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61.
Short DNA analogues with bridging dimethylene sulfide, sulfoxide, and sulfone groups replacing the phosphate diesters (S-DNAs) were synthesized from building blocks prepared via two routes, both starting from D-glucose. Building blocks for RNA analogues were prepared by stereoselective introduction of nucleobase into a 2'-acylated ribose analogue. The ribose analogues were converted to deoxyribose analogues by replacement of a 3'-OH group by a thioacetyl unit, followed by photolytic deoxygenation or radical-based 2'-deoxygenation. DNA analogues joined via CH(2)(-)S-CH(2) units were prepared by S(N)2 displacement of a 6'-mesyl group on one building block using a thiolate nucleophile of another. 4,4'-Dimethoxytrityl protection and deprotection schemes were established for both the thiol and hydroxyl groups. The corresponding sulfoxide DNA analogues were obtained by oxidation with hydrogen peroxide. Sulfone DNA analogues were obtained by oxidation of the sulfide DNA with persulfate or hydrogen peroxide in the presence of a titanium silicate catalyst. The physical properties of several representative oligonucleotide analogues were examined, and interpreted in light of a "second-generation" model for DNA strand-strand recognition, a model that emphasizes the role of the polyanionic backbone in diminishing unwanted tendencies of highly functionalized molecules to form "structure" in solution. Even short sulfide-linked DNA analogues displayed association properties different from those displayed by standard DNA molecules. Complex formation observed with sulfide-linked tetramers by HPLC study in different solvents suggested that the complex is formed using hydrogen bonding. Sulfone-linked dinucleotides display Watson-Crick behavior; the tetramer, however, displayed self-structure. Self-structure and self-aggregation become more prominent as the length of the oligonucleotide analogues increases. The tendency to self-aggregate can be decreased by adding a charged sulfonate group to the 3'-end of the DNA analogue. Features of the second-generation model are important for many areas of nucleic acid chemistry, from the design of nucleic acid therapeutic agents to the search for life on other planets. 相似文献
62.
The ENDOR spectrum of ~(14)N-~(63)Cu-HAP complex in DMSO/EtOH (5:1) freezing solution at 20 K has been studied using orientational selective method in this paper. The anisotropic superhyperfine coupling tensor and qusdrupole coupling tensor of ligand ~(14)N nucleus, and the superhyperfine coupling tensor of various ~1H nuclei have been measured precisely. Comparing the superhyperfine coupling tensor of ~(14)N-nucleus with previous work shows that the analytical method of spectrum is reasonable and the data are reliable in our previous work. 相似文献
63.
64.
A one-pot procedure for the efficient synthesis of a small library of t-RNA inhibitor analogues was developed. Thus,Rh2(OAc)4 catalyzed three-component 1,3-dipolar cycloaddition reactions of carbonyl ylides derived from diazoindan-1,3-dione and aldehydes with other dipolarophiles in 1,1,2,2-tetrachloroethane at 80 ℃ gave ring fused tetrahydrofurans having three stereocenters in good yield. 相似文献
65.
ZHANG Peng-Fei CHEN Zhen-Chu 《有机化学》2003,23(Z1):87-89
During the last few years alkenyl(phenyl)iodonium salts have risen from mere chemical curiosities to valuable synthetic intermediates. [1] Because of an excellent leaving group ability of a phenyliodonyl moiety, alkenyl(phenyl) iodonium salts undergo nucleophilic vinyl substitutions under mild conditions, thus providing a useful route for the synthesis of various kinds of olefins. Recently, some of functionalized alkenyl iodonium salts have been prepared. [2] 相似文献
66.
CHEN Kai ZHU Zhong-liang ZHANG De-jun 《高等学校化学研究》2006,22(4):435-438
IntroductionStudies on reversible kinetic systems are consi-dered as a hotspot of chemical and biochemical kineticresearches[1,2]. Of late, some researches have been fo-cused on the simultaneous optimization of the obverseand reverse rate constants[3,4].H… 相似文献
67.
从光干涉方式,瞳窗关系和光源带宽等基本关系出发,利用空间不变系统理论解析了相移显微干涉检测系统中衍射效应的影响。为了减小横向分辨率对纵向分辨率的影响,利用相关信息提取或数字滤波的方法,获得了纳米分辨率的三维形貌。 相似文献
68.
流动注射电化学发光测定维生素B1的研究 总被引:2,自引:0,他引:2
基于发现在强碱性介质维生素 B1对电生BrO-氧化Luminol的强化学发光有很强的抑制作用, 将在线恒电流电解产生BrO-与流动注射技术结合,建立了流动注射电化学发光测定维生素B1的新方法.该方法测定维生素B1的线性范围为1.0×10-8~6.0×10-6g·ml-1,检出限为3.2×10-9g·ml-1,相对标准偏差为1.2%(n=11).该法具有灵敏度高,可控性强等优点,用于片剂中的维生素B1含量测定,结果满意. 相似文献
69.
α-Bromo benzolymethylene triphenylphosphorane 3 has been synthesized by the reaction of benzoylmethylene triphenylphosphorane 1 with N-bromosuccinimide in the yield of 87% and can react with aromatic aldehydes 4 to give α-bromochalcones 5 in good yields. 相似文献
70.
离子型溶液聚合速度方程式一般可写成: r=-dM/dθ=kM~mC~n式中M,C分别代表溶液中单体与催化剂的浓度,m,n是两个动力学参数。为了控制聚合过程或设计适当的反应器,必须考虑体系的动力学特性与传热特性的紧密联系。本文 对恒温下分批式聚合操作的各种实施方案进行了讨论。 相似文献