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941.
Cheng‐Xiong Liu Zhi‐yong Guo Yan‐Hong Xue Hong‐Yan Zhang Hong‐Qi Zhang Kun Zou Nian‐Yu Huang 《Magnetic resonance in chemistry : MRC》2012,50(4):320-324
Three new steroidal compounds with polyhydroxy groups, tupisteroide A–C (1–3), were obtained from the roots of Tupistra chinensis, together with one known compound (4) that was isolated from this plant for the first time. The structures of tupisteroide A–C were determined on the basis of one‐ and two‐dimensional NMR spectroscopy, including 1H–1H Correlation Spectroscopy, Heteronuclear Multiple Bond Correlation, and Heteronuclear Single Quantum Coherence experiments. The isolated compounds were evaluated for their cytotoxic activities against A549, HepG2, and CaSki cancer cell lines in vitro. Among them, compounds 1, 2, and 4 did not show significant inhibitory activity, but compound 3 showed cytotoxicity against A549 cancer cell lines with IC50 values of 25.0 μM. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
942.
Xiao‐Jie Liu Zhen‐Yu Li Zhong‐Feng Li Xiao‐Xia Gao Yu‐Zhi Zhou Hai‐Feng Sun Li‐Zeng Zhang Xiao‐Qing Guo Guan‐Hua Du Xue‐Mei Qin 《Magnetic resonance in chemistry : MRC》2012,50(3):187-192
Chronic unpredictable mild stress (CUMS) is a well‐validated model of depression. In this study, a urinary metabonomics method based on the NMR spectrometry was used to study the metabolic perturbation in CUMS‐induced rat depression model. With pattern recognition analysis, a clear separation of CUMS rats and healthy controls was achieved, and nine endogenous metabolites contributing to the separation were identified. CUMS‐treated rats were characterized by the increase of glycine, pyruvate, glutamine, and asparagines, as well as the decrease of 2‐oxoglutarate, dimethylglycine, citrate, succinate, and acetate. The urinary biochemical changes related to the metabolic disturbance in CUMS induced depression, and the possible correlations with live qi stagnation in traditional Chinese medicine are discussed. The work shows that CUMS is a reliable model for studying depression, and the noninvasive urinary metabolomic method is a valuable tool to investigate the biochemical pertubations in depression as an early diagnostic means. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
943.
A synthetic strategy for the preparation of cyclic peptide mimetics based on SET-promoted photocyclization processes 总被引:2,自引:0,他引:2
Yoon UC Jin YX Oh SW Park CH Park JH Campana CF Cai X Duesler EN Mariano PS 《Journal of the American Chemical Society》2003,125(35):10664-10671
A novel method for the synthesis of cyclic peptide analogues has been developed. The general approach relies on the use of SET-promoted photocyclization reactions of peptides that contain N-terminal phthalimides as light absorbing electron acceptor moieties and C-terminal alpha-amidosilane or alpha-amidocarboxylate centers. Prototypical substrates are prepared by coupling preformed peptides with the acid chloride of N-phthalimidoglycine. Irradiation of these substrates results in the generation of cyclic peptide analogues in modest to good yields. The chemical efficiencies of these processes are not significantly affected by (1) the lengths of the peptide chains separating the phthalimide and alpha-amidosilane or alpha-amidocarboxylate centers and (2) the nature of the penultimate cation radical alpha-heterolytic fragmentation process (i.e., desilylation vs decarboxylation). An evaluation of the effects of N-alkyl substitution on the amide residues in the peptide chain showed that N-alkyl substitution does not have a major impact on the efficiencies of the photocyclization reactions but that it profoundly increases the stability of the cyclic peptide. 相似文献
944.
Glycopeptide 1 with the fucosylated trisaccharide, beta-d-GlcNAc(1-->4)[alpha-l-Fuc(1-->6)]-beta-d-GlcNAc, linked to the Asn of CD52 peptide was prepared by two methods, both of which used the free glycosyl Asn 12 and glycotripeptide 21 as key intermediates. Thus, after the trisaccharide was prepared and linked to Asn, the carbohydrate moiety was deprotected to give 12. From 12, 21 was constructed in homogeneous NMP solutions by elongating the peptide chain alone the N-terminus. Though the glycopeptides were easily soluble in NMP, they were barely soluble in diethyl ether, because of the free trisaccharide. Consequently, addition of diethyl ether to the reaction mixtures could precipitate the glycopeptides, and the products were conveniently isolated and purified in the solid form. The coupling of 21 with a free nonapeptide 24 in NMP afforded 1. 1 was also prepared by solid-phase synthesis, using the acid-sensitive 2-chlorotrityl resin. In this case, 21 was attached to the nonapeptide on the resin, and the resulting glycopeptide was then released with dilute acetic acid. Deprotection of the peptide under moderate acidic conditions gave 1. The acid-labile alpha-fucose was not affected in these syntheses. 相似文献
945.
Insulating tubular BN sheathing on semiconducting nanowires 总被引:1,自引:0,他引:1
Zhu YC Bando Y Xue DF Xu FF Golberg D 《Journal of the American Chemical Society》2003,125(47):14226-14227
An effective method was developed for generation of insulating tubular boron nitride (BN)-sheathed nanostructures. ZnS nanowires and multilayered Si-SiO2 nanowires were successfully sheathed with insulating tubular BN-forming nanocables. Both the semiconductor nanowire cores and the BN sheaths are crystalline with well-uniform morphologies. 相似文献
946.
