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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 1,063 records · Page 59
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Exosomes derived from PEDF modified adipose-derived mesenchymal stem cells ameliorate cerebral ischemia-reperfusion injury by regulation of autophagy and apoptosis

Increasing evidence suggest that exosomes from mesenchymal stem cells have therapeutic effects in cerebral ischemia-reperfusion (I/R) injury, but the underlying mechanisms are unclear. Pigment epithelium-derived factor (PEDF) is a multifunctional protein that exhibits anti-inflammatory, antioxidative, and neuroprotective properties. We investigated the involvement of PEDF in I/R, using adipose-derived mesenchymal stem cells (ADSCs) isolated from rat. PEDF-overexpressing ADSCs were constructed and exosomes from ADSCs were isolated. SY-5Y cells were employed to identify the protective effects of exosomes in oxygen-glucose deprivation (OGD) experiments. Exosome treatment suppressed OGD-induced apoptosis by inhibiting the two-step caspase dependent (caspase-9 and caspase-3) apoptotic pathway. Increasing the PEDF content of exosomes further promoted the protective effect against OGD-induced apoptosis by activating autophagy, while blocking autophagy reduced the effect of PEDF-containing exosomes. We constructed a middle cerebral artery occlusion-reperfusion (MCAO) model using male Sprague-Dawley rats to identify the role of PEDF in exosome-mediated neuroprotection. These in vivo experiments further confirmed that exosomes from PEDF-modified ADSCs ameliorated cerebral I/R injury by activating autophagy and suppressing neuronal apoptosis. These findings suggest that PEDF plays a role in exosome-mediated prevention of cerebral I/R injury by modulating apoptotic factors and promoting autophagy.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2021

Formation and surface melting of nanoparticle superlattices in a solution

The wisdom in the saying of “There are no two snowflakes alike” lies in the importance of history or kinetic pathways in the phase transitions of solids. Likewise, “artificial solids,” namely superlattices consisting of functional nanoparticles, have lattice size, surface morphology, crystallinity, symmetry, and structural reconfiguration (for example, transition into a disordered state) highly dependent on the kinetic pathways as the nanoparticles interact with each other in solution [1]. Great progresses have been made in understanding the formation pathways of superlattices using liquid-phase transmission electron microscopy (TEM) [2-4]. For example, by tracking single nanoparticle’s trajectories, especially aided by U-net neural network-based machine learning, previous studies mapped the fundamental nanoparticle interactions at nanometer resolution [5]. Nonclassical, two-step nucleation pathway has also been elucidated in the system of nanoprisms, by optimizing protocols such as loading nanoparticle suspensions over the supersaturation threshold and minimizing particle‒substrate interaction [2]. Surface morphologies or exposed facets of superlattices have been shown to follow the principles of Wulff construction rule, where the facet-dependent surface energy can be measured based on the capillary wave theory [4]. However, the reverse process of crystallization of superlattices, the conversion from crystalline to disordered state, has been much less explored. On one hand, the melting of nanoparticle superlattices can provide a preferred pathway to induce structural reorganization or shuffling of building blocks for them to transform into different types of crystal structures. On the other hand, understanding nanoscale superlattice melting and comparing such behaviors with the prevailing surface melting theories developed for atomic/molecular solids can provide a potent way to engineer phase transitions of supra- and hierarchical structures constructed from nanoscale entities (e.g., DNA-coated nanoparticles, proteins), for their applications in reprogrammable and switchable materials with multifunctional properties [6, 7]. The experimental challenges to observe melting of superlattices are twofold. Practically it is difficult to load the initial superlattice form, in an intact manner, into the highly confined liquid-phase TEM chamber for in-situ observation. Here, the triggering of melting also needs meticulous manipulation of nanoparticle concentration, interparticle interaction, and solution environment.

