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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Application of Cell Painting for chemical hazard evaluation in support of screening-level chemical assessments

‘Cell Painting’ is an imaging-based high-throughput phenotypic profiling (HTPP) method in which cultured cells are fluorescently labeled to visualize subcellular structures (i.e., nucleus, nucleoli, endoplasmic reticulum, cytoskeleton, Golgi apparatus / plasma membrane and mitochondria) and to quantify morphological changes in response to chemicals or other perturbagens. HTPP is a high-throughput and cost-effective bioactivity screening method that detects effects associated with many different molecular mechanisms in an untargeted manner, enabling rapid in vitro hazard assessment for thousands of chemicals. Here, 1201 chemicals from the ToxCast library were screened in concentration-response up to ~100 μM in human U-2 OS cells using HTPP. A phenotype altering concentration (PAC) was estimated for chemicals active in the tested range. PACs tended to be higher than lower bound potency values estimated from a broad collection of targeted high-throughput assays, but lower than the threshold for cytotoxicity. In vitro to in vivo extrapolation (IVIVE) was used to estimate administered equivalent doses (AEDs) based on PACs for comparison to human exposure predictions. AEDs for 18/412 chemicals overlapped with predicted human exposures. Phenotypic profile information was also leveraged to identify putative mechanisms of action and group chemicals. Of 58 known nuclear receptor modulators, only glucocorticoids and retinoids produced characteristic profiles; and both receptor types are expressed in U-2 OS cells. Thirteen chemicals with profile similarity to glucocorticoids were tested in a secondary screen and one chemical, pyrene, was confirmed by an orthogonal gene expression assay as a novel putative GR modulating chemical. Most active chemicals demonstrated profiles not associated with a known mechanism-of-action. However, many structurally related chemicals produced similar profiles, with exceptions such as diniconazole, whose profile differed from other active conazoles. Overall, the present study demonstrates how HTPP can be applied in screening-level chemical assessments through a series of examples and brief case studies.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2024

Learning From User Behavior: A Survey-Assist Algorithm for Longitudinal Mobility Data Collection

GPS-based travel surveys are widely used in mobility studies to gather crucial qualitative data, like purpose, transportation mode and replaced mode. However, survey response still poses a burden to users, especially in long-term mobility studies, leading to response fatigue. We explore a survey-assist strategy to ease this burden by a novel, user-level modeling approach that leverages past responses from each user to predict responses for new trips, without relying on external data sources like GIS data. We investigate three main algorithms for predicting responses: (i) clustering trips and extrapolating responses for similar trips, (ii) using random forest classification, and (iii) clustering that uses a hybrid algorithm to determine spatial structure, which is then fed as input to a classic random forest classifier. The clustering approach can flexibly predict responses for even complex qualitative survey questions; it achieved F-scores of 65%. The random forest pipeline uses architecture that restricts it to predicting three predetermined survey questions: trip purpose, mode, and replaced mode. However, it achieved F-scores of 78%. While the survey-assist approach has been implemented by several proprietary systems, to our knowledge, this is the first exploration in the academic literature. It follows that this is also the first rigorous evaluation of multiple algorithms that can implement the approach. The evaluation uses a large scale, publicly available, longitudinal dataset consisting of ~ 92k trips from 235 users over a period of roughly one and a half years. With this approach, travel surveys can be pre-filled with the predicted responses for each trip, thus streamlining the survey process for users. Combined with an active learning system that requests user input on low-confidence predictions, models can be updated and improved over time to better support the long-term collection of longitudinal qualitative data.

clustering↗
DOE OSTI2018

From utility disconnection to universal access

By some estimates, 31% of Americans face some sort of “energy insecurity”, but the full extent of the issue and the magnitude of its effect often difficult to quantify. This case study examines disconnection policies in Minnesota and attempts to extrapolate lessons learned for other states and the nation as a whole. The case study concludes with discussion about the relevance of utility shut off to US universal access.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2022

A Quantitative Method for In Situ Pump-Beam Metrology in 4D Ultrafast Electron Microscopy

In this work, we report a method for measuring spot size and focusing conditions of the femtosecond (fs) excitation laser in situ at the specimen location in 4D ultrafast electron microscopy (UEM). The method makes use of threshold laser ablation behaviors of thin amorphous carbon membranes. For Gaussian beam profiles and for ablation threshold fluence values, we analytically derive expressions describing the relationship between ablated hole size and the actual laser spot size. Using these expressions, we developed experimental procedures for characterizing the shape and spot size of the pump beam at the specimen. We demonstrate the viability of the approach for incident excitation wavelengths of 343 nm and 515 nm, thus illustrating the applicability of the method to a range of optical wavelengths without modification. Further, we show that by measuring ablated hole size as a function of focusing condition, a full metrological characterization of the Gaussian beam propagation properties can be performed. Finally, we find good agreement for spot sizes determined with this method and with those determined by extrapolation from measurements taken outside the microscope column. Overall, this method is a simple, cost-effective means for accurate and precise determination of key pump-beam parameters in situ at the specimen location in UEM experiments.

