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At least 1,495 records · Page 83

Time-resolved multiple probe spectroscopy

Time-resolved multiple probe spectroscopy combines optical, electronic, and data acquisition capabilities to enable measurement of picosecond to millisecond time-resolved spectra within a single experiment, using a single activation pulse. This technology enables a wide range of dynamic processes to be studied on a single laser and sample system. The technique includes a 1 kHz pump, 10 kHz probe flash photolysis-like mode of acquisition (pump-probe-probe-probe, etc.), increasing the amount of information from each experiment. We demonstrate the capability of the instrument by measuring the photolysis of tungsten hexacarbonyl (W(CO){sub 6}) monitored by IR absorption spectroscopy, following picosecond vibrational cooling of product formation through to slower bimolecular diffusion reactions on the microsecond time scale.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

The role of electron-electron interaction in the process of charge-carrier capture in deep quantum wells

The role of electron-electron interaction in the process of electron capture to a deep quantum well is investigated. Using two-level and three-level quantum wells as examples, the basic electron-capture mechanisms, i.e., the interaction with optical phonons and the Coulomb electron-electron interaction, are considered, and the corresponding capture probabilities and electron lifetimes are calculated. The effect of Auger recombination on the charge-carrier distribution in a quantum well is also taken into account. With this taken into consideration, a set of rate equations is solved for a nonsteady-state mode, and the time dependences of the electron concentration at the ground energy level in the quantum well are found. The contributions of each of the recombination processes under consideration are shown.

74 ATOMIC AND MOLECULAR PHYSICS↗

Combustion of Metals in Reduced-Gravity and Extraterrestrial Environment

As a result of the ongoing exploration of Mars and the several unmanned and manned missions planned for the future, increased attention has been given to the use of the natural resources of the planet for rocket propellant production and energy generation. Since the atmosphere of Mars consists of approximately 95% carbon dioxide (CO2), this gas is the resource of choice to be employed for these purposes. Unfortunately, CO2 is also a final product in most combustion reactions, requiring further processing to extract useful reactants such as carbon monoxide (CO), oxygen (O2), and hydrocarbons. An exception is the use Of CO2 as an oxidizer reacting directly with metal fuel. Since many metals burn vigorously with CO2, these may be used as an energy source and as propellants for an ascent/descent vehicle in sample-collection missions on Mars. In response to NASA's Human Exploration and Development of Space (HEDS) Enterprise to search for appropriate in-situ resource utilization techniques, this investigation will study the burning characteristics of promising metal/CO2 combinations. The use of reduced gravity is essential to eliminate the intrusive buoyant flows that plague the high-temperature metal reactions, to remove the destructive effect of gravity on the shape of molten metal samples, and to study the influence of radiative heat transfer from solid oxides undisturbed by natural convection. In studies with large metal specimens, the burning process is invariably influenced by strong convective currents that accelerate the reaction and shorten the burning times. Although these currents are nearly absent from small burning particles, the high emissivity of the flames, rapid reaction, small length scales, and intermittent explosions make the gathering of any useful information on burning rates and flame structure very difficult. This investigation has the ultimate goal of providing a careful probing of flame structure and dynamics by taking advantage of large, free-floating spherical metal samples and their corresponding long burning times available in reduced gravity. The first set of experiments has been conducted with magnesium (Mg) samples burning in the low-gravity environment generated by an aircraft flying parabolic trajectories. Owing to its high adiabatic flame temperature, oxidizer/fuel ratio, and heat per unit mass of fuel, as well as its low toxicity and low ignition temperature, Mg has been identified as a promising metal fuel with CO2 as oxidizer. The experimental effort is complemented by the development of a numerical model combining gas-phase chemical kinetics and transport mechanisms.

