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At least 901 records · Page 50
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

A reaction–diffusion model for grayscale digital light processing 3D printing

We report that digital light processing (DLP) 3D printing is an additive manufacturing process that utilizes light patterns to photopolymerize a liquid resin into a solid. Due to the accuracy of modern digital micromirror devices (DMD) and recent advances in resin chemistry, it is now possible to create functionally graded structures using different light intensity values, also known as grayscale DLP (g-DLP). Different intensities of light lead to differences in the polymer crosslinking density after curing, which ultimately produces a part with gradients of material properties. However, g-DLP is a complicated process. First, the DLP printing is a highly coupled chemical and physical process that involves light propagation, chemical reactions, species diffusion, heat transfer, volume shrinkage, and changes in mechanical behaviors of the curing resin. Second, in g-DLP, light gradients create strong in plane gradients of chemical species concentrations in the curing liquid resin due to the strong dependence of light intensity on the rate of monomer crosslinking. Furthermore, light gradients through the depth create concentration gradients due to the degree of cure dependent light absorption and the use of photoabsorbers. These complex physical features of the printing process must be understood in order to properly control printing parameters such as light exposure time, printing speed, and grayscale variations to achieve accurate mechanical properties. In this paper, a photopolymerization reaction–diffusion model is developed and used in conjunction with experiments to investigate the coupled effects of light propagation, chemical reaction rates, and species diffusion during g-DLP 3D printing. The model is implemented numerically utilizing the finite difference method and simulation results are compared to experimental findings of simple printed structures. The agreement between experimental and model predictions of simple quantities of interest, such as geometric feature sizes, shows that the model can capture the overcure due to free-radical and other species diffusion during printing when grayscale patterns are employed. This model lays the groundwork for future extensions that can incorporate more complex coupled physics such as heat transfer, volume shrinkage, and material property evolution, which are critically important in utilizing g-DLP 3D printing for the fabrication of high-performance parts which excellent geometric and material property tolerances.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Controllable depolymerization of lignin using carbocatalyst graphene oxide under mild conditions

Many efforts have been devoted to depolymerizing lignin to high-value aromatic monomers. However, a controllable and complete lignin inter-unit bond cleavage remains difficult because of the randomness in lignin structure and low selectivity in catalysis. Herein, we demonstrate that a sole carbocatalyst graphene oxide (GO) can selectively oxidize aryl- and alkyl-hydroxyl groups of lignin without the presence of any additional oxidizers, leading to lignin degradation under mild conditions. The results from lignin dimers, lignin oligomers, and organosolv lignin indicate that the depolymerization is catalyzed via an oxidative mechanism through an enol ether intermediate, a stable intermediate that has been chemically isolated here. Quantum chemistry calculations at the density functional theory level indicate that the phenolic –OH group in lignin facilitates the formation of radical cations and thus prohibits ring opening reactions, leading to the complete conversion of lignin dimers to guaiacol through the enol ether intermediate.

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

Assessment of the impact of reactor residence time distribution on non-equilibrium product selectivity of polypropylene pyrolysis using reactive molecular dynamics simulations

Mass residence time distribution (RTD) is considered to be an important factor controlling the product selectivity in the pyrolysis of biomass and plastic wastes along with the pyrolysis chemistry. However, due to the complex pyrolysis chemistry of biomass and plastic waste, the coupling between the reaction chemistry, RTD, and product selectivity is challenging to understand. Here, we introduce a reaction molecular dynamics-based method to examine pyrolysis chemistry and species timescales to assess the impact of RTD on product selectivity and yield. To validate this method, reactive molecular dynamics simulations were conducted for polypropylene pyrolysis and its non-equilibrium product selectivity using 6 different RTDs. We find that the RTD and the reaction chemistry control the peak non-equilibrium product concentrations. The peak monomer (C 3 H 6 ) concentration during pyrolysis can be increased by up to 25 % by using a narrow RTD in the case of polypropylene pyrolysis. We also find that product selectivity is strongly affected by the average residence time and RTD. This coupling between the reaction chemistry, RTD, and product selectivity highlights the need to understand detailed reaction chemistry to control RTD and optimize non-equilibrium product selectivity during polymer and biomass pyrolysis. The present method provides a new way to design RTD for reactors to reach maximized product selectivity of plastic waste and biomass.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2020

