NMR investigations of hexamethyldisilane confined in controlled pore glasses: Pore size distribution and molecular dynamics studies

In this work, the melting-point depression and molecular dynamics of hexamethyldisilane confined within five controlled pore glasses, with mean diameters ranging from 7.9 to 23.9 nm, are studied by high-field (9.4 T) nuclear magnetic resonance (NMR), and the results are discussed with reference to the bulk substance. The melting-point depression in pores with radiusR follows the simplified Gibbs-Thompson equation ΔT=k _p/(R−s) with ak _p value of 74 K · nm and ans value of 1 nm. To our knowledge, this is the first time thek _p value of hexamethyldisilane is reported. Proton spin-lattice relaxation times (T ₁), spin-spin relaxation times (T ₂), and diffusivities (D) are reported as a function of temperature. The confinement in the pores gives rise to substantial changes in the molecular dynamics and the phase behavior. The line-shape measurements reveal a two-phase system assigned to a relatively mobile component at the pore walls and a crystalline solid at the center of the pores. However, theT ₂ measurements show that the mobile phase also embraces a minor component attributed to nonfrozen liquid in pockets or micropores. The diffusivity of the major narrow-line component is approximately three orders of magnitude larger than that in the plastic bulk phase, reflecting fast diffusion of mobile molecules. Below the melting region,T ₁ of the narrow line is significantly shorter thanT ₁ of the broad line, suggesting that the molecular reorientation is more hindered close to the surface than at the center of the pore.     

Combined supercritical-fluid chromatography/mass spectrometry in the analysis of diuron in plasma using on-line phase-system switching

On-line sample pretreatment by means of the phase-system switching approach is an interesting technique for the analysis of aqueous samples, e.g., plasma, by means of supercritical-fluid chromatography. In order to analyse plasma samples the following analytical procedure is used. The plasma sample is injected on to a short precolumn, which is washed with water and subsequently dried with nitrogen. Next, the solutes are desorbed with the supercritical mobile phase, analysed with packed-column supercritical-fluid chromatography and detected with either a UV detector or a mass spectrometer, equipped with a moving-belt interface. The herbicide diuron is selected as a test compound to study the feasibility of this approach. Using a selective detector the procedure is sufficiently sensitive to detect diuron in plasma, but not appropriate to detect the diuron metabolites in a post-mortem plasma sample. These have been identified with liquid chromatography/mass spectrometry. The detection limit of diuron in plasma using the procedure described is about 30 ng/mL.     

On the continuation for variational inequalities depending on an eigenvalue parameter

In this paper we generalize recent theoretical results on the local continuation of parameter-dependent non-linear variational inequalities. The variational inequalities are rather general and describe, for example, the buckling of beams, plates or shells subject to obstacles. Under a technical hypothesis that is satisfied by the simply supported beam, we obtain the existence of a continuation of both the solution and the eigenvalue with respect to a local parameter. A numerical continuation method is presented that easily overcomes turning points. Numerical results are presented for the non-linear beam.     

Photochemistry of trifluromethyl substituted 1‐methylpyrazoles

Trifluromethyl substitution on the pyrazole ring was found to enhance photoreactivity via the P₄ pathway which involves interchange of the N2‐C3 ring atoms. Thus, 1‐methyl‐3‐(trifluromethyl)pyrazole (1) and 1‐methyl‐5‐(trifluromethyl)pyrazole (3) transposed with a P₄/P₆ or P₄/P₆+P₇ ratio of 2.1:1. 1‐methyl‐4‐(trifluromethyl)pyrazole (2) transposed regiospecifically by the P₄ transposition pathway. Compounds 2 and 3 were also observed to undergo photocleavage to yield enaminonitrile and enaminoisocyanide products.     

The structure of CeAlO3 by Rietveld refinement of X-ray powder diffraction data

The room temperature structure of perovskite CeAlO₃ has been reinvestigated by X-ray powder diffraction. The Rietveld refinement has confirmed the tetragonal symmetry; but revealed a super cell, a=5.32489(6) Å and c=7.58976(10) Å, with the space group I4/mcm. In CeAlO₃, the distortion from the ideal cubic perovskite is caused by the cooperative tilting of the AlO₆ octahedra around the primitive cubic [001]_p-axis.     

Criteria for right disfocality of linear difference equations

Right disfocality and criteria for right disfocality of linear difference equations are considered. The criteria require the positivity of appropriate minors of a Wronskian determinant and are analogues to criteria for the disconjugacy of linear ordinary differential equations and linear difference equations.