SEARCH · Search NASA
Results for “VC”
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.
Respiratory Vinyl Chloride Reductive Dechlorination to Ethene in TceA-Expressing Dehalococcoides mccartyi
Bioremediation of chlorinated ethenes in anoxic aquifers hinges on organohalide-respiring Dehalococcoidia expressing vinyl chloride (VC) reductive dehalogenase (RDase). The tceA gene encoding the trichloroethene-dechlorinating RDase TceA is frequently detected in contaminated groundwater but not recognized as a biomarker for VC detoxification. We demonstrate that tceA-carrying Dehalococcoides mccartyi (Dhc) strains FL2 and 195 grow with VC as an electron acceptor when sufficient vitamin B 12 (B 12 ) is provided. Strain FL2 cultures that received 50 μg L –1 B 12 completely dechlorinated VC to ethene at rates of 14.80 ± 1.30 μM day –1 and attained 1.64 ± 0.11 × 10 8 cells per μmol of VC consumed. Strain 195 attained similar growth yields of 1.80 ± 1.00 × 10 8 cells per μmol of VC consumed, and both strains could be consecutively transferred with VC as the electron acceptor. Proteomic analysis demonstrated TceA expression in VC-grown strain FL2 cultures. Resequencing of the strain FL2 and strain 195 tceA genes identified non-synonymous substitutions, although their consequences for TceA function are currently unknown. The finding that Dhc strains expressing TceA respire VC can explain ethene formation at chlorinated solvent sites, where quantitative polymerase chain reaction analysis indicates that tceA dominates the RDase gene pool.
New echocardiographic windows for quantitative determination of aortic regurgitation volume using color Doppler flow convergence and vena contracta
Color Doppler images of aortic regurgitation (AR) flow acceleration, flow convergence (FC), and the vena contracta (VC) have been reported to be useful for evaluating severity of AR. However, clinical application of these methods has been limited because of the difficulty in clearly imaging the FC and VC. This study aimed to explore new windows for imaging the FC and VC to evaluate AR volumes in patients and to validate this in animals with chronic AR. Forty patients with AR and 17 hemodynamic states in 4 sheep with strictly quantified AR volumes were evaluated. A Toshiba SSH 380A with a 3.75-MHz transducer was used to image the FC and VC. After routine echo Doppler imaging, patients were repositioned in the right lateral decubitus position, and the FC and VC were imaged from high right parasternal windows. In only 15 of the 40 patients was it possible to image clearly and measure accurately the FC and VC from conventional (left decubitus) apical or parasternal views. In contrast, 31 of 40 patients had clearly imaged FC regions and VCs using the new windows. In patients, AR volumes derived from the FC and VC methods combined with continuous velocity agreed well with each other (r = 0.97, mean difference = -7.9 ml +/- 9.9 ml/beat). In chronic animal model studies, AR volumes derived from both the VC and the FC agreed well with the electromagnetically derived AR volumes (r = 0.92, mean difference = -1.3 +/- 4.0 ml/beat). By imaging from high right parasternal windows in the right decubitus position, complementary use of the FC and VC methods can provide clinically valuable information about AR volumes.
Cometabolic Vinyl Chloride Degradation at Acidic pH Catalyzed by Acidophilic Methanotrophs Isolated from Alpine Peat Bogs
Remediation of toxic chlorinated ethenes via microbial reductive dechlorination can lead to ethene formation; however, the process stalls in acidic groundwater, leading to the accumulation of carcinogenic vinyl chloride (VC). This study explored the feasibility of cometabolic VC degradation by moderately acidophilic methanotrophs. Furthermore, two novel isolates, Methylomonas sp. strain JS1 and Methylocystis sp. strain MJC1, were obtained from distinct alpine peat bogs located in South Korea. Both isolates cometabolized VC with CH 4 as the primary substrate under oxic conditions at pH at or below 5.5. VC cometabolism in axenic cultures occurred in the presence (10 μM) or absence (<0.01 μM) of copper, suggesting that VC removal had little dependence on copper availability, which regulates expression and activity of soluble and particulate methane monooxygenases in methanotrophs. The model neutrophilic methanotroph Methylosinus trichosporium strain OB3b also grew and cometabolized VC at pH 5.0 regardless of copper availability. Bioaugmentation of acidic peat soil slurries with methanotroph isolates demonstrated enhanced VC degradation and VC consumption below the maximum concentration level of 2 μg L –1 . Community profiling of the microcosms suggested species-specific differences, indicating that robust bioaugmentation with methanotroph cultures requires further research.
