Experimental and Computational Study of the Thermal Decomposition of 3‐Methyl‐3‐buten‐1‐ol in m‐Xylene Solution

An experimental study of the thermal decomposition of a β‐hydroxy alkene, 3‐methyl‐3‐buten‐1‐ol, in m‐xylene solution, has been carried out at five different temperatures in the range of 513.15–563.15 K. The temperature dependence of the rate constants for the decomposition of this compound in the corresponding Arrhenius equation is given by ln k (s^?1) = (25.65 ± 1.52) ? (17,944 ± 814) (kJ·mol^?1)·T^?1. A computational study has been carried out at the M05–2X/6–31+G(d,p) level of theory to calculate the rate constants and the activation parameters by the classical transition state theory. There is a good agreement between the experimental and calculated rate constants and activation Gibbs energies. The bonding characteristics of reactant, transition state, and products have been investigated by the natural bond orbital analysis, which provides the natural atomic charges and the Wiberg bond indices. Based on the results obtained, the mechanism proposed is a one‐step process proceeding through a six‐membered cyclic transition state, being a concerted and slightly asynchronous process. The results have been compared with those obtained previously by us (Struct Chem 2013, 24, 1811–1816) for the thermal decomposition of 3‐buten‐1‐ol, in m‐xylene solution. We can conclude that in the compound studied in this work, 3‐methyl‐3‐buten‐1‐ol, the effect of substitution at position 3 by a weakly activating CH₃ group is the stabilization of the transition state formed in the reaction and therefore a small increase in the rate of thermal decomposition.     

Structural and Kinetic Aspects of Blood Plasma Protein Adsorption on the Surface of Hydrophobic Polymers

Abstract

Due to the wide use of polymers in medicine, researchers are required to solve a very important problem–to understand the interaction between materials of nonphysiological origin and the surrounding biological liquids, and tissues, particularly blood.     

Time-resolved X-ray spectrometry of UV laser produced plasmas

Preliminary experiments using an X-ray streak filter spectrometer employing a Au/CsI bifurcated photocathode to investigate the X-ray history of UV (350 nm) laser produced plasmas are reported. Novel use of the streak spectrometer permits a direct and precise fiducial record of the laser pulse to be made from specularly scattered laser light, in true streak time relative to the X-ray record. Initial data indicates a constant 700 eV temperature during the laser pulse; time-resolved particulars are compared to simulations made by the design code LILAC.     

Effects of nonuniform illumination on implosion asymmetry in direct-drive inertial confinement fusion

Target areal density (rhoR) asymmetries in OMEGA direct-drive spherical implosions are studied. The rms variation / for low-mode-number structure is approximately proportional to the rms variation of on-target laser intensity / with an amplification factor of approximately 1/2(C(r)-1), where C(r) is the capsule convergence ratio. This result has critical implications for future work on the National Ignition Facility as well as OMEGA.     

Time-dependent electron thermal flux inhibition in direct-drive laser implosions

We simulate direct-drive CH target implosions with square laser pulses by a one-dimensional Fokker-Planck solver combined with a hydrodynamic code, and compare the results with those simulated by the flux-limited Spitzer-H?rm model. We find that the electron thermal flux inhibition is time dependent, resulting in longer density scale length, larger laser absorption, and smaller growth of Rayleigh-Taylor instability. The time of peak neutron production calculated from Fokker-Planck simulations agrees with experiments for both 1-ns and 400-ps pulses.     

Progress in direct-drive inertial confinement fusion research at the laboratory for laser energetics

Direct-drive inertial confinement fusion (ICF) is expected to demonstrate high gain on the National Ignition Facility (NIF) in the next decade and is a leading candidate for inertial fusion energy production. The demonstration of high areal densities in hydrodynamically scaled cryogenic DT or D₂ implosions with neutron yields that are a significant fraction of the “clean” 1-D predictions will validate the ignition-equivalent direct-drive target performance on the OMEGA laser at the Laboratory for Laser Energetics (LLE). This paper highlights the recent experimental and theoretical progress leading toward achieving this validation in the next few years. The NIF will initially be configured for X-ray drive and with no beams placed at the target equator to provide a symmetric irradiation of a direct-drive capsule. LLE is developing the “polar-direct-drive” (PDD) approach that repoints beams toward the target equator. Initial 2-D simulations have shown ignition. A unique “Saturn-like” plastic ring around the equator refracts the laser light incident near the equator toward the target, improving the drive uniformity. LLE is currently constructing the multibeam, 2.6-kJ/beam, petawatt laser system OMEGA EP. Integrated fast-ignition experiments, combining the OMEGA EP and OMEGA Laser Systems, will begin in FY08.     

A simple method for extracting both active oily and water soluble extract (WSE) from Nigella sativa (L.) seeds using a single solvent system

The current study provides a way of extraction for both active NSO and WSE from Nigella sativa seeds using 98% methanol. About 1?kg of ground seeds was macerated by 1:2.5 w/v (g/mL) for 72?hours. After rotary evaporation and 7 days of continuous drying and chilling at 50 and 4?°C, NSO and WSE were obtained at the same instant. Solubility tests of 24 solvents and 11 thin layer chromatographic analyses while 2, 2-diphenyl-1-picrylhydrazyl free radical scavenging assay of NSO (73.66) , WSE (33.32) and NSO?+?WSE (78.22) against ascorbic acid (IC50?=?4.28?mg/mL) was performed. WSE was found to be highly soluble in water and 5% NaOH exhibiting the same Rf value of 0.95 for EtOH:DMSO (9:1) against the honey. WSE has revealed more than twofold higher anti-oxidant activity than others. Formulation of WSE with Tualang honey may provide better targeted hydrophilic drug delivery systems.