Synthesis and spectroscopic characterization of actinyl(VI) tetrahalide coordination compounds containing 2, 2'-bipyridine

A series of three new actinide tetrahalide coordination compounds containing 2,2'-bipyridinium (H 2 bpy) have been synthesized by room temperature evaporation and characterized via single crystal X-ray diffraction, Raman spectroscopy, and infrared spectroscopy. The solid-state compounds (Np1, U1, and U2) contain the AnO 2 2+ cation coordinated to four halide (chloride or bromide) atoms to form the anionic tetrahalide molecular unit [AnO 2 X 4 ] 2– (X = Cl, Br) and are charge balanced by the 2,2'-bipyridinium cations that engage in electrostatic interactions with the actinyl complex. Np1 (N 2 C 10 H 10 )[NpO 2 Cl 4 ] contains 2,2'-bipyridine in the cis conformation where both the nitrogen atoms are directed towards the [NpO 2 Cl 4 ] 2– monomer. Within U1 (N 2 C 10 H 9 )[UO 2 Cl 4 ], the 2,2'-bipyridine is in a trans conformation, and found in the same orientation in the isomorphous structure U2 (N 2 C 10 H 9 )[UO 2 Br 4 ]. The compounds were further characterized by vibrational spectroscopy with specific interest in the actinyl cation. Raman spectroscopy provided information on the actinyl symmetric stretch (ν 1 ) whereas IR spectroscopy is used to determine the location of the asymmetric stretch (ν 3 ). Here, spectral similarities are observed between the two isomorphous structures, but slight variations across the series of structures are found to be associated with bipyridine bands in the various conformations. Additional analysis of these vibrational features in U1 and U2 provided information on the actinyl force constants, allowing insight into the relative uranyl bond strength that was compared to similar tetrahalide compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Iron-based sulfur and nitrogen dual doped porous carbon as durable electrocatalysts for oxygen reduction reaction

The widespread use of fuel cell technology is hampered by the use of expensive and scarce platinum metal in electrodes which is required to facilitate the sluggish oxygen reduction reaction (ORR). In this work, a viable synthetic approach was developed to prepare iron-based sulfur and nitrogen dual doped porous carbon (Fe@SNDC) for use in ORR. Benzimidazole, a commercially available monomer, was used as a precursor for N doped carbon and calcined with potassium thiocyanate at different temperatures to tune the pore size, nitrogen content and different types of nitrogen functionality such as pyridinic, pyrrolic and graphitic. The Fe@SNDC–950 with high surface area, optimum N content of about 5 at% and high amount of pyridinic and graphitic N displayed an onset potential and half-wave potential of 0.98 and 0.83 V vs RHE, respectively, in 0.1 M KOH solution. The catalyst also exhibits similar oxygen reduction reaction performance compared to Pt/C (20 wt%) in acidic media. Furthermore, when compared to commercially available Pt/C (20 wt%), Fe@SNDC–950 showed enhanced durability over 6 h and poison tolerance in case of methanol crossover with the concentration up to 3.0 M in oxygen saturated alkaline electrolyte. Finally, our study demonstrates that the presence of N and S along with Fe-N moieties synergistically served as ORR active sites while the high surface area with accessible pores allowed for efficient mass transfer and interaction of oxygen molecules to the active sites contributing to the ORR activity of the catalyst.

08 HYDROGEN↗
DOE OSTI2022

High-pressure hydrogen decompression in sulfur crosslinked elastomers

High-pressure storage and cyclic (de)pressurization of hydrogen gas is known to result in degradation and failure of gas canisters, hoses, linings, and O-rings as the relatively small hydrogen molecule can readily permeate most materials. Hence, identifying material compositions that are less susceptible to hydrogen-induced damage is of significant importance to the hydrogen energy infrastructure. Here, we use classical atomistic molecular dynamics simulations to study hydrogen exposed ethylene-propylene-diene monomer (EPDM) rubber, an elastomer typically used in O-rings. We make chemical modifications to the model by adjusting the crosslink density and report on gas solubility, diffusivity, and molecular restructuring in response to rapid decompression. Our simulations indicate that increases in crosslink density can reduce volumetric expansion during decompression and result in smaller free volume pore sizes. However, these favorable properties for sealing materials come with a tradeoff. At pressure, crosslinks introduce extra free volume, providing potential sites for gas localization, the precursor to cavitation-induced failure.

