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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 415 records · Page 23

Dual Tunability for Uncatalyzed N‐Alkylation of Primary Amines Enabled by Plasma‐Microdroplet Fusion

Abstract The fusion of non‐thermal plasma with charged microdroplets facilitates catalyst‐free N‐alkylation for a variety of primary amines, without halide salt biproduct generation. Significant reaction enhancement (up to >200×) is observed over microdroplet reactions generated from electrospray. This enhancement for the plasma‐microdroplet system is attributed to the combined effects of energetic collisions and the presence of reactive oxygen species (ROS). The ROS (e.g., O 2 ⋅ − ) act as a proton sink to increase abundance of free neutral amines in the charged microdroplet environment. The effect of ROS on N‐alkylation is confirmed through three unique experiments: (i) utilization of radical scavenging reagent, (ii) characterization of internal energy distribution, and (iii) controls performed without plasma, which lacked reaction acceleration. Establishing plasma discharge in the wake of charged microdroplets as a green synthetic methodology overcomes two major challenges within conventional gas‐phase plasma chemistry, including the lack of selectivity and product scale‐up. Both limitations are overcome here, where dual tunability is achieved by controlling reagent concentration and residence time in the microdroplet environment, affording single or double N‐alkylated products. Products are readily collected yielding milligram quantities in eight hours. These results showcase a novel synthetic strategy that represents a straightforward and sustainable C−N bond‐forming process.

Chemistry↗

Decomposition of Irganox 1010 in plastic bonded explosives

Abstract Degradation pathways of Irganox 1010 in aged plastic bonded explosive (PBX) 9501 were investigated using ultrahigh performance liquid chromatography coupled to quadrupole time of flight mass spectrometry (UHPLC‐QTOF). Using a targeted approach, a total of 44 Irganox 1010 decomposition products were discovered. These decomposition products were formed through hydrolysis, scission, and/or oxidation of Irganox 1010. The hydrolytic decomposition of Irganox is a straightforward process resulting in the cleavage of the ester group(s) while oxidation and scission are more complicated and can happen at multiple locations on the Irganox 1010 molecule. Moreover, due to the symmetric nature of Irganox 1010, multiple decomposition reactions can occur. Indeed some decomposition products exhibited hydrolysis, oxidation, and scission. In order to probe any trends in the aged PBX 9501 samples, principal component analysis (PCA) was implemented. The greatest chemical differences between the aged PBX samples was hydrolysis of the ester functional groups on Irganox 1010. Despite the negative connotations of hydrolysis, the Irganox 1010 decomposition products are still able to function as a radical scavenger in PBX 9501 as intended.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Significance of aerosol radiative effect in energy balance control on global precipitation change

Historical changes of global precipitation in the 20th century simulated by a climate model are investigated. The results simulated with alternate configurations of cloud microphysics are analyzed in the context of energy balance controls on global precipitation, where the latent heat changes associated with the precipitation change is nearly balanced with changes to atmospheric radiative cooling. The atmospheric radiative cooling is dominated by its clear-sky component, which is found to correlate with changes to both column water vapor and aerosol optical depth (AOD). The water vapor-dependent component of the clear-sky radiative cooling is then found to scale with global temperature change through the Clausius–Clapeyron relationship. This component results in a tendency of global precipitation increase with increasing temperature at a rate of approximately 2%K -1 . Another component of the clear-sky radiative cooling, which is well correlated with changes to AOD, is also found to vary in magnitude among different scenarios with alternate configurations of cloud microphysics that controls the precipitation efficiency, a major factor influencing the aerosol scavenging process that can lead to different aerosol loadings. These results propose how different characteristics of cloud microphysics can cause different aerosol loadings that in turn perturb global energy balance to significantly change global precipitation. This implies a possible coupling of aerosol–cloud interaction with aerosol–radiation interaction in the context of global energy balance.