Dehalogenation of Chlorinated Ethenes to Ethene by a Novel Isolate, “ Candidatus Dehalogenimonas etheniformans”
Dehalococcoides mccartyi strains harboring vinyl chloride (VC) reductive dehalogenase (RDase) genes are keystone bacteria for VC detoxification in groundwater aquifers, and bioremediation monitoring regimens focus on D. mccartyi biomarkers. We isolated a novel anaerobic bacterium, “Candidatus Dehalogenimonas etheniformans” strain GP, capable of respiratory dechlorination of VC to ethene. This bacterium couples formate and hydrogen (H2) oxidation to the reduction of trichloro-ethene (TCE), all dichloroethene (DCE) isomers, and VC with acetate as the carbon source. Cultures that received formate and H2 consumed the two electron donors concomitantly at similar rates. A 16S rRNA gene-targeted quantitative PCR (qPCR) assay measured growth yields of (1.2 ± 0.2) × 10 8 and (1.9 ± 0.2) × 10 8 cells per μmol of VC dechlorinated in cultures with H 2 or formate as electron donor, respectively. About 1.5-fold higher cell numbers were measured with qPCR targeting cerA, a single-copy gene encoding a putative VC RDase. A VC dechlorination rate of 215 ± 40 μmol L -1 day -1 was measured at 30°C, with about 25% of this activity occurring at 15°C. Increasing NaCl concentrations progressively impacted VC dechlorination rates, and dechlorination ceased at 15 g NaCl L -1 . During growth with TCE, all DCE isomers were intermediates. Tetrachloroethene was not dechlorinated and inhibited dechlorination of other chlorinated ethenes. Carbon monoxide formed and accumulated as a metabolic by-product in dechlorinating cultures and impacted reductive dechlorination activity. Finally, the isolation of a new Dehalogenimonas species able to effectively dechlorinate toxic chlorinated ethenes to benign ethene expands our understanding of the reductive dechlorination process, with implications for bioremediation and environmental monitoring.
The infall velocity toward Virgo, the Hubble constant, and a search for motion toward the microwave background
The perturbation of the local velocity field due to the overdensity of the Virgo complex (VC) is investigated theoretically, using an idealized spherically symmetric Virgocentric flow model and testing for a correlation between cos theta (where theta is the angle from the VC direction to eight groups and clusters with velocity 800-2500 km/s) and the relevant velocity residuals. The data and results are presented in extensive tables, graphs, and a map in extragalactic coordinates. The infall of the Local Group (LG) toward the VC is estimated as 200 + or - 50 km/s, corresponding to a mean mass/light ratio M/L(B) = about 70 for a sphere centered at the VC core and extending to the LG. The rate of free expansion within the VC is estimated as 52 + or 2 km/s Mpc for a VC distance of 21.6 Mpc. It is pointed out that the LG infall toward the VC cannot account for observations of an apparent 630-km/s motion of the LG toward the microwave background.