08 HYDROGEN↗
DOE OSTI2025

Effects of high-pressure hydrogen exposure on filler-elastomer adhesion

Elastomers are known to gain enhanced mechanical properties through compounding with nanosized filler particles such as silica or carbon black. Filler dispersion and filler-polymer interfacial strength are key contributing factors to this improvement. The interfacial strength is critical to part lifetime in pressurized gas sealing applications such as O-rings, where weak binding between the filler particle and polymer matrix can lead to internal void structures. With the aim to build a fundamental understanding of precursors to pressurized hydrogen-induced failure in elastomers, we use all-atom molecular dynamics simulations to study the impact of hydrogen oversaturation on filler-polymer interaction strength. We systematically study the interface between a commonly used elastomer, ethylene-propylene-diene monomer (EPDM) and silica by varying gas concentration, crosslink density, and surface chemistry. Our simulations predict that decompression leads to a localization of excess gas near the interface. In conclusion, we demonstrate that this localized gas can weaken interfacial adhesion and quantify the interaction using thermodynamic approaches.

EPDM↗
DOE OSTI2025

Ectopic expression of pectate lyase PtxtPL1-27 in aspen affects leaf cuticle development

Cuticle - a hydrophobic barrier of cutin and waxes covering the outer cell wall surface of plants - enables survival in terrestrial habitats. However, it is not understood how the hydrophobic cuticle precursors travel through the homogalacturonan-rich hydrophilic cell wall. To elucidate the role of homogalacturonan in cuticle development, we disrupted its integrity by overexpressing a pectate lyase, PtxtPL1-27, in aspen. PtxtPL1-27 had pleiotropic effects on shoot development, including the reduction of cuticle thickness and changes in cutin and wax composition, but the expression of cutin biosynthetic genes was little affected. Despite a reduction in homogalacturonan content in the leaves, labeling with the homogalacturonan-specific antibody JIM5 in the outer epidermal cell wall layer increased and displayed an altered pattern. Moreover, the ultrastructure of cell walls was changed concomitant with lipid accumulation. We propose that the disruption of homogalacturonan integrity affected the cutinsome-dependent transport and polymerization of cutin monomers in the cell wall.

Plant Biology↗
DOE OSTI2020

The effect of moisture on hydrocarbon-based solvent liquefaction of pine, cellulose and lignin

In this report we examined the effect of moisture on the solvent liquefaction of loblolly pine, cellulose, and lignin in tetralin at 280 °C and pressures ranging from 15 to 70 bar. Solvent liquefaction experiments were conducted in a quasi-batch reactor capable of continuous pressure control and external vapor condensation. Moisture was varied by the controlled addition of de-ionized water. Control over the system pressure subsequently impacted the removal of water vapor from the reactor. Liquid yield decreased by 25, 21, and 35 wt%, for pine, cellulose, and lignin, respectively, when moisture content was increased from 1 to 50 wt% at 42 bar. Humins were observed in the solid residue from liquefaction of wet cellulose. Wet lignin yielded a substantial amount of solid residue compared to dry lignin with a corresponding decrease in total phenolic monomer production. It was concluded that the ionic dissociation of water was an important factor in loss of liquid yield in the presence of water. Although water was less than 20 wt% of the solvent loading in these experiments, it strongly influenced the liquefaction of biomass and biomass components.

09 BIOMASS FUELS↗
DOE OSTI2022

Product specific thermal degradation kinetics of bisphenol F epoxy in inert and oxidative atmospheres using evolved gas analysis–mass spectrometry

