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Kesheng Feng Farah Mahdavi-Anary Richard E. Partch Yuzhuo Li 《Photochemistry and photobiology》1995,62(5):813-817
Abstract— Photochemical reactions of 6-azidocoumarin and 7-azido-4-methylcoumarin in the presence of secondary amines have been investigated for their potential applications in photoaffinity labeling. It was found that the singlet nitrene generated from 6-azidocoumarin isomerized to a dehydroazepine intermediate that reacted with an amine to yield two isomeric adducts. Photolysis of 7-azido-4-meth-ylcoumarin, in contrast, gave a triplet nitrene that abstracted hydrogen atoms from secondary amine molecules to form 7-amino-4-methylcoumarin as the major product. The difference in the intersystem crossing rate between the two compounds originates from the azido position relative to the carbonyl group. Because of its ability to form a covalent linkage with a nucleophile, 6-azidocoumarin is deemed to have a greater potential as a photoaffinity label than 7-azido-4-methylcoumarin. 相似文献
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Synthesis,Crystal Structure,Fluorescent and Antioxidation Properties of Cerium(III) and Europium(III) Complexes with Bis(3‐methoxysalicylidene)‐3‐oxapentane‐1,5‐diamine 下载免费PDF全文
Two aliphatic ether Schiff base lanthanide complexes (Ln = Eu, Ce) with bis(3‐methoxysalicylidene)‐3‐oxapentane‐1,5‐diamine (Bod), were synthesized and characterized by physicochemical and spectroscopic methods. [Eu(Bod)(NO3)3] ( 1 ) is a discrete mononuclear species and [Ce(Bod)(NO3)3DMF]∞ ( 2 ) exhibits an inorganic coordination polymer. In the two complexes, the metal ions both are ten‐coordinated and the geometric structure around the LnIII atom can be described as distorted hexadecahedron. Under excitation at room temperature, the red shift in the fluorescence band of the ligand in the complexes compared with that of the free ligand can be attributed to coordination of the rare earth ions to the ligand. Moreover, the antioxidant activities of the two complexes were investigated. The results demonstrated that the complexes have better scavenging activity than both the ligand and the usual antioxidants on the hydroxyl and superoxide radicals. 相似文献
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Yu‐Hui Zhang Prof. Dr. Kesheng Song Dr. Nian‐Yong Zhu Dr. Dan Yang Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(2):577-587
As a new type of foldamer, β‐aminoxy peptides have the ability to adopt novel β N? O turns or β N? O helices in solution. Herein, we describe a new subclass of β‐aminoxy peptide, that is, peptides of acyclic β2, 3‐aminoxy acids (NH2OCHR1CHR2COOH), in which the presence of two chiral centers provides insight into the effect of backbone stereochemistry on the folding of β‐aminoxy peptides. Acyclic β2, 3‐aminoxy peptides with syn and anti configurations have been synthesized and their conformations investigated by NMR, IR, and circular dichroism (CD) spectroscopic, and X‐ray crystallographic analysis. The β N? O turns or β N? O helices, which feature nine‐membered rings with intramolecular hydrogen bonds and have been identified previously in peptides of β3‐ and β2, 2‐aminoxy acids, are also predominantly present in the acyclic β2, 3‐aminoxy peptides with a syn configuration and N? O bonds gauche to the Cα? Cβ bonds in both solution and the solid state. In the acyclic β2, 3‐aminoxy peptides with an anti configuration, an extended strand (i.e., non‐hydrogen‐bonded state) is found in the solid state, and several conformations including non‐hydrogen‐bonded and intramolecular hydrogen‐bonded states are present simultaneously in nonpolar solvents. These results suggest that the backbone stereochemistry does affect the folding of the acyclic β2, 3‐aminoxy peptides. Theoretical calculations on the conformations of model acyclic β2, 3‐aminoxy peptides with different backbone stereochemistry were also conducted to elucidate structural characteristics. Our present work may provide useful guidelines for the design and construction of new foldamers with predicable structures. 相似文献
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Jiang J Song K Chen Z Zhou Q Tang Y Gu F Zuo X Xu Z 《Journal of chromatography. A》2011,1218(24):3763-3770