Abbud-Madrid, A.↗

Almost medium-free measurement of the Hoyle state direct-decay component with a TPC

The structure of the Hoyle state, a highly α -clustered state at 7.65 MeV in 12 C, has long been the subject of debate. Understanding if the system comprises of three weakly interacting α particles in the 0s orbital, known as an α-condensate state, is possible by studying the decay branches of the Hoyle state. The direct decay of the Hoyle state into three α particles, rather than through the 8 Be ground state, can be identified by studying the energy partition of the three α particles arising from the decay. This paper provides details on the breakup mechanism of the Hoyle stating using a new experimental technique. Method: By using β-delayed charged-particle spectroscopy of 12 N using the Texas active target time-projection chamber, a high-sensitivity measurement of the direct 3α decay ratio can be performed without contributions from pileup events. A Bayesian approach to understanding the contribution of the direct components via a likelihood function shows that the direct component is <0.043% at the 95% confidence level. This value is in agreement with several other studies, and, here, we can demonstrate that a small nonsequential component with a decay fraction of about 10 –4 is most likely. Here, the measurement of the non-sequential component of the Hoyle state decay is performed in an almost medium-free reaction for the first time. The derived upper limit is in agreement with previous studies and demonstrates sensitivity to the absolute branching ratio. Further experimental studies would need to be combined with robust microscopic theoretical understanding of the decay dynamics to provide additional insight into the idea of the Hoyle state as an α condensate.

6 ≤ A ≤ 19↗

Photodissociation of gaseous CH{sub 3}COSH at 248 nm by time-resolved Fourier-transform infrared emission spectroscopy: Observation of three dissociation channels

Upon one-photon excitation at 248 nm, gaseous CH{sub 3}C(O)SH is dissociated following three pathways with the products of (1) OCS + CH{sub 4}, (2) CH{sub 3}SH + CO, and (3) CH{sub 2}CO + H{sub 2}S that are detected using time-resolved Fourier-transform infrared emission spectroscopy. The excited state {sup 1}(n{sub O}, {pi}{sup *}{sub CO}) has a radiative lifetime of 249 {+-} 11 ns long enough to allow for Ar collisions that induce internal conversion and enhance the fragment yields. The rate constant of collision-induced internal conversion is estimated to be 1.1 Multiplication-Sign 10{sup -10} cm{sup 3} molecule{sup -1} s{sup -1}. Among the primary dissociation products, a fraction of the CH{sub 2}CO moiety may undergo further decomposition to CH{sub 2}+ CO, of which CH{sub 2} is confirmed by reaction with O{sub 2} producing CO{sub 2}, CO, OH, and H{sub 2}CO. Such a secondary decomposition was not observed previously in the Ar matrix-isolated experiments. The high-resolution spectra of CO are analyzed to determine the ro-vibrational energy deposition of 8.7 {+-} 0.7 kcal/mol, while the remaining primary products with smaller rotational constants are recognized but cannot be spectrally resolved. The CO fragment detected is mainly ascribed to the primary production. A prior distribution method is applied to predict the vibrational distribution of CO that is consistent with the experimental findings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stability of Actinolite on Venus

