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At least 1,351 records · Page 75

Comparative differential cuproproteomes of Rhodobacter capsulatus reveal novel copper homeostasis related proteins

Abstract Copper (Cu) is an essential, but toxic, micronutrient for living organisms and cells have developed sophisticated response mechanisms towards both the lack and the excess of Cu in their environments. In this study, we achieved a global view of Cu-responsive changes in the prokaryotic model organism Rhodobacter capsulatus using label-free quantitative differential proteomics. Semi-aerobically grown cells under heterotrophic conditions in minimal medium (∼0.3 μM Cu) were compared with cells supplemented with either 5 μM Cu or with 5 mM of the Cu-chelator bathocuproine sulfonate. Mass spectrometry based bottom-up proteomics of unfractionated cell lysates identified 2430 of the 3632 putative proteins encoded by the genome, producing a robust proteome dataset for R. capsulatus. Use of biological and technical replicates for each growth condition yielded high reproducibility and reliable quantification for 1926 of the identified proteins. Comparison of cells grown under Cu-excess or Cu-depleted conditions to those grown under minimal Cu-sufficient conditions revealed that 75 proteins exhibited statistically significant (p < 0.05) abundance changes, ranging from 2- to 300-fold. A subset of the highly Cu-responsive proteins was orthogonally probed using molecular genetics, validating that several of them were indeed involved in cellular Cu homeostasis.

59 BASIC BIOLOGICAL SCIENCES↗

Electrocatalytic nitrate reduction on rhodium sulfide compared to Pt and Rh in the presence of chloride

Chloride poisoning is a serious problem for the electrocatalytic reduction of aqueous nitrate (NO 3 – ) and improved electrocatalysts are needed. Here we study the electrocatalytic activity of rhodium sulfide supported on carbon (Rh x S y /C) for the reduction of nitrate and compare it against Pt/C and Rh/C in the presence of chloride. Between 0.05–0.15 V vs. RHE, Rh x S y /C has a steady-state nitrate reduction current density in 1 M H 2 SO 4 + 1 M NaNO 3 that is 1.6–5.6 times greater than Rh/C (the most active metal electrocatalyst) and 10–24 times greater than Pt/C. Current densities are decreased by 37% for Rh x S y /C, 62% for Rh/C, and 40% for Pt/C at 0.1 V vs. RHE in the presence of 1 mM chloride. The decrease in nitrate reduction activity for Pt, Rh, and Rh x S y is due to the competitive adsorption of chloride and nitrate on the surface. Density functional theory (DFT) modeling predicts that chloride poisoning will persistently inhibit nitrate reduction on metals due to linear adsorbate scaling relations between nitrate and chloride. DFT calculations and microkinetic modeling of our experimental measurements predict that nitrate converts to nitrite via an H-assisted dissociation mechanism on Pt and direct nitrate dissociation on Rh and Rh x S y . Pristine Rh x S y (i.e., Rh 3 S 4 , Rh 2 S 3 , and Rh 17 S 15 ) terraces are predicted to be inactive toward nitrate reduction. In contrast, sulfur vacancies in Rh 3 S 4 terraces are predicted to be active for nitrate reduction, but also bind chloride strongly. Furthermore, sulfur-defected Rh 3 S 4 rationalize the experimentally observed high activity but moderate chloride poison-resistance of Rh x S y /C for nitrate reduction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Polyolefin plastic waste hydroconversion to fuels, lubricants, and waxes: a comparative study

Hydroconversion technologies have surged to the forefront of deconstructing plastic waste. Recent studies have been performed over several catalysts with varying conditions and plastics that make comparisons difficult. We compile and compare data from the literature by introducing various metrics and perform a simple energy analysis. We draw mechanistic similarities to and differences from the past literature on small alkane hydroconversion and leverage the former to propose standard approaches to tune product selectivity. We exemplify the plastics materials gap and the challenges it creates. Lastly, we discuss the current limitations and suggest future work.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Expanding the Zinc Precursor Toolbox: A Comparative Study of Precursors for Thermal ALD of ZnO Thin Films

Atomic layer deposition (ALD) of zinc oxide (ZnO) has been widely researched using diethyl zinc (DEZ)-based methods. The significant importance of thin films of ZnO as transparent conductive oxides (TCO) in optoelectronic devices and photovoltaics warrants examining alternative Zn precursors for ZnO ALD as potential replacements for the pyrophoric DEZ. In this study, we investigated three alternative Zn precursors: Zn(EEKI)2, Zn(DMP)2, ZnEt(HMDS), in the process development for high-quality ZnO thin films and compared them to DEZ. The ALD processes were studied using in situ spectroscopic ellipsometry. The properties of the ALD ZnO films were characterized using ex situ X-ray photoelectron spectroscopy (XPS), Rutherford backscattering spectrometry and nuclear reaction analysis (RBS/NRA), X-ray diffraction (XRD), atomic force microscopy (AFM), transmission electron microscopy (TEM), and ultraviolet-visible (UV/Vis) spectrophotometry. These measurements confirmed the formation of pure, stoichiometric, and polycrystalline ZnO films using all four Zn precursors. Although the selected precursors are chemically diverse Zn compounds, they all yielded saturating ALD processes and high-quality ZnO thin films at 200 °C. This study highlights the potential benefits of alternative zinc precursors in designing ALD processes for ZnO thin films.

