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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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Organic Synthetic Advanced Materials for Optoelectronic and Energy Applications (at National Taipei University of Technology)

These slides cover Hung-Ju Yen's recent work in the synthesis and structural design of functional materials, which were further used for optoelectronic and energy applications, such as lithium ion battery, solar cell, LED, electrochromic, and fuel cells. This was for a job interview at National Taipei University of Technology. The following topics are detailed: current challenges for lithium-ion batteries; graphene, graphene oxide and nanographene; nanographenes with various functional groups; fine tune d-spacing through organic synthesis: varying functional group; schematic view of LIBs; nanographenes as LIB anode; rate performance (charging-discharging); electrochromic technology; electrochromic materials; advantages of triphenylamine; requirement of electrochromic materials for practical applications; low driving voltage and long cycle life; increasing the electroactive sites by multi-step synthetic procedures; synthetic route to starburst triarylamine-based polyamide; electrochromism ranging from visible to NIR region; transmissive to black electrochromism; RGB and CMY electrochromism.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Organic Synthetic Advanced Materials for Optoelectronic and Energy Applications (at Center for Condensed Matter Sciences)

These slides cover Hung-Ju Yen's recent work in the synthesis and structural design of functional materials, which were further used for optoelectronic and energy applications, such as lithium ion battery, solar cell, LED, electrochromic, and fuel cells. This was for a job interview at Center for Condensed Matter Sciences. The following topics are detailed: current challenges for lithium-ion batteries; graphene, graphene oxide and nanographene; nanographenes with various functional groups; fine tune d-spacing through organic synthesis: varying functional group; schematic view of LIBs; nanographenes as LIB anode; rate performance (charging-discharging); electrochromic technology; electrochromic materials; advantages of triphenylamine; requirement of electrochromic materials for practical applications; low driving voltage and long cycle life; increasing the electroactive sites by multi-step synthetic procedures; synthetic route to starburst triarylamine-based polyamide; electrochromism ranging from visible to NIR region; transmissive to black electrochromism; RGB and CMY electrochromism.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Organic Synthetic Advanced Materials for Optoelectronic and Energy Applications (at National Sun Yat-sen University)

These slides cover Hung-Ju Yen's recent work in the synthesis and structural design of functional materials, which were further used for optoelectronic and energy applications, such as lithium ion battery, solar cell, LED, electrochromic, and fuel cells. This was for a job interview at National Sun Yat-sen University. The following topics are detailed: current challenges for lithium-ion batteries; graphene, graphene oxide and nanographene; nanographenes with various functional groups; fine tune d-spacing through organic synthesis: varying functional group; schematic view of LIBs; nanographenes as LIB anode; rate performance (charging-discharging); electrochromic technology; electrochromic materials; advantages of triphenylamine; requirement of electrochromic materials for practical applications; low driving voltage and long cycle life; increasing the electroactive sites by multi-step synthetic procedures; synthetic route to starburst triarylamine-based polyamide; electrochromism ranging from visible to NIR region; transmissive to black electrochromism; RGB and CMY electrochromism.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Influence of natural and synthetic organic ligands on the stability and mobility of reduced tc(iv)

The primary objectives were (1) to quantify the interactions of organic ligands with Tc(IV) through the generation of thermodynamic (complexation) and kinetic parameters needed to assess and predict the mobility of reduced Tc(IV) at DOE contaminated sites; and (2) to determine the impact of organic ligands on the mobility and fate of reduced Tc(IV) under field geochemical conditions.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2018

Synthetic Biology: Molecular Tools for Engineering Organisms

Synthetic biology is a biological engineering discipline based on abstracting living systems through the lens of physical engineering concepts. In particular, synthetic biology places an emphasis on the characterisation of simple parts that can be modularly assembled into configurations that give rise to complex, higher-order behaviours. Within the past two decades, this approach has enabled the development number of new molecular biology tools for modifying living systems in order to investigate fundamental processes or imbuing functions into cells that do not exist in nature. While specific synthetic biology applications span a huge range of seemingly unrelated disciplines (from biofuel producing microbes, to malaria-resistant mosquitoes, to living medical therapies), these distinct examples derive from reuse and rearrangement of relatively limited set of cell engineering technologies. The continuing development of these core molecular biology tools for controlling gene expression, protein activity and signalling networks can promote evermore ambitious biological engineering projects.