Venus currently has a hostile surface environment with temperatures of ~460 ºC, pres-sures near 92 bars, and an atmosphere composed of super critical CO2 hosting a myriad of other potentially reactive gases (e.g., SO2, HCl, HF). However, it has been proposed that its surface may not have always been so harsh. Models suggest there may have been billions of years of clement conditions allowing an Earth-like environment with liquid water oceans. If such conditions existed, it is possible Venus formed a similar array of hydrous or aqueous minerals as seen on other planets with liquid surface water (e.g., Mars, Earth). Based on thermodynamic modeling, many of these phases would not be stable under the current atmospheric conditions on Venus, dehydrating due to the high temperatures and low concentration of H2O in the atmosphere. However, the rate of decomposition of these phases may allow them to remain present on the surface over geologic time. For example, experiments on the reaction rate of tremolite (Ca2Mg5Si8O22(OH)2) show a 50% decomposition time of 2.7 Gyr for micrometer sized grains in unreactive atmospheres (i.e., without SO2) at 740 K, and a 50% decomposition time of 70 Gyr for crystals several millimeters to centimeters in size. If hydrous minerals can remain on the surface of Venus over geologic time, it has implications for our detection of evidence of these past environments, and also for the overall water budget of the planet. If after surficial dehydration the planet was able to still store water in its crust, possible processes such as subduction or metamorphism could still have operated using stored water long after liquid surface water evaporated. Several previous studies have focused on experimental investigations of mineral stability on Venus. In particular, the works of studied the decomposition rate of tremolite under conditions relevant to Venus. As their focus was on decomposition of the mineral due to lack of water in the atmosphere, their experiments were undertaken using only CO2 or N2 gas at atmospheric pressure. Re-cent experiments have examined reactivity of other minerals with the Venusian atmosphere using more complex gas compositions at similar pressures to those seen on Venus. These studies show reaction of silicate minerals with atmospheric components on relatively short timescales (i.e., on the order of days). The reported reactions of silicate materials in both studies produced iron oxides, Ca sulfates, and Na sulfates. These ions are present in many amphiboles, and Ca was proposed by Johnson and Fegley to potentially have an important role in the decomposition mechanism for tremolite, with the Ca-O bond being the first to break during decomposition. The potential involvement of Ca in both processes raises the question of whether or not the reaction to form a secondary mineral phase will influence the rate of amphibole break-down (e.g., discussion in for tremolite). Additionally, reaction of Ca with atmospheric gases may result in a different secondary mineral assemblage than simple amphibole decomposition, which will need to be recognized when searching for evidence of past hydrated minerals on the Venusian surface. In order to understand the effect of this reaction on the overall preservation potential of amphibole on the surface of Venus, we are conducting experiments in both reactive and nonreactive atmospheres using the mineral actinolite (Ca2(Mg,Fe)5Si8O22(OH)2), an amphibole with similar crystal structure to tremolite that contains both Ca and Fe.

Santos, A. R.↗

Microscale Colocalization of Cascade Enzymes Yields Activity Enhancement

Colocalization of cascade enzymes is broadly discussed as a phenomenon that can boost the cascade reaction throughput, although a direct experimental verification is often challenging. This is mainly due to difficulties in establishing proper size regimes and in the analytical quantification of colocalization effect with adequate experimental systems and simulations. In this study, by taking advantage of reversible DNA-directed colocalization of enzymes on microspheres, we established a cascade system that can be used to directly evaluate the colocalization effect with exactly the same experimental settings except for the state of enzyme dispersion. In the regime of highly dilute microspheres of particular sizes, the colocalized cascade shows enhanced activity compared with the freely diffusing cascade, as evidenced by a shortened lag phase in the time-course production. Reaction-diffusion modeling reveals that the enhancement can be ascribed to the initial accumulation of intermediate substrate around the colocalized enzymes and is found to be carrier-size-dependent. Further, this work demonstrates the dependence of the colocalization effect of enzyme cascades on an interplay of nano-and microscales, lending theoretical support to the rational design of highly efficient multienzyme catalysts.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Fast imaging of intact and shattered cryogenic neon pellets

Compact condensed-matter injection technologies are increasingly used in magnetic fusion. One recent application is in disruption mitigation. An imaging system with less-than-100-µm- and sub-µs-resolution is described and used to characterize intact and shattered cryogenic neon pellets. Shattered pellets contain fine particles ranging from tens of µm to about 7 mm. Time-of-flight analyses indicate that pellets could slow down if hitting the wall of the guide tube. Fast high-resolution imaging systems are thus useful to neon and other condensed-matter injector development.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Multiply accelerated ReaxFF molecular dynamics: coupling parallel replica dynamics with collective variable hyper dynamics