Kim, Ahyoung↗
DOE OSTI2012

Chemical Analysis of Complex Organic Mixtures Using Reactive Nanospray Desorption Electrospray Ionization Mass Spectrometry

Reactive nanospray desorption electrospray ionization (nano-DESI) combined with high-resolution mass spectrometry was utilized for the analysis of secondary organic aerosol produced through ozonolysis of limonene (LSOA). Previous studies showed that LSOA constituents are multifunctional compounds containing aldehyde and ketone groups. In this study, we used the selectivity of the Girard T (GT) reagent towards carbonyl compounds to examine the utility of reactive nano-DESI for the analysis of complex organic mixtures. In these experiments, 1-100 {micro}M GT solution was used as a working solvent for reactive nano-DESI analysis. Abundant products of a single addition of GT to LSOA constituents were observed at GT concentrations in excess of 10 {micro}M. We found that LSOA compounds with 18-20 carbon atoms (dimers) and 27-30 carbon atoms (trimers) react with GT through a simple addition reaction resulting in formation of the carbinolamine derivative. In contrast, reactions of GT with monomeric species result in formation of both the carbinolamine and the hydrazone derivatives. In addition, several monomers did not react with GT on the timescale of our experiment. These molecules were characterized by relatively high values of the double bond equivalent (DBE) and low oxygen content. Furthermore, because addition of a charged GT tag to a neutral molecule eliminates the discrimination against the low proton affinity compounds in the ionization process, reactive nano-DESI analysis enables quantification of individual compounds in the complex mixture. For example, we were able to estimate for the first time the amounts of dimers and trimers in the LSOA mixture. Specifically, we found that the most abundant LSOA dimer was detected at ca. 0.5 pg level and the total amount of dimers and trimers in the analyzed sample was just around 11 pg. Our results indicate that reactive nano-DESI is a valuable approach for examining the presence of specific functional groups and quantification of compounds possessing these groups in complex mixtures.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2023

Protection against Chemical Warfare Agents and Biological Threats Using Metal–Organic Frameworks as Active Layers

The SARS-CoV-2 pandemic outbreak and the unfortunate misuse of toxic chemical warfare agents (CWAs) highlight the importance of developing functional materials to protect against these chemical and pathogen threats. Metal–organic frameworks (MOFs), which comprise a tunable class of crystalline porous materials built from inorganic nodes and organic linkers, have emerged as a class of heterogeneous catalysts capable of rapid detoxification of multiple classes of these harmful chemical or biological hazards. In particular, zirconium-based MOFs (Zr-MOFs) feature Lewis acidic nodes that serve as active sites for a wide range of catalytic reactions, including the hydrolysis of organophosphorus nerve agents within seconds in basic aqueous solutions. In addition, postsynthetic modification of Zr-MOFs enables the release of active species capable of reacting with and deactivating harmful pathogens. Despite this impressive performance, utilizing Zr- MOFs in powder form is not practical for application in masks or protective uniforms. To address this challenge, our team sought to develop MOF/fiber composite systems that could be adapted for use under realistic operating conditions to protect civilians, military personnel, and first responders from harmful pathogens and chemical warfare agents. Over the last several years, our group has designed and fabricated reactive and biocidal MOF/fiber composites that effectively capture and deactivate these toxic species. In this Account, we describe the evolution of these porous and reactive MOF/fiber composites and focus on key design challenges and considerations. First, we devised a scalable method for the integration of Zr-MOFs onto textile substrates using aqueous precursor solutions and without using pretreated textiles, highlighting the potential scalability of this method. Moving beyond standard textiles, we also developed a microbial synthesis strategy to prepare hierarchically porous MOF/bacterial cellulose nanofiber composite sponges that can both capture and detoxify nerve agents when exposed to contaminated gas flows. The mass loading of the MOF in the nanofibrous composite sponge is up to 90%, affording higher work capacities compared to those of textile-fiber-based composites with relatively lower MOF loadings. Next, we demonstrated that heterogeneous polymeric bases are suitable replacements for volatile liquid bases typically used in solution-phase reactions, and we showed that these composite systems are capable of effectively hydrolyzing nerve agents in the solid state by using only water that is present as humidity. Moreover, incorporating a reactive dye precursor into the composite affords a dual function sensing and detoxifying material that changes color from white to orange upon reaction with the byproduct following nerve agent hydrolysis, demonstrating the versatility of this platform for use in decontamination applications. We then created chlorine-loaded MOF/fiber composites that act as biocidal and reactive textiles that are capable of not only detoxifying sulfur-mustard-based chemical warfare agents and simulants but also deactivating both bacteria and the SARS-CoV-2 virus within minutes of exposure. Lastly, we synthesized a mixed-metal Ti/Zr-MOF coating on cotton fibers to afford a photoactive biocidal cloth that shows fast and broad-spectrum biocidal performance against viruses and Gram-positive and Gram-negative bacteria under visible light irradiation. Given the tunable, multifunctional nature of these MOF/fiber composites, we believe that this Account will offer new insights for the rational design and preparation of functional MOF/fiber composites and pave the way toward the development of next-generation reactive and protective textiles.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Data-Driven Strategies for Accelerated Materials Design

