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31.
Kocher N Henn J Gostevskii B Kost D Kalikhman I Engels B Stalke D 《Journal of the American Chemical Society》2004,126(17):5563-5568
The concept of hypervalency in molecules, which hold more than eight valence electrons at the central atom, still is a topic of constant debate. There is general interest in silicon compounds with more than four substituents at the central silicon atom. The dispute, whether this silicon is hypervalent or highly coordinated, is enlightened by the first experimental charge density determination and subsequent topological analysis of three different highly polar Si-E (E = N, O, F) bonds in a hexacoordinated compound. The experiment reveals predominantly ionic bonding and much less covalent contribution than commonly anticipated. For comparison gas-phase ab initio calculations were performed on this compound. The results of the theoretical calculations underline the findings of the experiment. 相似文献
32.
Chromatographic speciation of anionic and neutral selenium compounds in Se-accumulating Brassica juncea (Indian mustard) and in selenized yeast 总被引:1,自引:0,他引:1
Selenium-accumulating plants such as Brassica juncea (Indian mustard) concentrate the element in plant shoots and roots. Such behavior may provide a cost-effective technology to clean up contaminated soils and waters that pose major environmental and human health problems (phytoremediation). Such ability to transform selenium into bioactive compounds has important implications for human nutrition and health. Element selective characterization of B. juncea grown in the presence of inorganic selenium under hydroponic conditions provides valuable information to better understand selenium metabolism in plants. The present work determines both previously observed organoselenium species such as selenomethionine and Se-methylselenocysteine and for the first time detects the newly characterized S-(methylseleno)cysteine in plant shoots and roots when grown in the presence of selenate or selenite as the only selenium source. A key feature of this study is the complementary role of selenium and sulfur specific chromatographic detection by HPLC with interfaced inductively coupled plasma mass spectrometry (ICP-MS) detection and by derivatization GC with interfaced atomic spectral emission. HPLC-ICP-MS limits of detection for such species were in the range 5-50 ng Se mL(-1) in the injected extracts. Speciation profiles are compared with those of selenium-enriched yeast by both HPLC-ICP-MS and GC-AED. 相似文献
33.
Alan R. Katritzky Zouquan Wang Jianqing Li Julian R. Levell 《Journal of heterocyclic chemistry》1997,34(4):1379-1381
1,2,3-Triarylpyrroles 7 have been synthesized by sequential lithiation and alkylation of 1-benzylbenzo-triazoles 1 with 2-bromoacetaldehyde diethyl acetal (2) and N-benzylideneaniline (4), followed by treatment with formic acid in ethanol. 相似文献
34.
35.
Julian Fink 《Acta Analytica》2013,28(4):471-482
This paper argues that practical reasoning is a mental process which leads a person from a set of existent mental states to an intention. In Section 1, I defend this view against two other proposals according to which practical reasoning either concludes in an action itself or in a normative belief. Section 2 discusses the correctness of practical reasoning and explains how the correctness of instrumental reasoning can be explained by the logical relations that hold between the contents of the mental states. In Section 3, I explore the correctness of normative practical reasoning. I conclude with the sceptical view that correct practical reasoning cannot require us to intend to do what we believe we ought to do. 相似文献
36.
37.
Dr. Sunewang R. Wang Dr. Merle Arrowsmith Julian Böhnke Prof. Dr. Holger Braunschweig Dr. Theresa Dellermann Dr. Rian D. Dewhurst Hauke Kelch Dr. Ivo Krummenacher James D. Mattock Jonas H. Müssig Torsten Thiess Dr. Alfredo Vargas Dr. Jiji Zhang 《Angewandte Chemie (International ed. in English)》2017,56(27):8009-8013
The diborene 1 was synthesized by reduction of a mixture of 1,2-di-9-anthryl-1,2-dibromodiborane(4) ( 6 ) and trimethylphosphine with potassium graphite. The X-ray structure of 1 shows the two anthryl rings to be parallel and their π(C14) systems perpendicular to the diborene π(B=B) system. This twisted conformation allows for intercalation of the relatively high-lying π(B=B) orbital and the low-lying π* orbital of the anthryl moiety with no significant conjugation, resulting in a small HOMO–LUMO gap (HLG) and ultimately a C−H borylation of the anthryl unit. The HLG of 1 was estimated to be 1.57 eV from the onset of the long wavelength band in its UV/Vis absorption spectrum (THF, λonset=788 nm). The oxidation of 1 with elemental selenium afforded diboraselenirane 8 in quantitative yield. By oxidative abstraction of one phosphine ligand by another equivalent of elemental selenium, the B−B and C1−H bonds of 8 were cleaved to give the cyclic 1,9-diborylanthracene 9 . 相似文献
38.
Dr. Patrick Feicht Dr. Johannes Biskupek Dr. Tatiana E. Gorelik Julian Renner Dr. Christian E. Halbig Maria Maranska Florian Puchtler Prof. Dr. Ute Kaiser Prof. Dr. Siegfried Eigler 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(38):8955-8959
Synthesis and studies of graphite oxide started more than 150 years ago and turned into a boom by the measurements of the outstanding physical properties of graphene. A series of preparation protocols emanated trying to optimize the synthesis of graphene oxide in order to obtain a less defective material, as source for graphene. However, over-oxidation of the carbon framework hampered establishing structure-property relationships. Here, the fact that two different synthetic methods for graphene oxide preparation lead to very similar types of graphene oxide with a preserved graphene lattice is demonstrated. Either sodium chlorate in nitric acid (similar to Brodie's method) or potassium permanganate in sulfuric acid (similar to Hummers’ method) treatment are possible; however, reaction conditions must be controlled. With a preserved carbon lattice analytical differences between the samples relate to the altered on-plane functionality. Consequently, terming preparation protocols “according to Brodie's/Hummers’ method” is not sufficient. 相似文献
39.
Julia Ertl Dr. Maria Elena Ortiz-Soto Thien Anh Le Julian Bechold Junwen Shan Dr. Jörg Teßmar Prof. Bernd Engels Prof. Jürgen Seibel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(26):6533-6541
Selective chemical modification of proteins plays a pivotal role for the rational design of enzymes with novel and specific functionalities. In this study, a strategic combination of genetic and chemical engineering paves the way for systematic construction of biocatalysts by tuning the product spectrum of a levansucrase from Bacillus megaterium (Bm-LS), which typically produces small levan-like oligosaccharides. The implementation of site-directed mutagenesis followed by a tyrosine-specific modification enabled control of the product synthesis: depending on the position, the modification provoked either enrichment of short oligosaccharides (up to 800 % in some cases) or triggered the formation of high molecular weight polymer. The chemical modification can recover polymerization ability in variants with defective oligosaccharide binding motifs. Molecular dynamic (MD) simulations provided insights into the effect of modifying non-native tyrosine residues on product specificity. 相似文献