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At least 1,513 records · Page 84

Transient and permanent changes in DNA methylation patterns in inorganic arsenic-mediated epithelial-to-mesenchymal transition

Chronic low dose inorganic arsenic exposure causes cells to take on an epithelial-to-mesenchymal phenotype, which is a crucial process in carcinogenesis. Inorganic arsenic is not a mutagen and thus epigenetic alterations have been implicated in this process. Indeed, during the epithelial-to-mesenchymal transition, morphologic changes to cells correlate with changes in chromatin structure and gene expression, ultimately driving this process. However, studies on the effects of inorganic arsenic exposure/withdrawal on the epithelial-to-mesenchymal transition and the impact of epigenetic alterations in this process are limited. In this study we used high-resolution microarray analysis to measure the changes in DNA methylation in cells undergoing inorganic arsenic-induced epithelial-to-mesenchymal transition, and on the reversal of this process, after removal of the inorganic arsenic exposure. We found that cells exposed to chronic, low-dose inorganic arsenic exposure showed 30,530 sites were differentially methylated, and with inorganic arsenic withdrawal several differential methylated sites were reversed, albeit not completely. Furthermore, these changes in DNA methylation mainly correlated with changes in gene expression at most sites tested but not at all. This study suggests that DNA methylation changes on gene expression are not clear-cut and provide a platform to begin to uncover the relationship between DNA methylation and gene expression, specifically within the context of inorganic arsenic treatment. - Highlights: • Transient and permanent methylation patterns are modulated by iAs exposure. • Arsenite contributes to the epithelial-to-mesenchymal transition. • Arsenite mediated epigenetic changes play a role in EMT.

60 APPLIED LIFE SCIENCES↗

High vacuum measurements and calibrations, molecular flow fluid transient effects

High vacuum pressure measurements and calibrations below 1 × 10 -8 Torr are problematic. Specifically, measurement accuracies change drastically for vacuum gauges when pressures are suddenly lowered in vacuum systems. How can gauges perform like this? A brief system description is first required to answer this question. Calibrations were performed using a vacuum calibration chamber with attached vacuum gauges. To control chamber pressures, vacuum pumps decreased the chamber pressure while nitrogen tanks increased the chamber pressure. By balancing these opposing pressures, equilibrium in the chamber was maintained at selected set point pressures to perform calibrations. When pressures were suddenly decreased during set point adjustments, a sudden rush of gas from the chamber also caused a surge of gas from the gauges to decrease the pressures in those gauges. Gauge pressures did not return to equilibrium as fast as chamber pressures due to the sparse distribution of gas molecules in the system. This disparity in the rate of pressure changes caused the pressures in different gauges to be different than expected. This discovery was experimentally proven to show that different gauge designs return to equilibrium at different rates, and that gauge accuracies vary for different gauge designs due to fluid transients in molecular flow.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Thickness-Dependent Interlayer Charge Transfer in MoSe 2 /MoS 2 Heterostructures Studied by Femtosecond Transient Absorption Measurements

We report observations of a strong thickness dependence for charge transfer (CT) from MoSe 2 to MoS 2 , as evidenced by transient absorption measurements. By time-resolving CT from MoSe 2 monolayers (1Ls) to MoS 2 flakes of varying thicknesses, including 1L, bilayer (2L), and trilayer (3L), we find that the CT time is several picoseconds in the 1L-MoSe 2 /3L-MoS 2 heterostructure, which is much longer than that of 1L-MoSe 2 /1L-MoS 2 and 1L-MoSe 2 /2L-MoS 2 heterostructures. In addition, the recombination lifetime of the interlayer excitons in the 1L/3L heterostructure is several times longer than that of 1L/1L and 1L/2L heterostructures, reaching 800 ps. Furthermore, we show that a prepulse can reduce the CT time and enhance the interlayer exciton recombination in the 1L/3L heterostructure. Furthermore, these findings illustrate that layer thickness can be an important parameter to control the CT property of van der Waals heterostructures. These experimental results also provide important information for further refining the understanding of the physical mechanisms of CT in van der Waals heterostructures.

