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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 451 records · Page 25
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Biorefinery upgrading of herbaceous biomass to renewable hydrocarbon fuels, Part 1: Process modeling and mass balance analysis

Process simulation has long been a well-established tool to track key operational, design, and mass and energy balance metrics for pre-commercial technologies such as advanced lignocellulosic biofuels. While tools such as this are well-documented in the public literature around 2nd-generation cellulosic ethanol technologies (which have been scaled up to commercial deployment to some degree over the past decade), such models and analysis information remain more sparse for more complex biorefinery pathways focused on producing drop-in hydrocarbon fuels and blend-stocks, particularly regarding information required to support air emissions or other environmental analysis. In this work, we summarize key details for an established "design case" modeling the conversion of herbaceous lignocellulosic biomass into a renewable diesel hydrocarbon blend-stock based on a representative lipid pathway from oleaginous yeast. The process is based on a biochemical deconstruction and upgrading approach utilizing deacetylation and dilute acid pretreatment, followed by enzymatic hydrolysis, fermentation, and catalytic upgrading of hydrolysate sugars to fuels. We provide key mass and energy balance outputs from the process models, with accompanying stream tables and component-level flowrates. A total of 12 model scenarios are presented spanning two feedstocks, three biorefinery scales, and two processing approaches for the lignin/residual solids waste streams. This "Part 1" manuscript presents the resulting impacts across the 12 cases on fuel yields and key output streams, focused here on direct biorefinery air emissions for selected components including CO 2 as well as sulfur (SOx) and nitrogen oxides (NOx). In the context of cleaner production, the latter focus on selected biorefinery air emission outputs establishes an initial baseline estimate and accompanying framework of the model cases, upon which an accompanying "Part 2" study will build to refine the values for these and other air pollutants across these scenarios, also considering mitigation options to comply with applicable regulatory standards. We also highlight further optimization opportunities based on potential tradeoffs identified here between air emissions versus life-cycle greenhouse gas profiles attributed to the disposition of lignin/residual solids.

09 BIOMASS FUELS↗
DOE OSTI2022

Engineering of holocellulase in biomass-degrading fungi for sustainable biofuel production

Biofuels, such as bioethanol, are a clean and sustainable form of energy and have emerged as a viable alternative to fossil fuels. Plant biomass is an important raw material for the production of clean and renewable energy. The holocellulose contained in the composition of plants may be broken down into simple sugars, such as glucose, which are fermented by yeast to produce bioethanol. The conversion of glucose polymers into fermentable sugars is accomplished by enzymes known as holocellulases, which are produced by lignocellulolytic fungi. These enzymes act synergistically for the efficient degradation of cellulose polymers, and the fine and coordinated regulation of this process is performed by transcription factors (TFs). TFs are regulatory proteins that bind to the promoter region of their target genes (CAZymes, sugar transporters, signaling proteins, other TFs, etc.) to induce or repress their transcription. This review aims to understand the main regulatory mechanisms involved in plant biomass degradation by the most studied lignocellulolytic fungi Trichoderma sp., Aspergillus sp., Penicillium sp., and Neurospora crassa. In this context, the most studied TFs related to holocellulose degradation and genetic modification of TFs or promoters as a valuable tool to improve enzyme production for biotechnological purposes have been discussed. Furthermore, this review enables the expansion of knowledge on the regulation of the cellulolytic system of filamentous fungi and the application of this knowledge to the improvement of numerous bioproducts. Engineering TFs and promoters may yield more efficient strains that may be active in plant biomass hydrolysis. In this way, the technological processes for obtaining ethanol from lignocellulose may become more commercially viable.

09 BIOMASS FUELS↗
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 OSTI2026

Aqueous ionic liquid–mediated depolymerization of textile waste

Textile waste, dominated by polyester-cotton blends, largely evades recycling and ends up in landfills or incinerators. Here, we demonstrate an aqueous ionic liquid–mediated route for selective depolymerization of textile waste, including polyester and polycotton (polyester/cotton blend). Using aqueous cholinium lysinate ([Ch][Lys]), we depolymerized poly(ethylene terephthalate) (PET) textiles with over 95 % terephthalic acid (TPA) yields, comparable to virgin PET resin. Notably, colored fabrics showed no inhibitory effect from dyes. While protic ionic liquids such as ethanolammonium acetate showed limited efficiency, their precursor amine enabled near-complete PET conversion—ethanolamine promoted aminolysis with byproduct formation whereas butylamine achieved higher TPA recovery through combined hydrolysis and aminolysis. Importantly, polycotton blends achieved complete PET depolymerization with TPA yield above 85 % and preserved cotton. These results establish aqueous ionic liquids as efficient, selective agents for deconstructing polyester in blended textiles, offering flexible product and ionic liquid management pathways toward scalable and facile textile recycling.