gene expression↗
DOE OSTI2015

Biocontainment of genetically modified organisms by synthetic protein design

Genetically modified organisms (GMOs) are increasingly deployed at large scales and in open environments. Genetic biocontainment strategies are needed to prevent unintended proliferation of GMOs in natural ecosystems. Existing biocontainment methods are insufficient because they impose evolutionary pressure on the organism to eject the safeguard by spontaneous mutagenesis or horizontal gene transfer, or because they can be circumvented by environmentally available compounds. In this paper, we computationally redesign essential enzymes in the first organism possessing an altered genetic code (Escherichia coli strain C321.ΔA) to confer metabolic dependence on non-standard amino acids for survival. The resulting GMOs cannot metabolically bypass their biocontainment mechanisms using known environmental compounds, and they exhibit unprecedented resistance to evolutionary escape through mutagenesis and horizontal gene transfer. Finally, this work provides a foundation for safer GMOs that are isolated from natural ecosystems by a reliance on synthetic metabolites.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2019

Hierarchically porous metal–organic frameworks: synthetic strategies and applications

Abstract Despite numerous advantages, applications of conventional microporous metal–organic frameworks (MOFs) are hampered by their limited pore sizes, such as in heterogeneous catalysis and guest delivery, which usually involve large molecules. Construction of hierarchically porous MOFs (HP-MOFs) is vital to achieve the controllable augmentation of MOF pore size to mesopores or even macropores, which can enhance the diffusion kinetics of guests and improve the storage capacity. This review article focuses on recent advances in the methodology of HP-MOF synthesis, covering preparation of HP-MOFs with intrinsic hierarchical pores, and modulated, templated and template-free synthetic strategies for HP-MOFs. The key factors which affect the formation of HP-MOF architectures are summarized and discussed, followed by a brief review of their applications in heterogeneous catalysis and guest encapsulation. Overall, this review presents a roadmap that will guide the future design and development of HP-MOF materials with molecular precision and mesoscopic complexity.

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

Resource Recovery and Environmental Protection in Wyoming’s Greater Green River Basin Using Selective Nanostructured Membranes (Final Report)

Produced water (PW) represents a sizable waste stream that is co-generated with oil and natural gas production. In 2021 Wyoming ranked 8th and 9th, respectively in domestic oil and natural gas production. In 2017 Wyoming ranked as the 4th highest generator of PW in the U.S, accounting for 7% of the total volume generated. In the context of being the 3rd most arid state in the U.S., the value of water reuse becomes obvious. PW reuse, and resource recovery, in any form requires some level of treatment to remove particulates, residual (free, dispersed) hydrocarbons, organics, and salts. The level of treatment depends on the requirements of the reuse, or resource recovery, application. PW management systems in Wyoming employ in order of volume of PW managed the following management strategies: reinjection for enhanced oil recovery, surface discharge, deep well injection, evaporation ponds (impoundments), and commercial management/treatment. Complicating treatment efforts are the relatively high concentrations of organics (natural and synthetic), dispersed/free hydrocarbons, benzene-toluene-ethylbenzene, and xylenes (BTEX) compounds, biologicals, salts, and minerals. Hydrocarbons (dispersed/dissolved crude oils) and BTEX compounds, as well as synthetic organics, present economic and environmental concerns. The former represents lost revenue, while the latter results in negative environmental impacts like emissions from surface impoundments. The overall objective of this proposal was to synthesize superhydrophilic/oleophobic and superhydrophobic/oleophilic membranes for selectively concentrating and then separating BTEX compounds and oil and grease (O&G) from PW originating from the Greater Green River Basin (GGRB) in Wyoming. Three specific research aims were pursued to accomplish this overall objective. This final report details the development of the superhydrophobic and superhydrophilic membranes, as well as the design of the membrane module prototypes specifically. The technoeconomic assessment is separately reported in another document. 1. Aim #1 – Material optimization and performance evaluation of superhydrophilic/oleophobic and superhydrophobic/oleophilic membranes made by electrospinning/spraying. 2. Aim #2 – Design and construction of cross-flow membrane modules for selectively concentrating and then separating BTEX/oil from GGRB produced water. 3. Aim #3 – Techno-economic assessment of BTEX/oil recovery, and clean water production, using superhydrophilic/oleophobic and superhydrophobic/oleophilic membrane separation for GGRB PW. Superhydrophobic membranes were synthesized by electrospinning poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) nanofibers onto polyester (PET) substrates and electrospraying nano-carbon black/PVDF-HFP onto the nanofibrous layer. These membranes were characterized by high (>8000 liters per square meter per hour per bar (LMH/bar)) permeance values for pure hydrocarbon phases and a high hydrocarbon selectivity (>96%) when treating GGRB PW. All results were obtained when operating the membrane in a crossflow configuration representative of actual field operating conditions. Solvent/oil properties, specifically viscosity and total surface energy/tension, affected permeance across the membrane, which resulted in light mineral oil (394 LMH/bar) and o-xylene (1834 LMH/bar) being characterized by lower permeance values in the pure phase tests. Mixed phase fluxes between 40 to 80 LMH were obtained for the PW when operating the membrane at a feed pressure of 0.3 bar. Flux decreased as the mixed phase concentration in the feed decreased pointing to the importance of maximizing the collision efficiency between the emulsion and the membrane surface and maximizing the emulsion concentration in the feed and the turbulence within the feed channel. These tests demonstrated that the superhydrophobic membranes developed here are a viable hydrocarbon recovery method for GGRB PWs and should be pursued for testing in pilot-scale trials. Superhydrophilic membranes were successfully synthesized via electrospinning/spraying using polyacrylonitrile (PAN) nanofibers as a base nanofibrous matrix. Integration of polyaniline (PANI) into the nanofibrous matrix produced a superior membrane, for water filtration applications, relative to PAN alone and reduced graphene oxide (RGO) when integrated into the nanofibrous matrix. This conclusion was based on the PANI-PAN resistance to flux loss (fouling) when treating model solvent/oil solutions representative of GGRB PWs and field collected PW from the GGRB. The synthesized PAN membranes outperformed a commercially available PAN membrane designed for oil/water separation. This finding indicates that the surface chemical and physical characteristics of the electrospun membranes presents improved properties for filtration of challenging waters like GGRB PWs. The electrospun membranes therefore show promise overall as a substitute for conventionally polymerized membranes in PW treatment applications. The PANI-PAN membrane specifically presents superior performance characteristics for concentration O&G prior to treatment by the hydrocarbon recovery membrane and producing high-quality filtrate for reuse and/or additional treatment (desalination).