The crystal structure of Vibrio cholerae (6-4) photolyase reveals interactions with cofactors and a DNA-binding region
Photolyases (PLs) reverse UV-induced DNA damage using blue light as an energy source. Of these PLs, (6-4) PLs repair (6-4)-lesioned photoproducts. We recently identified a gene from Vibrio cholerae (Vc) encoding a (6-4) PL, but structural characterization is needed to elucidate specific interactions with the chromophore cofactors. Here, we determined the crystal structure of Vc (6-4) PL at 2.5 Å resolution. Our high-resolution structure revealed that the two well-known cofactors, flavin adenine dinucleotide and the photoantenna 6,7-dimethyl 8-ribityl-lumazin (DMRL), stably interact with an α-helical and an α/β domain, respectively. Additionally, the structure has a third cofactor with distinct electron clouds corresponding to a [4Fe-4S] cluster. Moreover, we identified that Asp106 makes a hydrogen bond with water and DMRL, which indicates further stabilization of the photoantenna DMRL within Vc (6-4) PL. Further analysis of the Vc (6-4) PL structure revealed a possible region responsible for DNA binding. The region located between residues 478 to 484 may bind the lesioned DNA, with Arg483 potentially forming a salt bridge with DNA to stabilize further the interaction of Vc (6-4) PL with its substrate. Our comparative analysis revealed that the DNA lesion could not bind to the Vc (6-4) PL in a similar fashion to the Drosophila melanogaster (Dm, (6-4)) PL without a significant conformational change of the protein. The 23rd helix of the bacterial (6-4) PLs seems to have remarkable plasticity, and conformational changes facilitate DNA binding. In conclusion, our structure provides further insight into DNA repair by a (6-4) PL containing three cofactors.
Functionalized Silicon Particles for Enhanced Half- and Full-Cell Cycling of Si-Based Li-Ion Batteries
Vinylene carbonate (VC) and polyethylene oxide (PEO) have been investigated as functional agents that mimic the solid electrolyte interphase (SEI) chemistry of silicon (Si). VC and PEO are known to contribute to the stability of Si-based lithium-ion batteries as an electrolyte additive and as a SEI component, respectively. In this work, covalent surface functionalization was achieved via a facile route, which involves ball-milling the Si particles with sacrificial VC and PEO. Thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), and magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy indicate that the additives are strongly bound to Si. In particular, MAS NMR shows Si–R or Si–O–R groups, which confirm functionalization of the Si after milling in VC or PEO. Particle size analysis by dynamic light scattering reveals that the additives facilitate particle size reduction and that the functionalized particles result in more stable dispersions based on zeta potential measurements. Raman mapping of the electrodes fabricated from the VC and PEO-coated active material with a polyacrylic acid (PAA) binder reveals a more homogenous distribution of Si and the carbon conductive additive compared to the electrodes prepared from the neat Si. Furthermore, the VC-milled Si strikingly exhibited the highest capacity in both half- and full-cell configurations, with more than 200 mAh g –1 measured capacity compared to the neat Si in the half-cell format. This is linked to an improved electrode processing based on the Raman and zeta potential measurements as well as a thinner SEI (with more organic components for the functionalized Si relative to the neat Si) based on XPS analysis of the cycled electrodes. In conclusion, the effect of binder was also investigated by comparing PAA with P84 (polyimide type), where an increased capacity is observed in the latter case.
Comparative Study of Vinylene Carbonate and Lithium Difluoro(oxalate)borate Additives in a SiO x /Graphite Anode Lithium-Ion Battery in the Presence of Fluoroethylene Carbonate
The SiO x /graphite composite is recognized as a promising anode material for lithium-ion batteries (LIBs), owing to the high theoretical capacity of SiO x combined with the excellent stability of graphite. However, the inherent disadvantage of volume expansion in silicon-based anodes places significant challenges on the solid electrolyte interphase (SEI) and severely degrades the electrochemical performance. Rational formulation of electrolyte, including its additives, is crucial in accommodating and optimizing the composition of the SEI and enhancing the cell performance. In this work, we present a comparative study of vinylene carbonate (VC) and lithium difluoro(oxalate)borate (LiDFOB) additives combined with fluoroethylene carbonate (FEC) in the electrolyte for SiO x /graphite∥LiNi 1–x–y–z Co x Mn y Al z O 2 full cells. VC outperformed LiDFOB as an additive, delivering higher capacity cycling, higher Coulombic efficiency, and better cycle stability up to 400 cycles. XPS and impedance analyses reveal that LiDFOB contributed to SEI/CEI with both a lower proportion of LiF and a higher proportion of poly(VC), which tended to produce higher cell impedance. XRD and XANES further indicated that using the LiDFOB additive, the NCMA cycled to a shallower degree than that of the VC additive. Although the VC additive maintained a higher capacity up to 400 cycles, microstrain and SEM analyses show a higher strained NCMA along with clear evidence of cracking over the surface of the NCMA particle in VC-based electrolyte but not in LiDFOB. In conclusion, this suggests that the negative influence of LiDFOB at the anode (inferior SEI) supersedes the negative impact of both a cracked NCMA and a deeper cycled NCMA and SiO x -based anode.
