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排序方式: 共有167条查询结果,搜索用时 15 毫秒
161.
János Daru Zsuzsanna Benda Ádám Póti Dr. Zoltán Novák Dr. András Stirling 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(47):15395-15400
Density functional calculations and experiments have been carried out to unravel the mechanism of a silver‐mediated furan formation by oxidative coupling. Various possible reaction paths were considered and the most favorable channel has been identified on the basis of the calculated solvent‐corrected Gibbs free‐energy profiles. The mechanism represented by this route consists of a radical and a subsequent ionic route. The silver cation has a double role in the mechanism: it is the oxidant in the radical steps and the catalyst for the ionic steps, which is in accordance with the experimental observations. The two most important aspects of the optimal route are the formation of a silver–acetylide, reacting subsequently with the enolate radical, and the aromatic furan‐ring formation in a single step at the latter, ionic segment of the reaction path. Our findings could explain several experimental observations, including the “key‐promoter role” of silver, the preference for ionic cyclization, and the reduced reactivity of internal acetylides. 相似文献
162.
M Herczeg L Lázár Z Bereczky KE Kövér I Timári J Kappelmayer A Lipták S Antus A Borbás 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(34):10643-10652
Two pentasaccharide sulfonic acids that were related to the antithrombin-binding domain of heparin were prepared, in which two or three primary sulfate esters were replaced by sodium-sulfonatomethyl moieties. The sulfonic-acid groups were formed on a monosaccharide level and the obtained carbohydrate sulfonic-acid esters were found to be excellent donors and acceptors in the glycosylation reactions. Throughout the synthesis, the hydroxy groups to be methylated were masked in the form of acetates and the hydroxy groups to be sulfated were masked with benzyl groups. The disulfonic-acid analogue was prepared in a [2+3] block synthesis by using a trisaccharide disulfonic acid as an acceptor and a glucuronide disaccharide as a donor. For the synthesis of the pentasaccharide trisulfonic acid, a more-efficient approach, which involved elongation of the trisaccharide acceptor with a non-oxidized precursor of the glucuronic acid followed by post-glycosidation oxidation at the tetrasaccharide level and a subsequent [1+4] coupling reaction, was elaborated. In vitro evaluation of the anticoagulant activity of these new sulfonic-acid derivatives revealed that the disulfonate analogue inhibited the blood-coagulation-proteinase factor?Xa with outstanding efficacy; however, the introduction of the third sulfonic-acid moiety resulted in a notable decrease in the anti-Xa activity. The difference in the biological activity of the disulfonic- and trisulfonic-acid counterparts could be explained by the different conformation of their L-iduronic-acid residues. 相似文献
163.
Weigelt S Huber T Hofmann F Jost M Ritzefeld M Luy B Freudenberger C Majer Z Vass E Greie JC Panella L Kaptein B Broxterman QB Kessler H Altendorf K Hollósi M Sewald N 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(2):478-487
The efrapeptin family of peptide antibiotics produced by the fungus Tolypocladium niveum, and the neo‐efrapeptins from the fungus Geotrichum candidumare inhibitors of F1‐ATPase with promising antitumor, antimalaria, and insecticidal activity. They are rich in Cα‐dialkyl amino acids (Aib, Iva, Acc) and contain one β‐alanine and several pipecolic acid residues. The C‐terminus bears an unusual heterocyclic cationic cap. The efrapeptins C–G and three analogues of efrapeptin C were synthesized using α‐azido carboxylic acids as masked amino acid derivatives. All compounds display inhibitory activity toward F1‐ATPase. The conformation in solution of the peptides was investigated with electronic CD spectroscopy, FT‐IR spectroscopy, and VCD spectroscopy. All efrapeptins and most efrapeptin analogues were shown to adopt helical conformations in solution. In the case of efrapeptin C, VCD spectra proved that a 310‐helix prevails. In addition, efrapeptin C was conformationally studied in detail with NMR and molecular modeling. Besides NOE distance restraints, residual dipolar couplings (RDC) observed upon partial alignment with stretched PDMS gels were used for the conformational analysis and confirmed the 310‐helical conformation. 相似文献
164.
