The Chiral Trimer and a Metastable Chiral Dimer of Achiral Hexafluoroisopropanol: A Multi‐Messenger Study

1,1,1,3,3,3‐hexafluoro‐propan‐2‐ol aggregates preferentially into an achiral dimer of achiral monomers, but the trimer is found to prefer three metastable chiral monomer units arranged into a strained OH???O hydrogen‐bonded ring, which is reinforced by secondary CH???FC interactions. This is shown by a combination of infrared, microwave, and Raman spectroscopy in supersonic jet expansions and supported by high‐level quantum chemical calculations. It involves an activation of the monomers by >15 kJ mol^?1, clearly driven by the much stronger hydrogen‐bond interaction available to the gauche and even more to the cis monomer units.     

Zur Thermochemie und Struktur von Berylliumchlorid

Thermochemistry and Structure of Beryllium Chloride BeCl₂ is dimorphous, with a transition point at 405°C. The transition enthalpy and transition entropy have been determined by solution calorimetry: Δ_UH° = 2.9 kJmol^?1 and Δ_US° = 9.7 JK^?1mol^?1. The previously known SiS₂-type structure of BeCl₂ is that of the high temperature phase. The structure of the phase stable at room temperature has been determined from single crystal data. a = 1 062.4(6) pm, c = 1 804(2) pm, I4₁/acd, Z = 32, R = 0.038 (Mg(NH₂)₂-type). The structure consists of P₄O₁₀-like [Be₄Cl₆Cl_4/2]-units, connected by their terminal anions.     

Resveratrol,EGCG and Vitamins Modulate Activated T Lymphocytes

Vitamins and bioactives, which are constituents of the food chain, modulate T lymphocyte proliferation and differentiation, antibody production, and prevent inflammation and autoimmunity. We investigated the effects of vitamins (vitamin A (VA), D (VD), E (VE)) and bioactives (i.e., resveratrol (Res), epigallocatechin-3-gallate (EGCG)) on the adaptive immune response, as well as their synergistic or antagonistic interactions. Freshly isolated T lymphocytes from healthy individuals were activated with anti-CD3/CD28 antibodies for 4–5 days in the presence of bioactives and were analyzed by cytofluorometry. Interleukins, cytokines, and chemokines were measured by multiple ELISA. Gene expression was measured by quantitative RT-PCR. Res and EGCG increased CD4 surface intensity. EGCG led to an increased proportion of CD8⁺ lymphocytes. Anti-CD3/CD28 activation induced exuberant secretion of interleukins and cytokines by T lymphocyte subsets. VD strongly enhanced T_h2 cytokines (e.g., IL-5, IL-13), whereas Res and EGCG favored secretion of T_h1 cytokines (e.g., IL-2, INF-γ). Res and VD mutually influenced cytokine production, but VD dominated the cytokine secretion pattern. The substances changed gene expression of interleukins and cytokines in a similar way as they did secretion. Collectively, VD strongly modulated cytokine and interleukin production and favored T_h2 functions. Resveratrol and EGCG promoted the T_h1 response. VA and VE had only a marginal effect, but they altered both T_h1 and T_h2 response. In vivo, bioactives might therefore interact with vitamins and support the outcome and extent of the adaptive immune response.     

Empirical correction of crosstalk in a low-background germanium γ–γ analysis system

The Pacific Northwest National Laboratory (PNNL) is currently developing a custom software suite capable of automating many of the tasks required to accurately analyze coincident signals within gamma spectrometer arrays. During the course of this work, significant crosstalk was identified in the energy determination for spectra collected with a new low-background intrinsic germanium (HPGe) array at PNNL. The HPGe array is designed for high detection efficiency, ultra-low-background performance, and sensitive γ–γ coincidence detection. The first half of the array, a single cryostat containing seven HPGe crystals, was recently installed into a new shallow underground laboratory facility. This update will present a brief review of the germanium array, describe the observed crosstalk, and present a straight-forward empirical correction that significantly reduces the impact of this crosstalk on the spectroscopic performance of the system.     

Geometric and electronic structure of clusters

The interplay between electronic and geometric structure is investigated for covalently bonded phosphorus clusters. We use a modification of the molecular dynamics/ density functional (MD/DF) method of Car and Parrinello, describing the electronic structure by a simplified linear combination of atomic orbitals (LCAO) approach. The results show clearly the tendency of phosphorus to threefold coordination, and substantial variations in bond angles lead to a large variety of isomers.     

Calculations of molecules,clusters, and solids with a simplified LCAO-DFT-LDA scheme

A simplified LCAO-DFT-LDA scheme for calculations of structure and electronic structure of large molecules, clusters, and solids is presented. Forces on the atoms are calculated in a semiempirical way considering the electronic states. The small computational effort of this treatment allows one to perform molecular dynamics (MD ) simulations of molecules and clusters up to a few hundred atoms as well as corresponding simulations of condensed systems within the Born-Oppenheimer approximation. The accuracy of the method is illustrated by the results of calculations for a series of small molecules and clusters. © 1996 John Wiley & Sons, Inc.