Knowledge of the degradation kinetics for polymer materials is important for understanding thermal stability. In this study, evolved gas analysis–mass spectrometry and pyrolysis gas-chromatography-mass spectrometry were evaluated for the potential to deliver additional insight into thermal degradation kinetics of diglycidal ether of bisphenol F (DGEBF) epoxy thermoset under inert and oxidative atmospheres. Degradation products of selected precursor ions were evaluated for their uniqueness to the specific precursor using extracted ion thermographs. Unique mass peaks, solely attributed to a single reaction pathway of a specific product, were determined from extracted ion thermographs and used to determine both activation energy (E a ) and pre-exponential factors for the specific primary reaction pathways. These primary reaction pathways for DGEBF epoxy degradation were then evaluated in the context of transition state theory (TST) and related transition state enthalpies (ΔH ‡ ) and entropies (ΔS ‡ ) of activation to further elucidate the degradation process. It was determined under pyrolysis conditions, as suggested by the E a , the formation of bisphenol F monomer was the rate-limiting step toward the formation of xanthene and phenol. In contrast, under thermo-oxidative conditions, reactions involving oxygen containing species were identified as the rate-limiting step for all observed products based on the large negative ΔS ‡ calculated from TST. This work demonstrates a powerful combination of technique and theory that can provide new insight into the degradation of polymer materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Structural characterization of HIV-1 matrix mutants implicated in envelope incorporation

During the late phase of HIV-1 infection, viral Gag polyproteins are targeted to the plasma membrane (PM) for assembly. Gag localization at the PM is a prerequisite for the incorporation of the envelope protein (Env) into budding particles. Gag assembly and Env incorporation are mediated by the N-terminal myristoylated matrix (MA) domain of Gag. Nonconservative mutations in the trimer interface of MA (A45E, T70R, and L75G) were found to impair Env incorporation and infectivity, leading to the hypothesis that MA trimerization is an obligatory step for Env incorporation. Conversely, Env incorporation can be rescued by a compensatory mutation in the MA trimer interface (Q63R). The impact of these MA mutations on the structure and trimerization properties of MA is not known. In this study, we employed NMR spectroscopy, X-ray crystallography, and sedimentation techniques to characterize the structure and trimerization properties of HIV-1 MA A45E, Q63R, T70R, and L75G mutant proteins. NMR data revealed that these point mutations did not alter the overall structure and folding of MA but caused minor structural perturbations in the trimer interface. Analytical ultracentrifugation data indicated that mutations had a minimal effect on the MA monomer–trimer equilibrium. The high-resolution X-ray structure of the unmyristoylated MA Q63R protein revealed hydrogen bonding between the side chains of adjacent Arg-63 and Ser-67 on neighboring MA molecules, providing the first structural evidence for an additional intermolecular interaction in the trimer interface. These findings advance our knowledge of the interplay of MA trimerization and Env incorporation into HIV-1 particles.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2021

Covalent inhibition of hAChE by organophosphates causes homodimer dissociation through long-range allosteric effects

Acetylcholinesterase (EC 3.1.1.7), a key acetylcholine-hydrolyzing enzyme in cholinergic neurotransmission, is present in a variety of states in situ, including monomers, C-terminally disulfide-linked homodimers, homotetramers, and up to three tetramers covalently attached to structural subunits. Could oligomerization that ensures high local concentrations of catalytic sites necessary for efficient neurotransmission be affected by environmental factors? Using small-angle X-ray scattering (SAXS) and cryo-EM, we demonstrate that homodimerization of recombinant monomeric human acetylcholinesterase (hAChE) in solution occurs through a C-terminal four-helix bundle at micromolar concentrations. We show that diethylphosphorylation of the active serine in the catalytic gorge or isopropylmethylphosphonylation by the R P enantiomer of sarin promotes a 10-fold increase in homodimer dissociation. We also demonstrate the dissociation of organophosphate (OP)-conjugated dimers is reversed by structurally diverse oximes 2PAM, HI6, or RS194B, as demonstrated by SAXS of diethylphosphoryl-hAChE. However, binding of oximes to the native ligand-free hAChE, binding of high-affinity reversible ligands, or formation of an S P -sarin-hAChE conjugate had no effect on homodimerization. Dissociation monitored by time-resolved SAXS occurs in milliseconds, consistent with rates of hAChE covalent inhibition. OP-induced dissociation was not observed in the SAXS profiles of the double-mutant Y337A/F338A, where the active center gorge volume is larger than in wildtype hAChE. These observations suggest a key role of the tightly packed acyl pocket in allosterically triggered OP-induced dimer dissociation, with the potential for local reduction of acetylcholine-hydrolytic power in situ. Computational models predict allosteric correlated motions extending from the acyl pocket toward the four-helix bundle dimerization interface 25 Å away.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Structure of a dimeric photosystem II complex from a cyanobacterium acclimated to far-red light

