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81.
Substituted 5-hexen-1-oxyl radicals have been generated from N-(5-hexen-1-oxy)-5-(p-methoxyphenyl)-4-methylthiazole-2(3H)-thiones under tin-free conditions and have been successfully applied as reactive intermediates in a mechanistic study on the formation of bromomethyl-substituted tetrahydropyrans via 6-exo-trig selective cyclizations. 相似文献
82.
Witke K Götze J Rössler R Dietrich D Marx G 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2004,60(12):2903-2912
Samples of different three-dimensionally preserved fossil plants (Medullosa sp., Dadoxylon sp., Calamodendron striatum, Psaronius sp.) from the Lower Permian petrified forest of Chemnitz were examined with regard to their chemical composition and structural order. Raman spectroscopy and cathodoluminescence microscopy are shown to be powerful tools for such investigations. Silicified wood from Chemnitz-Hilbersdorf generally shows yellow cathodoluminescence (CL) of the cell walls and only weak yellow-brownish CL of the cell lumina. By time-resolved cathodoluminescence spectroscopy, a secondary mineralisation of hydrothermal origin was recognized. The latter is shown by short-lived blue CL at the cell walls extinguishing the yellow signal. Therefore, after the primary silicification step a secondary mineralisation step initiated by hydrothermal processes, seems to have taken place at probably slightly higher temperatures. The resulting silica matrix consists of phanerocrystalline and microcrystalline alpha-quartz as well as microcrystalline moganite, both partially associated with iron oxides. Dadoxylon sp. is a prominent example for parallel permineralisation by alpha-quartz and fluorspar, which is outstanding for the Chemnitz Petrified Forest. CL on this samples shows parallel silicification and fluoritisation, followed by infiltration of iron oxides. Permineralised samples show very low percentage of original organic remains. The seed fern Medullosa, for example, shows dispersed carbon, which is mainly restricted to the centres of the typical star-shaped vascular bundles. Raman spectroscopy revealed that these carbonaceous particles are of an anthracite structure. For experimental confirmation coal samples of different rank, especially anthracite from different geological times and localities, were studied by means of Raman spectroscopy. The remaining pith of the vascular bundles is white-coloured and consists of alpha-quartz and moganite, whereas surrounding tracheides exhibit white and reddish coloured parts. The reddish parts, mainly found in the rays, additionally contain alpha-Fe2O3 and Fe3O4 among the SiO2 polymorphs of alpha-quartz and moganite. Sometimes iron oxides could have dominated permineralisation processes as the peak intensities of distinct parts of the samples suggest. 相似文献
83.
Over the past few decades, advances in genetics and molecular biology have revolutionized our understanding of cancer initiation and progression. Molecular progression models outlining genetic events have been developed for many solid tumors, including colon cancer. Previous reports in the literature have shown a relationship between different KRAS mutations and prognosis and response to medical treatment in colon cancer patients. Furthermore, the presence of a mutated KRAS has been correlated with different clinicopathological variables including age and gender of patients and tumor location. To our knowledge, few institutions screen for KRAS mutations on regular basis in colon cancer patients despite such evidence that knowledge of KRAS exon 1 status is informative. Here, we report on a mutation analysis method adapted to a 96-capillary electrophoresis instrument that allows identification of all 12 oncogenic mutations in KRAS exon 1 under denaturing conditions. To determine the optimal parameters, a series of DNA constructs generated by site-directed mutagenesis was analyzed and the migration times of all mutant peaks were measured. A classification tree was then made based on the differences in migration time between the mutants and an internal standard. A randomized series of 500 samples constructed with mutagenesis as well as 60 blind samples from sporadic colon carcinomas was analyzed to test the method. No wild-type samples were scored as mutants and all mutants were correctly identified. Post polymerase chain reaction (PCR) analysis time of 96 samples was performed within 40 min. 相似文献
84.
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86.
New Oxonium Bromochalcogenates(IV) — Synthesis, Structure, and Properties of [H3O][TeBr5] · 3 C4H8O2 and [H3O]2[SeBr6] Dark red crystals of the composition [H3O][TeBr5] · 3 C4H8O2 ( 1 ) were isolated from a saturated solution of TeBr4 in 1,4-dioxane containing a small amount of water. In this compound (space group P21/m, a = 8.922(4) Å, b = 13.204(7) Å, c = 9.853(5) Å, β = 91.82(4)° at 150 K) a square pyramidal [TeBr5]? anion has been isolated for the first time. The coordination sphere of the anion is completed to a distorted octahedron by weak interaction with a dioxane molecule of the cationic system. The [H3O]+ cations are connected to chains by dioxane molecules. At room temperature the compound is stable only in its mother liquor. Crystalline [H3O]2[SeBr6] ( 2 ) (space group Fm3m, a = 10.421(1) Å at 170 K) is a bromoselenous acid of high symmetry. The [H3O]+ ion is only weakly coordinated by Br atoms of the anion. The anions are isolated octahedral [SeBr6]2? units. The structure is isotypic to the K2[PtCl6] structure. Despite being a halogenochalcogen(IV) acid, 2 exhibits a remarkable thermal stability. Both oxonium compounds were characterized by single-crystal X-ray structure analyses. Vibrational spectra of 2 are reported. 相似文献
87.