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

Rapid discrimination of plastic packaging materials using MIR spectroscopy coupled with independent components analysis (ICA)

Highlights: • An innovative technique, MIR-ICA, was applied to plastic packaging separation. • This study was carried out on PE, PP, PS, PET and PLA plastic packaging materials. • ICA was applied to discriminate plastics and 100% separation rates were obtained. • Analyses performed on two spectrometers proved the reproducibility of the method. • MIR-ICA is a simple and fast technique allowing plastic identification/classification. - Abstract: Plastic packaging wastes increased considerably in recent decades, raising a major and serious public concern on political, economical and environmental levels. Dealing with this kind of problems is generally done by landfilling and energy recovery. However, these two methods are becoming more and more expensive, hazardous to the public health and the environment. Therefore, recycling is gaining worldwide consideration as a solution to decrease the growing volume of plastic packaging wastes and simultaneously reduce the consumption of oil required to produce virgin resin. Nevertheless, a major shortage is encountered in recycling which is related to the sorting of plastic wastes. In this paper, a feasibility study was performed in order to test the potential of an innovative approach combining mid infrared (MIR) spectroscopy with independent components analysis (ICA), as a simple and fast approach which could achieve high separation rates. This approach (MIR-ICA) gave 100% discrimination rates in the separation of all studied plastics: polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polystyrene (PS) and polylactide (PLA). In addition, some more specific discriminations were obtained separating plastic materials belonging to the same polymer family e.g. high density polyethylene (HDPE) from low density polyethylene (LDPE). High discrimination rates were obtained despite the heterogeneity among samples especially differences in colors, thicknesses and surface textures. The reproducibility of the proposed approach was also tested using two spectrometers with considerable differences in their sensitivities. Discrimination rates were not affected proving that the developed approach could be extrapolated to different spectrometers. MIR combined with ICA is a promising tool for plastic waste separation that can help improve performance in this field; however further technological improvements and developments are required before it can be applied at an industrial level given that all tests presented here were performed under laboratory conditions.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2015

Quantification of methane emissions from 15 Danish landfills using the mobile tracer dispersion method

Highlights: • Quantification of whole landfill site methane emission at 15 landfills. • Multiple on-site source identification and quantification. • Quantified methane emission from shredder waste and composting. • Large difference between measured and reported methane emissions. - Abstract: Whole-site methane emissions from 15 Danish landfills were assessed using a mobile tracer dispersion method with either Fourier transform infrared spectroscopy (FTIR), using nitrous oxide as a tracer gas, or cavity ring-down spectrometry (CRDS), using acetylene as a tracer gas. The landfills were chosen to represent the different stages of the lifetime of a landfill, including open, active, and closed covered landfills, as well as those with and without gas extraction for utilisation or flaring. Measurements also included landfills with biocover for oxidizing any fugitive methane. Methane emission rates ranged from 2.6 to 60.8 kg h{sup −1}, corresponding to 0.7–13.2 g m{sup −2} d{sup −1}, with the largest emission rates per area coming from landfills with malfunctioning gas extraction systems installed, and the smallest emission rates from landfills closed decades ago and landfills with an engineered biocover installed. Landfills with gas collection and recovery systems had a recovery efficiency of 41–81%. Landfills where shredder waste was deposited showed significant methane emissions, with the largest emission from newly deposited shredder waste. The average methane emission from the landfills was 154 tons y{sup −1}. This average was obtained from a few measurement campaigns conducted at each of the 15 landfills and extrapolating to annual emissions requires more measurements. Assuming that these landfills are representative of the average Danish landfill, the total emission from Danish landfills were calculated at 20,600 tons y{sup −1}, which is significantly lower than the 33,300 tons y{sup −1} estimated for the national greenhouse gas inventory for 2011.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2017

