Optical Kerr effect in supercooled water

We present molecular dynamics simulations of the optical Kerr effect in liquid and supercooled water and compare with recent time-resolved Kerr spectroscopy measurements [R. Torre, Nature (London) 428, 296 (2004)]. The short time features of the Kerr response, characterized by peaks near 15, 60, and 160 fs, are weakly temperature dependent. The long-time decay is well described by a stretched exponential with a nearly constant stretch parameter and relaxation times that follow a power law approximately (T-T(S))(-gamma), with T(S)=198.3 K and gamma=2.35. Our findings are discussed in the light of the spectroscopy data and previous simulation analyzes of the structural relaxation in supercooled water.     

Possible one-dimensional 3He quantum fluid formed in nanopores

Heat capacity measurements have been made down to 5 mK for 3He fluid films adsorbed in one-dimensional (1D) nanometer-scale pores, 28 A in diameter, preplated with 4He of 1.47 atomic layers. At low 3He density, the heat capacity shows a density-dependent, Schottky-like peak near 150 mK asymptoting to the value corresponding to a 2D Boltzmann gas at high temperatures. The peak behavior is attributed to the crossover from a 2D gas to a 1D state at low temperatures. The degenerate state of the 1D 3He fluid is indicated by a predominantly linear temperature dependence below about 30 mK.     

Determination of molecular parameters for 1,3-butadiene and propylene using infrared tunable diode laser absorption spectroscopy

A technique has been developed for the determination of molecular parameters, including infrared absorption line positions, strengths, and nitrogen-broadened half-widths for 1,3-butadiene (C(4)H(6)) and propylene (C(3)H(6)). The parameters for these two molecules are required for quantitation using Tunable Diode Laser Absorption Spectroscopy (TDLAS). These molecules have populations of highly overlapping infrared absorption lines in their room temperature spectra. The technique reported here provides a procedure for estimating the molecular parameters for these overlapping absorption lines from quantitative reference spectra taken with the TDLAS instrument at different pressures and concentrations. The system was developed for the quantitation of gaseous constituents in a single puff of cigarette smoke and this paper will describe the procedure and some of the factors that influence the accuracy of quantitation for 1,3-butadiene, including the approach taken to minimize the adverse effects of the absorption due to propylene in the same spectral region.     

Quad quantum cascade laser spectrometer with dual gas cells for the simultaneous analysis of mainstream and sidestream cigarette smoke

A compact, fast response, infrared spectrometer using four pulsed quantum cascade (QC) lasers has been applied to the analysis of gases in mainstream (MS) and sidestream (SS) cigarette smoke. QC lasers have many advantages over the traditional lead-salt tunable diode lasers, including near room temperature operation with thermoelectric cooling and single mode operation with improved long-term stability. The new instrument uses two 36 m, 0.3 l multiple pass absorption gas cells to obtain a time response of 0.1s for the MS smoke system and 0.4s for the SS smoke system. The concentrations of ammonia, ethylene, nitric oxide, and carbon dioxide for three different reference cigarettes were measured simultaneously in MS and SS smoke. A data rate of 20Hz provides sufficient resolution to determine the concentration profiles during each 2s puff in the MS smoke. Concentration profiles before, during and after the puffs also have been observed for these smoke constituents in SS smoke. Also, simultaneous measurements of CO(2) from a non-dispersive infrared (NDIR) analyzer are obtained for both MS and SS smoke. In addition, during this work, nitrous oxide was detected in both the MS and SS smoke for all reference cigarettes studied.     

Design and synthesis of organochalcogen (Se or Te) based multifunctional derivatives: structural determination and dynamic behavior of 2-chloro-4,6-bis(phenylselenoethylamino)-1,3,5-triazines

A novel class of multifunctional and multinucleate chalcogen (selenium and tellurium) containing derivatives (1-10) has been developed based on sequential chloride substitution of 2,4,6-trichloro-1,3,5-triazine with chalcogen-bearing amines. The structure of compound 1 has been determined in the solid state by X-ray crystallography.     

Dynamic nuclear polarization studies of nitroxyl spin probes in agarose gel using Overhauser‐enhanced magnetic resonance imaging

Agarose is a tissue‐equivalent material and its imaging characteristics similar to those of real tissues. Hence, the dynamic nuclear polarization studies of 3‐carboxy‐2,2,5,5‐tetramethyl‐pyrrolidine‐1‐oxyl (carboxy‐PROXYL) in agarose gel were carried out. The dynamic nuclear polarization parameters such as spin lattice relaxation time, longitudinal relaxivity, leakage factor, saturation parameter and coupling parameter were estimated for 2 mM carboxy‐PROXYL in phosphate‐buffered saline solution and water/agarose mixture (99 : 1). From these results, the spin probe concentration was optimized as 2 mM, and the reduction in enhancement was observed for carboxy‐PROXYL in water/agarose mixture (99 : 1) compared with phosphate‐buffered saline solution. Phantom imaging was also performed with 2 mM concentration of carboxy‐PROXYL in various concentrations of agarose gel at various radio frequency power levels. The results from the dynamic nuclear polarization measurements agree well with the phantom imaging results. These results pave the way for designing model system for human tissues suited to the biological applications of electron spin resonance/Overhauser‐enhanced magnetic resonance imaging.     

The crystal and molecular structure of 9-methylphenanthro[4,3-a]dibenzothiophene

The crystal structure of 9-methylphenanthro[4,3-a]dibenzothiophene, C₂₅H₁₆S, M_r = 348.47, has been determined. Monoclinic, P2₁/c, a = 11.364(3), b, = 14.257(3), c = 11.575(2)Å, β = 116.26(2)°, V = 1681.9(7)ų, Z = 4, D_x = 1.38 g/cc, MoKα radiation λ = .71069 Å, F(000) = 728, T = 163K, R = .0458 for 2330 reflections. The structure compares favorably with that of hexahelicene and methylated derivatives. The thiophene moiety increases the helical core radius and decreases the pitch with respect to hexahelicene and its derivatives.     

A new controlled release system of chlorhexidine and chlorhexidine:βcd inclusion compounds based on porous silica

The purpose of this study was to prepare and characterize a controlled release system based on porous silica loaded with chlorhexidine (Cx) and its inclusion compounds in β-cyclodextrin (βcd), and to evaluate its antimicrobial activity. Acetate chlorhexidine (CxA), gluconate chlorhexidine (CxG), βcd:chlorhexidine acetate 2:1 (βcd:CxA) and βcd:chlorhexidine gluconate 2:1 (βcd:CxG) were incorporated into porous silica. Drug loading was characterized by FTIR, powder X-ray diffraction, thermal analysis and BET, and was shown to be in an amorphous state and porous matrix. The kinetics release parameter of the drug was established, which showed that the Cx systems release profile followed zero order release until 400 h and Higuchi model release until 750 h, after the burst effect at the first 8 h. Chlorhexidine therapeutic range was reached near first hour for all systems. The chlorhexidine porous silica system was biologically active against Enterococcus faecalis and Candida albicans in vitro. The systems showed an efficient Cx controlled release modulated by the presence of the β-cyclodextrin and by the porous silica matrices, providing effective antimicrobial activity.