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At least 1,405 records · Page 78

TEM Analysis of Diffusion-Bonded Silicon Carbide Ceramics Joined Using Metallic Interlayers

SiC fiber-bonded ceramics (SA-Tyrannohex: SA-THX) diffusion-bonded with TiCu metallic interlayers were investigated. Thin samples of the ceramics were prepared with a focused ion beam (FIB) and the interfacial microstructure of the prepared samples was studied by transmission electron microscopy (TEM) and scanning TEM (STEM). In addition to conventional microstructure observation, for detailed analysis of reaction compounds in diffusion-bonded area, we performed STEM-EDS measurements and selected area electron diffraction (SAD) experiments. The TEM and STEM experiments revealed the diffusion-bonded area was composed of only one reaction layer, which was characterized by TiC precipitates in Cu-Si compound matrix. This reaction layer was in good contact with the SA-THX substrates, and it is concluded that the joint structure led to the excellent bonding strength.

Ceramics↗

Synthesis of aviation biofuel precursors from biomass-derived ketones: Substrate adsorption configuration-catalytic activity

The production of aviation biofuel precursors from biomass-derived ketones by heterogeneous catalysis has been hindered by the low catalytic activity. Herein, a series of Cu-doped metal oxide catalysts were prepared for the conversion of biomass-derived ketones to aviation biofuel precursors. Solvent-free cyclopentanone conversion via aldol condensation reached 91.1 % over Cu/Al 2 O 3 with 100 % selectivity toward dimer and trimer oxygenated species, all of which are aviation biofuel precursors. This catalyst primarily contains Cu 2 O and Cu nanoparticles which are uniformly dispersed across the Al 2 O 3 surface. From in situ DRIFTS and DFT results, the incorporation of Cu species onto Al 2 O 3 not only increased the diversity of Lewis acidic sites, but also changed the adsorption of C = O groups, which lead to the increased aldol condensation activity of Cu/Al 2 O 3 . In conclusion, this study provides insight on the design of heterogeneous catalysts suitable for the solvent-free synthesis of aviation biofuel precursors from biomass-derived ketones.

Adsorption configuration↗

Selection of the silicon sensor thickness for the Phase-2 upgrade of the CMS Outer Tracker

During the operation of the CMS experiment at the High-Luminosity LHC the silicon sensors of the Phase-2 Outer Tracker will be exposed to radiation levels that could potentially deteriorate their performance. Previous studies had determined that planar float zone silicon with n-doped strips on a p-doped substrate was preferred over p-doped strips on an n-doped substrate. The last step in evaluating the optimal design for the mass production of about 200 m$^{2}$ of silicon sensors was to compare sensors of baseline thickness (about 300 μm) to thinned sensors (about 240 μm), which promised several benefits at high radiation levels because of the higher electric fields at the same bias voltage. This study provides a direct comparison of these two thicknesses in terms of sensor characteristics as well as charge collection and hit efficiency for fluences up to 1.5 × 10$^{15}$ n$_{eq}$/cm$^{2}$. The measurement results demonstrate that sensors with about 300 μm thickness will ensure excellent tracking performance even at the highest considered fluence levels expected for the Phase-2 Outer Tracker.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Alcohol Selectivity in a Synthetic Thermophilic n-Butanol Pathway Is Driven by Biocatalytic and Thermostability Characteristics of Constituent Enzymes

n-Butanol is generated as a natural product of metabolism by several microorganisms, but almost all grow at mesophilic temperatures. In this paper, a synthetic pathway for n-butanol production from acetyl coenzyme A (acetyl-CoA) that functioned at 70°C was assembled in vitro from enzymes recruited from thermophilic bacteria to inform efforts for engineering butanol production into thermophilic hosts. Recombinant versions of eight thermophilic enzymes (β-ketothiolase [Thl], 3-hydroxybutyryl-CoA dehydrogenase [Hbd], and 3-hydroxybutyryl-CoA dehydratase [Crt] from Caldanaerobacter subterraneus subsp. tengcongensis; trans-2-enoyl-CoA reductase [Ter] from Spirochaeta thermophila; bifunctional acetaldehyde dehydrogenase/alcohol dehydrogenase [AdhE] from Clostridium thermocellum; and AdhE, aldehyde dehydrogenase [Bad], and butanol dehydrogenase [Bdh] from Thermoanaerobacter sp. strain X514) were utilized to examine three possible pathways for n-butanol. These pathways differed in the two steps required to convert butyryl-CoA to n-butanol: Thl-Hbd-Crt-Ter-AdhE (C. thermocellum), Thl-Hbd-Crt-Ter-AdhE (Thermoanaerobacter X514), and Thl-Hbd-Crt-Ter-Bad-Bdh. n-Butanol was produced at 70°C, but with different amounts of ethanol as a coproduct, because of the broad substrate specificities of AdhE, Bad, and Bdh. A reaction kinetics model, validated via comparison to in vitro experiments, was used to determine relative enzyme ratios needed to maximize n-butanol production. By using large relative amounts of Thl and Hbd and small amounts of Bad and Bdh, >70% conversion to n-butanol was observed in vitro, but with a 60% decrease in the predicted pathway flux. With more-selective hypothetical versions of Bad and Bdh, >70% conversion to n-butanol is predicted, with a 19% increase in pathway flux. Finally and thus, more-selective thermophilic versions of Bad, Bdh, and AdhE are needed to fully exploit biocatalytic n-butanol production at elevated temperatures.

