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At least 487 records · Page 27

Effect of variable cerium concentration on photoluminescence behaviour in ZrO{sub 2} phosphor synthesized by combustion synthesis method

Present paper reports synthesis and characterization of trivalent cerium (Ce{sup 3+}) doped zirconium dioxide (ZrO{sub 2}) phosphors. Effect of variable concentration of cerium on photoluminescence (PL) is studied. Samples were prepared by combustion synthesis technique which is suitable for less time taking techniques also for large scale production for phosphors. Starting material used for sample preparation are Zr(NO{sub 3}){sub 3} and Ce(NO{sub 3}){sub 3} and urea used as a fuel. All prepared phosphor with variable concentration of Ce{sup 3+} (0.1 to 2mol%) was studied by photoluminescence analysis it is found that the excitation spectra of prepared phosphor shows broad excitation centred at 390nm. The excitation spectra with variable concentration of Ce{sup 3+} show strong peaks at 447nm. Spectrophotometric determinations of peaks are evaluated by Commission Internationale de I’Eclairage technique. Using this phosphor, the desired CIE values including emissions throughout the violet (390 nm) and blue (427 nm) of the spectra were achieved. Efficient blue light emitting diodes were fabricated using Ce{sup 3+} doped phosphor based on near ultraviolet (NUV) excited LED lights.

36 MATERIALS SCIENCE↗

Fracture Sustainability Pressure, Temperature, Differential Pressure, and Aperture Closure Data

In these data sets, the experiment time, actual date and time, room temperature, sample temperature, upstream and downstream pressures (measured independently), corrected differential pressure (measured independently and corrected for offset and room temperature) indication of aperture closure by linear variable differential transformer are presented. An indication of the sample is in the file name and in the first line of data.

15 GEOTHERMAL ENERGY↗

Block Design with Common Reference Samples Enables Robust Large-Scale Label-Free Quantitative Proteome Profiling

Label-free quantitative proteomics has become an increasingly popular tool for profiling global protein abundances. However, one major weakness is the potential performance drift of the LC-MS platform over time, which in turn limits its utility for analyzing large-scale sample sets. To address this, in this work we introduce an experimental and data analysis scheme based on a block-design with common controls within each block for enabling LC-MS-based large-scale label-free quantification. In this scheme, a large number of samples (e.g., >100 samples) are analyzed in smaller, and more manageable blocks, minimizing instrument drift and variability within a block. Furthermore, each designated block also contains common controls (or reference) samples for normalization within and across blocks. We demonstrated the effectiveness of this method by profiling the proteome response of human macrophage THP-1 cells to 11 engineered nanomaterials (ENMs) at two different doses. A total of 116 samples were analyzed in six blocks, yielding an average coverage of 4500 proteins per sample. The data revealed consistent quantification of proteins across all six blocks, as shown by highly stable quantification of house-keeping proteins in all samples and high levels of quantification correlation among samples from different blocks. The data also demonstrated that label-free quantification is robust and accurate enough to quantify even very subtle abundance changes as well as large fold-changes without potential ratio compression as often encountered with isobaric labeling. Our streamlined workflow is easy to implement and can be readily adapted to other large cohort studies for reproducible label-free proteome quantification.

59 BASIC BIOLOGICAL SCIENCES↗

Kepler and the long-period variables

High-precision Kepler photometry is used to explore the details of asymptotic giant branch (AGB) light curves. Since AGB variability has a typical timescale on the order of a year, we discuss at length the removal of long-term trends and quarterly changes in Kepler data. Photometry for a small sample of nine semi-regular (SR) AGB stars is examined using a 30 minute cadence over a period of 45 months. While undergoing long-period variations of many magnitudes, the light curves are shown to be smooth at the millimagnitude level over much shorter time intervals. No flares or other rapid events were detected on a sub-day timescale. The shortest AGB period detected is on the order of 100 days. All the SR variables in our sample are shown to have multiple modes. This is always the first overtone, typically combined with the fundamental. A second common characteristic of SR variables is shown to be the simultaneous excitation of multiple closely separated periods for the same overtone mode. Approximately half the sample had a much longer variation in the light curve, likely a long secondary period (LSP). The light curves were all well represented by a combination of sinusoids. However, the properties of the sinusoids are time variable, with irregular variations present at low levels. No non-radial pulsations were detected. It is argued that the LSP variation seen in many SR variables is intrinsic to the star and linked to multiple mode pulsation.