Using choice architecture to exploit a university Distinct Urban Mine

Highlights: • More than USD 11 million lie within this UK DUM for small household appliances. • Different collection systems should be established for working or broken appliances. • Consumer behaviour should inform choice architecture. •DUM evaluations should inform future collection system investments. - Abstract: There are widespread concerns regarding the potential future scarcity of ferrous and non-ferrous materials. However, there are already potentially rich reserves of secondary materials via high ownership of Electrical and Electronic Equipment (EEE) in economically-developed nations. Young people are particularly high consumers of EEE, thus university students and campuses may present an opportunity to harness this potential. University Distinct Urban Mines (DUM) may be used to exemplify how potential reserves of secondary metals may be exploited, and could contribute to the transition from a linear to a circular economy. This study aimed to evaluate small household appliances (SHA) DUM from a UK university, with the objectives to identify and quantify student households’ SHA ownership, WEEE recycling, stockpiling and discarding habits amongst student households, assess and evaluate the monetary potential of SHA DUM at UK level, and propose methods to exploit DUM for universities in the UK. To this purpose, a quantitative survey was undertaken to measure students’ ownership and discarding behaviour with respect to SHA. The amounts of ferrous and non-ferrous materials were then estimated and converted to monetary values from secondary materials market data to appraise the SHA DUM overall value. Thirty-five per cent of SHA are discarded in the general refuse. Broken personal care appliances (PCA) tend to be discarded due to hygiene and small size factors. When in working order, SHA tend to be equally reused, recycled or stockpiled. We conclude that a total of 189 tonnes of ferrous and non-ferrous materials were available via discarding or being stockpiled at the University of Southampton. Extrapolated to UK higher education level, discarded and stockpiled SHA represent a potential worth ∼USD 11 million. To initiate DUM exploitation within Higher Education campuses, we suggest improving users’ choice architecture by providing collection methods specific to broken SHA.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Chemodiversity of riverine dissolved organic matter: Effects of local environments and watershed characteristics

Riverine dissolved organic matter (DOM) is crucial to global carbon cycling and aquatic ecosystems. However, the geographical patterns and environmental correlates of DOM chemodiversity remain elusive especially in surface waters and sediments of global rivers. Here, we systematically analyzed DOM molecular diversity and composition in surface waters and sediments across 97 globally distributed rivers using data from the Worldwide Hydrobiogeochemistry Observation Network for Dynamic River Systems (WHONDRS) consortium. Here, we further examined the associations of molecular richness and composition with geographical, climatic, physicochemical variables, as well as the watershed characteristics. We found that molecular richness significantly decreased toward higher latitudes, but only in sediments (r = -0.24, P < 0.001). The environmental variables like precipitation and non-purgeable organic carbon showed strong associations with DOM molecular richness and composition. Interestingly, we identified that less-documented factors like watershed characteristics were also related to DOM molecular richness and composition, and were stronger in waters than sediments. Such associations were further supported by the fact that 11 out of 13 watershed characteristics (e.g., land cover variables) showed more positive than negative correlations with molecular abundance especially in waters. The molecules positively and negatively correlated with specific watershed characteristics had distinct traits, such as stoichiometric ratios and aromaticity. Land covers shifted from natural (e.g., forests) to human-modified (e.g., impervious area) were associated with systematic changes in DOM molecular chemistry. Our findings imply that it may be possible to use a small set of broadly available data types to predict DOM molecular richness and composition across diverse river systems. Elucidation of mechanisms underlying these relationships will provide further enhancements to such predictions, especially when extrapolating to unsampled systems.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2015

Unique proliferation response in odontoblastic cells derived from human skeletal muscle stem cells by cytokine-induced matrix metalloproteinase-3

