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At least 235 records · Page 13

AMINO ACID ANALYSES OF THE ANTARCTIC CM2 METEORITES ALH 83100 AND LEW 90500 USING LIQUID CHROMATOGRAPHY-TIME OF FLIGHT-MASS SPECTROMETRY

The investigation of organic compounds in primitive carbonaceous meteorites provides a record of the chemical processes that occurred in the early solar system. In particular, amino acids have been shown to be potential indicators in tracing the nature of carbonaceous chondrite parent bodies [ 13. The delivery of amino acids by carbonaceous chondrites to the early Earth could have been any important source of the Earth's prebiotic organic inventory [2]. Over 80 different amino acids have been detected in the Murchison CM2 meteorite, most of them completely non-existent in the terrestrial biosphere [3]. We have optimized a new liquid chromatography-time-of-flight-mass spectrometry (LC-ToF-MS) technique coupled with OPAMAC derivatization in order to detect amino acids in meteorite extracts by UV fluorescence and exact mass simultaneously. The detection limit of the LC-ToF-MS instrument for amino acids is at least 3 orders of magnitude lower than traditional GC-MS techniques. Here we report on the first analyses of amino acids and their enantiomeric abundances in the CM2 carbonaceous meteorites ALH 83100, LEW 90500, and Murchison using this new LC-ToF-MS instrument configuration. Amino acid analyses of any kind for the CM meteorite ALH 83100 have not previously been reported.

Glavin, D. P.↗

Tailorable Cellulose II Nanocrystals (CNC II) Prepared in Mildly Acidic Lithium Bromide Trihydrate (MALBTH)

Preparing cellulose II nanocrystals (CNC II) requires a polymorph transformation of natural cellulose I feedstocks. The transformation is usually achieved via a process such as mercerization or dissolution–regeneration. This study demonstrated a new method to prepare CNC II directly from bleached kraft pulp (BKP, a commercially available cellulose I feedstock) in a mildly acidic lithium bromide trihydrate (MALBTH) system, a concentrated (~61 wt%) solution of LiBr in water with a very low concentration (2.5 mM) of sulfuric acid. First, the BKP was treated in the MALBTH system to generate a cellulose II hydrolysis solid residue (CHR) with a yield of 64–86%, during which the selective hydrolysis of disordered cellulose and the polymorph transformation were completed simultaneously. Then, subsequent oxidation of the CHR by ammonium persulfate (APS, 0.1–0.6 M) resulted in the CNC II with high yield (up to 62%), high crystallinity (over 90%), rich surface carboxyl group (0.3–1.2 mmol g-1 cellulose), excellent colloidal stability (up to -59 mV zeta potential), and high thermal stability. The CNC II had a tunable length (26–57 nm), determined by the conditions of the MALBTH hydrolysis and the APS oxidation, but similar lateral dimension (8–10 nm). The characterization of the CHR by wide-angle X-ray diffraction and Fourier transform infrared spectroscopy verified the polymorphic transformation from cellulose I to II during the MALBTH treatment. The swelling of the BKP in the MALBTH enabled cellulose crystallites to slide and reassemble, which completed the rearrangement of cellulose chains from parallel to anti-parallel conformation (polymorph transformation from cellulose I to II). This study provided an efficient and green method to produce cellulose II nanocrystals with controllable aspect ratios via the simultaneous hydrolysis and polymorph transformation of cellulose I feedstocks.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Baseline Testing of the Club Car Carryall With Asymmetric Ultracapacitors

The NASA John H. Glenn Research Center initiated baseline testing of the Club Car Carryall with asymmetric ultracapacitors as a way to reduce pollution in industrial settings, reduce fossil fuel consumption, and reduce operating costs for transportation systems. The Club Car Carryall provides an inexpensive approach to advance the state of the art in electric vehicle technology in a practical application. The project transfers space technology to terrestrial use via non-traditional partners, and provides power system data valuable for future space applications. The work was done under the Hybrid Power Management (HPM) Program, which includes the Hybrid Electric Transit Bus (HETB). The Carryall is a state of the art, ground up, electric utility vehicle. A unique aspect of the project was the use of a state of the art, long life ultracapacitor energy storage system. Innovative features, such as regenerative braking through ultracapacitor energy storage, are planned. Regenerative braking recovers much of the kinetic energy of the vehicle during deceleration. The Carryall was tested with the standard lead acid battery energy storage system, as well as with an asymmetric ultracapacitor energy storage system. The report concludes that the Carryall provides excellent performance, and that the implementation of asymmetric ultracapacitors in the power system can provide significant performance improvements.