The ongoing revolution of the natural sciences by the advent of machine learning and artificial intelligence sparked significant interest in the material science community in recent years. The intrinsically high dimensionality of the space of realizable materials makes traditional approaches ineffective for large-scale explorations. Modern data science and machine learning tools developed for increasingly complicated problems are an attractive alternative. An imminent climate catastrophe calls for a clean energy transformation by overhauling current technologies within only several years of possible action available. Tackling this crisis requires the development of new materials at an unprecedented pace and scale. For example, organic photovoltaics have the potential to replace existing silicon-based materials to a large extent and open up new fields of application. In recent years, organic light-emitting diodes have emerged as state-of-the-art technology for digital screens and portable devices and are enabling new applications with flexible displays. Reticular frameworks allow the atom-precise synthesis of nanomaterials and promise to revolutionize the field by the potential to realize multifunctional nanoparticles with applications from gas storage, gas separation, and electrochemical energy storage to nanomedicine. In the recent decade, significant advances in all these fields have been facilitated by the comprehensive application of simulation and machine learning for property prediction, property optimization, and chemical space exploration enabled by considerable advances in computing power and algorithmic efficiency. In this Account, we review the most recent contributions of our group in this thriving field of machine learning for material science. We start with a summary of the most important material classes our group has been involved in, focusing on small molecules as organic electronic materials and crystalline materials. Specifically, we highlight the data-driven approaches we employed to speed up discovery and derive material design strategies. Subsequently, our focus lies on the data-driven methodologies our group has developed and employed, elaborating on high-throughput virtual screening, inverse molecular design, Bayesian optimization, and supervised learning. We discuss the general ideas, their working principles, and their use cases with examples of successful implementations in data-driven material discovery and design efforts. Furthermore, we elaborate on potential pitfalls and remaining challenges of these methods. Finally, we provide a brief outlook for the field as we foresee increasing adaptation and implementation of large scale data-driven approaches in material discovery and design campaigns.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Interfacial Engineering Enabled Novel Bi-Based Layered Oxide Supercells with Modulated Microstructures and Tunable Physical Properties

Two-dimensional layered materials hold great significance to fundamental scientific research and future nanoscale device applications. Besides the well-studied graphene and dichalcogenides, oxide-based layered materials are another family attracting significant research interests, for example, the Bi-based Bi 3 Fe 2 Mn 2 O 10-δ layered supercell (called BFMO322 SC) structure. BFMO322 SC is an excellent room-temperature multiferroic material, but its growth mechanism is unclear. In this work, Bi 2 Fe 1–x Mn x O 6 thin films with different Fe/Mn molar ratios were deposited on CeO 2 buffer layers by pulsed laser deposition. By varying the Fe/Mn molar ratios, it has been determined that Mn can favor the growth of Bi-based layered structures, while Fe cannot facilitate the growth. A series of novel layered supercell structures can be obtained by manipulating the growth kinetics at the substrate/film interface, as achieved by precisely controlling the growth conditions. More interestingly, the magnetization and optical band gap of the Bi-based layered structures can be tuned by varying the Fe/Mn molar ratios. This original work has demonstrated the power of interfacial engineering in enabling new Bi-based layered structures and thus is of great significance for the design of new layered structures with multifunctionalities.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Frontal Polymerization of Dihydrofuran Comonomer Facilitates Thermoset Deconstruction

Frontal ring-opening metathesis polymerization (FROMP) is a rapid, low-energy manufacturing reaction that is useful for curing thermosetting materials. FROMP of dicyclopentadiene (DCPD) results in poly(dicyclopentadiene) (p(DCPD)), a tough thermoset with excellent mechanical performance and chemical stability. Like most thermosets, p(DCPD) cannot be reprocessed and is therefore difficult to recycle. Previous work demonstrated that the incorporation of a small quantity of cleavable units in the strand segments of p(DCPD) networks enables their deconstruction. Here, we report that a commercially available multifunctional comonomer, 2,3-dihydrofuran (DHF), both acts as a potent Grubbs catalyst inhibitor during FROMP and introduces acid cleavable units. The resulting materials retain high performance characteristics, including glass-transition temperatures ranging from 115 to 165 °C and ultimate strength ranging from 35 to 40 MPa. The addition of DHF above critical loading levels enables deconstructable thermosets. Here, we further demonstrate freeform three-dimensional (3D) printing of deconstructable thermosets via frontal polymerization.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Molecular Catalysts with Diphosphine Ligands Containing Pendant Amines