79 ASTRONOMY AND ASTROPHYSICS↗

Strength and ductility of additively manufactured 316L stainless steel: Impact of neutron irradiation and data variability

Here, this article presents the mechanical properties of additively manufactured (AM) 316L stainless steel processed via the laser powder bed fusion (LPBF) method, focusing on the effects of neutron irradiation on mechanical properties and the variability in strength and ductility data. The rapid melting-solidification process and multiple heating-cooling cycles inherent in LPBF typically result in a fine, metastable microstructure with significant local variability. AM 316L builds of varying thicknesses were fabricated, and SS-J3 miniature tensile specimens were machined from six different locations. These specimens were irradiated with fast neutrons to doses of 2 and 10 dpa at target temperatures of 300 °C and 600 °C. Post-irradiation tensile tests were conducted at room temperature, 300 °C, and 600 °C. Compared to conventional 316L stainless steel, AM 316L exhibited higher initial strength but lower ductility. Irradiation at 300 °C caused significant hardening and prompt necking at yield, with limited uniform ductility, although embrittlement was not observed up to 10 dpa. While neutron irradiation, particularly at 600 °C, increased the variability in strength and ductility data, no clear dependence of mechanical properties on build thickness or sampling location was found—contrary to the conventional perception that AM materials may exhibit high property variability. Furthermore, we observed that the variability in property data for LPBF-processed 316L was relatively low compared to that of wrought 316L stainless steel. This reduced variability in AM 316L steel may be attributed to its highly metastable, stress-containing microstructure, which is discussed in the context of general tensile property variations.

Additively manufactured 316L stainless steel↗

Standardized protocols and procedures can precisely and accurately quantify non-structural carbohydrates

Non-structural carbohydrates (NSCs), the stored products of photosynthesis, building blocks for growth, and fuel for respiration, are central to plant metabolism, but their measurement is challenging. Differences in methods and procedures among laboratories can cause results to vary widely, limiting our ability to integrate and generalize patterns in plant C balance among studies. A recent assessment found that NSC concentrations measured for a common set of samples can vary by an order of magnitude, but sources for this variability were unclear. We measured a common set of nine plant material types, and two synthetic samples with known NSC concentrations, using a common protocol for sugar extraction and starch digestion, and three different sugar quantification methods (ion chromatography, enzyme, acid) in six laboratories. We also tested how sample handling, extraction solvent, and centralizing parts of the procedure in one laboratory affected results. NSC concentrations measured for synthetic samples were within about 11.5% of known values for all three methods. However, differences among quantification methods were the largest source of variation in NSC measurements for natural plant samples because the three methods quantify different NSCs. The enzyme method quantified only glucose, fructose, and sucrose, with ion chromatography we additionally quantified galactose, while the acid method quantified a large range of mono- and oligosaccharides. For some natural samples, acid method quantification doubled sugar relative to the other methods, demonstrating that trees allocate C to a range of sugar molecules. Sample handling had little effect on measurements, while ethanol sugar extraction improved accuracy over water extraction. Our results demonstrate that reasonable accuracy of NSC measurements can be achieved when different methods are used, as long as protocols are robust and standardized. Thus, we provide detailed protocols for the extraction, digestion and quantification of NSCs in plant samples, which should improve the comparability of NSC measurements among laboratories.

Landhäusser, Simon M.↗

A Stochastic Covariance Shrinkage Approach in Ensemble Transform Kalman Filtering

The Ensemble Kalman Filters (EnKF) employ a Monte-Carlo approach to represent covariance information, and are affected by sampling errors in operational settings where the number of model realizations is much smaller than the model state dimension. To alleviate the effects of these errors EnKF relies on model-specific heuristics such as covariance localization, which takes advantage of the spatial locality of correlations among the model variables. This work proposes an approach to alleviate sampling errors that utilizes a locally averaged-in-time dynamics of the model, described in terms of a climatological covariance of the dynamical system. We use this covariance as the target matrix in covariance shrinkage methods, and develop a stochastic covariance shrinkage approach where synthetic ensemble members are drawn to enrich both the ensemble subspace and the ensemble transformation. We additionally provide for a way in which this methodology can be localized similar to the state-of-the-art LETKF method, and that for a certain model setup, our methodology significantly outperforms it.

