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941.
Foldable polymers with alternating single-strand deoxyribonucleic acid and planar conjugated organic perylene tetracarboxylic diimide units were found to self-organize into loosely folded nanostructures. Upon heating, the loosely folded structures become more ordered as evidenced by pi-stacking in the perylene segments. The folding and unfolding processes driven by the molecular interactions of adjacent perylenes were monitored in both aqueous and organic solutions. Heat-promoted folding, or inverse temperature behavior, which originates from positive enthalpy changes, was only observed in water. Therefore, we attributed this inverse temperature dependence to hydrophobic effects rather than pi-pi molecular orbital overlap between the perylene planes. These findings shed light on the design of new thermophiles in protein engineering as well as the construction of macromolecular-based nanodevices with actuator and sensory properties. 相似文献
942.
Dakoji S Li D Agnihotri G Zhou HQ Liu HW 《Journal of the American Chemical Society》2001,123(40):9749-9759
The inhibitory properties of (methylenecyclopropyl)formyl-CoA (MCPF-CoA), a metabolite derived from a natural amino acid, (methylenecyclopropyl)glycine, against bovine liver enoyl-CoA hydratase (ECH) were characterized. We have previously demonstrated that MCPF-CoA specifically targets ECHs, which catalyze the reversible hydration of alpha,beta-unsaturated enoyl-CoA substrates to the corresponding beta-hydroxyacyl-CoA products. Here, we synthesized (R)- and (S)-diastereomers of MCPF-CoA to examine the stereoselectivity of this inactivation. Both compounds were shown to be competent inhibitors for bovine liver ECH with nearly identical second-order inactivation rate constants (k(inact)/K(I)) and partition ratios (k(cat)/k(inact)), indicating that the inactivation is nonstereospecific with respect to ring cleavage. The inhibitor, upon incubation with bovine liver ECH, labels a tryptic peptide, ALGGGXEL, near the active site of the protein, where X is the amino acid that is covalently modified. Cloning and sequence analysis of bovine liver ECH gene revealed the identity of the amino acid residue entrapped by MCPF-CoA as Cys-114 (mature sequence numbering). On the basis of gHMQC (gradient heteronuclear multiple quantum coherence) analysis with [3-(13)C]-labeled MCPF-CoA, the ring cleavage is most likely induced by the nucleophilic attack at the terminal carbon of the exomethylene group (C(2)'). We propose a plausible inactivation mechanism that involves relief of ring strain and is consistent with examples found in the literature. In addition, these studies provide important clues for future design of more efficient and selective inhibitors to control and/or regulate fatty acid metabolism. 相似文献
943.
Tonggang Jiu Yongjun Li Haiyang Gan Yuliang Li Huibiao Liu Shu Wang Weidong Zhou Chunru Wang Xiaofang Li Xiaofeng Liu Daoben Zhu 《Tetrahedron》2007,63(1):232-240
The oligo(p-phenylene vinylene)-porphyrin-oligo(p-phenylene vinylene) (P-OPVn, n=2, 4, where n is the number of phenyl rings) and the complex with Zn2+ based on P-OPVn were synthesized for investigating their photophysical properties via UV-vis, voltammetry, steady-state and time-resolved fluorescence spectra. In these molecules two OPV moieties as energy donors were linked to porphyrin center by virtue of Wittig reaction. The detailed studies of photophysical properties indicate that OPV group can act as an antenna unit for effective intramolecular energy transfer. 相似文献
944.
Zhou D Piper JD Abell C Klenerman D Kang DJ Ying L 《Chemical communications (Cambridge, England)》2005,(38):4807-4809
We show that direct coupling of a dye-labelled DNA (acceptor) to a quantum dot (QD) donor significantly reduces the donor-acceptor distance and improves the FRET efficiency: a highly efficient FRET (approximately 88%) at a low acceptor-to-donor ratio of 2 has been achieved at the single-molecule level. 相似文献
945.
GMA熔融接枝EPDM的研究 总被引:10,自引:0,他引:10
以甲基丙烯酸缩水甘油酯(GMA)为接枝单体,过氧化二异丙苯(DCP)为引发剂,对三元乙丙胶(EPDM)进行了熔融接枝,在烃链上引入极性基团,以改善EPDM与极性聚合物的相容性。用差示扫描量热计(DSC)研究了GMA的聚合温度,用富里叶红外(FT-IR)、凝胶渗透色谱(GPC)对接枝产物进行了表征。实验结果表明,产物的接枝率和凝胶量可以通过反应条件(温度、时间、反应物组成及加料方式)来控制。 相似文献
946.
电沉积条件对锌镀层织构的影响 总被引:14,自引:1,他引:14
采用XRD方法研究添加剂,络合剂,以及电流密度对锌酸盐镀锌层的织构和晶粒尺寸的影响,结果表明,添加剂AA-1的存在有利于(101)晶面取向;而DIE则使镀层转变为110择优;两种添加剂同时存在下,可在一定的电流密度范围内获得高择优取向的锌镀层,而当又有络合剂TEA和EDTA同时存在时,则可在更宽广的电流密度范围内制得日 粒细密、表面光亮、择优系数TC(110)在985以上的高择优取向锌沉积层。 相似文献
947.
948.
本文将气液色谱法用于测定环丁砜含盐溶液中以烃、芳烃、氯代烃、醇和酮为溶质的盐效应常数,结果表明,大多数溶质的盐效应关系可用Setschenow方程描述;负离子的性质对盐效应的影响比正离子更重要;负离子的电子向氯代烃中氯原子3d空轨道的迁移作用对其k_s的影响很大。 相似文献
949.
人造芥子油中异硫氰酸烯丙酯与硫氰酸烯丙酯的气相色谱分析 总被引:4,自引:0,他引:4
采用2m×3mm玻璃柱,涂布0.5%EGA的80~100目GaschromQ为固定相,以异辛醇为内标物,分析芥子油中异硫氰酸烯丙酯与硫氰酸烯丙酯异构体。该方法既可用于人造芥子油的含量分析,也可用于市售芥子油的质量鉴定。 相似文献
950.
Zhang Yongqiang Wang Baiquan Xu Shansheng Zhou Xiuzhong Sun Jie 《Transition Metal Chemistry》1999,24(6):722-725
Reactions of diiron complexes (E)[5-t-BuC5H3)Fe(CO)]2(-CO)2 [E = Me2Si (1), Me2SiSiMe2 (2), and Me2SiOSiMe2 (3)] with iodine in CHCl3 yielded diiodide complexes (E)[5-t-BuC5H3)Fe(CO)2I]2 [E=Me2Si (5), Me2SiSiMe2 (6), and Me2SiOSiMe2 (7)]. Like (1–3), complexes (5–7) also exists as mixtures of cis and trans isomers even though the Fe–Fe bond in (1–3) has been cleaved. When the pure isomers (1–3) reacted with iodine respectively in CHCl3, the cis isomers (1c–3c) yielded only the cis products (5c–7c), whereas the trans isomers (1t–3t) yielded only the trans isomers (5t–7t). This indicates that iodination of bridged diiron complexes is stereospecific. Similar treatment of trans-(Me2Si)[{5-t-(heptyl)C5H3}Fe(CO)]2(-CO)2 (4t) with iodine gave only the trans product (Me2Si)[{5-t-(heptyl)C5H3}Fe(CO)2I]2 (8t). The molecular structure of (5t) was determined by X-ray diffraction. 相似文献