54 ENVIRONMENTAL SCIENCES↗

Influence of Metal-Alkyls on Early-Stage Ethylene Polymerization over a Cr/SiO 2 Phillips Catalyst: A Bulk Characterization and X-ray Chemical Imaging Study

The Cr/SiO 2 Phillips catalyst has taken a central role in ethylene polymerization since its invention in 1953. The uniqueness of this catalyst is related to its ability to produce broad molecular weight distribution (MWD) PE materials as well as that no co-catalysts are required to attain activity. Nonetheless, co-catalysts in the form of metal-alkyls can be added for scavenging poisons, enhancing catalyst activity, reducing the induction period, and tailoring polymer characteristics. The activation mechanism and related polymerization mechanism remain elusive, despite extensive industrial and academic research. Here, we show that by varying the type and amount of metal-alkyl co-catalyst, we can tailor polymer properties around a single Cr/SiO 2 Phillips catalyst formulation. Furthermore, we show that these different polymer properties exist in the early stages of polymerization. We have used conventional polymer characterization techniques, such as size exclusion chromatography (SEC) and 13 C NMR, for studying the metal-alkyl co-catalyst effect on short-chain branching (SCB), long-chain branching (LCB) and molecular weight distribution (MWD) at the bulk scale. In addition, scanning transmission X-ray microscopy (STXM) was used as a synchrotron technique to study the PE formation in the early stages: allowing us to investigate the produced type of early-stage PE within one particle cross-section with high energy resolution and nanometer scale spatial resolution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural and Biochemical Studies of Actin in Complex with Synthetic Macrolide Tail Analogues

The actin filament-binding and filament-severing activities of the aplyronine, kabiramide, and reidispongiolide families of marine macrolides are located within the hydrophobic tail region of the molecule. Two synthetic tail analogues of aplyronine C (SF-01 and GC-04) are shown to bind to G-actin with dissociation constants of (285±33) and (132±13) nM, respectively. The crystal structures of actin complexes with GC-04, SF-01, and kabiramide C reveal a conserved mode of tail binding within the cleft that forms between subdomains (SD) 1 and 3. Our studies support the view that filament severing is brought about by specific binding of the tail region to the SD1/SD3 cleft on the upper protomer, which displaces loop-D from the lower protomer on the same half-filament. With previous studies showing that the GC-04 analogue can sever actin filaments, it is argued that the shorter complex lifetime of tail analogues with F-actin would make them more effective at severing filaments compared with plasma gelsolin. In conclusion, structure-based analyses are used to suggest more reactive or targetable forms of GC-04 and SF-01, which may serve to boost the capacity of the serum actin scavenging system, to generate antibody conjugates against tumor cell antigens, and to decrease sputum viscosity in children with cystic fibrosis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interfacial Electron Transfer Dynamics Following Laser Flash Photolysis of [Ru(bpy)2((4,4'-PO3H2)2bpy)]2+ in TiO2 Nanoparticle Films in Aqueous Environments

Nanosecond laser flash photolysis has been used to investigate injection and back electron transfer from the complex [(Ru(bpy)2(4,4'-(PO3H2)2bpy)]2+ surface-bound to TiO2 (TiO2-RuII). The measurements were conducted under conditions appropriate for water oxidation catalysis by known single-site water oxidation catalysts. Systematic variations in average lifetimes for back electron transfer, <τbet>, were observed with changes in pH, surface coverage, incident excitation intensity, and applied bias. The results were qualitatively consistent with a model involving rate-limiting thermal activation of injected electrons from trap sites to the conduction band or shallow trap sites followed by site-to-site hopping and interfacial electron transfer, TiO2(e-)-Ru3+→TiO2-Ru2+. The appearance of pH-dependent decreases in the efficiency of formation of TiO2-Ru3+ and in incident-photon-to-current efficiencies with the added reductive scavenger hydroquinone point to pH-dependent back electron transfer processes on both the sub-nanosecond and millisecond–microsecond time scales, which could be significant in limiting long-term storage of multiple redox equivalents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Protective effects of mung bean ( Vigna radiata L.) and pea ( Pisum sativum L.) against high‐fat‐induced oxidative stress