Amines↗
DOE OSTI2020

3D-printing methacrylate/chitin nanowhiskers composites via stereolithography: Mechanical and thermal properties

We report on the mechanical and thermal properties of stereolithography (SLA) 3D-printed methacrylate (MA) resin reinforced by chitin nanowhiskers (CNWs). CNWs were synthesized by acid hydrolysis of crab shell chitin and nanocomposites with 0 wt%, 0.5 wt%, 1.0 wt%, and 1.5 wt% CNWs loading were prepared by slurry compounding method. The obtained CNWs (diameter = 23 ± 5 nm, length = 253 ± 100 nm, and aspect ratio = 11 ± 3) are well dispersed within the bulk of MA at 1.0 wt% loading, implying good interfacial adhesion between the nanofiller and the resin matrix possibly due to hydrogen bonding interactions. The addition of up to 1.0 wt% CNWs to neat MA enhances the tensile strength, strain at break, modulus, and maximum thermal degradation temperatures of the nanocomposites. Moreover, the incorporation of CNWs not only improves the mechanical and thermal properties, but also preserves the excellent resolution and accuracy of 3D-printed MA/CNWs nanocomposites.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Enhancing membrane performance for CO 2 capture from flue gas with ultrahigh MW polyvinylamine

Membranes for post-combustion CO 2 capture are required to have a high CO 2 permeance due to the limited driving force. For facilitated transport membranes synthesized with polyvinylamine (PVAm), a defect-free selective layer of <200 nm is usually required to render sufficient permeance with high CO 2 /N 2 selectivity. In order to meet such a demand through the knife-coating process, the coating solution needs to have a high viscosity at a relatively low concentration to minimize its penetration into the substrate. The demand was met by synthesizing PVAm with an ultrahigh molecular weight (MW) via inverse emulsion polymerization (IEP) in this study. Compared to solution polymerization, IEP isolates the reaction in inverse micelles suspended in a continuous organic phase, which allows excellent dissipation of the heat generated by the reaction and reduces gel formation drastically. The polymerization parameters, including monomer concentration, initiator concentration, and reaction temperature, were investigated to obtain the optimal MW of PVAm for membrane performance. As compared to solution polymerization, IEP enhanced the MW of PVAm from 1.2 to 12.7 MDa, which minimized the penetration of the coating solution into the substrate and hence the extra mass transfer resistance. The effect of MW and degree of hydrolysis of PVAm on the membrane transport properties were studied. Furthermore, by employing PVAm with a MW of 12.7 MDa to strengthen the polymer matrix, the loading of piperazine glycinate in the membrane was increased up to 85 wt.%. In conclusion, the resultant membrane achieved a CO 2 permeance of 839 GPU and a CO 2 /N 2 selectivity of 161 at the typical flue gas temperature of 57°C.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2024

Sulfide precipitation characteristics of Mn, Ni, Co, and Zn in the presence of contaminant metal ions

In this study, the effects of Al 3+ and Fe 2+ on the precipitation characteristics of four valuable metals, including Mn 2+ , Ni 2+ , Co 2+ , and Zn 2+ , were investigated by conducting solution chemistry calculations, sulfide precipitation tests, and mineralogy characterizations. It was found that the ability of the valuable metals to form sulfide precipitates followed an order of Zn 2+ > Ni 2+ > Co 2+ > Mn 2+ . The sulfide precipitate of Zn 2+ was the most stable and did not re-dissolve under the acidic condition (pH 4.00 ± 0.05). In addition, the sulfide precipitation characteristics of Zn 2+ was barely affected by the contaminant metal ions. However, in the presence of Al 3+ , the precipitation recoveries of Mn 2+ , Ni 2+ , and Co 2+ were noticeably reduced due to simultaneous hydrolysis and competitive adsorption. The precipitation recoveries of Ni 2+ and Co 2+ in solutions containing individual valuable metals also reduced when Fe 2+ was present, primarily due to competitive precipitation. However, the recovery of Mn 2+ was enhanced due to the formation of ferrous sulfide precipitate, providing abundant active adsorption sites for Mn species. Here, in the solution containing all the valuable metals, Fe 2+ promoted the recovery of the valuable metals due to the higher concentration of Na 2 S and the formation of ferrous sulfide precipitate.