Eichenberg, Dennis J.↗

Experimental Investigation of Organic Synthesis in Hydrothermal Environments

Seafloor hydrothermal systems may be the most likely locations on the early Earth for the emergence of life. Because of the disequilibrium inherent in such dynamic, mixing environments, abundant chemical energy would have been available for formation of the building blocks of life. In addition, theoretical studies suggest that organic compounds in these conditions would reach metastable states, due to kinetic barriers to the formation of stable equilibrium products (CO2 and methane). The speciation of organic carbon in metastable states is highly dependent on the oxidation state, pH, temperature, pressure and bulk composition of the system. The goal of our research is to investigate the effects of a number external variables on the formation, transformation, and stability of organic compounds at hydrothermal conditions. We have begun experimental work to attempt to control the oxidation state of simulated hydrothermal systems by using buffers composed of mineral powders and gas mixtures. We are also beginning to test the stability of organic compounds under these conditions. The experiments are being performed using the hydrothermal bomb apparatus at the U.S. Geological Survey in Menlo Park, CA and the supercritical water oxidizer (SCWO) at NASA Ames Research Center in Moffet Field, CA. The amino acids decomposed rapidly. Even after the approximately 15 minutes between addition of the amino acids and the first sampling, no amino acids were detected in the PPM system by GC- MS, while in the FeFeO system the amino acids were present at a level of less than 50% of original. Carboxylic acids, ammonia, and CO2 were the main products, along with some unidentified compounds. The ratios of carboxylic acids and concentrations of other products seem to have remained stable during the experiments, consistent with observations of other metastable systems and theoretical predictions.

Shock, Everett L.↗

2D Metal/Graphene and 2D Metal/Graphene/Metal Systems for Electrocatalytic Conversion of CO 2 to Formic Acid

Abstract Efficiently transforming CO 2 into renewable energy sources is crucial for decarbonization efforts. Formic acid (HCOOH) holds great promise as a hydrogen storage compound due to its high hydrogen density, non‐toxicity, and stability under ambient conditions. However, the electrochemical reduction of CO 2 (CO 2 RR) on conventional carbon black‐supported metal catalysts faces challenges such as low stability through dissolution and agglomeration, as well as suffering from high overpotentials and the necessity to overcome the competitive hydrogen evolution reaction (HER). In this study, we modify the physical/chemical properties of metal surfaces by depositing metal monolayers on graphene (M/G) to create highly active and stable electrocatalysts. Strong covalent bonding between graphene and metal is induced by the hybridization of sp and d orbitals, especially the sharp , , and orbitals of metals near the Fermi level, playing a decisive role. Moreover, charge polarization on graphene in M/G enables the deposition of another thin metallic film, forming metal/graphene/metal (M/G/M) structures. Finally, evaluating overpotentials required for CO 2 reduction to HCOOH, CO, and HER, we find that Pd/G, Pt/G/Ag, and Pt/G/Au exhibit excellent activity and selectivity toward HCOOH production. Our novel 2D hybrid catalyst design methodology may offer insights into enhanced electrochemical reactions through the electronic mixing of metal and other p‐block elements.

Cho, Jinwon↗

2D Metal/Graphene and 2D Metal/Graphene/Metal Systems for Electrocatalytic Conversion of CO 2 to Formic Acid