Abstract Hyperlipidemia is closely related to oxidative stress, and it has been proved that the intake of legumes can protect the body from chronic diseases related to oxidative stress. In this study, we investigated the protective effects of mung beans and peas against high‐fat‐diet‐induced rats. It was found that, with 50% addition of mung beans or peas, the intake of mung beans and peas could significantly restore the levels of serum total cholesterol, low‐density lipoprotein cholesterol, and high‐density lipoprotein cholesterol. Liver staining also showed that high‐fat diet (HFD) led to liver lesions, whereas whole‐grain intake could significantly relieve these symptoms. Compared with the HFD group, the antioxidant defense system and antioxidant gene expression in administered legume groups improved markedly. Furthermore, the antioxidant activities of the two legume extracts were determined. Characterization showed that the ethanol extracts of mung beans and peas possessed high antioxidant activities, for their ability to scavenge ABTS and DPPH, reduce Fe 3+ and their antilipid peroxidation capacity. Treatments with ethanol extracts at different doses could restore the levels of intracellular lipid, malondialdehyde, and antioxidant enzyme activities in oleic acid‐induced HepG2 cells. All these results suggested that mung beans and peas or their extracts may be utilized as good candidates of natural antioxidant agents.

Liu, Dandan↗

A bulk adjusted linear combination of atomic orbitals (BA-LCAO) approach for nanoparticles

We describe a bulk adjusted linear combination of atomic orbitals (BA-LCAO) approach for nanoparticles. In this method, we apply a many-body scaling function (in similar manner as in the environment-modified total energy based tight-binding method) to the DFT-derived diatomic AO interaction potentials (like in the conventional orbital-based density-functional tight binding approach) strictly according to atomic valences acquired naturally in a bulk structure. This modification, (a) facilitates all atom orbital-based electronic structure calculations of charge carrier dynamics in nanoscale structures with a molecular acceptor, and (b) allows to closely match high-level density functional calculation data (previously adjusted to the available experimental findings) for bulk structures. To advance practical application of the BA-LCAO approach we parameterize the Hamiltonian of wurtzite CdSe by fitting its band structure to a high-level DFT reference, corrected for experimentally measured band edges. Here, unlike in conventional DFTB approach, we: (1) use hydrogen-like AOs for the basis as exact atomic eigenfunctions, while orbital energies of which are taken from experimentally measured ionization potentials, and (2) parameterize the many-body scaling functions rather than the atomic wavefunctions. Development of this approach and parameters is guided by our aim to devise a method capable of simultaneously treating the problems of (i) interfacial electron/hole transfer between finite, variable size nanoparticles and electron scavenging molecules, and (ii) high-energy electronic transitions (Auger transitions) that mediate multi-exciton decay in quantum dots. Electronic structure results are described for CdSe quantum dots of various sizes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Optical, physical, and chemical properties of springtime aerosol over Barrow Alaska in 2008

Airborne observations from four flights during the 2008 Indirect and Semi-Direct Aerosol Campaign (ISDAC) are used to examine some cloud-free optical, physical, and chemical properties of aerosol particles in the springtime Arctic troposphere. The number concentrations of particles larger than 0.12 μm (Na>120), important for light extinction and cloud droplet formation, ranged from 15 to 2260 cm -3 , with the higher Na>120 cases dominated by measurements from two flights of long-range transported biomass burning (BB) aerosols. The two other flights examined here document a relatively clean aerosol and an Arctic Haze aerosol impacted by larger particles largely composed of dust. For observations from the cleaner case and the BB cases, the particle light scattering coefficients at low relative humidity (RH<20%) increased nonlinearly with increasing Na>120, driven mostly by an increase in mean sizes of particles with increasing Na>120 (BB cases). For those three cases, particle light absorption coefficients also increased nonlinearly with increasing Na>120 and linearly with increasing submicron particle volume concentration. In addition to black carbon, brown carbon was estimated to have increased light absorption coefficients by 27% (450 nm wavelength) and 14% (550 nm) in the BB cases. For the case with strong dust influence, the absorption relative to submicron particle volume was small compared with the other cases. There was a slight gradient of Passive Cavity Aerosol Spectrometer Probe (PCASP) mean volume diameter (MVD) towards smaller sizes with increasing height, which suggests more scavenging of the more elevated particles, consistent with a typically longer lifetime of particles higher in the atmosphere. However, in approximately 10% of the cases, the MVD increased (>0.4 μm) with increasing altitude, suggesting transport of larger fine particle mass (possibly coarse particle mass) at high levels over the Arctic. This may be because of transport of larger particles at higher elevations and relatively slow deposition to the surface.