A pro-inflammatory cytokine mixture (CM: interleukin (IL)-1β, tumor necrosis factor-α and interferon-γ) and IL-1β-induced matrix metalloproteinase (MMP)-3 activity have been shown to increase the proliferation of rat dental pulp cells and murine stem cell-derived odontoblast-like cells. This suggests that MMP-3 may regulate wound healing and regeneration in the odontoblast-rich dental pulp. Here, we determined whether these results can be extrapolated to human dental pulp by investigating the effects of CM-induced MMP-3 up-regulation on the proliferation and apoptosis of purified odontoblast-like cells derived from human skeletal muscle stem cells. We used siRNA to specifically reduce MMP-3 expression. We found that CM treatment increased MMP-3 mRNA and protein levels as well as MMP-3 activity. Cell proliferation was also markedly increased, with no changes in apoptosis, upon treatment with CM and following the application of exogenous MMP-3. Endogenous tissue inhibitors of metalloproteinases were constitutively expressed during all experiments and unaffected by MMP-3. Although treatment with MMP-3 siRNA suppressed cell proliferation, it also unexpectedly increased apoptosis. This siRNA-mediated increase in apoptosis could be reversed by exogenous MMP-3. These results demonstrate that cytokine-induced MMP-3 activity regulates cell proliferation and suppresses apoptosis in human odontoblast-like cells. - Highlights: • Pro-inflammatory cytokines induce MMP-3 activity in human odontoblast-like cells. • Increased MMP-3 activity can promote cell proliferation in odontoblasts. • Specific loss of MMP-3 increases apoptosis in odontoblasts. • MMP-3 has potential as a promising new target for pupal repair and regeneration.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2021

Homotypic aggregates contribute to heterogeneity in B cell fates due to an intrinsic gradient of stimulant exposure

Highlights: • CD40-signaled B cells in cultures form three-dimensional homotypic aggregates. • These tight aggregates hinder the free diffusion of large molecule stimulants. • The resulting concentration gradient of stimulants leads to heterogeneous cell fates. • We describe a flow cytometric approach to quantify this positional information. Monocultures of several cell types result in the formation of robust clusters called homotypic aggregates (HAs). How this physical aggregation affects cell fates in immune cell cultures, is poorly understood. We studied anti-CD40-stimulated primary B cell cultures, where cells assembled into large three-dimensional LFA1-driven HAs by 72 h. The dense packing in these aggregates restricts the infiltration of stimulants, such as antibodies, to cells inside the clusters. This creates a concentration gradient of stimulant availability across the cross-section of HAs. We describe a method to retain this positional information even after the disruption of HAs, for analysis by flow cytometry. Comparison of stage-specific cell-surface markers showed that the extent of stimulant-binding affected multiple fates non-uniformly. While germinal center and lineage markers were moderately upregulated, immunoglobulins and markers associated with memory were more than doubled in the peripheral cells binding more anti-CD40. These cells also experienced a strong repression of the plasma cell regulator Prdm1 and an upregulation of the oncogene Myc. Thus, cells at different locations in HAs are subjected to unequal doses of stimulants, leading to a hitherto unreported source of heterogeneity in cell fates. These findings can be extrapolated to understand the dose-dependent effects of stimulants in other three-dimensional cell clusters.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2023

Neural network ensembles and uncertainty estimation for predictions of inelastic mechanical deformation using a finite element method-neural network approach

The finite element method (FEM) is widely used to simulate a variety of physics phenomena. Approaches that integrate FEM with neural networks (NNs) are typically leveraged as an alternative to conducting expensive FEM simulations in order to reduce the computational cost without significantly sacrificing accuracy. However, these methods can produce biased predictions that deviate from those obtained with FEM, since these hybrid FEM-NN approaches rely on approximations trained using physically relevant quantities. In this work, an uncertainty estimation framework is introduced that leverages ensembles of Bayesian neural networks to produce diverse sets of predictions using a hybrid FEM-NN approach that approximates internal forces on a deforming solid body. The uncertainty estimator developed herein reliably infers upper bounds of bias/variance in the predictions for a wide range of interpolation and extrapolation cases using a three-element FEM-NN model of a bar undergoing plastic deformation. This proposed framework offers a powerful tool for assessing the reliability of physics-based surrogate models by establishing uncertainty estimates for predictions spanning a wide range of possible load cases.

42 ENGINEERING↗
DOE OSTI2018

Local Spatial Heterogeneity of Holocene Carbon Accumulation throughout the Peat Profile of an Ombrotrophic Northern Minnesota Bog