59 BASIC BIOLOGICAL SCIENCES↗

Ultra-thin skin carbon hollow fiber membranes for sustainable molecular separations

Here, a transformative platform is reported to derive ultra-thin carbon molecular sieve (CMS) hollow fiber membranes from dual-layer precursor hollow fibers with independently tuned skin layer and substrate properties. These ultra-thin CMS hollow fiber membranes show attractive CO 2 /CH 4 separation factors and excellent CO 2 permeances up to similar to 1,400% higher than state-of-the-art asymmetric CMS hollow fiber membranes. They offer a unique combination of permeance and selectivity competitive with zeolite membranes, yet with much higher membrane packing density and potentially much lower costs.

36 MATERIALS SCIENCE↗

Improving olefin tolerance and production in E. coli using native and evolved AcrB

ABSTRACT Microorganisms can be engineered for the production of chemicals utilized in the polymer industry. However many such target compounds inhibit microbial growth and might correspondingly limit production levels. Here, we focus on compounds that are precursors to bioplastics, specifically styrene and representative alpha‐olefins; 1‐hexene, 1‐octene, and 1‐nonene. We evaluated the role of the Escherichia coli efflux pump, AcrAB‐TolC, in enhancing tolerance towards these olefin compounds. AcrAB‐TolC is involved in the tolerance towards all four compounds in E. coli . Both styrene and 1‐hexene are highly toxic to E. coli . Styrene is a model plastics precursor with an established route for production in E. coli (McKenna and Nielsen, 2011). Though our data indicates that AcrAB‐TolC is important for its optimal production, we observed a strong negative selection against the production of styrene in E. coli . Thus we used 1‐hexene as a model compound to implement a directed evolution strategy to further improve the tolerance phenotype towards this alpha‐olefin. We focused on optimization of AcrB, the inner membrane domain known to be responsible for substrate binding, and found several mutations (A279T, Q584R, F617L, L822P, F927S, and F1033Y) that resulted in improved tolerance. Several of these mutations could also be combined in a synergistic manner. Our study shows efflux pumps to be an important mechanism in host engineering for olefins, and one that can be further improved using strategies such as directed evolution, to increase tolerance and potentially production. Biotechnol. Bioeng. 2015;112: 879–888. © 2015 Wiley Periodicals, Inc.

60 APPLIED LIFE SCIENCES↗

Synthesis of magnetically recyclable ZIF-8@SiO{sub 2}@Fe{sub 3}O{sub 4} catalysts and their catalytic performance for Knoevenagel reaction

Novel magnetic ZIF-8@SiO{sub 2}@Fe{sub 3}O{sub 4} catalysts were synthesized by encapsulating magnetic SiO{sub 2}@Fe{sub 3}O{sub 4} nanoparticles into ZIF-8 through in situ method. The structures of the catalysts were characterized by TEM, SEM, XRD, FT-IR, VSM, N{sub 2} adsorption/desorption and CO{sub 2}-TPD technology. The catalytic activity and recovery properties of the catalysts for the Knoevenagel reaction of p-chlorobenzaldehyde with malononitrile were evaluated. The results showed that the magnetic ZIF-8@SiO{sub 2}@Fe{sub 3}O{sub 4} catalysts had the larger surface areas, the suitable superparamagnetism, and good catalytic activity for Knoevenagel reaction. The conversion of p-chlorobenzaldehyde can reach ~98% and the selectivity of the production can reach ~99% over35.8%ZIF-8@SiO{sub 2}@Fe{sub 3}O{sub 4} (MZC-5) catalyst under the reaction condition of 25 °C and 4 h. The magnetic ZIF-8@SiO{sub 2}@Fe{sub 3}O{sub 4} catalysts also had good substrates adaptation. After reaction, the catalyst can be easily separated from the reaction mixture by an external magnet. The recovery catalyst can be reused five times and the conversion of p-chlorobenzaldehyde can be kept over 90%. - Graphical abstract: Novel magnetically recyclable ZIF-8@SiO{sub 2}@Fe{sub 3}O{sub 4} catalysts were synthesized by encapsulating magnetic SiO{sub 2}@Fe{sub 3}O{sub 4} nanoparticles into ZIF-8 and the as-synthesized catalysts exhibited a good catalytic activity for the Knoevenagel reaction. - Highlights: • A series of novel magnetic ZIF-8@SiO{sub 2}@Fe{sub 3}O{sub 4} catalysts were synthesized. • The catalysts had the larger surface areas and the suitable superparamagnetism. • The catalysts exhibited good catalytic activity for the Knoevenagel reaction. • After reaction the catalyst can be easily separated by an external magnet. • The recovery catalyst can be reused five times and can keep its catalytic activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Lignin Depolymerization with Nitrate-Intercalated Hydrotalcite Catalysts