54 ENVIRONMENTAL SCIENCES↗

Quantifying sampling noise and parametric uncertainty in atomistic-to-continuum simulations using surrogate models

We present a methodology to assess the predictive fidelity of multiscale simulations by incorporating uncertainty in the information exchanged between the components of an atomistic-to-continuum simulation. We account for both the uncertainty due to finite sampling in molecular dynamics (MD) simulations and the uncertainty in the physical parameters of the model. Using Bayesian inference, we represent the expensive atomistic component by a surrogate model that relates the long-term output of the atomistic simulation to its uncertain inputs. We then present algorithms to solve for the variables exchanged across the atomistic-continuum interface in terms of polynomial chaos expansions (PCEs). We also consider a simple Couette flow where velocities are exchanged between the atomistic and continuum components, while accounting for uncertainty in the atomistic model parameters and the continuum boundary conditions. Results show convergence of the coupling algorithm at a reasonable number of iterations. As a result, the uncertainty in the obtained variables significantly depends on the amount of data sampled from the MD simulations and on the width of the time averaging window used in the MD simulations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Subnanogram proteomics: Impact of LC column selection, MS instrumentation and data analysis strategy on proteome coverage for trace samples

One of the greatest challenges for mass spectrometry (MS)-based proteomics is the limited ability to analyze small samples. Here we investigate the relative contributions of liquid chromatography (LC), MS instrumentation and data analysis methods with the aim of improving proteome coverage for sample sizes ranging from 0.5 ng to 50 ng. We show that the LC separations utilizing 30-µm-i.d. columns increase signal intensity by >3-fold relative to those using 75-µm-i.d. columns, leading to 32% increase in peptide identifications. The Orbitrap Fusion Lumos mass spectrometer significantly boosted both sensitivity and sequencing speed relative to earlier generation Orbitraps (e.g., LTQ-Orbitrap), leading to a ~3× increase in peptide identifications and 1.7× increase in identified protein groups for 2 ng tryptic digests of bacterial lysate. The Match Between Runs algorithm of open-source MaxQuant software further increased proteome coverage by ~ 95% for 0.5 ng samples and by ~42% for 2 ng samples. The present platform is capable of identifying >3000 protein groups from tryptic digestion of cell lysates equivalent to 50 HeLa cells and 100 THP-1 cells (~10 ng total proteins), respectively, and >950 proteins from subnanogram bacterial and archaeal cell lysates. The present ultrasensitive LC-MS platform is expected to enable deep proteome coverage for subnanogram samples, including single mammalian cells.

Environmental Molecular Sciences Laboratory↗

The variability structure function of the highest luminosity quasars on short time-scales

ABSTRACT The stochastic photometric variability of quasars is known to follow a random-walk phenomenology on emission time-scales of months to years. Some high-cadence rest-frame optical monitoring in the past has hinted at a suppression of variability amplitudes on shorter time-scales of a few days or weeks, opening the question of what drives the suppression and how it might scale with quasar properties. Here, we study a few thousand of the highest luminosity quasars in the sky, mostly in the luminosity range of $L_{\rm bol}$$=[46.4, 47.3]$ and redshift range of $z=[0.7, 2.4]$. We use a data set from the NASA/Asteroid Terrestrial-impact Last Alert System facility with nightly cadence, weather permitting, which has been used before to quantify strong regularity in longer term rest-frame-UV variability. As we focus on a careful treatment of short time-scales across the sample, we find that a linear function is sufficient to describe the UV variability structure function. Although the result can not rule out the existence of breaks in some groups completely, a simpler model is usually favoured under this circumstance. In conclusion, the data are consistent with a single-slope random walk across rest-frame time-scales of $\Delta t=[10, 250]$ d.