We designed and synthesized a cinchonine derivative to be used as a novel chiral monomer. It was employed in a dual role of functional monomer and cross-linking monomer, displaying multi-binding sites for the template (S)-ketoprofen. Monodisperse molecularly imprinted core-shell microspheres were prepared using surface imprinting method on silica gel. The results show a substantial synergistic effect in the enantioselective recognition, confirming our initial hypothesis. Computational simulation of the monomer and template pre-arrangement strongly supports our proposed chiral recognition mechanism for the imprinted microspheres. 相似文献
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In this study, mixed fuel droplets of ethyl alcohol and biodiesel with different volumes or ratios were prepared and the related expansion, injection and micro-explosion phenomena were investigated. During the tests, a mixed-fuel droplet was hung on a high-temperature-resistant Cr-Ni wire, which was transported to the preheating piston for heating and then was ignited automatically. Micro-needles and an infusion set also were employed to prepare mixed droplets with identical ratios but different volumes. Using a single-lens-reflex (SLR) camera, colour videos that captured the combustion process of the mixed droplets were taken and were processed into colour images using Adobe Premiere Pro CC. The colour image series were analysed to determine the ignition delay time, the burnout time and the flame characteristics during combustion of mixed droplets with different ratios. Instantaneous grey images were obtained by means of high-speed photography during combustion of the mixed droplets with different volumes and different ratios, and of droplets of E40 (in which the volume ratio of ethyl alcohol was 40%). Using Image pro plus and Origin software, the variation of normalised mean droplet diameter with time over the whole combustion cycle was calculated and the underlying reasons for various combustion phenomena were analysed. 相似文献
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Kesheng Shen Xintong Han Chuang Li Guozhen Huang Shanshan Mao Xinkui Shi 《Journal of Coordination Chemistry》2018,71(7):980-990
N,N-bis(N-methyl-2-ylmethylbenzimidazole)aniline (EtAIDB) and its transition metal complexes, [Cu(EtAIDB)Br2]·EtOH {dibromo[N,N-bis(N-methyl-2-ylmethylbenzimidazole)aniline] copper(II) ethanol} (1) and [Zn(EtAIDB)Br2] {dibromo[N,N-bis(N-methyl-2-ylmethylbenzimidazole)aniline] zinc(II)} (2), have been synthesized and characterized by elemental analysis, molar conductivity, UV–visible, and IR spectroscopy. The X-ray crystallographic studies of 1 and 2 have shown two different arrangements: 1 is distorted square-based pyramidal, while 2 can be treated as distorted tetrahedral. The cyclic voltammogram of 1 represents quasi-reversible Cu2+/Cu+ pairs. In vitro antioxidant tests showed that 1 had significant antioxidant activity against superoxide and hydroxy radicals. 相似文献
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Sound relaxational absorption spectroscopy of excitable gas mixtures is potentially applied for gas composition detection. The relaxation of vibrational modes of gas molecules determines the sound relaxational absorption. However, to our knowledge, the contribution of each vibrational mode available in gas mixtures to sound multi-relaxation absorption has not been calculated in existing literature. In this paper, based on the decoupled expression of the effective isochoric molar heat for a gas mixture, a sound multi-relaxation absorption spectrum is decomposed into the sum of single-relaxation spectra. From this decomposable characteristic, the contribution of each vibrational mode available in the gaseous medium to the multi-relaxation absorption is obtained at room temperature. For various gas compositions including carbon dioxide, methane, nitrogen etc., the calculated contributions of vibrational modes are verified by the comparison with experiment data. We prove the following views with quantifiable outcomes that the primary molecular relaxation process associated with the lowest mode plays the major role in acoustic relaxational absorption of gas mixtures; the mode with lower vibrational frequency provides higher contribution to the primary relaxation process. This work could provide a deeper insight into the relationship between the sound relaxational absorption spectroscopy and gas molecules. 相似文献
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