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Eckhard K Erichsen T Stratmann M Schuhmann W 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(13):3968-3976
For a better understanding of the initiation of localised corrosion, there is a need for analytical tools that are capable of imaging corrosion pits and precursor sites with high spatial resolution and sensitivity. The lateral electrochemical contrast in alternating-current scanning electrochemical microscopy (AC-SECM) has been found to be highly dependent on the frequency of the applied alternating voltage. In order to be able to obtain data with optimum contrast and high resolution, the AC frequency is swept in a full spectrum at each point in space instead of performing spatially resolved measurements at one fixed perturbation frequency. In doing so, four-dimensional data sets are acquired (4D AC-SECM). Here, we describe the instrument set-up and modus operandi, along with the first results from the imaging of corroding surfaces. Corrosion precursor sites and local defects in protective organic coatings, as well as an actively corroding pit on 304 stainless steel, have been successfully visualised. Since the lateral electrochemical contrast in these images varies with the perturbation frequency, the proposed approach constitutes an indispensable tool for obtaining optimum electrochemical contrast. 相似文献
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Resistomycin is a bacterial polyphenolic metabolite from Streptomyces resistomycificus with a unique pentacyclic "discoid" ring system that clearly differs from the typical linear or angular architectures of aromatic polyketides. The first comprehensive cyclase amino acid sequence-function correlation revealed that the enzymes directing the nascent polyketide chain into a peri-fused system clearly differ from canonical linear and angular cyclases. All genes that are required and sufficent for resistomycin (rem) biosynthesis were identified through systematic dissection and reconstitution of the type II polyketide synthase (PKS) complex. The minimal rem PKS and the first cyclase were successfully cross-complemented with orthologues from the linear tetracenomycin polyketide pathway, indicating that both dekaketide pathways share early biosynthetic steps. In total three cyclases that are involved in discoid cyclization (RemI, RemF, and RemL) were identified by mutational analyses and in vivo pathway reconstitution. Analyses of the metabolic profiles of mutants expressing incomplete gene sets led to the discovery of a novel tetracenomycin derivative, TcmR1. The most surprising finding is that only the concerted action of the PKS and all three cyclases leads to the discoid ring structure. These results provide strong support for a model according to which the multienzyme complex forms a cage in which the polyketide is shaped, rather than a sequential cyclization of the polyketide chain by individual enzymes. 相似文献
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Kirchmair J Ristic S Eder K Markt P Wolber G Laggner C Langer T 《Journal of chemical information and modeling》2007,47(6):2182-2196
In continuation of our recent studies on the quality of conformational models generated with CATALYST and OMEGA we present a large-scale survey focusing on the impact of conformational model quality and several screening parameters on pharmacophore-based and shape-based virtual high throughput screening (vHTS). Therefore, we collected known active compounds of CDK2, p38 MAPK, PPAR-gamma, and factor Xa and built a set of druglike decoys using ilib:diverse. Subsequently, we generated 3D structures using CORINA and also calculated conformational models for all compounds using CAESAR, CATALYST FAST, and OMEGA. A widespread set of 103 structure-based pharmacophore models was developed with LigandScout for virtual screening with CATALYST. The performance of both database search modes (FAST and BEST flexible database search) as well as the fit value calculation procedures (FAST and BEST fit) available in CATALYST were analyzed in terms of their ability to discriminate between active and inactive compounds and in terms of efficiency. Moreover, these results are put in direct comparison to the performance of the shape-based virtual screening platform ROCS. Our results prove that high enrichment rates are not necessarily in conflict with efficient vHTS settings: In most of the experiments, we obtained the highest yield of actives in the hit list when parameter sets for the fastest search algorithm were used. 相似文献
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Improved STR typing of telogen hair root and hair shaft DNA 总被引:1,自引:0,他引:1
Today the STR typing of telogen hair and hair shafts is regarded as a challenge. The small DNA quantity in the hair is highly degraded. Another problem are PCR inhibitors in the hair. In particular hair pigments, the melanins, are known to inhibit PCR. Hairs are exposed to sunlight and partly to chemical oxidation processes, which make them even more difficult to analyze. To increase the chances of a correct typing of hair, the small amount of DNA must be successfully isolated and the inhibitors have to be removed or neutralized. Furthermore, miniSTR typing improves the analysis of stains with degraded DNA like it is the case with hair. We introduce a nonorganic extraction method and in addition a miniSTR concept which is promising in typing stains with little and degraded DNA, especially hairs. The miniSTR concept including five database STRs (SE33, VWA, TH01, FGA, D3S1358) and the gender typing system Amelogenin was optimized for the amplification of hair DNA. Compared to commercial STR kits, this approach resulted in considerably higher success rates. 相似文献