Elastic Properties across the y→α Volume Collapse in Cerium versus Pressure and Temperature
Here, the longitudinal and transverse sound speeds, c L and c T , of polycrystalline cerium were measured isothermally vs pressure up to the critical temperature across the iso-structural γ-α volume collapse (VC) phase transition. We deduce values for the adiabatic bulk modulus BS, the shear modulus G = ρc T 2 , the Poisson’s ratio ν and the Debye temperature, θ D (p). We find that the elastic constant C 12 is solely responsible for the decrease of B S with pressure towards the VC at RT. With increasing temperature, the lattice contribution ΔS vib (γ→α) to the total entropy change across the VC decreases more rapidly to zero than the total entropy itself suggesting that another mechanism, possibly disorder, assists in stabilizing the γ-phase entropically against the α-phase. Also, with increasing temperature, the Poisson’s ratio becomes negative near the VC transition, meaning that cerium metal takes on auxetic characteristics over a small pressure range. At the critical point the Poisson’s ratio ought to be -1, since the isothermal bulk modulus vanishes and the shear modulus remains nonzero.
Ultrafast vibrational control of organohalide perovskite optoelectronic devices using vibrationally promoted electronic resonance
Vibrational control (VC) of photochemistry through the optical stimulation of structural dynamics is a nascent concept only recently demonstrated for model molecules in solution. Extending VC to state-of-the-art materials may lead to new applications and improved performance for optoelectronic devices. Metal halide perovskites are promising targets for VC due to their mechanical softness and the rich array of vibrational motions of both their inorganic and organic sublattices. Here, we demonstrate the ultrafast VC of FAPbBr 3 perovskite solar cells via intramolecular vibrations of the formamidinium cation using spectroscopic techniques based on vibrationally promoted electronic resonance. The observed short (~300 fs) time window of VC highlights the fast dynamics of coupling between the cation and inorganic sublattice. First-principles modelling reveals that this coupling is mediated by hydrogen bonds that modulate both lead halide lattice and electronic states. Cation dynamics modulating this coupling may suppress non-radiative recombination in perovskites, leading to photovoltaics with reduced voltage losses.
Solvent oligomerization pathways facilitated by electrolyte additives during solid-electrolyte interphase formation
The solid–electrolyte interphase (SEI) layer formation is known to play an important role in determining the lifetime of lithium-ion batteries. A thin, stable SEI layer is linked to overall improved battery performance and longevity, however, the factors and mechanisms that lead to optimal SEI morphology and composition are not well understood. Inclusion of electrolyte additives (fluoroethylene carbonate, FEC; and vinylene carbonate, VC) is often necessary for improving SEI characteristics. To understand how these electrolyte additives impact SEI formation, we employed molecular dynamics (MD) and density functional theory (DFT) simulations to study the reaction networks and oligomerization pathways, respectively, for three systems containing ethylene carbonate (EC), a lithium ion, and FEC or VC. MD simulations suggest radical oligomerization pathways analogous to traditional oligomerization with nucleophilic alkoxide species via SN1 reaction mechanisms. Both S N 1 and S N 2 mechanisms were studied for all three systems using DFT. Oligomerization reactions were studied with both a standard alkoxide species and a ring-opened EC radical as the nucleophiles and EC, FEC, and VC as the electrophiles. For all cases, FEC and VC exhibited lower free energy barriers and more stable adducts when compared with EC. We conclude that one of the role of additives is to modify the oligomerization process of EC by introducing branching points (FEC) or termination points (VC).