Here, we evaluated the spatial heterogeneity of historical carbon accumulation rates in a forested, ombrotrophic bog in Minnesota to aid understanding of responses to an ongoing decade-long warming manipulation. Eighteen peat cores indicated that the bog has been accumulating carbon for over 11,000 years, to yield 176±40 kg C m –2 to 225±58 cm of peat depth. Estimated peat basal ages ranged from 5100 to 11,100 cal BP. The long-term apparent rate of carbon accumulation over the entire peat profile was 22±2 kg C m –2 yr –1 . Plot location within the study area did not affect carbon accumulation rates, but estimated basal ages were younger in profiles from plots closer to the bog lagg and farther from the bog outlet. In addition, carbon accumulation varied considerably over time. Early Holocene net carbon accumulation rates were 30±6 g C m –2 yr –1 . Around 3300 calendar BP, net carbon accumulation rates dropped to 15±8 g C m –2 yr –1 until the last century when net accumulation rates increased again to 74±57 g C m –2 yr –1 . During this period of low accumulation, regional droughts may have lowered the water table, allowing for enhanced aerobic decomposition and making the bog more susceptible to fire. These results suggest that experimental warming treatments, as well as a future warmer climate may reduce net carbon accumulation in peat in this and other southern boreal peatlands. Furthermore, our we caution against historical interpretations extrapolated from one or a few peat cores.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Turbulent impurity transport simulations in Wendelstein 7-X plasmas

A study of turbulent impurity transport by means of quasilinear and nonlinear gyrokinetic simulations is presented for Wendelstein 7-X (W7-X). The calculations have been carried out with the recently developed gyrokinetic code stella. Different impurity species are considered in the presence of various types of background instabilities: ion temperature gradient (ITG), trapped electron mode (TEM) and electron temperature gradient (ETG) modes for the quasilinear part of the work; ITG and TEM for the nonlinear results. While the quasilinear approach allows one to draw qualitative conclusions about the sign or relative importance of the various contributions to the flux, the nonlinear simulations quantitatively determine the size of the turbulent flux and check the extent to which the quasilinear conclusions hold. Although the bulk of the nonlinear simulations are performed at trace impurity concentration, nonlinear simulations are also carried out at realistic effective charge values, in order to know to what degree the conclusions based on the simulations performed for trace impurities can be extrapolated to realistic impurity concentrations. The presented results conclude that the turbulent radial impurity transport in W7-X is mainly dominated by ordinary diffusion, which is close to that measured during the recent W7-X experimental campaigns. Finally, it is also confirmed that thermodiffusion adds a weak inward flux contribution and that, in the absence of impurity temperature and density gradients, ITG- and TEM-driven turbulence push the impurities inwards and outwards, respectively.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

Astrovirology: how viruses enhance our understanding of life in the Universe

Abstract Viruses are the most numerically abundant biological entities on Earth. As ubiquitous replicators of molecular information and agents of community change, viruses have potent effects on the life on Earth, and may play a critical role in human spaceflight, for life-detection missions to other planetary bodies and planetary protection. However, major knowledge gaps constrain our understanding of the Earth's virosphere: (1) the role viruses play in biogeochemical cycles, (2) the origin(s) of viruses and (3) the involvement of viruses in the evolution, distribution and persistence of life. As viruses are the only replicators that span all known types of nucleic acids, an expanded experimental and theoretical toolbox built for Earth's viruses will be pivotal for detecting and understanding life on Earth and beyond. Only by filling in these knowledge and technical gaps we will obtain an inclusive assessment of how to distinguish and detect life on other planetary surfaces. Meanwhile, space exploration requires life-support systems for the needs of humans, plants and their microbial inhabitants. Viral effects on microbes and plants are essential for Earth's biosphere and human health, but virus–host interactions in spaceflight are poorly understood. Viral relationships with their hosts respond to environmental changes in complex ways which are difficult to predict by extrapolating from Earth-based proxies. These relationships should be studied in space to fully understand how spaceflight will modulate viral impacts on human health and life-support systems, including microbiomes. In this review, we address key questions that must be examined to incorporate viruses into Earth system models, life-support systems and life detection. Tackling these questions will benefit our efforts to develop planetary protection protocols and further our understanding of viruses in astrobiology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Stimulus-Responsive Modulation of Solvation Environments in Solid Catalysts