Obenlüneschloß, Jorit↗

Bypassing sulfides: comparing the morphology and performance of solution processed Cu(In,Ga)Se 2 films prepared via two selenide molecular precursor routes

Solution-processing of thin-film photovoltaics offers an alternative to vacuum-deposition based approaches. The amine–thiol reactive solvent system has become a focal point for the solution-processing of chalcogenide species, owing to the convenience of precursor preparation and comparatively high performance of prepared devices. Selenide species prepared via the amine–thiol route typically progress through a sulfide intermediate phase, and as such are commonly afflicted with sulfur and carbon impurities along- side the presence of a carbonaceous fine-grained layer. Here, two routes of preparing films directly to a selenide phase are examined; first by the co-dissolution of selenium in an amine–thiol solution and second via the novel use of reactive alkylammonium polyselenides. Lamella are cut from these selenide precursor films and final devices, and STEM-EDX and TEM are used to characterize film morphology and secondary phases. A champion device efficiency of 11.2% is reported for the novel polyselenide route, and clear paths of improvement are identified.

36 MATERIALS SCIENCE↗

Comparative c-type cytochrome expression analysis in Shewanella oneidensis strain MR-1 and Anaeromyxobacter dehalogenans strain 2CP-C grown with soluble and insoluble oxidised metal electron acceptors

The genomes of Shewanella oneidensis strain MR-1 and Anaeromyxobacter dehalogenans strain 2CP-C encode 40 and 69 putative c-type cytochrome genes, respectively. Deletion mutant and biochemical studies have assigned specific functions to a few c-type cytochromes involved in electron transfer to oxidised metals in Shewanella oneidensis strain MR-1. Although promising, the genetic approach is limited to gene deletions that produce a distinct phenotype, and organism for which a genetic system is available. To more comprehensively investigate and compare c-type cytochrome expression in Shewanella oneidensis strain MR-1 and Anaeromyxobacter dehalogenans strain 2CP-C, proteomic measurements were used to characterise lysates of cells grown with soluble Fe(III) (as ferric citrate) and insoluble Mn(IV) (as MnO2) as electron acceptors. Strain MR-1 expressed 19 and 20, and strain 2CP-C expressed 27 and 25 c-type cytochromes when grown with Fe(III) and Mn(IV), respectively. The majority of c-type cytochromes (77% for strain MR-1 and 63% for strain 2CP-C) were expressed under both growth conditions; however, the analysis also revealed unique c-type cytochromes that were specifically expressed in cells grown with soluble Fe(III) or insoluble Mn(IV). Proteomic characterisation proved to be a promising approach for determining the c-type cytochrome complement expressed under different growth conditions, and will help elucidating the specific functions of more c-type cytochromes that are the basis for Shewanella and Anaeromyxobacter respiratory versatility.

Anaeromyxobacter dehalogenans strain 2CP-C↗

The impact of environment on size: Galaxies are 50% smaller in the Fornax Cluster compared to the field

Size is a fundamental parameter for measuring the growth of galaxies and the role of the environment on their evolution. However, the conventional size definitions used for this purpose are often biased and miss the diffuse, outermost signatures of galaxy growth, including star formation and gas accretion. We address this issue by examining low surface brightness truncations or galaxy ‘edges’ as a physically motivated tracer of size based on star formation thresholds. Our total sample consists of ∼900 galaxies with stellar masses ranging from 10 5 M ⊙ < M ⋆ < 10 11 M ⊙ . This sample of nearby cluster, group satellite, and nearly isolated field galaxies was compiled using multi-band imaging from the Fornax Deep Survey, deep IAC Stripe 82, and Dark Energy Camera Legacy Surveys. We find that the edge radii scale as R edge ∝ M ⋆ 0.42 , with a very small intrinsic scatter (∼0.07 dex). The scatter is driven by the morphology and environment of galaxies. In both the cluster and field, early-type dwarfs are systematically smaller by approximately 20% compared to late-type dwarfs. However, galaxies in the Fornax cluster are the most impacted. At a fixed stellar mass, edges in the cluster can be found at about 50% smaller radii, and the average stellar surface density at the edges is a factor of two higher, ∼1 M ⊙ /pc 2 . Our findings support the rapid removal of loosely bound neutral hydrogen (H I ) in hot, crowded environments, which truncates galaxies outside-in earlier, preventing the formation of more extended sizes and lower density edges. Our results highlight the importance of deep imaging surveys to the study of low surface brightness imprints of the large-scale structure and environment on galaxy evolution.