54 ENVIRONMENTAL SCIENCES↗

Fabrication and characterization of dextran/zein hybrid electrospun fibers with tailored properties for controlled release of curcumin

Abstract BACKGROUND In recent years, there has been considerable interest in the use of biopolymer electrospun nanofibers for various food applications due to the biocompatibility, biodegradability, and high loading capacity. Herein, we fabricated and characterized novel hybrid electrospun fibers from dextran (50%, w/v ) and zein (0–30%, w/v ) solutions, and the effects of various zein concentrations on the properties of the hybrid electrospun fibers were investigated. RESULTS When zein was added at low concentrations (5% and 10%), dextran and zein showed poor miscibility, as reflected by significantly decreased viscosity of the solutions, and the poor mechanical properties of the derived fiber membranes. When zein was added at medium concentrations (15–25%), hydrogen bonds were formed between dextran and zein molecules, as indicated by the red shift of Fourier‐transform infrared bands and β‐sheet to α‐helix structural transformations. The fiber membranes electrospun from a solution with 25% zein showed the most hydrophobic surface, with a water contact angle of 116.9°. The homogenous dispersion of dextran and zein resulted in improved mechanical properties for fibers electrospun from a solution with 30% zein. Curcumin encapsulating dextran/zein electrospun fibers exhibited effective radical scavenging activity and ferric reducing power, along with the desired controlled release behavior for curcumin delivery. CONCLUSION Food grade dextran/zein hybrid electrospun fibers demonstrated tunable properties, and appear to be promising as delivery systems for bioactive and edible antimicrobial food packaging. © 2021 Society of Chemical Industry.

Luo, Shiyuan↗

Modeling golden eagle‐vehicle collisions to design mitigation strategies

ABSTRACT The incidental take of golden eagles ( Aquila chrysaetos ) as a result of wind energy development requires some form of compensatory mitigation. Although several options have been proposed, only one has been formerly accepted and implemented, and the lack of options can limit the permit process for wind facilities. We developed a model to estimate numbers of golden eagles that die when struck by vehicles when eagles scavenge road kill to evaluate removal of road‐killed carcasses as an additional mitigation option. Our model estimates vehicle collision rates as a function of eagle densities, road traffic volume, and animal carcass abundance at the scale of a Wyoming, USA, county during fall‐winter, and quantifies the effects of different mitigation strategies, including estimates of uncertainty. We evaluated the plausibility of our model estimates by predicting mortality rates for each county in Wyoming and comparing overall state mortality to current estimates of mortality using derived estimates from expert judgment. We also developed a context‐dependent analysis of potential mitigation credits controlling for carcass number, traffic volume, and background carcass removals. We found that mitigation credit should be highest in areas with greatest number of carcasses. Collision mitigation is a potentially useful addition to the mitigation toolbox for wind energy development or other activities that need to offset predicted golden eagle mortality and satisfy incidental take permit requirements. © 2018 The Authors. Journal of Wildlife Management Published by Wiley Periodicals, Inc.

Lonsdorf, Eric↗

Kinetic Monte Carlo simulations of excitation density dependent scintillation in CsI and CsI(Tl)

Nonlinear quenching of electron-hole pairs in the denser regions of ionization tracks created by γ-ray and high-energy electrons is a likely cause of the light yield nonproportionality of many inorganic scintillators. Therefore, kinetic Monte Carlo (KMC) simulations were carried out to investigate the scintillation properties of pure and thallium-doped CsI as a function of electron-hole pair density. The availability of recent experimental data on the excitation density dependence of the light yield of CsI following ultraviolet excitation allowed for an improved parameterization of the interactions between self-trapped excitons (STE) in the KMC model via dipole-dipole Förster transfer. The KMC simulations reveal that nonlinear quenching occurs very rapidly (within a few picoseconds) in the early stages of the scintillation process. In addition, the simulations predict that the concentration of thallium activators can affect the extent of nonlinear quenching as it has a direct influence on the STE density through STE dissociation and electron scavenging. This improved model will enable more realistic simulations of the nonproportional γ-ray and electron response of inorganic scintillators.

