The potential of pyrolysis/gas chromatography/mass spectrometry for determining the progress of lignification: An investigation of maturing asparagus sclerenchyma tissue

Sclerenchyma tissues from semi-mature and mature asparagus spears were analysed by pyrolysis/gas chromatography/mass spectrometry and by conventional chemical methods in order to determine the degree of lignification and compare analytical techniques. The pyrolysis data are similar to those obtained by a chemical method involving alkaline extraction at 70°C followed by spectrophotometric determination of phenolic content. The pyrolysis method was more rapid, sensitive and informative than the chemical technique and shows considerable potential for studying the chemical basis of the textural development of plant foods.     

Fluctuation conductivity in superconducting MgB2

According to the crystal structure of MgB₂ and band structure calculations, quasi-two-dimensional (2D) boron planes are responsible for the superconductivity. We report on critical-field and resistance measurements of 5.6-μm-thick MgB₂ films grown on a sapphire single-crystal substrate. Resistivity measurements yield a temperature dependence of the fluctuation conductivity above the critical temperature, which agrees with the Aslamazov-Larkin and Maki-Thompson theory of fluctuations in layered superconductors, indicating a quasi-two-dimensional nucleation of superconductivity in MgB₂.     

Pretransitional electro-optic response of 6CB liquid crystal in the isotropic phase

In this work, the electro-optic response of a 6CB liquid crystal layer is studied using a sensitive differential technique. The layer is held at a temperature just above the nematic to isotropic phase transition. Transverse magnetic (p) polarized light incident on the cell is coupled to guided modes in the liquid crystal layer using prism coupling. The modes manifest themselves as sharp dips in the reflectivity as the angle of incidence is scanned. When a low frequency sinusoidal voltage is applied to the cell, the resonant mode shapes and excitation angles are altered at a frequency which is twice that of the applied field, resulting in a modulation of the reflectivity for a given angle of incidence. By synchronous observation of the modulated signal, a differential signal is recorded. Comparing the data with modelling generated from multilayer optics theory, two effects are then quantified. The first of these is an induced birefringence, varying quadratically with applied voltage, which is well understood and can be expressed in terms of Landau-de Gennes theory. The second is a field induced perturbation in the imaginary part of the optical permittivity, δε_i, which implies a modification of the light scattering properties of the liquid crystal. The measurement of the latter effect is, as far as we know, a novel one, being only made possible by the remarkable sensitivity of the synchronous differential technique.     

Metal–Nitrosyl complexes as a source of new vasodilators: Strategies derived from systematic chemistry and nitrosyl ligand reactivity

A series of nitrosyl complexes of empirical formula K_n[M(CN)₅NO], where M = V, Cr, Mn and Co and n = 3, or M = Mo and n = 4, have been prepared which are notional analogues of the widely used vasodilator sodium nitroprusside. Their reactivity towards common nucleophiles (OH^?, NH₂R, NHR₂, HS^? and RS^?), acid and photolysis has been investigated to elucidate the desired properties required of new metal nitrosyls which may have some potential as new non-cyanide-based vasodilators.     

Working Methods Paper: Critical considerations with respect to the identification of tin species in the environment

Biogeochemical pathways of tin species in the environment are still controversial, e.g. with regard to methylation and transmethylation phenomena, owing to the fact that the identification of methylated tin-compounds is often difficult. The previous tentative identification of a mixed methylbutyltin compound in sediment and biological samples by GC/AAS after hydride generation gave an illustration of this problem. This compound was previously identified in sediments by other authors and also suspected to occur in a contaminated sediment sample from the Boyardville Marina, France. The retention time obtained by GC/AAS corresponded to the actual retention time of a mixed methylbutyltin calibrant. However, additional checks demonstrated that the compound detected was actually monophenyltin. This evidence was produced by a thorough analysis of a selected sediment sample by alternative techniques such as GC/AAS and GC/AES after pentylation, GC/FPD and GC/MS. The results presented highlight the need for a full identification of compounds to avoid mis-interpretation.     

Kinetic model for hydrocarbon-assisted particulate boron combustion

A kinetic model is presented to describe the high temperature (1800 K < T < 3000 K) surface oxidation of particulate boron in a hydrocarbon combustion environment. The model includes a homogeneous gas-phase B/O/H/C oxidation mechanism consisting of 19 chemical species and 58 forward and reverse elementary reactions, multi-component gas-phase diffusion, and a heterogeneous surface oxidation mechanism consisting of ‘elementary’ adsorption and desorption reaction steps. Thermochemical and kinetic parameters for the surface reactions are estimated from available experimental data and/or elementary transition state arguments. The kinetic processes are treated using a generalized kinetics code, with embedded sensitivity analysis, for the combustion of a one-dimensional (particle radius), spherical particle. Model results are presented for the oxidation of a 200 μm boron particle in a JP-4/air mixture at ambient temperatures of 1400 K and 2000 K. These results include temperature and gas-phase species profiles as a function of radial distance and particle burning rates. © 1994 John Wiley & Sons, Inc.     

Kinetics of solvolysis of 2-chloroquinoxaline

Pseudo-first-order rate constants and activation parameters have been measured for the solvolysis of 2-chloroquinoxaline in various aquo-organic mixtures using methanol, ethanol, and isopropanol as the organic solvent. Excellent linear correlations are found between lnk and the mol fraction of cosolvent and ln[H₂O]. The medium effect on the rates of solvolysis is assessed by Grunwald–Winstein's mY correlationship. The estimated values of m (0.55–0.72) and the entropy of activation (148–212 J deg^?1 mol^?1) for the reactions are well in the range for a bimolecular aromatic substitution reactions. © 1994 John Wiley & Sons, Inc.