Astronomy & Astrophysics↗

Ionization-induced dynamics of laser-matter interaction in a focused laser pulse: A comparative analysis

We study the laser-matter interaction via optical-field ionization of a medium in a focused ultrashort laser pulse by means of the finite-difference-time-domain modeling of Maxwell's equations. General aspects of the ionization-induced dynamics with TE- and TM-polarized laser pulses are analyzed. It is shown that there are two qualitatively different regimes of the interaction depending on the angle of the laser beam focusing. At comparatively low angles plasma distributions are smooth; however, due to departure from the quasioptical behavior of light rays in self-generated plasma, lateral large-scaled plasma structures can also be produced, leading to additional beam focusing and correspondingly to higher electron densities. At tight focusing, small-scaled plasma structures are generated that strongly influence field distribution, energy deposition, and scattering characteristics. The influence of electron collisions and the Kerr effect are also analyzed.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Comparative study on light-induced absorption between MgO:LiNbO{sub 3} and MgO:LiTaO{sub 3}

A comparative study on the light-induced absorption was performed for lithium niobate and lithium tantalate crystals in which the antisite defects were eliminated by MgO doping. The induced absorption was measured in a spectral window ranging from visible to near infrared with a time resolution of 10 ns. Upon pulsed-light irradiation, a broad absorption peaking near 1250 nm was induced in MgO-doped lithium niobate. It was attributed to the small free polaron, an electron trapped at the regular Nb ion site. In contrast, such absorption in the near infrared originating from the free polaron was absent in MgO-doped lithium tantalates. The findings are highly relevant to the frequency conversion performances of high-power and pulsed lasers based on the current periodically-poled devices. The results also suggest guidelines for improving the crystal qualities.

36 MATERIALS SCIENCE↗

A comparative study of the electrical properties of Pd/ZnO Schottky contacts fabricated using electron beam deposition and resistive/thermal evaporation techniques

A systematic investigation to check the quality of Pd Schottky contacts deposited on ZnO has been performed on electron beam (e-beam) deposited and resistively/thermally evaporated samples using current-voltage, IV, and conventional deep level transient spectroscopy (DLTS) measurements. Room temperature IV measurements reveal the dominance of pure thermionic emission on the resistively evaporated contacts, while the e-beam deposited contacts show the dominance of generation recombination at low voltages, <0.30 V, and the dominance of pure thermionic emission at high voltages, greater than 0.30 V. The resistively evaporated contacts have very low reverse currents of the order of 10{sup -10} A at a reverse voltage of 1.0 V whereas the e-beam deposited contacts have reverse currents of the order of 10{sup -6} A at 1.0 V. Average ideality factors have been determined as (1.43 {+-} 0.01) and (1.66 {+-} 0.02) for the resistively evaporated contacts and e-beam deposited contacts, respectively. The IV barrier heights have been calculated as (0.721 {+-} 0.002) eV and (0.624 {+-} 0.005) eV for the resistively evaporated and e-beam deposited contacts, respectively. Conventional DLTS measurements reveal the presence of three prominent defects in both the resistive and e-beam contacts. Two extra peaks with energy levels of 0.60 and 0.81 eV below the conduction band minimum have been observed in the e-beam deposited contacts. These have been explained as contributing to the generation recombination current that dominates at low voltages and high leakage currents. Based on the reverse current at 1.0 V, the degree of rectification, the dominant current transport mechanism and the observed defects, we conclude that the resistive evaporation technique yields better quality Schottky contacts for use in solar cells and ultraviolet detectors compared to the e-beam deposition technique. The 0.60 eV has been identified as possibly related to the unoccupied level for the doubly charged oxygen vacancy, V{sub o}{sup 2+}.

36 MATERIALS SCIENCE↗

A comparative study of ultraviolet photoconductivity relaxation in zinc oxide (ZnO) thin films deposited by different techniques

Photoresponse characteristics of ZnO thin films deposited by three different techniques namely rf diode sputtering, rf magnetron sputtering, and electrophoretic deposition has been investigated in the metal-semiconductor-metal (MSM) configuration. A significant variation in the crystallinity, surface morphology, and photoresponse characteristics of ZnO thin film with change in growth kinetics suggest that the presence of defect centers and their density govern the photodetector relaxation properties. A relatively low density of traps compared to the true quantum yield is found very crucial for the realization of practical ZnO thin film based ultraviolet (UV) photodetector.