58 GEOSCIENCES↗
DOE OSTI2021

Journal Pre-proof3D printed polylactic acid and acrylonitrile butadiene styrene fluidicstructures for biological applications: tailoring bio-material interfaceviasurface modification

Three-dimensional (3D) printing is a rapidly growing technology that best fits for cell culture and other biological applications due to its potential to build immensely complex structures from customized designs. However, use of 3D printed structures for cell adhesion, proliferation, and activation requires tailoring of surface characteristics. In this context, this work investigates the use of two biocompatible 3D printable polymer materials, Poly-L-lactic Acid (PLA) and Acrylonitrile Butadiene Styrene (ABS) for bio applications, and the effect of their post-printing surface modification processes to achieve desired bio functionality. Three post-printing surface modification techniques, alkaline hydrolysis, ultraviolet ozone plasma irradiation and gold thin film deposition are performed with the objective of introducing useful levels of surface functionalities. Poly-L-lysine (PLL) labelled with FITC chromophore is immobilized on the surface modified samples following standard protocols. The effect of surface roughness and porosity of the 3D printed structures on the polypeptide immobilization is compared on as-printed versus mechanically polished surfaces. Different characterization methods, viz., Fluorescence microscopy, Raman Spectroscopy and UV–vis spectroscopy, are used to study the efficacy of the surface modification and PLL immobilization techniques. Our results demonstrated denser PLL attachment on polished hydrolyzed PLA and ABS surfaces which enables the use of these printable polymers for a range of applications such as tissue scaffolds and microfluidics.

3D Printing, PLA, ABS, Biodegradable Polymer, Surf↗
DOE OSTI2020

Mechanistic insights into the colloidal assembly of mesoporous silica using in-operando cross-scale X-ray scattering and spectroscopic measurements

Advancing a mechanistic understanding of the colloidal to solid-phase transformations of silica allows us to tune these meso-scale structures. In this study, we probe the structural transformations associated with the formation of mesoporous silica particles, SBA-15 using in-operando Small Angle X-ray Scattering (SAXS) and Grazing Incidence-Small Angle X-ray Scattering (GI-SAXS). The chemical transformations associated with the hydrolysis and condensation of silica particles is investigated using Attenuated Total Reflection – Fourier Transform Infrared Spectroscopy (ATR-FTIR) measurements. Fast polymerization of Si-O-Si species to form mesoporous silica is noted when SBA-15 is synthesized in the presence of nitrate salts, due to the “salting-in” effect or enhanced solubility of polymers. However, aging the silica particles resulted in plate-like morphologies in the absence of the nitrate salt and spherical morphologies in the presence of nitrate salt. Early onset of nucleation of silica particles in the presence of nitrate salts was captured using GI-SAXS measurements. These studies show that the rational basis for developing new synthesis routes for accelerated kinetics or specific meso-scale structures can be informed by detailed characterization of the evolution in chemistry and meso-scale structure of these materials.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Chemometric modeling of power conversion efficiency of organic dyes in dye sensitized solar cells for the future renewable energy

The present study reports chemometric modeling of power conversion efficiency (PCE) of dye sensitized solar cells (DSSCs) using the biggest available data set till date which comprises around 1200 dyes covering 7 chemical classes. To extract the best structural features required for higher PCE, we have developed multiple partial least squares (PLS) quantitative structure-property relationship (QSPR) models for the Triphenylamine, Phenothiazine, Indoline, Porphyrin, Coumarin, Carbazole and Diphenylamine chemical classes using descriptors derived from the best subset selection method followed by selection of best five models in each dataset based on the Mean Absolute Error (MAE) values. The models were validated both internally and externally followed by the consensus predictions employing “Intelligent Consensus Predictor” tool to examine whether the quality of predictions can be improved with the “intelligent” selection of multiple PLS models. The quality of predictions for the respective external sets showed that the consensus models (CM) are better than the individual models (IM) in most of the cases. From the insights of the developed models, we concluded that attributes like a packed structure toward higher conductivity of electrons, auxiliary donor fragment of aromatic tertiary amines, number of thiophenes inducing the bathochromic shift and augmenting the absorption, presence of additional electron donors, enhancement of electron-donating abilities, number of non-aromatic conjugated C(sp 2 ) which helps as conjugation extension units to broaden the absorption and highly conjugated $π$-systems exert positive contributions to the PCE. On the contrary, features negatively contributing to PCE are the followings: fragments which lower the tendency of localized $π–π*$ transition, fragments related to larger volume and surface area of dyes along with hydrophobicity resulting in poor adhesion, fragment RC = N causing dye hydrolysis, steric hindrance for π electronic mobility, fragments enhancing polarity, etc. Finally, the identified features from the best QSPR model of the coumarin dataset was employed in designing of ten more efficient coumarin dyes (predicted %PCE ranging from 8.93 to 10.62) than the existing ones.