Hydrotalcites (HTCs) exhibit multiple adjustable parameters to tune catalytic activity, including interlayer anion composition, metal hydroxide layer composition, and catalyst preparation methods. Here in this paper, we report the influence of several of these parameters on β-O-4 bond scission in a lignin model dimer, 2-phenoxy-1-phenethanol (PE), to yield phenol and acetophenone. We find that the presence of both basic and NO 3 – anions in the interlayer increases the catalyst activity by 2–3-fold. In contrast, other anions or transition metals do not enhance catalytic activity in comparison to blank HTC. The catalyst is not active for C–C bond cleavage on lignin model dimers and has no effect on dimers without an α-OH group. Most importantly, the catalyst is highly active in the depolymerization of two process-relevant lignin substrates, producing a significant amount of low-molecular-weight aromatic species. The catalyst can be recycled until the NO 3 – anions are depleted, after which the activity can be restored by replenishing the NO 3 – reservoir and regenerating the hydrated HTC structure. These results demonstrate a route to selective lignin depolymerization in a heterogeneous system with an inexpensive, earth-abundant, commercially relevant, and easily regenerated catalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A high-performance spectrally-selective solar absorber based on a yttria-stabilized zirconia cermet with high-temperature stability

Spectrally-selective solar absorbers are widely used in solar hot water and concentrating solar power (CSP) systems. However, their performance at high temperatures (>450 °C) is still not satisfactory due to high infrared (IR) emittance and lack of long-term thermal stability. In this work, we explore yttria-stabilized zirconia (YSZ) cermet-based spectrally-selective surfaces for high-temperature solar absorber applications. The developed multilayer selective surface comprises two sunlight-absorbing W–Ni–YSZ cermet layers with different W–Ni volume fractions inside the YSZ matrix, two anti-reflection coatings (ARCs), and one tungsten IR reflection layer for reduced IR emittance and improved thermal stability, deposited on a polished stainless steel (SS) substrate. The fabricated solar absorbers are tested for their long-term thermal stability at 600 °C. We find a distinct change in the surface morphology of the solar absorbers when oxygen is highly deficient in the YSZ-ARC layers. The oxygen deficiency can be effectively overcome through increasing the oxygen partial pressure during sputtering, which leads to a stable solar absorber with a solar absorptance of ~0.91 and a total hemispherical emittance of ~0.13 at 500 °C. Those values are obtained at the actual operating temperature using an absolute and direct method that measures the total hemispherical emittance with high accuracy. In contrast, most reports on solar absorber development in the literature to date use only near room-temperature spectroscopy techniques that have been shown to significantly underestimate the total hemispherical emittance. This makes our experimentally demonstrated total hemispherical emittance value the lowest ever reported for a high-temperature stable solar absorber with solar absorptance above 0.9.

14 SOLAR ENERGY↗

Influence of excess silicon on polytype selection during metal-mediated epitaxy of GaN nanowires

For this work, we have examined the origins of polytype selection during metal-mediated molecular-beam epitaxy of GaN nanowires (NWs). High-angle annular dark-field scanning transmission electron microscopy reveals [111]-oriented zinc blende (ZB) NWs and [0001]-oriented wurtzite (WZ) NWs, with SixNy at the interface between individual NWs and the Si (001) substrate. Quantitative energy dispersive x-ray spectroscopy reveals a notably higher Si concentration of 7.0% ± 2.3% in zinc blende (ZB) NWs than 2.3% ± 1.2% in wurtzite (WZ) NWs. Meanwhile, density functional theory calculations show that incorporation of 8 at. % Si on the Ga sublattice inverts the difference in formation energies between WZ and ZB GaN, such that the ZB polytype of GaN is stabilized. This identification of Si and other ZB polytype stabilizers will enable the development of polytype heterostructures in a wide variety of WZ-preferring compounds.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Integrating Metal-Hydride and Gas-Detector for Tritium Gas Detection