Tang, Ji-Jia (ORCID:0000000218600886)↗

Impact of specimen preparation method on photovoltaic backsheet degradation during accelerated aging test

In this study, we highlight some important factors in the specimen preparation methods for evaluating photovoltaic backsheet properties after accelerated aging. Two different sequences are considered: Method (I) cut-then-age: cut into 1-cm wide strips and then expose to stress, and Method (II) age-then-cut: expose a larger sheet to stress and then cut into 1-cm widths for mechanical property measurements. We also compare the effect of three cutting methods, (a) tensile specimen punch, (b) paper cutter, and (c) fresh razor blade. Several commercial backsheets were evaluated, with stress exposures including (a) pressure cooker test (PCT), (b) dry ultraviolet (UV) radiation exposure, and (c) UV combined damp heat tests. Fourier transform infrared spectrometer (FTIR) and intrinsic viscosity (IV) were used to analyze the materials on unstressed materials and samples exposed to PCT. The results show that both the cutting method and the time of cutting have an impact on the backsheet mechanical properties. Additionally, under UV exposure, Method II, age-then-cut, generally resulted in a higher average value, with more variation than Method I; however, if the side strips from Method II were excluded, the variation dropped to the same level. This is because the specimens at the sides of the sheet get additional damage from UV light from the exposed sides of the sample. In contrast to UV exposure, PCT specimens prepared by Method II result in lower average values and higher variability. This is attributed to embrittlement through the bulk of the sample where the cutting of embrittled specimens appears to result in more edge defects which can then initiate a break at smaller strains. The data suggest that for UV exposures, the specimens should be cut after aging and the exposed side specimens discarded, and that for PCT exposures, the specimens should be cut before the exposure.

14 SOLAR ENERGY↗

Magnetic and Transport Properties of Bi{sub 0.5−x}Pr{sub x}Ca{sub 0.5}MnO{sub 3}(0.0 ≤ x ≤ 0.50) Manganites

In this work, the effect of Pr doping at the Bi site on the critical behavior and magnetocaloric and transport properties of Bi{sub 0.5−x}Pr{sub x}Ca{sub 0.5}MnO{sub 3} (0.0 ≤ x ≤ 0.50) manganite synthesized by sol–gel method is reported. An increase in Curie temperature (T{sub C}) with an increase in Pr content is observed. The samples with x = 0.0–0.40 show first-order phase transition whereas the sample with x = 0.50 shows second-order phase transition near T{sub C}. The estimated values of critical exponents β = 0.75 and γ = 0.82 for the sample with x = 0.50 do not fall into any universality class. The sample with x = 0.50 shows maximum magnetic entropy change (|ΔS{sub m}| = (1.22 J kg{sup −1} K{sup −1}) at T{sub C} in an applied magnetic field of 40 kOe, which is associated with magnetocaloric effect (MCE). All the samples show semiconducting behavior and also follow Mott’s variable range hopping (VRH) model below the charge ordering temperature (T{sub CO}). The changes in magnetic and transport properties are correlated with the changes in the structural parameters of the samples. The results are discussed in view of the effect of Pr doping on the 6s{sup 2} lone pair character of Bi{sup 3+} ions and disorder in the samples.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Oxidation Temperature-Dependent Electrochemical Doping of WO 3 Deposited via Atomic Layer Deposition