To address the time scales required to study complex chemical reactions, methods performing accelerated molecular dynamics are necessary even with the recent advancement in high-performance computing. A number of different acceleration techniques are available. Here we explore potential synergies between two popular acceleration methods – Parallel Replica Dynamics (PRD) and Collective Variable Hyperdynamics (CVHD), by analysing the speedup obtained for the pyrolysis of n-dodecane. We determine that PRD + CVHD provides additional speedup to CVHD by reaching the required time scales for the reaction at an earlier wall-clock time. Although some speedup is obtained with the additional replicas, we found that the effectiveness of the inclusion of PRD is depreciated for systems where there is a dramatic increase in reaction rates induced by CVHD. Similar observations were made in the simulation of ethylene-carbonate/Li system, which is inherently more reactive than pyrolysis, suggest that the speedup obtained via the combination of the two acceleration methods can be generalised to most practical chemical systems.

42 ENGINEERING↗

Time-dependent resonant UHF CI approach for the photo-induced dynamics of the multi-electron system confined in 2D QD

We extend the static multi-reference description (resonant UHF) to the dynamic system in order to include the correlation effect over time, and simplify the TD Schrödinger equation (TD-CI) into a time-developed rate equation where the TD external field Ĥ′(t) is then incorporated directly in the Hamiltonian without any approximations. We apply this TD-CI method to the two-electron ground state of a 2D quantum dot (QD) under photon injection and study the resulting two-electron Rabi oscillation.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Enhanced charge separation ability and visible light photocatalytic performance of graphitic carbon nitride by binary S, B co-doping

Highlights: • S, B hertroatoms were successfully doped into g-C{sub 3}N{sub 4} by thermal treatment. • S, B heteroatoms effectively change the intrinsic electronic structure of g-C{sub 3}N{sub 4}. • The SBCN shows much higher photocatalytic activity than CN, SCN and BCN. • The SBCN has high photocatalytic stability and reusability. - Abstract: As a metal-free visible light photocatalyst, the photocatalytic performance of graphitic carbon nitride (g-C{sub 3}N{sub 4}) is limited. To improve the activity of g-C{sub 3}N{sub 4}, we herein report a binary S, B co-doped g-C{sub 3}N{sub 4} (SBCN) by thermally treating the precursor mixture of thiourea, melamine and boron oxide. Characterization results show the obtained SBCN has ultrathin sheet-like morphology and these doped heteroatoms are uniform distributed in the sample. Compared to the pristine g-C{sub 3}N{sub 4}, the SBCN has a small band gap with additional absorption in visible light region, decreased photoluminescence emission and electric resistance and enhanced photocurrent response. These advantages endue SBCN with excellent photocatalytic activity for degradation of organic dyes, and its reaction rate is 6.5 times higher than that of the g-C{sub 3}N{sub 4}. Moreover, the successive cycles demonstrate that this SBCN possesses a superior stability and reusability. Finally, we propose a possible photocatalytic mechanism based on the band structure and mainly active species.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

The stopped-drop method: a novel setup for containment-free and time-resolved measurements

A novel setup for containment-free time-resolved experiments at a free-hanging drop is reported. Within a dead-time of 100 ms a drop of mixed reactant solutions is formed and the time evolution of a reaction can be followed from thereon by various techniques. As an example, a small-angle X-ray scattering study on the formation mechanism of EDTA-stabilized CdS both at a synchrotron and a laboratory X-ray source is presented here. While the evolution can be followed with one drop only at a synchrotron source, a stroboscopic mode with many drops is preferable for the laboratory source.

containment-free↗

Stabilization of the Active Ruthenium Oxycarbonate Phase for Low-Temperature CO 2 Methanation