02 PETROLEUM↗
DOE OSTI2020

Direct Oxidation of Primary Alcohols to Carboxylic Acids

Oxidation of primary alcohols to carboxylic acids is a fundamental transformation in organic chemistry, yet despite its simplicity, extensive use, and relationship to pH, it remains a subject of active research for synthetic organic chemists. Since 2013, a great number of new methods have emerged that utilize transition-metal compounds as catalysts for acceptorless dehydrogenation of alcohols to carboxylates. The interest in this reaction is explained by its atom economy, which is in accord with the principles of sustainability and green chemistry. Furthermore, the methods for the direct synthesis of carboxylic acids from alcohols is ripe for a modern survey, which we provide in this review.

acceptorless dehydrogenation↗
DOE OSTI2011

A superoxide anion-scavenger, 1,3-selenazolidin-4-one suppresses serum deprivation-induced apoptosis in PC12 cells by activating MAP kinase

Synthetic organic selenium compounds, such as ebselen, may show glutathione peroxidase-like antioxidant activity and have a neurotrophic effect. We synthesized 1,3-selenazolidin-4-ones, new types of synthetic organic selenium compounds (five-member ring compounds), to study their possible applications as antioxidants or neurotrophic-like molecules. Their superoxide radical scavenging effects were assessed using the quantitative, highly sensitive method of real-time kinetic chemiluminescence. At 166 {mu}M, the O{sub 2}{sup -} scavenging activity of 1,3-selenazolidin-4-ones ranged from 0 to 66.2%. 2-[3-(4-Methoxyphenyl)-4-oxo-1,3-selenazolidin-2-ylidene]malononitrile (compound b) showed the strongest superoxide anion-scavenging activity among the 6 kinds of 2-methylene-1,3-selenazolidin-4-ones examined. Compound b had a 50% inhibitory concentration (IC{sub 50}) at 92.4 {mu}M and acted as an effective and potentially useful O{sub 2}{sup -} scavenger in vitro. The effect of compound b on rat pheochromocytome cell line PC12 cells was compared with that of ebselen or nerve growth factor (NGF) by use of the MTT [3-(4, 5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide] assay. When ebselen was added at 100 {mu}M or more, toxicity toward PC12 cells was evident. On the contrary, compound b suppressed serum deprivation-induced apoptosis in PC12 cells more effectively at a concentration of 100 {mu}M. The activity of compound b to phosphorylate mitogen-activated protein kinase/extracellular signal-regulated protein kinase (ERK) 1/2 (MAP kinase) in PC12 cells was higher than that of ebselen, and the former at 100 {mu}M induced the phosphorylation of MAP kinase to a degree similar to that induced by NGF. From these results, we conclude that this superoxide anion-scavenger, compound b, suppressed serum deprivation-induced apoptosis by promoting the phosphorylation of MAP kinase. -- Highlights: Black-Right-Pointing-Pointer We newly synthesized 1,3-selenazolidin-4-ones to study their possible applications. Black-Right-Pointing-Pointer Among new compounds, compound b showed the strongest SOSA. Black-Right-Pointing-Pointer Compound b suppressed serum deprivation-induced apoptosis in PC12 cells. Black-Right-Pointing-Pointer Compound b suppressed apoptosis by promoting the activation of MAP kinase.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2022