14 SOLAR ENERGY↗
DOE OSTI2021

The surface triple-coupling on single crystalline cathode for lithium ion batteries

Single crystalline (SC) cathode materials, which are less susceptible to micro/nano-cracks formation and offer better structure stability compared to the polycrystalline counterpart, have attained great attention. However, the parasitic side reactions at the cathode-electrolyte interface induces the loss of active species, which consequently leads to continual degradation of the electrochemical performances. Herein, a triple coupling of concentration-gradient Na+, F- co-doping and surface NaF coating are exploited for the first time on SC LiNi 0.5C o 0.2 Mn 0.3 O 2 cathode by the hydrolysis of NaPF 6 . This process regulates the external structure of materials by constructing a “sandwich” configuration from surface to bulk: rock salt - mixing zone - layered phase. The detailed interface transformation mechanism is revealed by Neutron powder diffraction (NPD), spherical aberration corrected high-resolution scanning transmission electron microscopy (HR-STEM), electron energy loss spectroscopy (EELS), and Ar+ sputtering assisted X-ray photoelectron spectroscopy (XPS). The synergistic effects endow the SC cathode with outstanding capacity retentions: 91.3% at 25 °C and 85% at 45 °C, after 500 cycles at 5 C between 3.0 and 4.5 V. In addition, a high full-cell reversible capacity of 168.9 mAh g -1 with a capacity retention of 92.4% is achieved after 300 cycles at 1 C. Multiple characterizations further indicate that these superior results are mainly ascribed to the overall structure integrity of SC material, the thin cathode electrolyte interface, high content of lithium fluoride, and the low solubility of transition metal ions. This work opens a new avenue to construct a benign interface towards high-performance lithium ion batteries.

lithium ion batteries↗
DOE OSTI2022

Uncompetitive, adduct-forming SARM1 inhibitors are neuroprotective in preclinical models of nerve injury and disease

Axon degeneration is an early pathological event in many neurological diseases. The identification of the nicotinamide adenine dinucleotide (NAD) hydrolase SARM1 as a central metabolic sensor and axon executioner presents an exciting opportunity to develop novel neuroprotective therapies that can prevent or halt the degenerative process, yet limited progress has been made on advancing efficacious inhibitors. Here we describe a class of NAD-dependent active-site SARM1 inhibitors that function by intercepting NAD hydrolysis and undergoing covalent conjugation with the reaction product adenosine diphosphate ribose (ADPR). The resulting small-molecule ADPR adducts are highly potent and confer compelling neuroprotection in preclinical models of neurological injury and disease, validating this mode of inhibition as a viable therapeutic strategy. Additionally, we show that the most potent inhibitor of CD38, a related NAD hydrolase, also functions by the same mechanism, further underscoring the broader applicability of this mechanism in developing therapies against this class of enzymes.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2025

Thermo-mechanical deterioration and molecular degradation of 3D-printed methacrylate-based polymer in various chemical environments

