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排序方式: 共有455条查询结果,搜索用时 31 毫秒
91.
Franziska Hufsky Martin Rempt Florian Rasche Georg Pohnert Sebastian Böcker 《Analytica chimica acta》2012
The automated fragmentation analysis of high resolution EI mass spectra based on a fragmentation tree algorithm is introduced. Fragmentation trees are constructed from EI spectra by automated signal extraction and evaluation. These trees explain relevant fragmentation reactions and assign molecular formulas to fragments. The method enables the identification of the molecular ion and the molecular formula of a metabolite if the molecular ion is present in the spectrum. These identifications are independent of existing library knowledge and, thus, support assignment and structural elucidation of unknown compounds. The method works even if the molecular ion is of very low abundance or hidden under contaminants with higher masses. We apply the algorithm to a selection of 50 derivatized and underivatized metabolites and demonstrate that in 78% of cases the molecular ion can be correctly assigned. The automatically constructed fragmentation trees correspond very well to published mechanisms and allow the assignment of specific relevant fragments and fragmentation pathways even in the most complex EI-spectra in our dataset. This method will be very helpful in the automated analysis of metabolites that are not included in common libraries and it thus has the potential to support the explorative character of metabolomics studies. 相似文献
92.
Summary: An in‐situ mineralization process in the presence of thermo‐responsive microgels leads to the formation of well‐defined hybrid materials. Experimental data suggest that control of the mineralization process in the presence of the microgels offers the possibility to obtain sub‐micrometer‐sized hybrid particles or macroscopic hybrid hydrogels. The rapid formation of CaCO3 crystals in the microgel structure favors the preparation of the hybrid particles wherein inorganic crystals cover the shell layer of the microgel. The slow formation of CaCO3 crystals leads to the simultaneous self‐assembly of the microgel particles on the bottom of the reaction vessel, and the formation of a physical network. It has been demonstrated that hybrid hydrogel materials with different calcium carbonate contents and temperature‐dependent swelling‐deswelling properties can be prepared.
93.
94.
Dr. Katja Krell Bastian Pfeuffer Dr. Franziska Rönicke Dr. Zoeisha S. Chinoy Dr. Camille Favre Dr. Frédéric Friscourt Prof. Hans-Achim Wagenknecht 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(65):16093-16097
Sydnones are highly stable mesoionic 1,3-dipoles that react with cyclooctynes through strain-promoted sydnone-alkyne cycloaddition (SPSAC). Although sydnones have been shown to be valuable bioorthogonal chemical reporters for the labeling of proteins and complex glycans, nucleic acids have not yet been tagged by SPSAC. Evaluation of SPSAC kinetics with model substrates showed fast reactions with cyclooctyne probes (up to k=0.59 M−1 s−1), and two different sydnones were effectively incorporated into both 2’-deoxyuridines at position 5, and 7-deaza-2’-deoxyadenosines at position 7. These modified nucleosides were synthetically incorporated into single-stranded DNAs, which were successfully postsynthetically labeled with cyclooctyne probes both in vitro and in cells. These results show that sydnones are versatile bioorthogonal tags and have the premise to become essential tools for tracking DNA and potentially RNA in living cells. 相似文献
95.
W. Mathis Rink Dr. Franziska Thomas 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(7):1665-1677
Coiled coils (CCs) are well-understood protein-folding motifs. They appear in a variety of oligomer states and as homo- and heteromeric assemblies. This versatility and the general accessibility by de novo design makes them ideal building blocks for synthetic biology. This Minireview highlights the efforts being made in designing small peptide catalysts or reaction templates based on the CC scaffold. The first reports described autocatalysis or mediation of peptide ligation based on CC recognition. Over the years, the designs became more advanced, catalyzing ester hydrolysis, acyl transfer and redox reactions with partial enzyme-like reactivity. Due to the ability to control CC assembly, and, in heterodimeric systems, the association and dissociation, the CC motif has become a common peptide tag in chemical biology. 相似文献
96.
