Reagents for new heteroannelation reactions III. 2-(Methylthio)-2-thiazoline

Summary A variety of partly novel tri- and tetracyclic hetero systems were obtained by reaction of heteroaromatic 2-aminoesters with 2-(methylthio)-2-thiazoline, yielding double-annelation of a thiazolo[2,3-b]pyrimido moiety in a one-pot process.On leave from University of Chittagong, Bangladesh     

Dual-label autoradiographic analysis of human skin fibroblast and myoblast proteins by two-dimensional polyacrylamide gel electrophoresis using immobilised pH gradients in the first dimension

Horizontal two-dimensional polyacrylamide gel electrophoresis with immobilised pH gradients in the first dimension has been applied to the analysis of human skin fibroblast and muscle myoblast total cell proteins. Excellent two-dimensional separations of skin fibroblast proteins were obtained using pH 4-10 immobilised pH gradient gels with a long interelectrode distance (16 cm), but resolution was degraded, particularly of the more acidic proteins, by the use of shorter (10 cm) gels. Improved resolution of acidic and basic proteins was obtained using separate pH 4-7 and pH 7-10 immobilised pH gradient gels respectively in the first dimension. Two-dimensional protein maps of skin fibroblast proteins were visualised both by silver staining and by autoradiography of samples labelled synthetically with [35S]methionine. Horizontal two-dimensional electrophoresis, using pH 4-7 and pH 7-10 immobilised pH gradient gels in the first dimension, was applied to the analysis of protein samples from skin fibroblasts and muscle myoblasts dual-labelled synthetically with [35S]methionine and [75Se]selenomethionine in an attempt to identify sets of proteins specific to each cell type. In addition, two-dimensional maps or protein samples derived from normal individuals and patients with Duchenne muscular dystrophy were compared to search for protein changes associated with the disease state. Although sets of qualitative protein spot differences were observed by visual inspection of the two-dimensional gels, more rigorous qualitative and quantitative analysis of the patterns using a computerised analysis system will be required to obtain the maximum amount of information from these data.     

Synthesis and structure of a stabilized 10-membered cyclic enediyne

The synthesis and structure of an acetal protected 10-membered cyclic enediyne-1,2-diol rac-10 is reported. The conformational constrain of the unsaturated macrocycle by the acetal protection group prevents the thermal cyclization reaction of the endiyne during synthesis and purification.     

Rotational fluctuations of water inside the nanopores of SBA-type molecular sieves

The rotational molecular dynamics of water confined to nanoporous molecular sieves of a regular hexagonal (SBA-15) and of a foamlike pore structure was studied by dielectric spectroscopy in the frequency range from 10(-2) to 10(9) Hz and in a broad temperature interval. Two relaxation processes were observed: the process at lower frequencies is related to water molecules forming a layer, which is strongly adsorbed at the pore surface, whereas the relaxation process at higher frequencies is assigned to fluctuations of water molecules situated close to the center of the pore. The relaxation times of the low-frequency process for both materials and of the high-frequency process for the SBA-15 material have an unusual saddlelike temperature dependence, reported here for the first time. To describe this temperature dependence, a model developed for water confined to nanoporous glasses by Ryabov et al. [J. Phys. Chem. B 2001, 105, 1845] was applied, which considers two competing effects. The characteristic features of these two competing processes were compared with those reported for other porous systems.     

Application of main component fraction collection method for purification of compound libraries

In order to support high-throughput library purification, a novel UV triggered fraction collection method was developed in which a maximum-seeking-algorithm-driven, six-port valve collects the largest chromatographic peak. This straightforward strategy achieves the one sample-one fraction approach, thus resulting in a simpler and less error prone workup procedure. The effectiveness of this main component fraction collection method will be illustrated here by the results of the purification of compound libraries (altogether 6086 compounds, having an averaged success rate of 79.4%). Advanced applications, where the desired component differs from the main component, will also be discussed.     

The effects of oxygenation on the optical properties of dimethyl-dithienothiophenes: comparison between experiments and first-principles calculations

Modifications of the optical properties of dimethyl-dithienothiophenes due to the oxygen functionalization of the central sulfur atom are investigated. We have measured the absorption, photoluminescence (PL) and PL excitation spectra, the PL quantum efficiencies, and the PL decay times. These experimental results are interpreted and compared with first-principles time-dependent density-functional theory calculations, which predict, for the considered systems, excitation and emission energies with an accuracy of 0.1 eV. It is found that the oxygenation strongly changes optical and photophysical properties. These effects are related to the modifications of the energetically lowest-unoccupied molecular orbital and the energetically second highest occupied one, which change the relative position of the two lowest singlet and triplet excited states.     

Atomic resolution of defects in graphite studied by STM

Different kinds of defects in graphite with a resolution up to atomic scale have been investigated using STM. Mono-atomic steps on the surface as well as bended graphite layers with height differences less than 0.1 nm originating from defects (steps) in the bulk have been uncovered. The influence of such defects on the appearance of superstructures in the surrounding area is demonstrated. Ribbons, with a few nanometers width and less than 1 nm height, and prismatic loops were resolved. Height variations in the range of a few tenths of nanometer as a result of missed and inserted carbon layers have been revealed. To our knowledge, for the first time defect lines on graphite are presented with an atomic resolution. The defect lines are several microns long and only 1–3 atoms in width. Received: 24 June 1996 / Revised: 24 January 1997 / Accepted: 29 January 1997     

Nonresonant dielectric hole burning in neat and binary organic glass formers

Binary mixtures of the molecular glass former 2-picoline in oligostyrene, in which the dielectric response of 2-picoline exhibits a particularly broad distribution of correlation times, are investigated by nonresonant dielectric hole-burning (NDHB) spectroscopy and the results are compared with NDHB in neat systems, in particular, glycerol. It turns out that in both substance classes spectral selectivity is achieved, which indicates that dynamics is heterogeneous, i.e., slow and fast responses coexist in the material. However, in binary systems the position of the spectral modifications is completely determined by the spectral density of the pump field, and thus shifts linearly with burn frequency as expected, also at pump frequencies around the alpha-relaxation maximum. It is shown that in binary systems the lifetime tau(rec) of the spectral modifications is determined by the burn frequency omega(p) and exceeds its inverse by about one order of magnitude, indicating long-lived dynamic heterogeneity. The data are described in terms of a previously suggested model of dynamically selective heating, which was extended to include intrinsic nonexponential relaxation. It turns out that the spectral broadening in binary mixtures is not only due to pronounced dynamic heterogeneity, but partially also due to intrinsic broadening of the relaxation function.     

Almost constant sequences and well-distribution in compact groups

We study the properties of sequences (c _n ) in a compact groupG such that (x _n ) being (weakly) well-distributed implies (c _n x _n ) being (weakly) well-distributed and give a complete characterisation in terms of almost constant sequences as well as a generalisation to non-compact locally compact groups.