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61.
A model beta-hairpin dodecapeptide [EFGWVpGKWTIK] was designed by including a favorable D-ProGly Type II' beta-turn sequence and a Trp-zip interaction, while also incorporating a beta-strand unfavorable glycine residue in the N-terminal strand. This peptide is highly folded and monomeric in aqueous solution as determined by combined analysis with circular dichroism and 1H NMR spectroscopy. A peptide representing the folded conformation of the model beta-hairpin [cyclic(EFGWVpGKWTIKpG)] and a linear peptide representing the unfolded conformation [EFGWVPGKWTIK] yield unexpected relative deviations between the CD and 1H NMR spectroscopic results that are attributed to variations in the packing interactions of the aromatic side chains. Mutational analysis of the model beta-hairpin indicates that the Trp-zip interaction favors folding and stability relative to an alternate hydrophobic cluster between Trp and Tyr residues [EFGYVpGKWTIK]. The significance of select diagonal interactions in the model beta-hairpin was tested by rearranging the cross-strand hydrophobic interactions to provide a folded peptide [EWFGIpGKTYWK] displaying evidence of an unusual backbone conformation at the hydrophobic cluster. This unusual conformation does not appear to be a result of the glycine residue in the beta-strand, as replacement with a serine results in a peptide [EWFSIpGKTYWK] with a similar and seemingly characteristic CD spectrum. However, an alternate arrangement of hydrophobic residues with a Trp-zip interaction in a similar position to the parent beta-hairpin [EGFWVpGKWITK] results in a folded beta-hairpin conformation. The differences between side chain packing of these peptides precludes meaningful thermodynamic analysis and illustrates the caution necessary when interpreting beta-hairpin folding thermodynamics that are driven, at least in part, by aromatic cross strand interactions. 相似文献
62.
探讨了有机金属催化剂的组成及其对二氧化碳同环氧丙烷交替共聚产物结构的影响,发现二乙基锌—助剂体系的催化活性按如次顺序递降:二乙基锌—连苯三酚>二乙基锌—间苯二酚>二乙基锌—对苯二胺>二乙基锌—亚乙基脲。若用三异丁基铝代替二乙基锌同连苯三酚构成催化剂,则失去对二氧化碳同环氧丙烷交替共聚反应的活性同时,著者发现二乙基锌—二元芳胺催化体系与二乙基锌—二元酚催化体系的催化活性规律完全不同。 相似文献
63.
用柠檬酸盐法合成出La_(1-_x)Sr_xFeO_3(x=0.1,0.2,0.3,0.4)原粉,再经固相反应得到纳米晶粉末,用TG、DTA、XRD、IR进行了表征,确证复合氧化物La_(1-_x)Sr_xFeO_3为钙钛矿型结构,粒径在10~25nm之间。实验结果表明,随着固相反应条件不同,产物粒径呈规律性变化.气敏特性研究表明,该纳米晶材料对乙醇有较高的选择性和灵敏度,其选择性顺序为La_(0.9)Sr_(0.1)FeO_3>LaFeO_3>LaFeO_3(大晶粒)。 相似文献
64.
The structure of an unusual covalent adduct formed by thiol-activated neocarzinostatin chromophore (NCS-chrom) and a RNA-DNA hybrid having an overhang of four unpaired residues at the 3'-end of the RNA strand has been elucidated by MS and NMR spectroscopic analyses. Unlike previously characterized adducts formed by NCS-chrom on the sugar residue of the DNA target, this adduct has been found to be on one of the uracil bases in the RNA overhang. Covalent linkage is between C-6 of the post-activated NCS-chrom and C-5 of the uracil. A novel mechanism involving adduction of the NCS-chrom C-6 radical, generated by 2-mercaptoethanol activation, to C-5 of the uracil at the U9 position of the RNA 11-mer, oxidation by dioxygen, reduction by the thiol, and subsequent dehydration is proposed for adduct formation. 相似文献
65.
The static polarizabilities and the second-order hyperpolarizabilities of a series of tri-nuclear metal cluster models MS4(M′PPh3)2(M′PPh3)(M=Mo,W;M′=Cu,Ag,Au)have been calculated within the first-principle theoretical framework. The model clusters have two fragments of rhombic units and it is the charge ransfer from one of these moieties to the other that is responsible for nonlinear optical property. This kind of electronic delocaization, differentiated from that of planar π-system, is very interesting and is worthy for further investigation. 相似文献
66.
The paper reported the synthetic procedure and character of Copper(Ⅱ) binuclear coordination compound of 1,4-bis-(1′-phenyl-3′-methyl-5′-pyrazolone-4′)-1,4-butanedione. The non-isothermal kinetic of the thermal decomposition of the complex has been studied from the TG-DTG curves by means of the Achar et al and Coats-Redfern methods. The electrochemical characterization of the complex were studied by means of powder microelectrodes technique. 相似文献
67.
Platinum nanoclusters were deposited along the supercoiled DNA strands after incubation of cis-(trans-1R,2R-diaminocyclohexane)(dl-camphorato)platinum(Ⅱ) (Cdp), an analogue of the anti-tumor drug-carboplatin, with DNA and K2PtCl4 for 600 min and then through reduction of dimethylaminoborane (DMAB). The decrease of absorption of DNA at 260 nm indicates the coordination of Cdp and DNA. TEM and AFM were employed to characterize the morphologies and structures of platinum nanoclusters. 相似文献
68.
The gold nanoprisms (GNPs) have exhibited special plasmonic properties for biomedical applications because of their unique shapes and dimensions. Based on their optical performance, the NIR dye IR780 not only enabled the GNPs-based nanosystem as SERRS nanoparticles for Raman-encoded molecular imaging, but also enhanced the plasmonic photothermal property by laser irradiation. Meanwhile, the GNPs/IR780-Lyp-1 by introduction of tumor-homing peptide segment LyP-1, which presents high affinity to p32 protein, demonstrated the increased enrichment in tumor region and enhanced photothermal therapy efficacy. 相似文献
69.
郭黎平 《高等学校化学学报》1993,14(1):29-32
本文将自制Y式玻碳电极拉上两性接枝星形聚合物(GPSMA)的LB膜,用循环伏安法研究谈膜的屏蔽效应,讨论了接枝量、成膜条件等对膜缺陷的影响,并提出了减少缺陷的办法。 相似文献
70.
In continuation of our studies on Aconitum hemsleyanum Pritz.var. pengzhouense, two new norditerpenoid alkaloids, pengshenines A(1) and B(2),have isolated from the roots of the plants and their strucures were elucidated by 1D-and 2D-NMR. 相似文献