97.
A. Emmerling 《Fresenius' Journal of Analytical Chemistry》1887,26(1):244-247
Ohne Zusammenfassung 相似文献
98.
Expanded 5-(hetero)aryl-thien-2-yl substituted 3-ethynyl quinoxaline dyes with variable substitution pattern on the peripheral thiophene ring were synthesized in moderate to very good yields by Suzuki and Buchwald-Hartwig coupling of the corresponding brominated 3-ethynyl quinoxalines. Dumbbell-shaped bis(thienyl 3-ethynyl quinoxalines) are also accessible by the Suzuki protocol. The photophysical properties were investigated by UV and fluorescence spectroscopy. Most of the obtained compounds display fluorescence in solution and some of them also in the solid state. Additionally, tuning of the emission color of the quinoxaline based chromophores can be conveniently accomplished by the remote substituent group. The determined absorption and emission maximum as well as the Stokes shifts strongly correlate with Hammett σp+parameters. Besides,photophysical properties of selected derivatives in the solid state, biphasic solutions, and PMMA films, along with their relationships, are comparatively investigated. Moreover, two 5-(hetero)aryl-thien-2-yl substituted 3-ethynyl quinoxaline dyes are aggregation induced emission(AIE) chromophores indicated by restriction of molecular motions. A covalently restricted 3-ethynyl quinoxaline supports that the inhibition of molecular rotation is responsible for the significant enhancement of fluorescence in acetonitrile/water mixtures. 相似文献
99.
Aerogels are sol-gel derived nanostructured materials with extraordinary properties according to their high porosity. Though first prepared more than 60 years ago, silica aerogels became widely known only in the late 1980s when they were used in Cerenkov detectors and their potential was recognized as high performance thermal insulants. Nowadays, aerogel research has attracted many scientists from different fields, resulting in some 100 publications per year and the fifth aerogel symposium (ISA 5) in Montpellier/France in September 1997. This review will focus on recent developments in fast supercritical and ambient pressure drying processes. The state of the art with respect to structural characterization and measuring the material properties is reported including nondestructive techniques and alterations induced by invasive methods. A brief survey is given on modeling the aerogel structure and simulating properties. Special attention will be given to carbon aerogels and their organic precursors. Due to the high electrical conductivity of their graphitic backbone and the large specific inner surface areas, carbon aerogels can be considered ideal electrodes in supercapacitors and fuel cells. 相似文献
100.
Grant J. Sherborne Avetik G. Gevondian Ignacio Funes‐Ardoiz Amit Dahiya Christoph Fricke Franziska Schoenebeck 《Angewandte Chemie (International ed. in English)》2020,59(36):15543-15548
Selective C –C couplings are powerful strategies for the rapid and programmable construction of bi‐ or multiaryls. To this end, the next frontier of synthetic modularity will likely arise from harnessing the coupling space that is orthogonal to the powerful Pd‐catalyzed coupling regime. This report details the realization of this concept and presents the fully selective arylation of aryl germanes (which are inert under Pd0/PdII catalysis) in the presence of the valuable functionalities C?BPin, C?SiMe3, C?I, C?Br, C?Cl, which in turn offer versatile opportunities for diversification. The protocol makes use of visible light activation combined with gold catalysis, which facilitates the selective coupling of C?Ge with aryl diazonium salts. Contrary to previous light‐/gold‐catalyzed couplings of Ar–N2+, which were specialized in Ar–N2+ scope, we present conditions to efficiently couple electron‐rich, electron‐poor, heterocyclic and sterically hindered aryl diazonium salts. Our computational data suggest that while electron‐poor Ar–N2+ salts are readily activated by gold under blue‐light irradiation, there is a competing dissociative deactivation pathway for excited electron‐rich Ar–N2+, which requires an alternative photo‐redox approach to enable productive couplings. 相似文献