Efficiently transforming CO 2 into renewable energy sources is crucial for decarbonization efforts. Formic acid (HCOOH) holds great promise as a hydrogen storage compound due to its high hydrogen density, non-toxicity, and stability under ambient conditions. However, the electrochemical reduction of CO 2 (CO 2 RR) on conventional carbon black-supported metal catalysts faces challenges such as low stability through dissolution and agglomeration, as well as suffering from high overpotentials and the necessity to overcome the competitive hydrogen evolution reaction (HER). In this study, we modify the physical/chemical properties of metal surfaces by depositing metal monolayers on graphene (M/G) to create highly active and stable electrocatalysts. Strong covalent bonding between graphene and metal is induced by the hybridization of sp and d orbitals, especially the sharp $d_{z^2}$, $d_{yz}$, $d_{xz}$ orbitals of metals near the Fermi level, playing a decisive role. Moreover, charge polarization on graphene in M/G enables the deposition of another thin metallic film, forming metal/graphene/metal (M/G/M) structures. Finally, evaluating overpotentials required for CO 2 reduction to HCOOH, CO, and HER, we find that Pd/G, Pt/G/Ag, and Pt/G/Au exhibit excellent activity and selectivity toward HCOOH production. Our novel 2D hybrid catalyst design methodology may offer insights into enhanced electrochemical reactions through the electronic mixing of metal and other p-block elements.

2D Electrocatalysts↗

A novel mineral-acid free biphasic deep eutectic solvent/γ-valerolactone system for furfural production and boosting the enzymatic hydrolysis of lignocellulosic biomass

The failure of hemicellulose valorization in a deep eutectic solvent (DES) pretreatment has become a bottleneck that challenges its further development. Here, to address this issue, this study developed a DES/GVL (γ-valerolactone) biphasic system for effective hemicellulose-furfural conversion, enhanced cellulose saccharification and lignin isolation. The results indicated that the biphasic system could significantly improve the lignin removal (as high as 89.1%), 86.0% higher than the monophasic DES, accompanied by ~100% hemicellulose degradation. Notably, the GVL in the biphasic solvent restricted the condensation of hemicellulose degradation products, which as a result generated large amount of furfural in the pretreatment liquid with a yield of 68.6%. With the removal of hemicellulose and lignin, cellulose enzymatic hydrolysis yield was boosted and reached near 100%. This study highlighted that the novel DES/GVL is capable of fractionating the biomass and benefiting their individual utilization, which could provide a new biorefinery configuration for a DES pretreatment.

09 BIOMASS FUELS↗

Altered TNF-Alpha, Glucose, Insulin and Amino Acids in Islets Langerhans Cultured in a Microgravity Model System

The present studies were designed to determine effects of a microgravity model system upon lipopolysaccharide (LPS) stimulated tumor necrosis factor alpha (TNF-alpha) activity and indices of insulin and fuel homeostasis of pancreatic islets of Langerhans. Islets (1726+/-1 17,150 u IEU) from Wistar Furth rats were treated as: 1) HARV (High Aspect Ratio Vessel cell culture) , 2) HARV plus LPS, 3) static culture, 4) static culture plus LPS. TNF-alpha (L929 cytotoxicity assay) was significantly increased in LPS-induced HARV and static cultures, yet the increase was more pronounced in the static culture group (p<0.05). A decrease in insulin concentration was demonstrated in the LPS stimulated HARV culture (p<0.05). We observed a greater glucose concentration and increased disappearance of arginine in islets cultured in HARVs. While nitrogenous compound analysis indicated a ubiquitous reliance upon glutamine in all experimental groups, arginine was converted to ornithine at a two-fold greater rate in the islets cultured in the HARV microgravity model system (p<0.05). These studies demonstrate alterations in LPS induced TNF-alpha production of pancreatic islets of Langerhans, favoring a lesser TNF activity in the HARV. These alterations in fuel homeostasis may be promulgated by gravity averaged cell culture methods or by three dimensional cell assembly.

Tobin, Brian W.↗

Non-thermal atmospheric pressure plasma–liquid synthesis of organic acids in aqueous solution from carbon monoxide