Whittle M Gillet VJ Willett P Alex A Loesel J 《Journal of chemical information and computer sciences》2004,44(5):1840-1848
This paper evaluates the effectiveness of various similarity coefficients for 2D similarity searching when multiple bioactive target structures are available. Similarity searches using several different activity classes within the MDL Drug Data Report and the Dictionary of Natural Products databases are performed using BCI 2D fingerprints. Using data fusion techniques to combine the resulting nearest neighbor lists we obtain group recall results which, in many cases, are a considerable improvement on standard average recall values obtained for individual structures. It is shown that the degree of improvement can be related to the structural diversity of the activity class that is searched for, the best results being found for the most diverse groups. The group recall of active compounds using subsets of the class is also investigated: for highly self-similar activity classes, the group recall improvement saturates well before the full activity class size is reached. A rough correlation is found between the relative improvement using the group recall and the square of the number of unique compounds available in all of the merged lists. The Tanimoto coefficient is found unambiguously to be the best coefficient to use for the recovery of active compounds using multiple targets. Furthermore, when using the Tanimoto coefficient, the "MAX" fusion rule is found to be more effective than the "SUM" rule for the combination of similarity searches from multiple targets. The use of group recall can lead to improved enrichment in database searches and virtual screening. 相似文献
88.
Michael Limbach Markus Lweneck JürgV. Schreiber Jens Frackenpohl Dieter Seebach Andreas Billich 《Helvetica chimica acta》2006,89(7):1427-1441
β‐Peptides and, to a certain extent, also mixed α,β‐peptides, are resistant to degradation by a variety of proteolytic enzymes that rapidly degrade natural α‐peptides. This is one of many characteristics that make β‐peptides an attractive class of compounds for drug‐discovery studies. On the other hand, modern organometallic reactions such as the Suzuki–Miyaura cross‐coupling have become standard tools in industry laboratories to derivatize side chains of α‐peptidic compounds to build up libraries of unnatural peptides. Combining both features, we prepared (4‐bromo)‐β3‐homophenylalanine derivatives 3 – 5 and 12 as precursors for Suzuki–Miyaura couplings. From these bromo compounds, we synthesized biaryl‐substituted β‐homoamino acids 6 , and analogs 13 and 15 of the anti‐AIDS drug Saquinavir. 相似文献
89.
J. F. Geiger P. Beckmann K. D. Schierbaum W. Göpel 《Fresenius' Journal of Analytical Chemistry》1991,341(1-2):25-30
Summary We report about interaction processes between palladium (Pd) and tin dioxide (SnO2) studied with various surface spectroscopic techniques. Total sputter yields necessary for absolute depth calibration in SIMS are determined for SnO2. Clustering of palladium occurs at low temperatures. Small changes in the XPS relative core level intensities of Pd and Sn allow to determine cluster sizes. Oxidation of Pd in the presence of oxygen at T470 K is a prerequisite for diffusion of Pd2+ ions into SnO2 layers. The latter process is confirmed and described quantitatively by evaluating the SIMS and SNMS measurements. 相似文献
90.
R. Albrecht T. C. Awes P. Beckmann F. Berger D. Bock R. Bock G. Claesson G. Clewing L. Dragon A. Eklund R. L. Ferguson A. Franz S. Garpman R. Glasow H. Å. Gustafsson H. H. Gutbrod G. Hölker J. Idh P. Jacobs K. H. Kampert B. W. Kolb P. Kristiansson H. Löhner I. Lund F. E. Obenshain A. Oskarsson I. Otterlund T. Peitzmann F. Plasil A. M. Poskanzer M. Purschke H. G. Ritter R. Santo S. Saini H. R. Schmidt S. P. Sørensen K. Steffens D. Stüken E. Stenlund M. Tincknell G. R. Young 《Zeitschrift fur Physik C Particles and Fields》1991,51(1):1-10
The production of direct photons has been investigated in reactions ofp and16O projectiles at 60 and 200A·GeV with C and Au nuclei. Photon and 0 spectra have been measured in the pseudorapidity range 1.52.1 for the transverse momentum region 0.4 GeV/cp
T
2.8 GeV/c employing the lead-glass spectrometer SAPHIR. An upper limit of 15% at the 90% confidence level for the direct photon signal relative to the neutral pion production is obtained from the comparison of measured photon spectra with Monte Carlo simulations of the hadronic background based on the reconstructed yield of 0 and mesons. Consequences for a possible phase transition to a quark-gluon plasma are discussed. 相似文献