Photobiocatalysis for Abiological Transformations

Harnessing biocatalysts for novel abiological transformations is a longstanding goal of synthetic chemistry. Combining the merits of biocatalysis and photocatalysis allows for selective transformations fueled by visible light and offers many advantages including new reactivity, high enantioselectivity, greener syntheses, and high yields. Photoinduced electron or energy transfer enables synthetic methodologies that complement conventional two electron processes or offer orthogonal pathways for developing new reactions. Enzymes are well suited and can be tuned by directed evolution to exert control over radical intermediates thereby suppressing undesirable reactions and delivering high chemo- and stereoselectivities. Within the past decade, the combination of biocatalysis and photocatalysis was mainly focused on exploiting light-regenerated cofactors to increase native enzymatic activity. However, recent developments have demonstrated that the combination can unlock new-to-nature chemistry. Particularly, the discovery and application of new strategies are well poised to expand the applications of photobiocatalysis. In the past three years, our lab has been studying the combinations of photocatalysis and biocatalysis which can be applied to create new synthetic methodologies and solve challenges in synthetic organic chemistry. Our efforts have expanded the strategies for combining external photocatalysts with enzymes through the construction of a synergistic cooperative stereoconvergent reduction system consisting of photosensitized energy transfer and ene-reductase catalyzed alkene reduction. Additionally, our efforts have also extended the capability of cofactor-dependent photoenzymatic systems to include enantioselective bimolecular radical hydroalkylations of alkenes by irradiating electron donor-acceptor complexes comprised of enzymatic redox active cofactors and unnatural substrates. In this Account, we highlight strategies developed by our group and others for combining biocatalysis and photocatalysis with the aim of introducing nonnatural reactivity to enzymes. Presently, strategies applied to achieve this goal include the repurposing of newly discovered photoactive enzymes, the elucidation of new photoreactivity within cofactor-dependent enzymes, the combination of external photocatalysts with enzymes, and the construction of artificial photoenzymes. By demonstrating the successful application of these strategies for achieving selective new-to-nature transformations, we hope to spur interest in the expanding the scope of photobiocatalytic systems through the use and extension of these strategies and creation of new strategies. In addition, we hope to elucidate the intuition in synergizing the unique capabilities of biocatalysis and photocatalysis so that photobiocatalysis can be recognized as a potential solution to difficult challenges in synthetic organic chemistry.

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

Genetic Algorithms for Rapid Molecular Materials Screening

This project developed efficient methods for rapid computational screening of conjugated polymers and oligomers with optimal or near-optimal photovoltaic, dielectric, spintronic, and other unique electronic structure properties using genetic algorithms (GA). A key promise of organic materials is that using the incredible tailorability of synthetic organic chemistry enables experimental optimization of performance across multiple relevant properties (e.g., organic photovoltaics, organic lasers). The fundamental challenge is inverse design: how does one find the molecular or polymer structures with desired properties in the face of a near-infinite (e.g., >10 20 - 10 60 ) number of possible molecular structures, combined with time-consuming experiments or electronic structure calculations.

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

Accelerated tert -butyloxycarbonyl deprotection of amines in microdroplets produced by a pneumatic spray

Protection and deprotection of organic compounds in multistep reactions using functional groups such as tert-butoxycarbonyl (Boc), is widely performed in synthetic organic chemistry. Reaction rate acceleration studies in spray-based ionization methods (electrosonic spray, paper spray, nanospray) have become increasingly common. In this report, we demonstrate reaction rate acceleration of Boc deprotection using easy ambient sonic-spray ionization (EASI), a pneumatic technique which does not involve an applied voltage, in a teaching laboratory setting. The goal of this laboratory exercise was to explore acceleration in a previously unexplored spray-based reaction, while emphasizing in a pedagogic setting the importance of protecting groups for multistep synthesis. Rate acceleration factors of more than an order of magnitude were observed in the uncharged micron-sized droplets generated by EASI. The effect of reaction conditions on reaction acceleration was examined including changes in the type of acid, reagent concentration ratios and syringe pump flow rates. Student knowledge was assessed by pre-laboratory assignments, post-laboratory reports and oral interviews.

