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41.
Dr. Alvaro Gordillo Prof. Dr. Guy C. Lloyd‐Jones 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(9):2660-2665
An intermolecular Pd/PPh3‐catalyzed transesterification of diallyl carbonate with glycerol to generate glycerol carbonate has been developed. Analysis of the reaction kinetics in THF indicates a first‐order dependence on Pd and diallyl carbonate, that the Pd bears two phosphines during the turnover limiting event, and that increasing the glycerol concentration inhibits reaction, possibly via change in the polarity of the medium. 13C isotopic labeling studies demonstrate that the Pd‐catalyzed transesterification requires at least one allyl carbonate moiety and that there is rapid equilibrium of the allyl carbonate with CO2 in solution, even when present only at low concentrations. A mechanism that is consistent with these results involves oxidative addition of the allyl carbonate to Pd followed by reversible decarboxylation, with the intermediate η1‐ and η3‐allyl Pd alkoxides mediating direct and indirect transesterification reactions with the glycerol. Using this model, successful simulations of the kinetics of reactions conducted under atmospheres of N2 or CO2 could be achieved, including switching in selectivity between etherification and transesterification in the early stages of reaction. Reactions with the higher polyols threitol and erythritol are also efficient, generating the terminal (1,2) monocarbonates with high selectivity. 相似文献
42.
An ultrasensitive aptamer-based bio bar code immunomagnetic separation and electrochemiluminescence (IM-ECL) method for the detection of protein is developed. The target protein is captured by biotin-labeled aptamer (biotin probe) and [Ru(bpy)3]2+ (TBR)-Au bio bar code-labeled aptamer (ECL nanoprobe), to form a double aptamer–protein sandwich complex. The complex is then immobilized on the streptavidin microbeads through biotin–streptavidin linkage and detected by ECL assay. The ECL signal of the target protein is amplified by the TBR-bio bar code DNAs. As an example, platelet-derived growth factor B-chain homodimer (PDGF-BB) was detected by the method. Experimental results show that the detection limit of the assay is 1 pM of PDGF-BB. A calibration curve with a linearity range from 1 pM to 10 nM is established, thus, make quantitative analysis possible. The method has been used to detect PDGF-BB in fetal calf serum with minimum background interference. Due to the wide availability of aptamer for numerous proteins, this aptamer-based bio bar code IM-ECL method holds great promise in protein detection. 相似文献
43.
Predicting the location where a protein resides within a cell is important in cell biology. Computational approaches to this issue have attracted more and more attentions from the community of biomedicine. Among the protein features used to predict the subcellular localization of proteins, the feature derived from Gene Ontology (GO) has been shown to be superior to others. However, most of the sights in this field are set on the presence or absence of some predefined GO terms. We proposed a method to derive information from the intrinsic structure of the GO graph. The feature vector was constructed with each element in it representing the information content of the GO term annotating to a protein investigated, and the support vector machines was used as classifier to test our extracted features. Evaluation experiments were conducted on three protein datasets and the results show that our method can enhance eukaryotic and human subcellular location prediction accuracy by up to 1.1% better than previous studies that also used GO-based features. Especially in the scenario where the cellular component annotation is absent, our method can achieved satisfied results with an overall accuracy of more than 87%. 相似文献
44.
Recently developed strategies for late stage modification of peptides through CH activation, an arena of contemporary interest in chemical biology and drug discovery, are discussed. Through this tactic, non-polar amino acids in peptides have been selectively functionalized and CH activation enabled new CC and CX bond formations (arylation, alkynylation, fluorination, hydroxylation, azidation, etc.) are documented. Significant advances have been made in Pd or Au-catalyzed, racemization-free, tryptophan specific modifications of large peptides via CH arylation and alkynylation reactions without any protecting group requirement. Development of a new biaryl stapling technique for complex peptides, 18F radiofluorine introduction and diversity oriented post synthetic applications on bio-active cyclopeptides like valinomycin and aureobasidin are additional highlights which underscores the vast potential of late stage CH activation reactions in peptide based therapeutics research. 相似文献
45.
W. Graham Richards Department of Chemistry University of Oxford Central Chemistry South Parks Road Oxford OX QH UK 《高等学校化学研究》2002,18(2):107-108
IntroductionThesequencingofthehuman genomeisessen tiallycomplete .Thereappearstobealittleover4 0 0 0 0 genes .Scientificexcitementhasmovedontotheproteome ,thefewhundredthousandproteinsforwhichthe genesprovidethecode .These proteinstructuresarelikelytoemergewith… 相似文献
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Proteins play a central role in all domains of life, and precise regulation of their activity is essential for understanding the related biological processes and therapeutic functions. Nucleic acid aptamers, the molecular recognition components derived from systematic evolution of ligands by exponential enrichment(SELEX), can specifically identify proteins with antibody-like recognition characteristics and help to regulate their activity. This minireview covers the SELEX-based selection of protein-binding aptamers, membrane protein analytical techniques based on aptamer-mediated target recognition, aptamer-mediated functional regulation of proteins, including membrane receptors and non-membrane proteins(thrombin as a model), as well as the potential challenges and prospects regarding aptamer-mediated protein manipulation, aiming to supply some useful information for researchers in this field. 相似文献
49.
生物体内的细胞通常会分泌各种各样的蛋白质,这些蛋白质在生物体中发挥着重要作用,尤其是可被用于诊断各种疾病的发生和发展。多肽具有良好选择性、空间适应能力和识别灵活的特点,可与不同类型的蛋白分子形成非共价键,用于蛋白质的生物检测。将多肽与电化学生物传感器结合用于蛋白质的广谱检测具有良好的发展前景。本文介绍了多肽修饰的电化学传感器在不同蛋白质检测方面的研究进展,分析了待测蛋白质的不同对多肽修饰的电化学传感器分类的影响及其优缺点,提出了基于多肽的电化学传感器在不同蛋白质检测中存在的问题,并展望了其未来发展。 相似文献
50.
Takahiro Moriyama Daiki Mizukami Dr. Makoto Yoritate Dr. Kazuteru Usui Dr. Daisuke Takahashi Dr. Eisuke Ota Prof. Dr. Mikiko Sodeoka Prof. Dr. Tadashi Ueda Prof. Dr. Satoru Karasawa Prof. Dr. Go Hirai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(11):e202103925
Minimalist photo-reactive probes, which consist of a photo-reactive group and a tag for detection of target proteins, are useful tools in chemical biology. Although several diazirine-based and aryl azide-based minimalist probes are available, no keto-based minimalist probe has yet been reported. Here we describe minimalist probes based on a 2-thienyl-substituted α-ketoamide bearing an alkyne group on the thiophene ring. The 3-alkyne probe showed the highest photo-affinity labeling efficiency. 相似文献