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91.
Dr. Giuseppina Pieretti Sara Carillo Dr. Buko Lindner Kwang Kyu Kim Keun Chul Lee Jung‐Sook Lee Prof. Dr. Rosa Lanzetta Prof. Dr. Michelangelo Parrilli Prof. Dr. Maria Michela Corsaro 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(12):3729-3735
A novel core structure among bacterial lipopolysaccharides (LPS) that belong to the genus Halomonas has been characterized. H. stevensii is a moderately halophilic microorganism, as are the majority of the Halomonadaceae. It brought to light the pathogenic potential of this genus. On account of their role in immune system elicitation, elucidation of LPS structure is the mandatory starting point for a deeper understanding of the interaction mechanisms between host and pathogen. In this paper we report the structure of the complete saccharidic portion of the LPS from H. stevensii. In contrast to the finding that the O‐antigen is usually covalently linked to the outer core oligosaccharide, we could demonstrate that the O‐polysaccharide of H. stevensii is linked to the inner core of an LPS. By means of high‐performance anion‐exchange chromatography with pulsed amperometric detection we were able to isolate the core decasaccharide as well as a tridecasaccharide constituted by the core region plus one O‐repeating unit after alkaline degradation of the LPS. The structure was elucidated by one‐ and two‐dimensional NMR spectroscopy, ESI Fourier transform ion cyclotron resonance (FT‐ICR) mass spectrometry, and chemical analysis. 相似文献
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95.
Highly Efficient Solid‐Phase Labeling of Saccharides within Boronic Acid Functionalized Mesoporous Silica Nanoparticles
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Xianghua Pan Yang Chen Peixuan Zhao Daojin Li Dr. Zhen Liu 《Angewandte Chemie (International ed. in English)》2015,54(21):6173-6176
Labeling is critical for the detection, quantitation, and structural identification of saccharides. However, conventional liquid‐phase labeling suffers from apparent disadvantages, such as time‐consuming, the presence of excessive labeling reagent, and high applicable saccharide concentration. A solid‐phase approach is presented for highly efficient labeling of saccharides, using boronic acid functionalized mesoporous silica nanoparticles (MSNs) as a selective extraction sorbent and nanoscale reactor. The solid‐phase labeling approach exhibited several significant advantages, including: much faster reaction speed (taking only 2 min), high product purity, and much lower applicable saccharide concentration (four orders of magnitude lower than that of liquid‐phase labeling). Thus, this labeling approach opens up new avenues to the facile and efficient labeling of saccharides. 相似文献
96.
Highly Stereoselective Synthesis of Natural‐Product‐Like Hybrids by an Organocatalytic/Multicomponent Reaction Sequence
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M. Sc. Radell Echemendía M. Sc. Alexander F. de La Torre M. Sc. Julia L. Monteiro M. Sc. Michel Pila Prof. Dr. Arlene G. Corrêa Prof. Dr. Bernhard Westermann Prof. Dr. Daniel G. Rivera Prof. Dr. Márcio W. Paixão 《Angewandte Chemie (International ed. in English)》2015,54(26):7621-7625
In an endeavor to provide an efficient route to natural product hybrids, described herein is an efficient, highly stereoselective, one‐pot process comprising an organocatalytic conjugate addition of 1,3‐dicarbonyls to α,β‐unsaturated aldehydes followed by an intramolecular isocyanide‐based multicomponent reaction. This approach enables the rapid assembly of complex natural product hybrids including up to four different molecular fragments, such as hydroquinolinone, chromene, piperidine, peptide, lipid, and glycoside moieties. The strategy combines the stereocontrol of organocatalysis with the diversity‐generating character of multicomponent reactions, thus leading to structurally unique peptidomimetics integrating heterocyclic, lipidic, and sugar moieties. 相似文献
97.