Pendant amines play an invaluable role in chemical reactivity, especially for molecular catalysts based on Earth-abundant metals. As inspired by [FeFe]-hydrogenases, which contain a pendant amine positioned for cooperative bifunctionality, synthetic catalysts have been developed to emulate this multifunctionality through incorporation of a pendant amine in the second coordination sphere. Cyclic diphosphine ligands containing two amines serve as the basis for a class of catalysts that have been extensively studied and used to demonstrate the impact of a pendant base. These 1,5-diaza-3,7-diphosphacyclooctanes, now often referred to as “P 2 N 2 ” ligands, have profound effects on the reactivity of many catalysts. The resulting [Ni(P R 2 N R ´ 2 ) 2 ] 2+ complexes are electrocatalysts for both the oxidation and production of H 2 . Achieving the optimal benefit of the pendant amine requires that it has suitable basicity and is properly positioned relative to the metal center. In addition to the catalytic efficacy demonstrated with [Ni(P R 2 N R ´ 2 )2] 2+ complexes for the oxidation and production of H2, catalysts with diphosphine ligands containing pendant amines have also be demonstrated for a variety of metals for many different reactions, both in solution and immobilized on surfaces. Here, the impact of pendant amines in catalyst design has been demonstrated and continues to expand.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Organic–Inorganic Perovskites: Structural Versatility for Functional Materials Design

Although known since the late 19th century, organic–inorganic perovskites have recently received extraordinary research community attention because of their unique physical properties, which make them promising candidates for application in photovoltaic (PV) and related optoelectronic devices. In this review, we will explore beyond the current focus on three-dimensional (3-D) lead(II) halide perovskites, to highlight the great chemical flexibility and outstanding potential of the broader class of 3-D and lower dimensional organic-based perovskite family for electronic, optical, and energy-based applications as well as fundamental research. The concept of a multifunctional organic–inorganic hybrid, in which the organic and inorganic structural components provide intentional, unique, and hopefully synergistic features to the compound, represents an important contemporary target.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Modeling Novel Aqueous Particle and Cloud Chemistry Processes of Biomass Burning Phenols and Their Potential to Form Secondary Organic Aerosols

Phenols emitted from biomass burning contribute significantly to secondary organic aerosol (SOA) formation through the partitioning of semivolatile products formed from gas-phase chemistry and multiphase chemistry in aerosol liquid water and clouds. The aqueous-phase SOA (aqSOA) formed via hydroxyl radical (˙OH), singlet molecular oxygen ( 1 O 2 *), and triplet excited states of organic compounds ( 3 C*), which oxidize dissolved phenols in the aqueous phase, might play a significant role in the evolution of organic aerosol (OA). However, a quantitative and predictive understanding of aqSOA has been challenging. Here, we develop a stand-alone box model to investigate the formation of SOA from gas-phase ˙OH chemistry and aqSOA formed by the dissolution of phenols followed by their aqueous-phase reactions with ˙OH, 1 O 2 *, and 3 C* in cloud droplets and aerosol liquid water. Here, we investigate four phenolic compounds, i.e., phenol, guaiacol, syringol, and guaiacyl acetone (GA), which represent some of the key potential sources of aqSOA from biomass burning in clouds. For the same initial precursor organic gas that dissolves in aerosol/cloud liquid water and subsequently reacts with aqueous phase oxidants, we predict that the aqSOA formation potential (defined as aqSOA formed per unit dissolved organic gas concentration) of these phenols is higher than that of isoprene-epoxydiol (IEPOX), a well-known aqSOA precursor. Cloud droplets can dissolve a broader range of soluble phenols compared to aqueous aerosols, since the liquid water contents of aerosols are orders of magnitude smaller than cloud droplets. Further, our simulations suggest that highly soluble and reactive multifunctional phenols like GA would predominantly undergo cloud chemistry within cloud layers, while gas-phase chemistry is likely to be more important for less soluble phenols. But in the absence of clouds, the condensation of low-volatility products from gas-phase oxidation followed by their reversible partitioning to organic aerosols dominates SOA formation, while the SOA formed through aqueous aerosol chemistry increases with relative humidity (RH), approaching 40% of the sum of gas and aqueous aerosol chemistry at 95% RH for GA. Our model developments of biomass-burning phenols and their aqueous chemistry can be readily implemented in regional and global atmospheric chemistry models to investigate the aqueous aerosol and cloud chemistry of biomass-burning organic gases in the atmosphere.