The advancement of additive manufacturing (AM) has accelerated the development of stereolithographic (SLA) photo-curable resins, particularly methacrylate-based polymers, due to the ability to their high-resolution, robust mechanical properties, and suitability. However, their long-term performance in chemical environments remains poorly understood. This study investigates the extent and mechanisms of degradation on an SLA-printed methacrylate-based polymer subjected to various chemicals, including polar and non-polar solvents, as well as strongly acidic aqueous solutions over a 12-week accelerated aging period. A comprehensive analytical approach incorporating swelling kinetics, surface morphology, tensile and dynamic mechanical analysis (DMA), Fourier-transform infrared (FTIR) spectroscopy, and mass spectrometry (MS) was employed to characterize chemical absorption, structural integrity, and leached products. Results reveal that degradation severity is governed by both the polarity and reactivity of the chemical environment. Notably, exposure to 6 mol L -1 HNO₃ induced the most severe deterioration, with over threefold higher swelling compared to other media, and significant reductions in tensile strength, tensile modulus, and glass transition temperature (T g ). In contrast, specimens aged in non-polar solvents (xylene and dodecane) exhibited negligible chemical interaction and retained mechanical performance. FTIR and MS analyses identified acid-catalyzed hydrolysis of ester groups as prominent degradation pathways in acidic media, while diffusion-controlled plasticization prevailed in polar solvents. Furthermore, this study provides valuable insights into the chemical stability of SLA-printed polymers and develops predictive degradation profiles that are crucial for designing durable polymer systems for advanced industrial use.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Partitioning sources of CO 2 emission after soil wetting using high-resolution observations and minimal models

Wetting dry soil triggers a pulse of microbial respiration. Respiration pulses after wetting can be complex, evolving through several stages before subsiding—possibly reflecting contributions from multiple carbon (C) sources. In this work we hypothesized that respiration after wetting combines C from cellular sources (notably trehalose, a cellular osmo-protectant) and soluble extracellular C made available by the physical effects of wetting, with cellular sources contributing early during the pulse and extracellular C dominating later. We tested this hypothesis by making measurements of soil respiration, microbial biomass, trehalose, and water extractable organic C after wetting dry soil in the laboratory. We then devised several alternative minimal models to evaluate the potential contributions of trehalose and extracellular C to the respiration pulse. We found that the chloroform-labile fraction of the microbial biomass was comprised of 50% trehalose in dry soil. Both trehalose and water extractable organic C pools declined rapidly after wetting; trehalose disappeared within 3 h of water addition. Chloroform-labile glucose increased 3 h after water addition and then declined, suggesting rapid hydrolysis of trehalose and consumption of the resulting glucose. Respiration dynamics after wetting could be best explained by models that included two C sources, combining rapid metabolism of trehalose with slower consumption of extracellular soluble C. These results suggest that pulses of respiration after wetting reflect both osmolyte consumption within the microbial biomass and enhanced extracellular C availability; hence, models of microbial drought response must account for both processes to fully resolve soil C dynamics.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Dependence of adhesion on degradation mechanisms of ethylene co-vinyl acetate encapsulants over the lifetime of photovoltaic modules

The long-term reliability of encapsulation has a critical impact on the overall cost and effectiveness of photovoltaic modules. An often overlooked but important element of this reliability concerns adhesive degradation of the encapsulant, which results in delamination. This work critically examines the degradation mechanisms – deacetylation, β-scission, and hydrolytic depolymerization – primarily responsible for adhesion loss in ethylene co-vinyl acetate (EVA) encapsulants to provide evidence and clarity regarding the contribution of these mechanisms to the adhesive degradation over the lifetime of a module. EVA samples obtained from mini-modules exposed in two sets of controlled, accelerated conditions – with and without ultraviolet (UV) radiation – are characterized to find specific evidence for the proposed degradation mechanisms. The mini-modules were exposed up to 10,000 h, which represents up to 15–20 years in the field. Results affirm that initially, deacetylation dominates the degradation before scission takes over, followed by hydrolytic depolymerization. Additional analysis highlights the climacteric interdependency between deacetylation and hydrolytic depolymerization as it relates to eventual delamination, where deacetylation products catalyze interfacial hydrolysis reactions. Furthermore, effects occurring at a given interface are isolated, explicitly providing evidence for how these mechanisms are nonuniform throughout the thickness of the EVA. Results demonstrate that the EVA that interfaces with the glass as opposed to the cell experiences increased levels of degradation, explaining why this initially stronger interface becomes the preferential interface for delamination after longer periods of exposure. Additionally, elevated temperatures alone are shown to induce limited migration of sodium ions across the glass/EVA interface.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Material characterization of seven photovoltaic backsheets using seven accelerated test conditions