This work aims at understanding the conversion of CO to organic acids, namely oxalic acid and formic acid, using non-thermal atmospheric pressure plasma over aqueous solutions. CO exhibited significantly higher conversion to organic acids (more than 15×) compared to CO 2 under the same reaction conditions. The result bolsters a proposed two-step process for CO 2 fixation, whereby CO 2 is first converted to CO, and then CO is converted to organic acids. The organic acids produced from CO are intermediates in the water–gas shift (WGS) reaction of CO in the presence of an aqueous solution to dissolved CO 2 and hydrogen gas. Based on a simple thermodynamic analysis, the organic acid yield was increased by lowering the plasma–liquid reaction temperature using an ice bath to cool the reaction flask. The composition of the organic acids could be varied by changing the pH of the solution. Oxalate was formed in higher concentrations with increasing solution pH above the pK a of the radical species (CO 2 )˙ − . Below the pK a value, formate was the exclusive organic acid formed. The production of formate has a rather weak pH dependence but is enhanced slightly at a basic pH above 10. Furthermore, at basic pH, the effect of electrolyte concentration comes into play. Higher electrolyte concentrations, leading to shorter electrolyte Debye lengths, resulted in lowered organic acid yields. The highest yields of organic acids obtained in our system were 122 mg L −1 for oxalate and 77 mg L −1 for formate at an optimum 1 mM NaOH concentration in the starting solution. This work is a successful pioneering example of CO to organic acids conversion using non-thermal plasmas, which opens the pathway for a promising two-step conversion process of CO 2 to organic acids.

Sudagar, Alcina Johnson [Washington University in ↗

Recovery of Rare Earth Elements from Coal Mining Waste Materials

The objective of this proposed project was to locate coal overburden material that had rare earth elements (REEs) at concentrations of 300 ppm or higher. After securing the feedstock the next goal was to efficiently extract and purify the feedstocks to a purity of greater than 95%. A techno economic analysis was conducted to determine the economic viability of mining and processing REEs associated with Appalachian coal deposits. All aspects of mining, mineral processing, by-product potential, waste management, permitting and economics were examined. Attention was paid to the separation, degree of purification and marketing of Rare Earth elements. Along with REEs we evaluated the economics of the recovery of other metals of interest aong with the REEs. Our site location chosen was at the Jeddo Coal Site near Hazleton, Pennsylvania. The primary site was at the Upper Leigh High Mine. However, that changed to the North Eckley Mine site. We have analyzed a third site that will now be our second alternative to North Eckley. That site is the Highland mine site. This site is in a similar basin as the North Eckley site. During this project we evaluated various acids and extraction conditions. We have settled on using HCl as the acid of choice. One of the advantages of using HCl is it allows for easy removal of the highest contaminating metal, iron. When iron reacts with HCl in the presence of high chlorides it creates the anion complex FeCl 4 -1 . This FeCl 4 -1 complex will bind with an anion exchange resin. Greater than 99.8% of the iron is removed with this technique. Once the FeCl 4 -1 complex is bound to the anion exchange resin it can be released easily by just passing water over it. This water dilutes the FeCl 4 -1 to form FeCl 3 which is not anionic and therefore not attracted to the anion exchange resin. The FeCl 3 solution is a popular water flocculating agent used all over the world for water purification. We plan on this being one of our products produced. One of our goals was to create a multipurpose facility that was capable of handling multiple feedstocks. The proposed multipurpose facility will be able process all coal biproducts and coal products. These include 1.) clays that can easily be leached with ion exchange or acid 2.) Hard mineral deposits that can be leached with high pressure acid digestion 3.) Fly ash can be leached in the high-pressure acid digestion reactor. Fly ash is not a focus of this proposal but, the beneficial aspect of its utilization in this design cannot be overlooked. 4.) Acid Mine Drainage (AMD) Sludge is a high source of REE’s and can easily be dissolved to form a pregnant leach solution. Not shown on this simplified block flow diagram but crucial to its success is the recycle of acids. Our REE separation system is a continuous ion exchange process. The first stage is the separation of the non-REEs from the REEs. This is accomplished because the REEs are relatively larger than most of the non-REEs and typically have higher oxidation states (+3) than the non-REEs. In this step all the elements stick onto the column. However, as the columns are rinsed with various concentrations of acids different elements come off. For example, monovalent elements such as sodium and potassium elute off the column with a 1M HCl solution. Divalent elements such as calcium and magnesium do not elute until a 2M HCl solution is passed over the columns. The trivalent elements (REEs) are not eluted until a much higher concentrated acid is passed of the columns. Iron is also a trivalent, but it was removed in a prior anion exchange system. Aluminum is trivalent too, but it is much smaller than the REE atoms and elutes near the end of the 2 M HCl with the divalents. At the stage 2 and 3 our volume and masses have become too small to run on the continuous system. Therefore, we used a batch chromatography column or a flash chromatography column. The stage 2 process separates these REEs into 3 different fractions. A light, mid and heavy fraction. We calculated that we recovered greater than 90% of the REEs. This third column was packed with a different stationary phase. Five elements were chosen and purified to higher than 95% purity as shown by our internal testing. These elements were shipped to the DOE.