36 MATERIALS SCIENCE↗

Comparative analysis of LWR and FBR spent fuels for nuclear forensics evaluation

Some interesting issues are attributed to nuclide compositions of spent fuels from thermal reactors as well as fast reactors such as a potential to reuse as recycled fuel, and a possible capability to be manage as a fuel for destructive devices. In addition, analysis on nuclear forensics which is related to spent fuel compositions becomes one of the interesting topics to evaluate the origin and the composition of spent fuels from the spent fuel foot-prints. Spent fuel compositions of different fuel types give some typical spent fuel foot prints and can be estimated the origin of source of those spent fuel compositions. Some technics or methods have been developing based on some science and technological capability including experimental and modeling or theoretical aspects of analyses. Some foot-print of nuclear forensics will identify the typical information of spent fuel compositions such as enrichment information, burnup or irradiation time, reactor types as well as the cooling time which is related to the age of spent fuels. This paper intends to evaluate the typical spent fuel compositions of light water (LWR) and fast breeder reactors (FBR) from the view point of some foot prints of nuclear forensics. An established depletion code of ORIGEN is adopted to analyze LWR spent fuel (SF) for several burnup constants and decay times. For analyzing some spent fuel compositions of FBR, some coupling codes such as SLAROM code, JOINT and CITATION codes including JFS-3-J-3.2R as nuclear data library have been adopted. Enriched U-235 fuel composition of oxide type is used for fresh fuel of LWR and a mixed oxide fuel (MOX) for FBR fresh fuel. Those MOX fuels of FBR come from the spent fuels of LWR. Some typical spent fuels from both LWR and FBR will be compared to distinguish some typical foot-prints of SF based on nuclear forensic analysis.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Fundamental difference of subpicosecond laser interaction compared to longer pulses for ultrahigh acceleration

Interaction of picosecond laser pulses above terawatt power with high density plasmas shows a nearly 100% conversion of the laser energy into directed acceleration of the electron cloud by nonlinear (ponderomotive) forces giving the ion cloud accelerations several orders of magnitude higher than comparable nanosecond interaction based on thermal pressure processes.

43 PARTICLE ACCELERATORS↗

Comparative band alignment of plasma-enhanced atomic layer deposited high-k dielectrics on gallium nitride

Al{sub 2}O{sub 3} films, HfO{sub 2} films, and HfO{sub 2}/Al{sub 2}O{sub 3} stacked structures were deposited on n-type, Ga-face, GaN wafers using plasma-enhanced atomic layer deposition (PEALD). The wafers were first treated with a wet-chemical clean to remove organics and an in-situ combined H{sub 2}/N{sub 2} plasma at 650 Degree-Sign C to remove residual carbon contamination, resulting in a clean, oxygen-terminated surface. This cleaning process produced slightly upward band bending of 0.1 eV. Additional 650 Degree-Sign C annealing after plasma cleaning increased the upward band bending by 0.2 eV. After the initial clean, high-k oxide films were deposited using oxygen PEALD at 140 Degree-Sign C. The valence band and conduction band offsets (VBOs and CBOs) of the Al{sub 2}O{sub 3}/GaN and HfO{sub 2}/GaN structures were deduced from in-situ x-ray and ultraviolet photoemission spectroscopy (XPS and UPS). The valence band offsets were determined to be 1.8 and 1.4 eV, while the deduced conduction band offsets were 1.3 and 1.0 eV, respectively. These values are compared with the theoretical calculations based on the electron affinity model and charge neutrality level model. Moreover, subsequent annealing had little effect on these offsets; however, the GaN band bending did change depending on the annealing and processing. An Al{sub 2}O{sub 3} layer was investigated as an interfacial passivation layer (IPL), which, as results suggest, may lead to improved stability, performance, and reliability of HfO{sub 2}/IPL/GaN structures. The VBOs were {approx}0.1 and 1.3 eV, while the deduced CBOs were 0.6 and 1.1 eV for HfO{sub 2} with respect to Al{sub 2}O{sub 3} and GaN, respectively.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Improved composite targets for small scale {sup 64}Cu production comparing Au- and Pt-foils as {sup 64}Ni backing

Advantages of a stacked assembly of target support components for {sup 64}Cu production via {sup 64}Ni(p,n){sup 64}Cu reaction were reported recently. The present work shows the applicability of these composite targets for beam currents up to 22 {mu}A. Gold and platinum foils were evaluated as {sup 64}Ni backing. The effective specific activity (ESA) and specific activity (SA) were determined by TETA titration at room temperature and at 80 Degree-Sign C and compared with additional copper quantification results via ICP-MS and stripping voltammetric trace analysis (VA).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