Yeonjin Ko Mark W. Ruszczycky Sei‐Hyun Choi Prof. Dr. Hung‐wen Liu 《Angewandte Chemie (International ed. in English)》2015,54(3):860-863
DesII is a radical S‐adenosylmethionine (SAM) enzyme that catalyzes the C4‐deamination of TDP‐4‐amino‐4,6‐dideoxyglucose through a C3 radical intermediate. However, if the C4 amino group is replaced with a hydroxy group (to give TDP‐quinovose), the hydroxy group at C3 is oxidized to a ketone with no C4‐dehydration. It is hypothesized that hyperconjugation between the C4 C? N/O bond and the partially filled p orbital at C3 of the radical intermediate modulates the degree to which elimination competes with dehydrogenation. To investigate this hypothesis, the reaction of DesII with the C4‐epimer of TDP‐quinovose (TDP‐fucose) was examined. The reaction primarily results in the formation of TDP‐6‐deoxygulose and likely regeneration of TDP‐fucose. The remainder of the substrate radical partitions roughly equally between C3‐dehydrogenation and C4‐dehydration. Thus, changing the stereochemistry at C4 permits a more balanced competition between elimination and dehydrogenation. 相似文献
98.
Acceleration of Acetal Hydrolysis by Remote Alkoxy Groups: Evidence for Electrostatic Effects on the Formation of Oxocarbenium Ions
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Dr. Angie Garcia Douglas A. L. Otte Dr. Walter A. Salamant Jillian R. Sanzone Prof. K. A. Woerpel 《Angewandte Chemie (International ed. in English)》2015,54(10):3061-3064
In contrast to observations with carbohydrates, experiments with 4‐alkoxy‐substituted acetals indicate that an alkoxy group can accelerate acetal hydrolysis by up to 20‐fold compared to substrates without an alkoxy group. The acceleration of ionization in more flexible acetals can be up to 200‐fold when compensated for inductive effects. 相似文献
99.
A Separation‐Integrated Cascade Reaction to Overcome Thermodynamic Limitations in Rare‐Sugar Synthesis
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Nina Wagner Andreas Bosshart Jurek Failmezger Dr. Matthias Bechtold Prof. Sven Panke 《Angewandte Chemie (International ed. in English)》2015,54(14):4182-4186
Enzyme cascades combining epimerization and isomerization steps offer an attractive route for the generic production of rare sugars starting from accessible bulk sugars but suffer from the unfavorable position of the thermodynamic equilibrium, thus reducing the yield and requiring complex work‐up procedures to separate pure product from the reaction mixture. Presented herein is the integration of a multienzyme cascade reaction with continuous chromatography, realized as simulated moving bed chromatography, to overcome the intrinsic yield limitation. Efficient production of D ‐psicose from sucrose in a three‐step cascade reaction using invertase, D ‐xylose isomerase, and D ‐tagatose epimerase, via the intermediates D ‐glucose and D ‐fructose, is described. This set‐up allowed the production of pure psicose (99.9 %) with very high yields (89 %) and high enzyme efficiency (300 g of D ‐psicose per g of enzyme). 相似文献
100.
Fast quantification of endogenous carbohydrates in plasma using hydrophilic interaction liquid chromatography coupled with tandem mass spectrometry
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Bangjie Zhu Feng Liu Xituo Li Yan Wang Xue Gu Jieyu Dai Guiming Wang Chao Yan 《Journal of separation science》2015,38(1):34-41
Endogenous carbohydrates in biosamples are frequently highlighted as the most differential metabolites in many metabolomics studies. A simple, fast, simultaneous quantitative method for 16 endogenous carbohydrates in plasma has been developed using hydrophilic interaction liquid chromatography coupled with tandem mass spectrometry. In order to quantify 16 endogenous carbohydrates in plasma, various conditions, including columns, chromatographic conditions, mass spectrometry conditions, and plasma preparation methods, were investigated. Different conditions in this quantified analysis were performed and optimized. The reproducibility, precision, recovery, matrix effect, and stability of the method were verified. The results indicated that a methanol/acetonitrile (50:50, v/v) mixture could effectively and reproducibly precipitate rat plasma proteins. Cold organic solvents coupled with vortex for 1 min and incubated at –20°C for 20 min were the most optimal conditions for protein precipitation and extraction. The results, according to the linearity, recovery, precision, matrix effect, and stability, showed that the method was satisfactory in the quantification of endogenous carbohydrates in rat plasma. The quantified analysis of endogenous carbohydrates in rat plasma performed excellently in terms of sensitivity, high throughput, and simple sample preparation, which met the requirement of quantification in specific expanded metabolomic studies after the global metabolic profiling research. 相似文献