36 MATERIALS SCIENCE↗

Illuminating the Role of Alcohol Substrate in Nickel Photoredox Catalysis via Ground State and Transient Absorption Spectroscopy

Direct excitation of nickel photocatalysts has gained popularity over the last several years following the successful activation of nickel by Ir and Ru photosensitizers. The ability to pair these photosensitizers with Ni catalysts facilitates the formation of crucial chemical bonds under relatively mild conditions. However, there are still gaps in our understanding of what influences the performance of these Ni photocatalysts. Previous work from our group identified a nickel photocatalyst supported by a tridentate pyridinophane ligand that undergoes wavelength-dependent cross-coupling reactivity. Herein, we report detailed studies of the wavelength dependence of the C–O cross-coupling reactivity, illustrating that the catalytic activity has an optimal wavelength, and excitation on both the blue and red sides of this optimal wavelength leads to a reduction in product yield. We also reveal a crucial catalyst-alcohol preirradiation interaction that drastically alters the catalyst’s optical properties. Furthermore, we investigate both wavelength dependency and alcohol dependency via optical transient absorption spectroscopy and reveal a substrate binding process responsible for the observed wavelength-dependent cross-coupling catalysis.

alcohol↗

Light-Induced Transient Lattice Dynamics and Metastable Phase Transition in CH 3 NH 3 PbI 3 Nanocrystals

In this study, methylammonium lead iodide (MAPbI 3 ) perovskite nanocrystals (NCs) offer desirable optoelectronic properties with prospective utility in photovoltaics, lasers, and light-emitting diodes (LEDs). Structural rearrange-ments of MAPbI 3 in response to photoexcitation, such as lattice distortions and phase transitions, are of particular interest, as these engender long carrier lifetime and bolster carrier diffusion. Here, we use variable temperature X-ray diffraction (XRD) and synchrotron-based transient X-ray diffraction (TRXRD) to investigate lattice response following ultrafast optical excitation. MAPbI 3 NCs are found to slowly undergo a phase transition from the tetragonal to a pseudocubic phase over the course of 1 ns under 0.02-4.18 mJ/cm 2 fluence photoexcitation, with apparent nonthermal lattice distortions attributed to polaron formation. Lattice recovery exceeds time scales expected for both carrier recombination and thermal dissipation, indicating meta-stability likely due to the proximal phase transition, with symmetry-breaking along equatorial and axial directions. These findings are relevant for fundamental understanding and applications of structure-function properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tracking Optical Phonon Dynamics in InP Nanocrystals via Transient Absorption and Femtosecond Stimulated Raman Spectroscopy

Semiconductor nanocrystals (NCs) offer actualized and prospective utility in optoelectronic technologies, yet key aspects of their thermal and vibrational behaviors remain unresolved. Compared with bulk crystals, heat dissipation involving NCs can differ substantially owing to pervasiveness of interfacial scattering, phonon confinement, and relaxed phonon momentum selection rules, as well as influences of ligands. Here, in addition to transient absorption, we use femtosecond stimulated Raman spectroscopy to track nonequilibrium optical-phonon dynamics in InP NCs capped with myristic acid ligands and compare the same particles coated with a ZnS shell. We identify distinct phonon decay pathways in ligand-capped versus ZnS-shelled NCs. Increasing the excitation density and introducing the ZnS shell measurably modify optical-phonon lifetimes, whereas phonon formation times remain largely unchanged. In addition, we observe phonon mode softening in ligand-capped nanocrystals, consistent with lattice expansion. Together, these results demonstrate that core–shell structures can strongly govern nanocrystal thermal dissipation pathways and should be considered a key design parameter for optoelectronic operation.

dissipation↗

Reduction of Propionic Acid over a Pd-Promoted ReO x /SiO 2 Catalyst Probed by X-ray Absorption Spectroscopy and Transient Kinetic Analysis

A Pd-promoted Re/SiO 2 catalyst was prepared by sequential impregnation and compared to monometallic Pd/SiO 2 and Re/SiO 2 . All samples were characterized by electron microscopy, H 2 and CO chemisorption, H 2 temperature-programmed reduction, and in situ X-ray absorption spectroscopy at the Re L III and Pd K-edges. The samples were also tested in the reduction of propionic acid to 1-propanol and propionaldehyde at 433 K in 0.1–0.2 MPa H 2 . Whereas monometallic Pd was inactive for carboxylic acid reduction, monometallic Re catalyzed aldehyde formation but only after high-temperature prereduction that produced metallic Re. When Pd was present with Re in a bimetallic catalyst, Pd facilitated the reduction of Re in H 2 to ~+4 oxidation state at modest temperatures, producing an active catalyst for the conversion of propionic acid to 1-propanol. Under the conditions of this study, the orders of reaction in propionic acid and H 2 were approximately zero and one, respectively. Transient kinetic analysis of the carboxylic acid reduction to alcohols revealed that at least 50% of the Re in the bimetallic catalyst participated in the catalytic reaction. In conclusion, the Pd is proposed to enhance the catalytic activity of the bimetallic catalyst by spilling over hydrogen that can partially reduce Re and react with surface intermediates.