01 COAL, LIGNITE, AND PEAT↗

Hydrogen atom initiated chemistry

H Atoms have been created by the photolysis of H2S. These then initiated reactions in mixtures involving acetylene-ammonia-water and ethylene-ammonia-water. In the case of the acetylene system, the products consisted of two amino acids, ethylene and a group of primarily cyclic thio-compounds, but no free sulfur. In the case of the ethylene systems, seven amino acids, including an aromatic one, ethane, free sulfur, and a group of solely linear thio-compounds were produced. Total quantum yields for the production of amino acids were about 3 x 10 to the -5th and about 2 x 10 to the -4th with ethylene and acetylene respectively as carbon substrates. Consideration is given of the mechanism for the formation of some of the products and implications regarding planetary atmosphere chemistry, particularly that of Jupiter, are explored.

Hong, J. H.↗

SCOMAP-XD : atomistic deuterium contrast matching for small-angle neutron scattering in biology

The contrast-variation method in small-angle neutron scattering (SANS) is a uniquely powerful technique for determining the structure of individual components in biomolecular systems containing regions of different neutron scattering length density ρ . By altering the ρ of the target solute and the solvent through judicious incorporation of deuterium, the scattering of desired solute features can be highlighted. Most contrast-variation methods focus on highlighting specific bulk solute elements, but not on how the scattering at specific scattering vectors q , which are associated with specific structural distances, changes with contrast. Indeed, many systems exhibit q -dependent contrast effects. Here, a method is presented for calculating both bulk contrast-match points and q -dependent contrast using 3D models with explicit solute and solvent atoms and SASSENA , an explicit-atom SANS calculator. The method calculates the bulk contrast-match points within 2.4% solvent D 2 O accuracy for test protein–nucleic acid and lipid nanodisc systems. The method incorporates a general model for the incorporation of deuterium at non-exchangeable sites that was derived by performing mass spectrometry on green fluorescent protein. The method also decomposes the scattering profile into its component parts and identifies structural features that change with contrast. The method is readily applicable to a variety of systems, will expand the understanding of q -dependent contrast matching and will aid in the optimization of next-generation neutron scattering experiments.

59 BASIC BIOLOGICAL SCIENCES↗

Rejuvenation of Spent Media via Supported Emulsion Liquid Membranes

The overall goal of this project is to maximize the reuseability of spent fermentation media. Supported emulsion liquid membrane separation, a highly efficient extraction technique, is used to remove inhibitory byproducts during fermentation; thus, improving the yield while reducing the need for fresh water. The key objectives of this study are: Develop an emulsion liquid membrane system targeting low molecular weight organic acids which has minimal toxicity on a variety of microbial systems; Conduct mass transfer studies to allow proper modeling and design of a supported emulsion liquid membrane system; Investigate the effect of gravity on emulsion coalescence within the membrane unit; Access the effect of water re-use on fermentation yields in a model microbial system; Develop a perfusion-type fermentor utilizing a supported emulsion liquid membrane system to control inhibitory fermentation byproducts; Work for the coming year will focus on the determination of toxicity of various solvents, selection of the emulsifying agents, as well as characterizing the mass transfer of hollow-fiber contactors.

Wiencek, John M.↗

Rejuvenation of Spent Media via Supported Emulsion Liquid Membranes

The overall goal of this project was to maximize the reuseability of spent fermentation media. Supported emulsion liquid membrane separation, a highly efficient extraction technique, was used to remove inhibitory byproducts during fermentation; thus, improve the yield while reducing the need for fresh water. The key objectives of this study were: (1) Develop an emulsion liquid membrane system targeting low molecular weight organic acids which has minimal toxicity on a variety of microbial systems. (2) Conduct mass transfer studies to allow proper modeling and design of a supported emulsion liquid membrane system. (3) Investigate the effect of gravity on emulsion coalescence within the membrane unit. (4) Access the effect of water re-use on fermentation yields in a model microbial system. and (5) Develop a perfusion-type fermentor utilizing a supported emulsion liquid membrane system to control inhibitory fermentation byproducts (not completed due to lack of funds)