Interstitial carbon-doped RuO 2 catalyst with the newly reported ruthenium oxycarbonate phase is a key component for low-temperature CO 2 methanation. However, a crucial factor is the stability of interstitial carbon atoms, which can cause catalyst deactivation when removed during the reaction. In this work, the stabilization mechanism of the ruthenium oxycarbonate active phase under reaction conditions is studied by combining advanced operando spectroscopic tools with catalytic studies. Three sequential processes: carbon diffusion, metal oxide reduction, and decomposition of the oxycarbonate phase and their influence by the reaction conditions, are discussed. We present how the reaction variables and catalyst composition can promote carbon diffusion, stabilizing the oxycarbonate catalytically active phase under steady-state reaction conditions and maintaining catalyst activity and stability over long operation times. In addition, insights into the reaction mechanism and a detailed analysis of the catalyst composition that identifies an adequate balance between the two phases, i.e., ruthenium oxycarbonate and ruthenium metal, are provided to ensure an optimum catalytic behavior.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rate constants for H abstraction from benzo(a)pyrene and chrysene: a theoretical study

Density functional B3LYP/6-31G(d) and ab initio G3(MP2,CC) calculations have been carried out to determine thermal rate constants of direct H abstraction reactions from four- and five-ring polycyclic aromatic hydrocarbons (PAH) chrysene and benzo[a]pyrene by various radicals abundant in combustion flames, such as H, CH 3 , C 3 H 3 , and OH, using transition state theory. The results show that the H abstraction reactions with OH have the lowest barriers of ~4 kcal mol -1 , followed by those with H and CH 3 with barriers of 16–17 kcal mol -1 , and then with propargyl radicals with barriers of 24–26 kcal mol -1 . Thus, the OH radical is predicted to be the fastest H abstractor from PAH. Even at 2500 K, the rate constant for H abstraction by H is still 34% lower than the rate constant for H abstraction by OH. The reaction with H is calculated to have rate constants 35–19 times higher than those for the reaction with CH 3 due to a more favorable entropic factor. The reactions of H abstraction by C 3 H 3 are predicted to be orders of magnitude slower than the other reactions considered and their equilibrium is strongly shifted toward the reactants, making propargyl an inefficient H abstractor from the aromatics. The calculations showed strong similarity of the reaction energetics in different H abstraction positions of benzo[a]pyrene and chrysene within armchair and zigzag edges in these molecules, but clear distinction between the armchair and zigzag sites. The zigzag sites appear to be more reactive, with H abstraction rate constants by H, CH 3 , and OH being respectively 37–42%, a factor of 2.1, and factors of 8–9 higher than the corresponding rate constants for the H abstraction reactions from armchair sites. Although the barrier heights for the two types of edges are similar, the entropic factor makes zigzag sites more favorable for H abstraction. Rate expressions have been generated for all studied reactions with the goal to rectify current combustion kinetics mechanisms.

Semenikhin, A. S.↗

Deciphering atomistic mechanisms of the gas-solid interfacial reaction during alloy oxidation

Gas-solid interfacial reaction is critical to many technological applications from heterogeneous catalysis to stress corrosion cracking. A prominent question that remains unclear is how gas and solid interact beyond chemisorption to form a stable interphase for bridging subsequent gas-solid reactions. Here, we report real-time atomic-scale observations of Ni-Al alloy oxidation reaction from initial surface adsorption to interfacial reaction into the bulk. We found distinct atomistic mechanisms for oxide growth in O 2 and H 2 O vapor, featuring a “step-edge” mechanism with severe interfacial strain in O 2 , and a “subsurface” one in H 2 O. Ab initio density functional theory simulations rationalize the H 2 O dissociation to favor the formation of a disordered oxide, which promotes ion diffusion to the oxide-metal interface and leads to an eased interfacial strain, therefore enhancing inward oxidation. Our findings depict a complete pathway for the Ni-Al surface oxidation reaction and delineate the delicate coupling of chemomechanical effect on gas-solid interactions.

