO{sub 2} flower-like nanostructures were prepared with the use of Ti foil and 30% H{sub 2}O{sub 2}. • QDs of CdS and PbS were deposited using the SILAR method. • The SILAR method makes it possible to control the size of QDs. • Band gap energy of CdS was found to be 2.35 eV. • Sensitization of TiO{sub 2} with CdS or PbS improves the photoelectrochemical properties. - Abstract: Flower-like nanostructures of TiO{sub 2} were prepared by immersing Ti foil in 30% H{sub 2}O{sub 2} at 80 °C for times varying from 15 to 240 min. Upon annealing at 450 °C in an Ar atmosphere, the received amorphous samples crystallized in an anatase structure with rutile as a minority phase. SEM images revealed that partially formed flowers were present at the surface of the prepared samples as early as after 15 min of immersion. The size of the individual flowers increased from 400–800 nm after 15 min of reaction to 2.5–6.0 μm after 240 min. It was also found that surface is very rough and surface development is considerable. After 45 min of immersion, the nanoflowers were sensitized with CdS and PbS quantum dots (QDs-CdS/QDs-PbS) deposited using the SILAR method from water- and methanol-based precursor solutions at different concentrations (0.001–0.1 M). QDs-CdS crystallized in the hawleyite structure, while QDs-PbS in the galena form. SEM analysis showed the tendency of quantum dots to agglomerate at high concentrations of the precursor in water-based solutions. QDs obtained from methanol-based solutions were uniformly distributed. The produced QDs-PbS were smaller than QDs-CdS. Based on the optical reflectance spectra, the band-gap energies of TiO{sub 2} nanostructures with and without QDs were calculated to be 3.32 eV for flower-like TiO{sub 2} nanostructures and 2.35 eV for QDs-CdS. The photoelectrochemical behaviour of nanoflowers was found to improve significantly after the deposition of QDs-CdS.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Photoluminescence of ZnO/C Nanocomposites Formed by the Sol-Gel Method

Films of undoped zinc oxide (ZnO) and of ZnO/C nanocomposite were formed by the sol-gel method on glass substrates and on fiberglass using zinc acetate as a precursor and with the addition of zinc chloride respectively. Analysis of the photoluminescence spectra of ZnO/C films at high (N{sub 2}-laser) and low (HeCd-laser) excitation levels made it possible to establish the defining role of bound excitons in this process at 20–60 K, due to the presence of chlorine residues in the films. With the temperature raised to 300 K the role of recombination through the 1LO- and 2LO-phonon replicas of free exciton levels and impurity-defect levels begins to dominate in the photoluminescence of the ZnO/C films.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Coal-based graphene oxide-like materials: A comprehensive review

Coal is the most abundant energy and hydrocarbon resource in the United States which has been primarily used for power generation. With the increasing retirement of coal power plants and transition to a low-carbon emission economy, the future use of coal will likely shift to a feedstock source for production of valuable materials for different applications. In this review, the latest research reported on production of graphene-like materials in a powder form from coal is compiled and discussed. Here, this review includes: 1) brief background information on graphene and related materials (GRM); 2) relevant material, resource, economic, and socioeconomic information regarding suitability of coal as a potential feedstock for production of GRM; 3) a summary of common approaches for coal upgrading for preparation of more suitable precursors for production of GRM; 4) a compilation and analysis of the reported routes and methods for preparation of GRM from coal and coal derivatives; and 5) reported potential applications of coal-based GRM.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Conserved active site cysteine residue of archaeal THI4 homolog is essential for thiamine biosynthesis in Haloferax volcanii

Thiamine (vitamin B1) is synthesized de novo by certain yeast, fungi, plants, protozoans, bacteria and archaea. The pathway of thiamine biosynthesis by archaea is poorly understood, particularly the route of sulfur relay to form the thiazole ring. Archaea harbor structural homologs of both the bacterial (ThiS-ThiF) and eukaryotic (THI4) proteins that mobilize sulfur to thiazole ring precursors by distinct mechanisms. Results: Based on comparative genome analysis, halophilic archaea are predicted to synthesize the pyrimidine moiety of thiamine by the bacterial pathway, initially suggesting that also a bacterial ThiS-ThiF type mechanism for synthesis of the thiazole ring is used in which the sulfur carrier ThiS is first activated by ThiF-catalyzed adenylation. The only ThiF homolog of Haloferax volcanii (UbaA) was deleted but this had no effect on growth in the absence of thiamine. Usage of the eukaryotic THI4-type sulfur relay was initially considered less likely for thiamine biosynthesis in archaea, since the active-site cysteine residue of yeast THI4p that donates the sulfur to the thiazole ring by a suicide mechanism is replaced by a histidine residue in many archaeal THI4 homologs and these are described as D-ribose-1,5-bisphosphate isomerases. The THI4 homolog of the halophilic archaea, including Hfx. volcanii (HVO_0665, HvThi4) was found to differ from that of methanogens and thermococci by having a cysteine residue (Cys165) corresponding to the conserved active site cysteine of yeast THI4p (Cys205). Deletion of HVO_0665 generated a thiamine auxotroph that was trans-complemented by a wild-type copy of HVO_0665, but not the modified gene encoding an HvThi4 C165A variant. Based on our results, we conclude that the archaeon Hfx. volcanii uses a yeast THI4-type mechanism for sulfur relay to form the thiazole ring of thiamine. We extend this finding to a relatively large group of archaea, including haloarchaea, ammonium oxidizing archaea, and some methanogen and Pyrococcus species, by observing that these organisms code for THI4 homologs that have a conserved active site cysteine residue which is likely used in thiamine biosynthesis. Thus, archaeal members of IPR002922 THI4 family that have a conserved cysteine active site should be reexamined for a function in thiamine biosynthesis.

60 APPLIED LIFE SCIENCES↗