Silicon-based photoelectrochemical devices show promise for the performance of light-driven CO 2 reduction but suffer from instability under photoelectrochemical conditions relevant to CO 2 reduction. Coating silicon electrodes with thin layers of metal oxides has shown promise to passivate unstable silicon surfaces, and many different metal oxides can be deposited on silicon using various techniques. In this study, we investigate the fundamental photoelectrochemical performance of WO 3 -coated silicon photoelectrodes, which were generated by oxidation of W-metal films deposited via atomic layer deposition on both degenerately doped (nSi + ) and low-doped (pSi) silicon. Two different oxidation temperatures were investigated (400 and 600 °C), and it was found that the monoclinic phase of WO 3 predominates at both temperatures but that more grain boundaries are present in the 600 °C film. From X-ray photoelectron spectroscopy, the stoichiometry of both films was found to be 1:3 W:O, and low electron energy loss experiments indicate band gaps of 3.0 and 3.1 eV for 400 and 600 °C films, respectively. Cyclic voltammetry experiments showed that the electron transfer kinetics increased after continued redox cycling, particularly for the material produced at 400 °C. X-ray photoelectron spectra suggest that the observed increase in electrode conductivity is due to the formation of oxygen vacancies in the film. Electrochemical impedance spectroscopy indicated that charge transport through the films was impacted by the grain boundaries that formed during oxidation of the film. Photoelectrochemical studies on pSi/WO 3 electrodes were highly variable, only producing a photocurrent and photovoltage with some samples. Our best sample, formed at 400 °C, produced a photovoltage of 180 mV, which is lower than what has previously been reported for WO 3 -coated silicon (500 mV). We hypothesize that the variability in photoelectrochemical experiments arose from a roughened WSiO x interface that is generated during film preparation. WO 3 shows promise as a metal oxide coating for silicon, but our results suggest that formation of a high-quality interface between Si and WO 3 is vital for best performance.

Charge transfer↗

A study of Ni/La-Al 2 O 3 catalysts: A competitive system for CO 2 methanation

Ni/La-γ-Al 2 O 3 samples containing 13.6 wt.% Ni and a variable amount of lanthana (0, 4, 14 and 37 wt.%) were prepared by incipient wetness impregnation, using silica-free γ-Al 2 O 3 support. The materials were characterized, as such or after reaction, with XRD, H 2 -TPR, IR, UV–vis-NIR, XPS and FE-SEM techniques. They were tested as catalysts for CO 2 methanation at atmospheric pressure at GHSV 55000 h –1 . The reaction is under kinetic control at T < 650–673 K, while the product mixture is under thermodynamic control above this temperature range. Lanthanum addition strongly increases the activity of Ni/γ-Al 2 O 3 for CO 2 methanation. Methane selectivity is increased to nearly 100% at low temperatures (T < 650 K). The CO 2 methanation reaction on La-doped Ni/γ-Al 2 O 3 occurs with similar activation energies (80 kJ/mol), and with slightly higher reaction order for hydrogen and lower reaction order for CO 2 than those observed for undoped Ni/γ-Al 2 O 3 . Lanthanum acts as a promoter because of the stronger basicity of the lanthana-alumina support allowing stronger adsorption of CO 2 as surface carbonates that can be act as “reactant reservoirs”. Finally, the Ni/La-alumina catalysts studied here are similarly effective as Ru/alumina catalysts for the selective CO 2 methanation at low temperature and atmospheric pressure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spatial and temporal characterization of municipal solid waste based on resource recovery pathways

This study presents a two-year, quarterly assessment of MSW across four source sectors (residential, schools, restaurants, and grocery stores) from sixteen sites across five U.S. states. MSW was manually sorted into 27 categories and aggregated into pathway fractions: high-moisture (HM) organics, low-moisture (LM) organics, recyclable (RC) materials, and residuals for disposal. Organics represented 89 % of the MSW stream. The largest fraction was HM organics consisting of food waste (31 %) and yard waste (3 %), with large coefficient of variations (CV), 79 and 278 %, respectively, reflecting high seasonal and site variability that varied significantly (p < 0.01) across sampling periods. The HM fraction showed properties favorable for anaerobic digestion, with moisture content ranging from 56 to 95 % and volatile solids ranges of 86-95 %. In contrast, the LM and RC fractions remained more stable (plastics CV = 41 %; paper CV = 53 %) with heating values up to 26.9 MJ/kg across sources, reflecting suitability for gasification. Microstructural analysis revealed less porosity in residential waste sampled at the landfill, which can influence preprocessing efficiency and microbial accessibility. Pathway informed allocations showed that 35 % of MSW is suitable for anaerobic digestion, 36 % for gasification, and 18 % for recycling, leaving 11 % requiring landfill disposal. These results provide quantitative evidence to determine feedstock allocation, waste-to-energy system design, and the development of data-driven sustainability and resource recovery strategies within a circular bioeconomy.