09 BIOMASS FUELS↗
DOE OSTI2020

Determining Activity Coefficients of SOA from Isothermal Evaporation in a Laboratory Chamber

Nonideal molecular interactions in aerosol particles influence the partitioning of semivolatile organic compounds (SVOCs). However, few direct measurements exist that determine activity coefficients (γ), which quantify nonideality, for individual organic compounds in different atmospheric mixtures. By measuring the isothermal evaporation of SOA formed from multifunctional SVOCs in an environmental chamber, this study determines the mole-fraction-based γ of the bulk SOA in a variety of pre-existing chemically complex particles, approximated as if the bulk SOA behaved like a single SVOC. These multicomponent mixtures contain molecular structures commonly found in the atmosphere. When treated as a single liquid phase, γ of the bulk SOA tends to increase from ~1 to ~5 as the organic seeds and the SOA have more differing polarities. A high computed γ value of 74 for a wet ammonium sulfate-SOA system indicates phase separation. The γ for some individual species was also quantified based on gas-phase measurements and AIOMFAC model predictions. However, the bulk SOA γ cannot be explained by the simplified speciated SVOC–seed interactions, suggesting incomplete compositional understanding of the bulk SOA. In this work, these results demonstrate a method to quantify nonideal behavior and show that it can occur in multicomponent mixtures and therefore influence OA formation, evolution, and lifetimes.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2018

Synthesis of Operable Process Intensification Systems—Steady-State Design with Safety and Operability Considerations

In this work, we present an integrated approach to synthesize process intensification systems with guaranteed flexibility and safety performances. The synthesis of intensified equipment/flowsheets is addressed through the Generalized Modular Representation Framework (GMF), which utilizes an aggregation of multifunctional mass/heat exchange modules to represent chemical processes. Thus, the optimal design options are investigated as mass- and heat-transfer opportunities using superstructure-based optimization techniques without a prepostulation of plausible configurations. To ensure that the designs can be operated under a specified range of uncertain parameters, a multiperiod GMF representation is developed based on the critical operating conditions identified by flexibility test. Risk assessment, accounting for equipment failure frequency and consequence severity, is incorporated as a constraint into this synthesis model to derive inherently safer designs. The resulting safely operable intensified systems, which are represented via phenomenological modules, are then identified as corresponding equipment-based flowsheets and validated with steady-state simulation. We demonstrate the proposed approach through a case study for the production of methyl tert-butyl ether. Here, the results indicate that safety and operability considerations can result in significant changes in the structural and operating parameters of the optimal intensified design configuration.

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

Accessing One-Dimensional Chains of Halogenoindates(III) in Organic–Inorganic Hybrids

Organic-inorganic hybrids of halogenoindates(III) are typically represented by one of the zero-dimensional units: InX 4 – , InX 5 2– , InX 6 3– , or In 2 X 11 5– . Higher dimensional anionic forms, although not forbidden, have remained almost elusive. Here, in this study, we report for the first time In 3+ -based organic–inorganic hybrids, (C 4 H 5 N 2 S) 2 InCl 5 and (C 4 H 5 N 2 S) 2 InBr 5 , with 1D anionic chains of trans-halide-bridged InX 6 octahedra whose formation is guided by 2-mercaptopyrimidinium cations (C 4 H 5 N 2 S + ). The chains are characterized by the significant ease of deformation, which is reflected in the elongation of the bridging bonds or the displacement of In 3+ ions. The materials show a robust band gap predominantly governed by C 4 H 5 N 2 S + cations. Dielectric relaxation processes in (C 4 H 5 N 2 S) 2 InBr 5 arise from the cations’ dynamics and suggest the ability of the brominated system to accommodate even larger cations. Our work represents a successful attempt to expand the structural diversity of halogenoindates(III) and opens a pathway to reach multifunctional 1D In 3+ -based hybrids.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Zero thermal expansion and semiconducting properties in PbTiO 3 –Bi(Co, Ti)O 3 ferroelectric solid solutions