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

Thermally Activated Delayed Fluorescence (TADF) Path toward Efficient Electroluminescence in Purely Organic Materials: Molecular Level Insight

Since the seminal work of Tang and Vanslyke in 1987 on small-molecule emitters and that of Friend and co-workers in 1990 on conjugated-polymer emitters, organic light-emitting diodes (OLEDs) have attracted much attention from academia as well as industry, as the OLED market is estimated to reach the $30B mark by the end of 2018. In these first-generation organic emitters, on the basis of simple spin statistics, electrical excitation resulted in the formation of ~25% singlet excitons and ~75% triplet excitons. Radiative decay of the singlet excitons to the singlet ground state leads to a prompt fluorescence emission, while the triplet excitons only lead to weak phosphorescence due to the very small spin-orbit couplings present in purely organic molecules. The consequence is a ca. 75% energy loss, which triggered wide-ranging efforts to try and harvest as many of the triplet excitons as possible. In 1998, Thompson, Forrest, and their co-workers reported second-generation OLED emitters based on coordination complexes with heavy transition metals (e.g., iridium or platinum). Here, the triplet excitons stimulate efficient and fast phosphorescence due to the strong spin-orbit couplings enabled by the heavy-metal atoms. Internal quantum efficiencies (IQE) up to 100% have been reported, which means that for every electron injected into the device, a photon is emitted. Here, while these second-generation emitters are those mainly exploited in current OLED applications, there is strong impetus from both cost and environmental standpoints to find new ways of exploiting purely organic emitters, which in addition can offer greater flexibility to fine tune the electronic and optical properties by exploiting the synthetic organic chemistry toolbox.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Exploring chemistry with single-molecule and -particle fluorescence microscopy

The evolution of single-molecule and -particle fluorescence microscopy imaging techniques for the investigation of chemical reactions yielded achievements at all fronts, from synthetic organic chemistry to materials science. The removal of ensemble averaging effects uncovers unique, otherwise hidden reaction intermediates, reactivity, and kinetics. Thus, new insights can be obtained even for well-explored chemical reactions and processes. The aim of this article is to serve as a guide and a source of inspiration for scientists who wish to develop single-molecule and -particle fluorescence microscopy to answer questions in chemistry. Here, we describe the current status of technical accomplishments in the field and point out technical and conceptual obstacles for overcoming in the near future, with focus on improvement of bench-scale synthetic reactions.

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

Towards chloroplastic nanofactories: formation of proteinaceous scaffolds for metabolic engineering

The evolution of eukaryotic lipid-bound organelles allows for specialized metabolism to occur within spatially distinct metabolic landscapes within the same cell. However, this strategy of compartmentalization is not unique to eukaryotic organisms. Many bacteria, spread across 45 different phyla, contain loci that encode for specialized bacterial microcompartments (BMCs) (Sutter et al., 2021). The formation of a BMC involves self-assembly from three families of shell proteins to form the outer shell membrane, in addition to the encapsulation of an enzymatic core packaged within the lumen of a BMC (Kerfeld et al., 2018). These proteinaceous organelles provide a competitive growth advantage by enabling organisms to process inaccessible substrates by sequestering metabolic intermediates (i.e. aldehydes) that would otherwise be toxic within the cytoplasm. While BMCs perform specific metabolic functions in their native organism, synthetic, empty BMC shells can form without the requirement of native cargo inside (Doron and Kerfeld, 2024). This provides a transferable and tunable platform of protein scaffolding for guiding metabolic engineering within a host organism of choice (Raba and Kerfeld, 2022).

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Flavin-dependent halogenases catalyze enantioselective olefin halocyclization

Abstract Halocyclization of alkenes is a powerful bond-forming tool in synthetic organic chemistry and a key step in natural product biosynthesis, but catalyzing halocyclization with high enantioselectivity remains a challenging task. Identifying suitable enzymes that catalyze enantioselective halocyclization of simple olefins would therefore have significant synthetic value. Flavin-dependent halogenases (FDHs) catalyze halogenation of arene and enol(ate) substrates. Herein, we reveal that FDHs engineered to catalyze site-selective aromatic halogenation also catalyze non-native bromolactonization of olefins with high enantioselectivity and near-native catalytic proficiency. Highly selective halocyclization is achieved by characterizing and mitigating the release of HOBr from the FDH active site using a combination of reaction optimization and protein engineering. The structural origins of improvements imparted by mutations responsible for the emergence of halocyclase activity are discussed. This expansion of FDH catalytic activity presages the development of a wide range of biocatalytic halogenation reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