Liquid environments play a crucial role in the biological processes occurring in living organisms as well as in many human-made processes involving electrochemistry, photo-, and thermocatalysis. In the majority of these systems, aqueous phases are ubiquitous due to water’s natural abundance. Water molecules, however, can exert large changes in the chemical environment of catalytically active sites, altering the reaction rates, selectivity, and catalyst stability. These solvation effects induced by water molecules near catalytic sites can drastically change the energy landscape and unlock unique reaction pathways with far more favorable kinetics. In nature, living organisms couple these complex interactions with detection, communication, and actuation mechanisms to induce self-regulatory behavior, ensuring stability of the system and thus long-term durability. Extrapolating this behavior to heterogeneous catalysis is desirable because the resulting “smart materials” can potentially unlock new chemical conversion processes with higher atom efficiency, rates, and stability. The combination of polymer chemistry and heterogeneous catalysis has introduced versatile approaches for creating materials that can respond to cues in the reaction medium that alter the accessibility, intrinsic activity, and selectivity of the catalyst. To achieve this, one could combine stimulus-responsive polymers, which undergo a large volumetric phase transition in response to an external stimulus, with a solid catalyst. This chemo-mechanical response has been employed to create a variety of nanoreactor vessels with stimulus-responsive character that turn on- and off- depending on the reaction conditions. In this Account, we focus on the impact of these polymer coatings on the solvation environment around the active site and the implications of these effects on the reaction energy landscape, molecular arrangement of the solvent, electric fields at the catalyst–liquid interface, binding energy, and mobility of surface reaction intermediates. These seemingly subtle changes in solvent molecules induced by the presence of polymers can have a tremendous impact on the development of bioinspired heterogeneous catalysts, reliable chemical clocks, micro/nanoreactors, and robots. The large library of polymer chemistries offers a plethora of combinations of stimulus-responsive mechanisms (e.g., temperature, pH, light, magnetic field, solvent composition), providing the possibility of creating homeostatic catalysts à la carte.

catalysts↗
DOE OSTI2018

Structural, Biochemical, and Evolutionary Characterizations of Glyoxylate/Hydroxypyruvate Reductases Show Their Division into Two Distinct Subfamilies

The d-2-hydroxyacid dehydrogenase (2HADH) family illustrates a complex evolutionary history with multiple lateral gene transfers and gene duplications and losses. As a result, the exact functional annotation of individual members can be extrapolated to a very limited extent. Here, we revise the previous simplified view on the classification of the 2HADH family; specifically, we show that the previously delineated glyoxylate/hydroxypyruvate reductase (GHPR) subfamily consists of two evolutionary separated GHRA and GHRB subfamilies. We compare two representatives of these subfamilies from Sinorhizobium meliloti (SmGhrA and SmGhrB), employing a combination of biochemical, structural, and bioinformatics approaches. Our kinetic results show that both enzymes reduce several 2-ketocarboxylic acids with overlapping, but not equivalent, substrate preferences. SmGhrA and SmGhrB show highest activity with glyoxylate and hydroxypyruvate, respectively; in addition, only SmGhrB reduces 2-keto-d-gluconate, and only SmGhrA reduces pyruvate (with low efficiency). We present nine crystal structures of both enzymes in apo forms and in complexes with cofactors and substrates/substrate analogues. In particular, we determined a crystal structure of SmGhrB with 2-keto-d-gluconate, which is the biggest substrate cocrystallized with a 2HADH member. Here, the structures reveal significant differences between SmGhrA and SmGhrB, both in the overall structure and within the substrate-binding pocket, offering insight into the molecular basis for the observed substrate preferences and subfamily differences. In addition, we provide an overview of all GHRA and GHRB structures complexed with a ligand in the active site.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Short Intramolecular O···O Contact in Some o -Dialkoxybenzene Derivatives Generates Efficient Hydrogen Bonding Acceptor Area

Statistical analysis of data extracted from the Cambridge Structural Database (CSD) has been used to investigate the crystal structure properties of odialkoxybenzene derivatives, compounds containing two ether oxygen acceptors in ortho positions of benzene ring. It has been shown that in more than 90% of cases, the fragment has predictable geometrical characteristics where the two ether oxygens form short interatomic O center dot center dot center dot O contact (2.57 A in average), while O-substitutents take trans position, both approximately coplanar with the benzene ring. Such arrangement of oxygen acceptors produces a large and uniform area of the negative electrostatic potential suitable for multiple hydrogen bonding. The acceptor abilities of the O center dot center dot center dot O system have been investigated by the statistical CSD analysis. The ab initio estimation of the interaction energy in the dimer of o-dimethoxybenzene (DMB) and H2O, employed as a model system, is achieved via high-level electron correlation CCSD(T) calculation with the complete basis set extrapolation. The interaction energy is estimated to be 6.5 kcal/mol. The results indicate the existence of a very flat potential the region between methoxy oxygens and that DMB water is a highly flexible system. The structural role of the O center dot center dot center dot O acceptor system is particularly interesting considering its ability to form multiple hydrogen bonding.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