Photosystem II (PSII) is the water-splitting enzyme central to oxygenic photosynthesis. To drive water oxidation, light is harvested by accessory pigments, mostly chlorophyll (Chl) a molecules, which absorb visible light (400–700 nm). Some cyanobacteria facultatively acclimate to shaded environments by altering their photosynthetic machinery to additionally absorb far-red light (FRL, 700–800 nm), a process termed far-red light photoacclimation or FaRLiP. During far-red light photoacclimation, FRL-PSII is assembled with FRL-specific isoforms of the subunits PsbA, PsbB, PsbC, PsbD, and PsbH, and some Chl-binding sites contain Chls d or f instead of the usual Chl a. The structure of an apo-FRL-PSII monomer lacking the FRL-specific PsbH subunit has previously been determined, but visualization of the dimeric complex has remained elusive. Here, we report the cryo-EM structure of a dimeric FRL–PSII complex. The site assignments for Chls d and f are consistent with those assigned in the previous apo-FRL-PSII monomeric structure. All sites that bind Chl d or Chl f at high occupancy exhibit a FRL-specific interaction of the formyl moiety of the Chl d or Chl f with the protein environment, which in some cases involves a phenylalanine sidechain. The structure retains the FRL-specific PsbH2 subunit, which appears to alter the energetic landscape of FRL-PSII, redirecting energy transfer from the phycobiliprotein complex to a Chl f molecule bound by PsbB2 that acts as a bridge for energy transfer to the electron transfer chain. Collectively, these observations extend our previous understanding of the structure-function relationship that allows PSII to function using lower energy FRL.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Encapsulation of hygroscopic liquids via polymer precipitation in non-aqueous emulsions

Here, encapsulation of ionic liquids (ILs) and phase change materials (PCMs) can overcome limitations associated with bulk materials, e.g., slow mass transfer rates, high viscosities, or susceptibility to external environment. Single step soft-templated encapsulation methods commonly use interfacial polymerization for shell formation, with a multifunctional monomer in the continuous phase and another in the discontinuous phase, and thus do not give pristine core material. We posit that polymer precipitation onto emulsion droplets in non-aqueous emulsions could produce a robust shell without contamination of the core, ideal for the encapsulation of water-sensitive or water-miscible materials. Solutions of commodity polymers were added to the continuous phase of non-aqueous Pickering emulsions stabilized by alkylated graphene oxide (GO) nanosheets such that the change in solubility of the polymer led to formation of robust shells and the production of capsules that could be isolated. We demonstrate that a polymer precipitation approach can produce capsules with pristine core of the IL 1-ethyl-3-methylimidazolium hexafluorophosphate [Emim][PF 6 ] or the salt hydrate PCM magnesium nitrate hexahydrate (MNH) and shell of nanosheets and polystyrene, poly(methyl methacrylate), or polyethylene. The capsules are approximately 80 wt% [Emim][PF 6 ] or >90 wt% MNH, and the core can undergo multiple cycles of solidification and melting without leakage or destruction. This novel, single-step methodology provides a distinct advantage to access capsules with pristine core composition and is amenable to different core and shell, paving the way for tailoring capsule composition for desired applications.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Dispersion of high oxygen permeability ionomers in water-propanol solutions

There is a growing interest in high oxygen permeability ionomers (HOPI) for better-performing proton exchange membrane fuel cell (PEMFC) catalyst layers. In this study, we used small-angle x-ray scattering (SAXS) to analyze dispersions of two types of perfluorinated sulfonic acid (PFSA) ionomers and a HOPI in water and propanol solvents, at concentrations between 1 wt% and 15 wt%. HOPI dispersions exhibited the interference peak typical of ionomers; by separately fitting the peak and higher- q regions with several models, we demonstrated that HOPI aggregates have a closer average spacing than conventional PFSA ionomers, and smaller aggregate size when assuming a cylindrical geometry. By measuring conventional PFSA ionomers with two side chain lengths and several equivalent weights, we showed that these side chain parameters alone did not explain the differences in aggregate spacing or size. In addition, the pattern was present whether samples were prepared in a 50/50 water/propanol or a more propanol-rich mixture. As such, the structural differences of HOPI could be due to its different backbone monomer. A better understanding of the influence of the HOPI chemistry on dispersion properties could help explain the ink structure and drying characteristics of HOPI observed in prior work. Future study of ionomer-catalyst mixtures, such as measuring ionomer adsorption to carbon, would help elucidate the role of ionomer from ink formulation to the cast electrode.