1-Propanol↗

Transient Storage Model Parameter Optimization Using the Simulated Annealing Method

Hyporheic exchange in streams is critical to ecosystem functions such as nutrient cycling along river corridors, especially for slowly moving or small stream systems. The transient storage model (TSM) has been widely used for modeling of hyporheic exchange. TSM calibration, for hyporheic exchange, is typically used to estimate four parameters, including the mass exchange rate coefficient, the dispersion coefficient, stream cross-sectional area, and hyporheic zone cross-sectional area. Prior studies have raised concerns regarding the non-uniqueness of the inverse problem for the TSM, that is, the occurrence of different parameter vectors resulting in TSM solution that reproduces the observed in-stream tracer break through curve (BTC) with the same error. This leads to practical non-identifiability in determining the unknown parameter vector values even when global-optimal values exist, and the parameter optimization becomes practically non-unique. To address this problem, we applied the simulated annealing method to calibrate the TSM to BTCs, because it is less susceptible to local minima-induced non-identifiability. A hypothetical (or synthetic) tracer test data set with known parameters was developed to demonstrate the capability of the simulated annealing method to find the global minimum parameter vector, and it identified the “hypothetically-true” global minimum parameter vector even with input data that were modified with up to 10% noise without increasing the number of iterations required for convergence. The simulated annealing TSM was then calibrated using two in-stream tracer tests conducted in East Fork Poplar Creek, Tennessee. In conclusion, simulated annealing was determined to be appropriate for quantifying the TSM parameter vector because of its search capability for the global minimum parameter vector.

54 ENVIRONMENTAL SCIENCES↗

Solution techniques for transient stability-constrained optimal power flow – Part II

Transient stability-constrained optimal power flow is an important emerging problem with power systems pushed to the limits for economic benefits, dense and larger interconnected systems, and reduced inertia due to expected proliferation of renewable energy resources. In this study, two more approaches: single machine equivalent and computational intelligence are presented. Also discussed are various application areas, and future directions in this research area. In conclusion, a comprehensive resource for the available literature, publicly available test systems, and relevant numerical libraries is also provided.

24 POWER TRANSMISSION AND DISTRIBUTION↗

A simple Boltzmann transport equation for ballistic to diffusive transient heat transport

Developing simplified, but accurate, theoretical approaches to treat heat transport on all length and time scales is needed to further enable scientific insight and technology innovation. Using a simplified form of the Boltzmann transport equation (BTE), originally developed for electron transport, we demonstrate how ballistic phonon effects and finite-velocity propagation are easily and naturally captured. We show how this approach compares well to the phonon BTE, and readily handles a full phonon dispersion and energy-dependent mean-free-path. This study of transient heat transport shows (i) how fundamental temperature jumps at the contacts depend simply on the ballistic thermal resistance, (ii) that phonon transport at early times approach the ballistic limit in samples of any length, and (iii) perceived reductions in heat conduction, when ballistic effects are present, originate from reductions in temperature gradient. Importantly, this framework can be recast exactly as the Cattaneo and hyperbolic heat equations, and we discuss how the key to capturing ballistic heat effects is to use the correct physical boundary conditions.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Analyzing degradation effects of organic light-emitting diodes via transient optical and electrical measurements

Although the long-term stability of organic light-emitting diodes (OLEDs) under electrical operation made significant progress in recent years, the fundamental underlying mechanisms of the efficiency decrease during operation are not well understood. Hence, we present a comprehensive degradation study of an OLED structure comprising the well-known green phosphorescent emitter Ir(ppy){sub 3}. We use transient methods to analyze both electrical and optical changes during an accelerated aging protocol. Combining the results of displacement current measurements with time-resolved investigation of the excited states lifetimes of the emitter allows for a correlation of electrical (e.g., increase of the driving voltage due to trap formation) and optical (e.g., decrease of light-output) changes induced by degradation. Therewith, it is possible to identify two mechanisms resulting in the drop of the luminance: a decrease of the radiative quantum efficiency of the emitting system due to triplet-polaron-quenching at trapped charge carriers and a modified charge carrier injection and transport, as well as trap-assisted non-radiative recombination resulting in a deterioration of the charge carrier balance of the device.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Surface hopping with a manifold of electronic states. III. Transients, broadening, and the Marcus picture

In a previous paper [Dou et al., J. Chem. Phys. 142, 084110 (2015)], we have introduced a surface hopping (SH) approach to deal with the Anderson-Holstein model. Here, we address some interesting aspects that have not been discussed previously, including transient phenomena and extensions to arbitrary impurity-bath couplings. In particular, in this paper we show that the SH approach captures phonon coherence beyond the secular approximation, and that SH rates agree with Marcus theory at steady state. Finally, we show that, in cases where the electronic tunneling rate depends on nuclear position, a straightforward use of Marcus theory rates yields a useful starting point for capturing level broadening. For a simple such model, we find I-V curves that exhibit negative differential resistance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