36 MATERIALS SCIENCE↗

Integrated diagnostic analysis of inertial confinement fusion capsule performance

A conceptual model is developed for typical inertial confinement fusion implosion conditions that integrates available diagnostic information to determine the stagnation properties of the interior fill and surrounding shell. Assuming pressure equilibrium at peak compression and invoking radiative and equation-of-state relations, the pressure, density, and electron temperature are obtained by optimized fitting of the experimental output to smooth, global functional forms. Typical observational data that may be used includes x-ray self-emission, directional neutron time-of-flight signals, neutron yield, high-resolution x-ray spectra, and radiographic images. This approach has been validated by comparison with radiation-hydrodynamic simulations, producing semi-quantitative agreement. Model results implicate poor kinetic energy coupling to the hot core as the primary cause of the observed low thermonuclear burn yields.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

CD47 blockade enhances therapeutic efficacy of cisplatin against lung carcinoma in a murine model

Cisplatin (CDDP) is the first generation of platinum-based drug and is widely used to treat many cancers due to its potency. The present study aims to explore the effects of CDDP on lung carcinoma and its relationship with macrophage phagocytosis. In in vitro study, murine and human lung cancer cell lines were applied and treated with CDDP, CD47 antibody (aCD47), or CDDP plus aCD47. In in vivo study, a tumor xenograft animal model was treated with CDDP, aCD47, or CDDP plus aCD47. Real-time PCR was applied to determine the mRNA expressions. Enzyme-linked immunosorbent assay (ELISA), Western blotting, and Immunofluorescent staining were applied to determine the protein expressions. Flow cytometry was applied to analyze cell apoptosis, phagocytosis, and specific cell populations. CDDP enhanced the expressions of CD47 in lung cancer cells. Interestingly, the blockage of CD47 enhanced the macrophages' phagocytic activity on the CDDP-treated tumor cells. The treatment of CDDP and aCD47 exhibited anti-tumor effects and prolonged the LLC tumor-bearing mice survival time. Mechanistic studies revealed that the treatment of CDDP and aCD47 regulated the phagocytic activity of macrophage, percentage of CD8{sup +} T cells, and cytokines (tumor growth factor (TGF)-β, interleukin (IL)12p70, and interferon (IFN)-γ) in the tumor-bearing model. CD47 blockade enhanced therapeutic efficacy of cisplatin against lung carcinoma in vivo and in vitro.

60 APPLIED LIFE SCIENCES↗

In-situ monitoring of seeded and unseeded stage III corrosion using Raman spectroscopy

Abstract Stage III glass dissolution, the occasionally observed tendency for accelerated aqueous corrosion after extensive time spent at low reaction rates, is a major area of technical uncertainty in long-term glass performance modeling for vitreous nuclear waste forms. Stage III dissolution behavior is thought to be caused by the precipitation of zeolite phases that lower the activity of the rate-controlling orthosilicic acid ion and cause the acceleration of glass dissolution. The uncertainty lies mainly in a poor understanding of the growth kinetics of these key crystalline phases. It is particularly important to understand the impact of temperature and pH conditions on Stage III behavior. Accurate analysis of this phenomenon is complicated by the typically very long (e.g., years), and variable length of the induction period preceding the onset of Stage III behavior. In this study of a high-sodium aluminoborosilicate glass, we demonstrate the ability to initiate the onset of Stage III behavior in a controllable fashion so as to both reduce the time delay of the incubation period, and to also be able to initiate Stage III dissolution in controlled conditions. In this case, we demonstrate that Stage III glass corrosion behavior is possible at 70 °C, a lower temperature than previously observed (90 °C), even in an unseeded experiment. We confirm, through a comparison study, that seeded and unseeded Stage III corrosion rates are equivalent. This enables wide-scale testing of Stage III corrosion rates for many glass compositions in relatively short times through this technique. We also report further development of the use of in situ Raman spectroscopy monitoring of boron concentration and pH through simple and chemometric analysis methods.

36 MATERIALS SCIENCE↗