09 BIOMASS FUELS↗

Antibody-independent Targeted Quantification of TMPRSS2-ERG Fusion Protein Products in Prostate Cancer

Fusions between the transmembrane protease serine 2 (TMPRSS2) and ETS related gene (ERG) represent one of the most specific biomarkers that define a distinct molecular subtype of prostate cancer. The studies on TMPRSS2-ERG gene fusions have seldom been performed at the protein level, primarily due to the lack of high-quality antibodies or an antibody-independent method that is sufficiently sensitive for detecting the truncated ERG protein products resulting from TMPRSS2-ERG gene fusions and alternative splicing. Herein, we applied a recently developed PRISM (high-pressure high-resolution separations with intelligent selection and multiplexing)-SRM (selected reaction monitoring) strategy for quantifying ERG protein in prostate cancer cell lines and tumors. The highly sensitive PRISM-SRM assays led to confident detection of 6 unique ERG peptides in either the TMPRSS2-ERG positive cell lines or tissues but not in the negative controls, indicating that ERG protein expression is highly correlated with TMPRSS2-ERG gene rearrangements. Significantly, our results demonstrated for the first time that at least two groups of ERG protein isoforms were simultaneously expressed at variable levels in TMPRSS2-ERG positive samples as evidenced by concomitant detection of two mutually exclusive peptides. Three peptides shared across almost all fusion protein products were determined to be the most abundant peptides, and hence can be used as “signature” peptides for detecting ERG overexpression resulting from TMPRSS2-ERG gene fusion. These PRISM-SRM assays provide valuable tools for studying TMPRSS2-ERG gene fusion protein products, thus improving our understanding of the role of TMPRSS2-ERG gene fusion in the biology of prostate cancer.

Environmental Molecular Sciences Laboratory↗

Structural and Thermoelectric Properties of Black Arsenic–Phosphorus

Here, we report the structural and temperature dependent transport properties of As x P 1-x (x = 0, 0.2, 0.5, 0.83, 1) alloys. It is observed that black phosphorous (BP)-related phonon modes in the alloy samples are red-shifted with increasing arsenic concentration, while black arsenic-related modes in these samples are blue-shifted with increasing phosphorus concertation. As the arsenic concentration, x increases from 0 to 1, the 4-probe resistance of the As x P 1-x alloys is found to decrease by more than 3 orders of magnitude. The transport studies reveal that samples with the highest arsenic concentration (x = 1 and 0.83) show metallic behavior in the temperature dependence of resistance with a small thermopower at room temperature with an anomalous temperature dependence. In contrast, the samples with high phosphorus concentration (x = 0, 0.2, and 0.5) show very large thermopower values at room temperature reaching a value as high as 803 μV/k for x = 0.2. The temperature dependence of the thermopower of these samples can be well described by the variable range hopping (VRH) mechanism in two-dimensions (2-d), S ~ T 1/3 . Similarly, their 4-probe resistance (R) values can be fitted with 2-d VRH mechanism, R ~ exp(T -1/3 ).

36 MATERIALS SCIENCE↗

Experimental setup for investigation of nanoclusters at cryogenic temperatures by electron spin resonance and optical spectroscopies

We present the design and performance of an experimental setup for simultaneous electron spin resonance (ESR) and optical studies of nanoclusters with stabilized free radicals at cryogenic temperatures. A gas mixture of impurities and helium after passing through a RF discharge for dissociation of molecules is directed onto the surface of superfluid helium to form the nanoclusters of impurities. A specially designed ESR cavity operated in the TE{sub 011} mode allows optical access to the sample. The cavity is incorporated into a homemade insert which is placed inside a variable temperature insert of a Janis {sup 4}He cryostat. The temperature range for sample investigation is 1.25–300 K. A Bruker EPR 300E and Andor 500i optical spectrograph incorporated with a Newton EMCCD camera are used for ESR and optical registration, respectively. The current experimental system makes it possible to study the ESR and optical spectra of impurity-helium condensates simultaneously. The setup allows a broad range of research at low temperatures including optically detected magnetic resonance, studies of chemical processes of the active species produced by photolysis in solid matrices, and investigations of nanoclusters produced by laser ablation in superfluid helium.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