Detection of trace amounts of environmental tritium is a challenging problem, driving the need for field-deployable systems that offer high sensitivity, selectivity, and minimal false positives. We present a technique for high-sensitivity, high-selectivity tritium measurement, which integrates metal-hydride and gas-detector concepts into a compact field-deployable tritium sensor. A hydrogen-storage metal embedded in a gas proportional counter selectively absorbs protium (1H)/tritium (3H), which are subsequently released into the counter volume with a reduced radiation background. Ionizations induced by 3H beta particles are then measured in proportional counting mode, achieving high detection efficiency. Preliminary studies conducted with palladium (Pd) thin films coated on stainless-steel substrates demonstrated 3H absorption and metal-tritide formation, followed by 3H desorption upon heating the metal-tritide. These processes were confirmed using activity concentrations measured by a commercial tritium monitor and pulse height spectra acquired from a custom-built detector.

Gas-proportional counter↗

Enhanced Mixed Feedstock Processing Using Ionic Liquids

Biomass pretreatment using certain ionic liquids (ILs) is very efficient, generally producing a substrate that is amenable to saccharification with fermentable sugar yields approaching theoretical limits. Although promising, several challenges must be addressed before IL pretreatment technology becomes commercially viable. Once of the most significant challenges is the affordable and scalable recovery and recycle or the IL itself. Pervaporation is a highly selective and scalable membrane separation process for quantitatively recovering volatile solutes or solvents directly from non-volatile solvents that could prove more versatile for IL dehydration than traditional solvent extraction processes, as well as efficient and energetically more advantageous than standard evaporative techniques. In this study we evaluated a commercially available pervaporation system for IL dehydration and recycling as part of an integrated IL pretreatment process using 1-ethyl-3-methylimidazolium acetate ([C2C1Im][OAc]) that has been proven to be very effective as a biomass pretreatment solvent. We demonstrate that >99.9 wt% [C2C1Im][OAc] can be recovered from aqueous solution and recycled at least five times. A preliminary techno-economic analysis validated the promising role of pervaporation in improving overall biorefinery process economics, especially in the case where other IL recovery technologies might lead to significant losses. These findings establish the foundation for further development of pervaporation as an effective method of recovering and recycling ILs using a commercially viable process technology.

09 BIOMASS FUELS↗

Gene regulatory networks controlling carbohydrate selective deconstruction pathways in fungi

The work performed at Clark University (PI, David Hibbett) was a subcomponent of the research lead by Jonathan Schilling at University of Minnesota (award number DE-SC0019427). The overall goal of this project was to address how fungi metabolize lignocellulose. Specifically, we targeted a carbohydrate-selective group of fungi known as 'brown rot' fungi that are well-aligned to be harness for bioconversion to biofuels and other products. These organisms orchestrate a two-step mechanism that initiates decomposition using oxidative radical-based chemistry and follows with enzymatic attack. We have helped characterize that this mechanism occurs in this sequence, but currently lack the fundamental regulatory information needed to harness these fungi for application. Thus, the major goal of this project was to use systems biology to create an integrated model of brown rot wood decay that couples fungal gene regulation with the metabolite feedbacks used to coordinate a two-step oxidative-hydrolytic mechanism. The research at Clark University focused on phylogenomic analyses of data produced by other project partners. Hence, the Clark component of the research was staged to initiate somewhat after that in other partner laboratories. The major Clark-based accomplishment was to advise on selection of fungal species for analyses of brown rot decay chemistry, and to interpret results in a phylogenetic context. The Clark University group also performed complementary analyses of gene families encoding plant cell wall-degrading enzymes in the the basidiomycete genus Lentinula, as well as analyses of substrate-specific gene expression and RNA editing in brown rot fungi.

59 BASIC BIOLOGICAL SCIENCES↗

Cellular localization of Na(+), K(+)-ATPase in the mammalian vestibular system

Two different, but complementary, procedures for cellular localization of Na+, K+-ATPase in the guinea pig vestibular system were employed. One of these techniques, devised by Stirling, depends upon the well documented ability of the specific inhibitor ouabain to bind selectively to Na+,K+-ATPase, blocking catalytic activity. Microdisected vestibular tissues are incubated with tritium-labelled (3H-) ouabain, and regions with a high concentration of Na+,K+-ATPase are subsequently identified by light microscope autoradiography. A second method, originated by Ernst, detects inorganic phosphate released from an artificial substrate (nitrophenyl phosphate) by catalytic activity of the enzyme. In the presence of strontium ion, phosphate is precipitated near regions of high activity, then converted to a product which may finally be visualized in the electron microscope. This cytochemical enzymatic reaction is inhibited by ouabain.