Wang, Zhiguo↗

Detection and Mitigation of Radionuclides in the Environment: Toward a Clean Ecosystem

This research describes a straightforward approach to producing surface-engineered nanomaterials for the detection and mitigation of radionuclides generated in nuclear facilities. Here, a micelle forming surfactant ligand, namely cetyltrimethylammonium bromide (CTAB), was engineered on the surface of iron oxide nanoparticles and explored for the removal of radioactive materials, such as pertechnetate (TcO 4 – ), from aqueous environments. A series of analytical tools were employed to characterize the nanocomposite materials, such as SEM, EDS, UV-Vis spectroscopy, DLS, and PALS, and evaluated for their ability to capture a model analyte, perrhenate (ReO 4 – ) ions. The iron oxide magnetic nanoparticles retain their magnetic properties after surface functionalization and can be easily manipulated and collected with a magnet. Therefore, these nanocomposite materials can be used to remotely remediate environments by scavenging and collecting radionuclide species at the desired location.

63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTAN↗

Surface glycan-binding proteins are essential for cereal beta-glucan utilization by the human gut symbiont Bacteroides ovatus

The human gut microbiota, which underpins nutrition and systemic health, is compositionally sensitive to the availability of complex carbohydrates in the diet. The Bacteroidetes comprise a dominant phylum in the human gut microbiota whose members thrive on dietary and endogenous glycans by employing a diversity of highly specific, multi-gene polysaccharide utilization loci (PUL), which encode a variety of carbohydrases, transporters, and sensor/regulators. PULs invariably also encode surface glycan-binding proteins (SGBPs) that play a central role in saccharide capture at the outer membrane. Here, we present combined biophysical, structural, and in vivo characterization of the two SGBPs encoded by the Bacteroides ovatus mixed-linkage β-glucan utilization locus (MLGUL), thereby elucidating their key roles in the metabolism of this ubiquitous dietary cereal polysaccharide. In particular, molecular insight gained through several crystallographic complexes of SGBP-A and SGBP-B with oligosaccharides reveals that unique shape complementarity of binding platforms underpins specificity for the kinked MLG backbone vis-à-vis linear β-glucans. Reverse-genetic analysis revealed that both the presence and binding ability of the SusD homolog BoSGBP MLG -A are essential for growth on MLG, whereas the divergent, multi-domain BoSGBP MLG -B is dispensable but may assist in oligosaccharide scavenging from the environment. Overall, the synthesis of these data illuminates the critical role SGBPs play in concert with other MLGUL components, reveals new structure–function relationships among SGBPs, and provides fundamental knowledge to inform future (meta)genomic, biochemical, and microbiological analyses of the human gut microbiota.

59 BASIC BIOLOGICAL SCIENCES↗

Transition Metal (II) Complexes with a Novel Azo-azomethine Schiff Base Ligand: Synthesis, Structural and Spectroscopic Characterization, Thermal Properties and Biological Applications