Wiencek, John M.↗

Chemically Fueled Transient Geometry Changes in Diphenic Acids

Transient changes in molecular geometry are key to the function of many important biochemical systems. Here, we show that diphenic acids undergo out-of-equilibrium changes in dihedral angle when reacted with a carbodiimide chemical fuel. Treatment of appropriately functionalized diphenic acids with EDC (N-(3-(dimethylamino)propyl)-N'-ethylcarbodiimide hydrochloride) yields the corresponding diphenic anhydrides, reducing the torsional angle about the biaryl bond by ~45°, regardless of substitution. In the absence of steric resistance, the reaction is well-described by a simple mechanism; the resulting kinetic parameters can be used to derive important properties of the system, such as yields and lifetimes. In conclusion, the reaction tolerates steric hindrance ortho to the biaryl bond, although the competing formation of (transient) byproducts complicates quantitative analysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development and evaluation of a Novel RT‐PCR system for reliable and rapid SARS‐CoV ‐2 screening of blood donations

Abstract Background The ongoing outbreak of severe acute respiratory syndrome coronavirus 2 (SARS‐CoV‐2) has caused great global concerns. In contrast to SARS, some SARS‐CoV‐2–infected people can be asymptomatic or have only mild nonspecific symptoms. Furthermore, there is evidence that SARS‐CoV‐2 may be infectious during an asymptomatic incubation period. With the discovery that SARS‐CoV‐2 can be detected in plasma or serum, blood safety is worthy of consideration. Study Design and Methods We developed a nucleic acid test (NAT) screening system for SARS‐CoV‐2 targeting nucleocapsid protein (N) and open reading frame 1ab (ORF 1ab) gene that could screen 5076 samples every 24 hours. The 2019 novel coronavirus RNA standard was used to evaluate linearity of standard curves. Diagnostic sensitivity and reproducibility were evaluated using artificial SARS‐CoV‐2. Specificity was evaluated with 61 other respiratory pathogens. Diagnostic performance was evaluated by testing two sputum and nine oropharyngeal swab specimens. The reverse transcription polymerase chain reaction (RT‐PCR) assay was used to screen SARS‐CoV‐2 RNA in blood donor specimens collected during the outbreak of SARS‐CoV‐2 in Chengdu. Results Limits of detection of the SARS‐CoV‐2 RT‐PCR assay for N and ORF 1ab gene were 12.5 and 27.58 copies/mL, respectively. Intra‐assay and interassay for the SARS‐CoV‐2 RT‐PCR assay based on cycle threshold were acceptably low. No cross‐reactivity was observed with other respiratory virus and bacterial isolates. The overall agreement value between the SARS‐CoV‐2 RT‐PCR assay and clinical diagnostic results was 100%. A total of 16 287 blood specimens collected from blood donors during SARS‐CoV‐2 surveillance were tested negative. Conclusions A high‐throughput NAT screening system was developed for SARS‐CoV‐2 screening of blood donations during the outbreak of SARS‐CoV‐2.

Li, Meng↗

Investigation of the Prebiotic Synthesis of Amino Acids and RNA Bases from CO2 Using FeS/H2S As a Reducing Agent

An autotrophic theory of the origin of metabolism and life has been proposed in which carbon dioxide is reduced by ferrous sulfide and hydrogen sulfide by means of a reversed citric acid cycle, leading to the production of amino acids. Similar processes have been proposed for purine synthesis. Ferrous sulfide is a strong reducing agent in the presence of hydrogen sulfide and can produce hydrogen as well as reduce alkenes, alkynes, and thiols to saturated hydrocarbons and reduce ketones to thiols. However, the reduction of carbon dioxide has not been demonstrated. We show here that no amino acids, purities, or pyrimidines are produced from carbon dioxide with the ferrous sulfide and hydrogen sulfide system. Furthermore, this system does not produce amino acids from carboxylic acids by reductive amination and carboxylation. Thus, the proposed autotrophic theory, using carbon dioxide, ferrous sulfide, and hydrogen sulfide, lacks the robustness needed to be a geological process and is, therefore, unlikely to have played a role In the origin of metabolism or the origin of life.

Keefe, Anthony D.↗