A variety of polymeric backsheet materials can be found in fielded photovoltaic (PV) modules, mostly based on fluoropolymer and polyethylene terephthalate (PET) materials. Cost reduction and sustainability considerations drive the recent development of alternative backsheet materials and designs [1]. In some fielded PV installations, polymeric materials are susceptible to environmental degradation in the form of backsheet cracking. To prevent backsheet degradation that can result in a module failure, thorough laboratory reliability testing is needed. In this report we studied the durability of seven commercial and experimental PV backsheets through accelerated stress testing using seven photolytic, hygrometric, and custom tests with the goal to understand if novel fluoropolymer-free backsheets are sufficiently environmentally durable to be commercialized. We divided the mechanisms observed during aging into two categories: core degradation and surface degradation. Although core degradation due to hydrolysis was observed in all commercial PET-, and polyamide (PA)-based backsheets aged with 85 degrees C/85% relative humidity, this test is unlikely to be field relevant. Photo-oxidative reactions on the exposed surface during UV weathering affected all seven backsheets regardless of the outer layer polymer material and additives. This degradation was limited to the outermost micrometers of the surface, except for backsheets containing PA-12, which resulted in surface cracking. A custom test combining UV with water spray caused the most severe backsheet degradation, including surface erosion and loss of insulating properties in polyolefin (PO)- and PA-based backsheets. This highlights the importance of combined accelerated stress testing to screen for complex backsheet degradation mechanisms. We also showed that, with material and design optimization, coextruded experimental PO-based backsheets have the potential to be a durable alternative to commercial PET- and fluoropolymer-based PV backsheets.

14 SOLAR ENERGY↗
DOE OSTI2022

Structural and dynamic effects of paraoxon binding to human acetylcholinesterase by X-ray crystallography and inelastic neutron scattering

Organophosphorus (OP) compounds, including nerve agents and some pesticides, covalently bind to the catalytic serine of human acetylcholinesterase (hAChE), thereby inhibiting acetylcholine hydrolysis necessary for efficient neurotransmission. Oxime antidotes can reactivate the OP-conjugated hAChE, but reactivation efficiency can be low for pesticides, such as paraoxon (POX). Understanding structural and dynamic determinants of OP inhibition and reactivation can provide insights to design improved reactivators. Here, in this study, X-ray structures of hAChE with unaged POX, with POX and oximes MMB4 and RS170B, and with MMB4 are reported. A significant conformational distortion of the acyl loop was observed upon POX binding, being partially restored to the native conformation by oximes. Neutron vibrational spectroscopy combined with molecular dynamics simulations showed that picosecond vibrational dynamics of the acyl loop soften in the ~20–50 cm –1 frequency range. The acyl loop structural perturbations may be correlated with its picosecond vibrational dynamics to yield more comprehensive template for structure-based reactivator design.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Formation and energetics of amorphous rare earth (RE) carbonates in the RE 2 O 3 –CO 2 –H 2 O system

Amorphous materials are of interest in the genesis of crystalline solids. They are often the first to precipitate from supersaturated solutions and are in the nanometer size range, transforming into a nanocrystalline metastable phase, and then to thermodynamically stable phases. One must seek knowledge of the composition, structure, thermodynamics, kinetics, and reaction pathways that relate the amorphous and crystalline phases. The subject of this study is the amorphous phases in the system RE 2 O 3 -CO 2 –H 2 O (RE- La, Nd, Dy,Yb). They were synthesized via direct precipitation and urea hydrolysis, and characterized by powder XRD, DTA with mass spectrometric analysis of the evolved gases. Phases have the non-stoichiometric composition RE 2 O 3 ·xCO 2 ·yH 2 O (1 < x < 3, 3 < y <7), which is different from that of crystalline simple carbonates and hydroxycarbonates. Thus we consider them to be amorphous precursors, rather than amorphous carbonates. High temperature oxide melt solution calorimetry in molten sodium molybdate solvent was used to derive their enthalpies of formation from oxides and elements. Increase of energetic stability per mole of RE 2 O 3 compounds occurs in the order: RE 2 O 3 → 2RE(OH)3→ 2REO(OH) → RE 2 O 2 CO 3 → Amorphous precursor → 2(REOHCO 3 ) → RE 2 (CO 3 ) 3 ·yH 2 O. We calculated the enthalpies of possible transformations of amorphous precursors to crystalline phases and conclude that thermodynamics determines the dependence of the crystallizing products on the temperature and partial pressure of CO 2 and H 2 O. Amorphous precursors are clearly intermediate in the synthesis, and ternary phases containing both H 2 O and CO 2 compete with each other in terms of thermodynamic stability. The energy landscape obtained here will allow one to directly synthesize specific products and control their functionality.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