The pyrimidine based azo-linked Schiff base ligand, 5-benzoyl-1-((E)-(2-hydroxy-3-methoxy-5-((E)phenyldiazenyl)benzylidene)amino)-4-phenylpyrimidin-2(1H)-one (HL), and its transition metal (II) complexes were synthesized and defined by using {sup 1}H-NMR, {sup 13}C-NMR, Elemental analysis, FT-IR, MS, UV–vis, molar conductance, magnetic susceptibility and thermal analysis techniques. According to the conductance data obtained indicate all of the metal complexes have non-electrolytic nature. Square pyramidal geometry for Pd(II) and octahedral geometry for all the other complexes synthesized was concluded from the electronic absorption spectra and magnetic susceptibility measurements of the complexes. Investigation of the significant infrared bands of the active groups in the ligand and the solid complexes alludes that HL is coordinated to the metal ions ONO tridentate manner. Moreover, the absorption and emission properties of the azo-azomethine based ligand and its complexes were investigated. The results obtained show that fluorescence emissions of the ligand and its metal (II) complexes depend on the type of transition metal ions and the derivatives displayed moderate Stokes’ shift values between 44 and 107 nm. All the compounds exhibited superb photostability. Further, antioxidant, antimicrobial and pBR322 plasmid DNA cleavage activities were investigated. All compounds showed good DPPH• (1,1-diphenyl-2-picrylhydrazyl) radical scavenging activity and complexes of [MnL{sub 2}]•H{sub 2}O and [NiL{sub 2}]•H{sub 2}O exhibited excellent metal chelating activity. All the compounds tested demonstrated two strand DNA cleavage activities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bioactivity Potentials of Biodegradable Chitosan/Gelatin Film Forming Solutions Combined with Monoterpenoid Compounds

Novel food packaging systems including biodegradable/edible films have been introduced to the market for consumers who desire natural products for their nutrition. Biochemically active plant compounds are added to the biopolymer-based films to improve their functionality. Within the present study, chitosan (1%) and gelatin (4%) biopolymer-based film forming solutions (FFSs) combined with 1, 2, 5 and 10% (v/v) eugenol, pulegone and carvacrol, monoterpenoid compounds, were evaluated for their antimicrobial and antioxidative potential. Antioxidant activities and total phenolic contents (TPC) of the FFSs were determined by 1,1-diphenyl-2-picrylhydrazyl (DPPH) free radical scavenging activity and Folin–Ciocalteau assays, respectively. Screening the antimicrobial activity of FFSs were performed against food spoilage microorganisms including Bacillus cereus, Escherichia coli, Salmonella typhimurium, Staphylococcus aureus and Listeria monocytogenes and a fungi, Candida albicans by using agar well diffusion method. The chitosan FFS containing 10% carvacrol had greater TPC (3857.3 ± 0.07 mg gallic acid equivalent/L). The highest antioxidative capacity was observed for the chitosan FFS containing 10% eugenol as 97.92 ± 0.01%. FFSs with monoterpenoids showed promising antimicrobial activities against tested microorganisms. Based on antioxidative and antimicrobial potentials of the FFSs, it can be envisaged to use monoterpenoid incorporation to biopolymer films for food packaging applications.

60 APPLIED LIFE SCIENCES↗

Physicochemical, Microstructural and Thermal Characterization of Chitosan from Blue Crab Shell Waste and Its Bioactivity Characteristics

The aim of the present study was to characterize the chitosan synthesized from blue crab (Callinectes sapidus, Rathbun, 1986) shell waste and to investigate its physicochemical and microstructural analyses as well as its antioxidant and antibacterial potentials. Microstructural and elemental characterization of the synthesized and commercial chitosan powders were performed using fourier transform infra-red spectroscopy, scanning electron microscopy and energy dispersive X-ray spectroscopy. Thermal analysis were done using thermogravimetric analysis. Antioxidant and antimicrobial analysis were done using by DPPH (1,1-diphenyl-2-picrylhydrazyl) free radical scavenging assay and agar well diffusion assay, respectively. The yield of the synthesized chitosan was calculated as 7.47% with moisture and ash contents of 0.151 ± 0.0025% and 0.19 ± 0.01%, respectively. Synthesized chitosan demonstrated the values of degree of deacetylation (71%), water (620.029 ± 52.59%) and fat (437.93 ± 15.92%) binding capacities, solubility (94.15 ± 2.84%), viscosity (463.25 ± 13.10 cPs) and whiteness (90.23 ± 0.27%). Antioxidant activity of synthesized chitosan was found to be moderate (55.30 ± 5.05%) when compared to ascorbic acid standard (87.61 ± 1.34). Chitosan obtained from blue crab shell also showed moderate antibacterial activity against Staphylococcus aureus and Escherichia coli. The findings of the study indicated that blue crab shell waste might be a potentially effective biopolymer source for commercial applications especially in food industry.

36 MATERIALS SCIENCE↗