Kerr, T. P.↗

Optical detector having a plurality of matrix layers with cobalt disilicide particles embedded therein

Silicon and metal are coevaporated onto a silicon substrate in a molecular beam epitaxy system with a larger than stoichiometric amount of silicon so as to epitaxially grow particles of metal silicide embedded in a matrix of single crystal epitaxially grown silicon. The particles interact with incident photons by resonant optical absorption at the surface plasmon resonance frequency. Controlling the substrate temperature and deposition rate and time allows the aspect ratio of the particles to be tailored to desired wavelength photons and polarizations. The plasmon energy may decay as excited charge carriers of phonons, either of which can be monitored to indicate the amount of incident radiation at the selected frequency and polarization.

Fathauer, Robert W.↗

Interstellar Communication Channel Based on a Biological Universal

Cellular biosynthesis starts with sugar substrates and continues energetically downhill to yield amino acid, rapid, and nucleotide products. To understand the energetics of these processes, we calculated the energy for biosynthesis from sugars of E. cali's amino acids, nucleotides, and lipids. We found that the biosynthesis of amino acids and lipids from sugar substrates proceeds by redox disproportionation. of sugar carbon with a favorable energy of about -11 kcal/mole of carbon. Overall, redox disproportion of sugar carbon accounted for 84% and 96% (ATP only 6% and 1%) of the total biosynthetic energy of amino acids and lipids (the major cellular constituents). Next, we calculated for all 48 possible 3-carbon substrates the energy of maximal disproportionation to carbon dioxide and methane. We found no other carbon substrates than matched sugars in biosynthetic energy, efficiency, and simplicity. From this, we concluded that sugars are the optimal biosynthetic substrate. Since this conclusion is based on universal properties of carbon chemistry, other carbon-based life throughout the Universe would also use optimal sugar substrates. Furthermore, this rather obvious universal role of sugars as the optimal biosubstrate would probably be common knowledge of technological civilizations throughout the Universe. Since the elemental building block of all sugars is formaldehyde, the common knowledge that sugars are the universal optimal biosubstrate could reasonably lead to the selection of a line(s) in the microwave spectrum of formaldehyde as a frequency for interstellar communication.

Weber, Arthur L.↗

Conductivity based on selective etch for GaN devices and applications thereof

This invention relates to methods of generating NP gallium nitride (GaN) across large areas (>1 cm2) with controlled pore diameters, pore density, and porosity. Also disclosed are methods of generating novel optoelectronic devices based on porous GaN. Additionally a layer transfer scheme to separate and create free-standing crystalline GaN thin layers is disclosed that enables a new device manufacturing paradigm involving substrate recycling. Other disclosed embodiments of this invention relate to fabrication of GaN based nanocrystals and the use of NP GaN electrodes for electrolysis, water splitting, or photosynthetic process applications.

Zhang, Yu↗

Ionic Liquids as Additives to Polystyrene- Block -Poly(Methyl Methacrylate) Enabling Directed Self-Assembly of Patterns with Sub-10 nm Features

Polystyrene- block -poly(methyl methacrylate) (PS- b -PMMA) is one of the prototypical block copolymers in directed self-assembly (DSA) research and development, with standardized protocols in place for processing on industrially relevant 300 mm wafers. Scaling of DSA patterns to pitches below 20 nm using PS- b -PMMA, however, is hindered by the relatively low Flory–Huggins interaction parameter, $χ$. In this work, we investigate the approach of adding small amounts of ionic liquids (ILs) into PS- b -PMMA, which selectively segregates into the PMMA domain and effectively increases the $χ$ parameter and thus the pattern resolution. The amount of IL additive is small enough to result in limited changes in PS- b -PMMA’s surface and interfacial properties, thus maintaining industry-friendly processing by thermal annealing with a free surface. Three different ILs are studied comparatively regarding their compositional process window, capability of increasing $χ$, and thermal stability. By adding ~3.1 vol % of the champion IL into a low-molecular-weight PS- b -PMMA ( M n = 10.3k- b -9.5k), we demonstrated DSA on chemically patterned substrates of lamellar structures with feature sizes <8.5 nm. Compatibility of the PS- b -PMMMA/IL blends with the standardized processes that have been previously developed suggests that such blend materials could provide a drop-in solution for sub-10 nm lithography with the processing advantages of PS- b -PMMA.

36 MATERIALS SCIENCE↗