All-optical logic gate based on transient grating from disperse red 1 doped organic-inorganic hybrid films with an improved figure of merit

Azobenzene dyes have large refractive index near their main resonance, but the poor figure of merit (FOM) limits their potential for all-optical applications. To improve this situation, disperse red 1 (DR1) molecules were dispersed in a sol-gel germanium/Ormosil organic-inorganic hybrid matrix. Z-scan measurement results showed a good compatibility between the dopant and the matrix, and also, an improved FOM was obtained as compared to the DR1/polymer films reported previously. To demonstrate the all-optical signal processing effect, a cw Nd:YAG laser emitting at 532 nm and a He-Ne laser emitting at 632.8 nm were used as pump and probe beams, respectively. DR1 acts as an initiator of the photo-induced transient holographic grating, which is attributed to the trans-cis-trans photoisomerization. Thus, a three inputs AND all-optical logic gate was achieved by using choppers with different frequencies. The detailed mechanism of operation is discussed. These results indicate that the DR1 doped germanium/Ormosil organic-inorganic hybrid film with an improved FOM has a great potential in all-optical devices around its main resonance.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Suppression of transient enhanced diffusion in sub-micron patterned silicon template by dislocation loops formation

We investigate the evolution of two dimensional transient enhanced diffusion (TED) of phosphorus in sub-micron scale patterned silicon template. Samples doped with low dose phosphorus with and without high dose silicon self-implantation, were annealed for various durations. Dopant diffusion is probed with plane-view scanning capacitance microscopy. The measurement revealed two phases of TED. Significant suppression in the second phase TED is observed for samples with high dose self-implantation. Transmission electron microscopy suggests the suppressed TED is related to the evolution of end of range defect formed around ion implantation sidewalls.

36 MATERIALS SCIENCE↗

The steady-state and transient electron transport within bulk zinc-blende indium nitride: The impact of crystal temperature and doping concentration variations

Within the framework of a semi-classical three-valley Monte Carlo electron transport simulation approach, we analyze the steady-state and transient aspects of the electron transport within bulk zinc-blende indium nitride, with a focus on the response to variations in the crystal temperature and the doping concentration. We find that while the electron transport associated with zinc-blende InN is highly sensitive to the crystal temperature, it is not very sensitive to the doping concentration selection. The device consequences of these results are then explored.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Field transients of coherent terahertz synchrotron radiation accessed via time-resolving and correlation techniques

Decaying oscillations of the electric field in repetitive pulses of coherent synchrotron radiation in the terahertz frequency range was evaluated by means of time-resolving and correlation techniques. Comparative analysis of real-time voltage transients of the electrical response and interferograms, which were obtained with an ultrafast zero-bias Schottky diode detector and a Martin-Puplett interferometer, delivers close values of the pulse duration. Consistent results were obtained via the correlation technique with a pair of Golay Cell detectors and a pair of resonant polarisation-sensitive superconducting detectors integrated on one chip. The duration of terahertz synchrotron pulses does not closely correlate with the duration of single-cycle electric field expected for the varying size of electron bunches. We largely attribute the difference to the charge density oscillations in electron bunches and to the low-frequency spectral cut-off imposed by both the synchrotron beamline and the coupling optics of our detectors.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Level crossings, excess times, and transient plasma–wall interactions in fusion plasmas

Based on a stochastic model for intermittent fluctuations in the boundary region of magnetically confined plasmas, an expression for the level crossing rate is derived from the joint distribution of the process and its derivative. From this the average time spent by the process above a certain threshold level is obtained. This provides novel predictions of plasma–wall interactions due to transient transport events associated with a radial motion of blob-like structures in the scrape-off layer.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Communication: XUV transient absorption spectroscopy of iodomethane and iodobenzene photodissociation

Time-resolved extreme ultraviolet (XUV) transient absorption spectroscopy of iodomethane and iodobenzene photodissociation at the iodine pre-N{sub 4,5} edge is presented, using femtosecond UV pump pulses and XUV probe pulses from high harmonic generation. For both molecules the molecular core-to-valence absorption lines fade immediately, within the pump-probe time-resolution. Absorption lines converging to the atomic iodine product emerge promptly in CH{sub 3}I but are time-delayed in C{sub 6}H{sub 5}I. We attribute this delay to the initial π → σ{sup *} excitation in iodobenzene, which is distant from the iodine reporter atom. We measure a continuous shift in energy of the emerging atomic absorption lines in CH{sub 3}I, attributed to relaxation of the excited valence shell. An independent particle model is used to rationalize the observed experimental findings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