Two-dimensional spatiotemporal coding of linear acceleration in vestibular nuclei neurons
Response properties of vertical (VC) and horizontal (HC) canal/otolith-convergent vestibular nuclei neurons were studied in decerebrate rats during stimulation with sinusoidal linear accelerations (0.2-1.4 Hz) along different directions in the head horizontal plane. A novel characteristic of the majority of tested neurons was the nonzero response often elicited during stimulation along the "null" direction (i.e., the direction perpendicular to the maximum sensitivity vector, Smax). The tuning ratio (Smin gain/Smax gain), a measure of the two-dimensional spatial sensitivity, depended on stimulus frequency. For most vestibular nuclei neurons, the tuning ratio was small at the lowest stimulus frequencies and progressively increased with frequency. Specifically, HC neurons were characterized by a flat Smax gain and an approximately 10-fold increase of Smin gain per frequency decade. Thus, these neurons encode linear acceleration when stimulated along their maximum sensitivity direction, and the rate of change of linear acceleration (jerk) when stimulated along their minimum sensitivity direction. While the Smax vectors were distributed throughout the horizontal plane, the Smin vectors were concentrated mainly ipsilaterally with respect to head acceleration and clustered around the naso-occipital head axis. The properties of VC neurons were distinctly different from those of HC cells. The majority of VC cells showed decreasing Smax gains and small, relatively flat, Smin gains as a function of frequency. The Smax vectors were distributed ipsilaterally relative to the induced (apparent) head tilt. In type I anterior or posterior VC neurons, Smax vectors were clustered around the projection of the respective ipsilateral canal plane onto the horizontal head plane. These distinct spatial and temporal properties of HC and VC neurons during linear acceleration are compatible with the spatiotemporal organization of the horizontal and the vertical/torsional ocular responses, respectively, elicited in the rat during linear translation in the horizontal head plane. In addition, the data suggest a spatially and temporally specific and selective otolith/canal convergence. We propose that the central otolith system is organized in canal coordinates such that there is a close alignment between the plane of angular acceleration (canal) sensitivity and the plane of linear acceleration (otolith) sensitivity in otolith/canal-convergent vestibular nuclei neurons.
Atomic to Nanoscale Origin of Vinylene Carbonate Enhanced Cycling Stability of Lithium Metal Anode Revealed by Cryo-Transmission Electron Microscopy
Batteries using lithium (Li) metal as anode are considered promising energy storage systems because of their high specific energy densities. The crucial bottlenecks for Li-metal anode are Li dendrites growth and side reactions with electrolyte inducing low Coulombic efficiency (CE) and short cycle life. Vinylene carbonate (VC), as an effective electrolyte additive in Li-ion batteries, has been noticed to significantly enhance the CE, while the origin of such an additive remains unclear. Here we use cryo-TEM imaging combing with EDS elemental and EELS electronic structure analyses to reveal the role of VC additive. We discovered that the electrochemically deposited Li metal (EDLi) in VC-containing electrolyte is slightly oxidized with the SEI being a nanoscale-mosaic like structure comprised of organic species, Li 2 O and Li 2 CO 3 ; while the EDLi formed in VC-free electrolyte is featured by a combination of fully oxidized Li with Li 2 O SEI layer and pure Li metal with multilayer nano-structured SEI. These results highlight the possible tuning of crucial structural and chemical features of EDLi and SEI through additives and consequently direct correlation with electrochemical performance, providing valuable guidelines to rational selection, design and synthesis of additives for new battery chemistries.