A GPI of sperm CD52 was synthesized by a highly convergent procedure, representing the first chemical synthesis of a complex GPI having an acylated inositol. The presence of a large acyl group resulted in unusual properties and reactions of the relevant intermediates, which gave rise to a number of problems. To overcome the problems and achieve the target molecule, a new synthetic strategy was developed. First, the pseudodisaccharide of 2-O-palmitoylinositol was phospholipidated, and then the trimannose segment and the phosphoethanolamine group were sequentially attached. Global deprotection eventually afforded the sperm CD52 GPI. The method may be useful for the synthesis of other GPIs having an acylated inositol. 相似文献
947.
Arya DP Micovic L Charles I Coffee RL Willis B Xue L 《Journal of the American Chemical Society》2003,125(13):3733-3744
Neomycin is the most effective aminoglycoside (groove binder) in stabilizing a DNA triple helix. It stabilizes TAT, as well as mixed base DNA triplexes, better than known DNA minor groove binders (which usually destabilize the triplex) and polyamines. Neomycin selectively stabilizes the triplex (in the presence of salt), without any effect on the DNA duplex. (1) Triplex stabilization by neomycin is salt dependent (increased KCl and MgCl(2) concentrations decrease neomycin's effectiveness, at a fixed drug concentration). (2) Triplex stabilization by neomycin is pH dependent (increased pH decreases neomycin's effectiveness, at a fixed drug concentration). (3) CD binding studies indicate approximately 5-7 base triplets/drug apparent binding site, depending upon the structure/sequence of the triplex. (4) Neomycin shows nonintercalative groove binding to the DNA triplex, as evident from viscometric studies. (5) Neomycin shows a preference for stabilization of TAT triplets but can also accommodate CGC(+) triplets. (6) Isothermal titration calorimetry (ITC) studies reveal an association constant of approximately 2 x 10(5) M(-)(1) between neomycin and an intramolecular triplex and a higher K(a) for polydA.2polydT. (7) Binding/modeling studies show a marked preference for neomycin binding to the larger W-H groove. Ring I/II amino groups and ring IV amines are proposed to be involved in the recognition process. (8) The novel selectivity of neomycin is suggested to be a function of its charge and shape complementarity to the triplex W-H groove, making neomycin the first molecule that selectively recognizes a triplex groove over a duplex groove. 相似文献
948.
N-Glycopeptides containing 1 to 4 trisaccharide chains, with the carbohydrates vicinal to each other in the multivalent glycopeptides, were efficiently synthesized by using the glycosylated Fmoc-asparagine as a key building block. While the couplings of amino acids with glycopeptides could be achieved in the homogeneous solutions in N-methylpyrrolidinone (NMP) to give excellent yields, all products were conveniently isolated from the reaction mixtures through a precipitation method by using the free carbohydrate chains as phase tags. Commercially available pentafluorophenyl (Pfp) esters of amino acids were employed for the glycopeptide elongation. Longer glycopeptides were constructed by means of a highly convergent synthetic design that is based on the coupling of glycopeptide/peptide fragments. Hydrogen bond interactions between free oligosaccharides were proposed to explain the exceptionally high efficiency of the couplings between two glycosylated building blocks. 相似文献
949.
SHI Zuoqing XU Mancai LIN Xue XU Mingcheng FAN Yunge SHI Rongfu YANG Yizhong HE Binglin 《Chinese Journal of Reactive Polymers》2000,(1)
1 INTRODUCTIONPhenol and many substitUted phenols, such as nitrophenols, chlorophenols and aminophenolset al, are the common organic pollutantS existing in wane water of many chemical plants.Treatment of the wastewater containing phenols is an important project for environmentprotection and has been studied by various methods, such as dialysis ['l, microbial degradation ['1,oxidation l'l, extracting with solvents I4] and adsorption with polymeric adsorbents IS]. Theadsorption method is v… 相似文献
950.
Photoinduced reactions of chloranil with 1,1-diarylethenes and product photochemistry-intramolecular 总被引:1,自引:0,他引:1
Photoinduced reactions of chloranil (CA) with 1,1-diarylethenes 1 [(p-X-Ph)(2)C=CH(2), X = F, Cl, H, Me] in benzene afforded products 4-14, respectively, with the bicyclo[4.2.0]oct-3-ene-2,5-diones 4, the 6-diarylethenylcyclohexa-2,5-diene-1,4-diones 5, and 2,3,5, 6-tetrachlorohydroquinone 13 as the major primary products. The cyclobutane products 4 are formed via a triplet diradical intermediate without involvement of single electron transfer (SET) between the two reactants, while 5 is derived from a reaction sequence with initial SET interaction between (3)CA and the alkene. The 9-arylphenanthrene-1,4-diones 6 and its 10-hydroxy-derivatives 7 are secondary photochemical products derived from 5. The isomeric cage products 9-11 are formed from 4 via intramolecular benzene-alkene [2 + 2] (ortho-)photocycloadditions induced by the triplet excited enedione moiety. The relative amount of the two groups of products (4 and its secondary products 9-11 via non-SET route vs 5 and its secondary products 6, 7, 8, 12, and 14 via SET route) shows a rather regular change, with the ratio of non-SET route products gradually increasing with the increase in oxidation potential of the alkenes and in the positive free energy change for electron transfer (DeltaG(ET)) between (3)CA and the alkene, at the expense of the ratio of the products from the SET route. The competition between the SET and non-SET routes was also found to be drastically influenced by solvent polarity, with the SET pathways more favored in polar solvent. Photo-CIDNP investigations suggest the intermediacy of exciplexes or contact ion radical pairs in these reactions in benzene, while in acetonitrile, SET process led to the formation of CA(*)(-) and cation radical of the alkene in the form of solvent separated ion radical pairs and free ions. 相似文献