Aquivion↗
DOE OSTI2022

Valorization of Miscanthus x giganteus for sustainable recovery of anthocyanins and enhanced production of sugars

The increased awareness for eco-friendliness and sustainability has shifted the interest of stakeholders from synthetic colors to natural plant-based pigments. In this study, purple stemmed Miscanthus x giganteus was evaluated as a source of anthocyanins. Hydrothermal pretreatment was studied as a green, chemical-free process for recovering maximum anthocyanins in the pretreatment liquor. The highest recovery of 94.3 ± 1.5% w/w of the total anthocyanin concentration was obtained for a temperature and time combination of 170 °C and 10 min. The pretreatment also improved the enzymatic digestibility of the biomass and led to a 2.1-fold increase in the overall recovery of glucose (70.6 ± 0.5% w/w) at the end of 72 h. The sugar monomers obtained after the enzymatic hydrolysis of the pretreated biomass could be used for the production of biofuels or biochemicals in an integrated biorefinery based on purple-stemmed miscanthus. Altogether, this study demonstrates that the clean pretreatment method developed could lead to an additional product stream (rich in anthocyanins) along with its effect in reducing the recalcitrance of miscanthus biomass.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Effect of metal-free mesoporous silica incorporated ZSM-5 composite on thermo-catalytic pyrolysis of polypropylene

Although different zeolites impregnated with transition metals have been used in catalytic deconstruction of waste plastics to other products, the influence of hierarchical structures on conversion and product selectivity in plastic upcycling has not been thoroughly investigated. This research explores a transition metal free zeolite-based hierarchical composite, synthesized by incorporating SBA-15 in ZSM-5 framework, for efficient thermos-catalytic upcycling of polypropylene (PP). Thermogravimetric analysis reveals that ZSM-5@SBA-15 can break down PP at a significantly lower temperature, 240 °C, compared to that of pristine PP using ZSM-5 or SBA-15. In addition, pyrolysis of PP at 400 °C using ZSM-5@SBA-15 composite outperforms ZSM-5 or SBA-15 used separately and yields 90 % conversion with 70 % selectivity to propene. The presence of mesopores in the catalyst appears to reduce the diffusion resistance of intermediate products for successive scission, thereby reducing the activation energy of reaction and improving catalytic activity. In conclusion, the hierarchical composite ZSM-5@SBA-15 has significant potential for upcycling of PP into valuable monomers and lighter olefins, with lower energy demands, enhancing the economic feasibility of the process.

ZSM-5@SBA-15↗
DOE OSTI2022

Visualizing the gas channel of a monofunctional carbon monoxide dehydrogenase

Carbon monoxide dehydrogenase (CODH) plays an important role in the processing of the one–carbon gases carbon monoxide and carbon dioxide. In CODH enzymes, these gases are channeled to and from the Ni-Fe-S active sites using hydrophobic cavities. In this work, we investigate these gas channels in a monofunctional CODH from Desulfovibrio vulgaris, which is unusual among CODHs for its oxygen-tolerance. By pressurizing D. vulgaris CODH protein crystals with xenon and solving the structure to 2.10 Å resolution, we identify 12 xenon sites per CODH monomer, thereby elucidating hydrophobic gas channels. We find that D. vulgaris CODH has one gas channel that has not been experimentally validated previously in a CODH, and a second channel that is shared with Moorella thermoacetica carbon monoxide dehydrogenase/acetyl-CoA synthase (CODH/ACS). This experimental visualization of D. vulgaris CODH gas channels lays groundwork for further exploration of factors contributing to oxygen-tolerance in this CODH, as well as study of channels in other CODHs. We dedicate this publication to the memory of Dick Holm, whose early studies of the Ni-Fe-S clusters of CODH inspired us all.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