Development of incurred reference material for improving conditions of gluten quantification 总被引:1,自引:0,他引:1
Bugyi Z Török K Hajas L Adonyi Z Poms RE Popping B Diaz-Amigo C Kerbach S Tömösközi S 《Journal of AOAC International》2012,95(2):382-387
Celiac disease and wheat allergy are the most common adverse reactions triggered by cereal proteins, mainly gluten, which is one of the 14 allergenic food ingredients that must be labeled on food products in the European Union (EU). To meet the requirements of this regulation, reliable analytical methodology for proper quantification of gluten is necessary. However, validation of presently used methods (ELISA and lateral flow device) is limited partly due to the lack of reference methods and incurred reference materials. To solve this problem, the goal of our work was to develop an incurred reference material for the quantification of gluten under the auspices of EU-FP6 funded Network of Excellence MoniQA. During this work, we produced a processed model product (cookie) containing gliadin (major allergenic fraction of gluten) in a defined amount. This paper addresses the development process of this material together with the associated problems (insufficient homogeneity and low recovery) and their solutions. As a result, an incurred food matrix was produced on a laboratory-scale with a potential use as a reference material. The model product was tested by an ELISA method followed by a comparative study of commercially available ELISA kits to investigate the applicability of the product. Preliminary results of this study are also presented. 相似文献
165.
A liquid chromatographic tandem mass spectrometric (LC–MS–MS) method for the determination of five chemical coccidiostats (decoquinate, diclazuril, halofuginone, nicarbazin, and robenidine) and five ionophore coccidiostats (maduramicin, monensin, narasin, salinomycin, and semduramicin) in yoghurt, kefir, and sour cream is presented. Lasalocid, the sixth ionophore listed in 124/2009/EC was not included because of its extremely dissimilar behavior during sample preparation. Main steps of the method include extraction with acetonitrile, centrifugation, clean-up on Oasis HLB solid phase extraction cartridge, evaporation under nitrogen stream, and LC–MS–MS determination. Selectivity, linearity, sensitivity, accuracy, repeatability, within-laboratory reproducibility, limit of determination, and limit of quantitation were determined during the validation procedure. The method proved to be applicable for both qualitative and quantitative determination of the ten above-mentioned target compounds. In our in-house fermentation experiments, milk fortified with coccidiostats was fermented to get yoghurt, kefir, and sour cream. Our results show that the coccidiostat content did not change significantly during fermentation for any of the target compounds. 相似文献
166.
Attempted cyclisation of N-methylated spiro benzazepine-cyclohexenone (5) into the corresponding N-methyl tetracyclic unit of galanthamine-type alkaloids (6) instead gave an unexpected rearrangement to yield a cyclopentanoisoquinolinone derivative (7). Methylation of the tetrahydrobenzofurobenzazepine tetracycle resulted in the expected N-methyl derivative 6, and the anomalous product 8, with structure similar to that of 7. 相似文献
167.
Zsuzsanna Szabo Eva Juhasz Andrew V. Schally Balazs Dezso Sandor Huga Zoltan Hernadi Gabor Halmos Csongor Kiss 《Molecules (Basel, Switzerland)》2022,27(9)
Antagonists of growth hormone-releasing hormone (GHRH) inhibit the growth of various tumors, including endometrial carcinomas (EC). However, tumoral receptors that mediate the antiproliferative effects of GHRH antagonists in human ECs have not been fully characterized. In this study, we investigated the expression of mRNA for GHRH and splice variants (SVs) of GHRH receptors (GHRH-R) in 39 human ECs and in 7 normal endometrial tissue samples using RT-PCR. Primers designed for the PCR amplification of mRNA for the full length GHRH-R and SVs were utilized. The PCR products were sequenced, and their specificity was confirmed. Nine ECs cancers (23%) expressed mRNA for SV1, three (7.7%) showed SV2 and eight (20.5%) revealed mRNA for SV4. The presence of SVs for GHRH-Rs could not be detected in any of the normal endometrial tissue specimens. The presence of specific, high affinity GHRH-Rs was also demonstrated in EC specimens using radioligand binding studies. Twenty-four of the investigated thirty-nine tumor samples (61.5%) and three of the seven corresponding normal endometrial tissues (42.9%) expressed mRNA for GHRH ligand. Our findings suggest the possible existence of an autocrine loop in EC based on GHRH and its tumoral SV receptors. The antiproliferative effects of GHRH antagonists on EC are likely to be exerted in part by the local SVs and GHRH system. 相似文献