Zero thermal expansion (ZTE) behavior is rare but important for both fundamental studies and practical applications of functional materials. Up to now, most available ZTE materials are either electrical insulating oxides or conductive metallic compounds. Very few ZTE materials exhibit the semiconductor feature. Here we report a ZTE in semiconducting ferroelectric of 0.6PbTiO 3 -0.4Bi(Co 0.55 Ti 0.45 )O 3-δ . Its unit cell volume exhibits a negligible change over a broad temperature range from room temperature to 500 °C. The ZTE is supposed to be correlated with the spontaneous volume ferroelectronstriction. Intriguingly, the present ZTE material also exhibits the semiconducting characteristic accompanied by negative temperature coefficient of resistance. The mechanism of electric conduction is attributed to the electronic hopping from one ionic (Ti 3+ ) to another (Ti 4+ ). The semiconductor nature has also been confirmed by the noticeable visible-light absorption with the relative lower band-gap (E g ) value of 1.5 eV, while ferroelectric property can be well maintained with large polarization. The first-principles calculations reveal that the drastically narrowed E g is related to the Co-Ti substitution. Finally, the present multifunctional material containing ZTE, semiconducting and ferroelectric properties is suggested to enable new applications such as the substrate for solar conversion devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Inhibition of Inositol Polyphosphate Kinases by Quercetin and Related Flavonoids: A Structure–Activity Analysis

Dietary flavonoids inhibit certain protein kinases and phospholipid kinases by competing for their ATP-binding sites. These nucleotide pockets have structural elements that are well-conserved in two human small-molecule kinases, inositol hexakisphosphate kinase (IP6K) and inositol polyphosphate multikinase (IPMK), which synthesize multifunctional inositol phosphate cell signals. Herein, we demonstrate that both kinases are inhibited by quercetin and 16 related flavonoids; IP6K is the preferred target. Relative inhibitory activities were rationalized by X-ray analysis of kinase/flavonoid crystal structures; this detailed structure–activity analysis revealed hydrophobic and polar ligand/protein interactions, the degree of flexibility of key amino acid side chains, and the importance of water molecules. The seven most potent IP6K inhibitors were incubated with intact HCT116 cells at concentrations of 2.5 $μ$M; diosmetin was the most selective and effective IP6K inhibitor (>70% reduction in activity). Overall, our data can instruct on pharmacophore properties to assist the future development of inositol phosphate kinase inhibitors. Finally, we propose that dietary flavonoids may inhibit IP6K activity in cells that line the gastrointestinal tract.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Evaluating the Importance of Conformers for Understanding the Vacuum-Ultraviolet Spectra of Oxiranes: Experiment and Theory

Vacuum-ultraviolet (VUV) absorption spectroscopy enables electronic transitions that offer the unambiguous identification of molecules. As target molecules become more complex, multifunctional species present a great challenge to both experimental and computational spectroscopy. This research reports both experimental and theoretical studies of oxiranes. Computationally, the nuclear ensemble approach has been used to accurately predict experimental spectra for a variety of molecules. However, this approach incurs great computational cost, as ensembles generally consist of thousands of geometries. The present study aims to drastically reduce the ensemble by evaluating the significance of the conformers to the predicted spectra. This approach was applied to 11 substituted oxiranes using the Conformer Rotamer Ensemble Sampling Tool (CREST) of Grimme to generate an ensemble of unique conformers determined by their Boltzmann populations. Five TD-DFT functionals (BMK, CAM-B3LYP, M06-2X, MN15, ωB97X-D) and EOM-CCSD were used to simulate the spectrum of each substituted oxirane ensemble. Computed spectra were then compared to the experiment using both qualitative and quantitative metrics. Based on these metrics, it was observed that certain conformers may not be necessary to characterize this set of oxiranes despite the temperature (323 K) of the experiment. A single conformer can then be used with TD-DFT and EOM-CCSD to replicate the experimental spectra of these medium-sized combustion species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

On the Network Topology of Cross-Linked Acrylate Photopolymers: A Molecular Dynamics Case Study

A reactive molecular dynamics approach is used to simulate cross-linking of acrylate polymer networks. By employing the same force field and reactive scheme and studying three representative multifunctional acrylate monomers, we isolate the importance of the nonreactive moieties within these model monomers. Analyses of reactive trajectories benchmark the estimated gel points, cyclomatic character, and spatially resolved cross-linking tendencies of the acrylates as a function of conversion. The insights into the similarities and differences of the polymerization and resulting networks presented here suggest molecular mechanics as a useful tool in the rational design of photopolymerization resins.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