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以1,8-二甲基-1,4,8,11-四氮杂环十四烷为原料,以N,N'-二叔丁氧羰基-2-甲璜酰氧基-1,3-二氨基丙烷为烷基化试剂,合成了cyclam衍生物:1,8-二(N,N'-二叔丁氧羰基-1,3-二氨基异丙基)-4,11-二甲基-1,4,8,11-四氮杂环十四烷(L1);及其对应的系列单核金属配合物,Zn(L1)Cl2 (1),Ni(L1)Cl2 (2)和Cu(L1)Cl2 (3);核磁结果表明,L1为C2对称结构,且cyclam环上每一个亚甲基碳上的2个氢化学不等价;利用2D[1H,15N]HSQC对比配体配位前后N-H化学位移的变化,确定配合物的结构是金属与配体cyclam环上的4个氮原子配位;利用变温核磁1H NMR和13C NMR,结合2D[1H,15N]HSQC核磁共振波谱表明,配合物1在溶液中主要以两种构型并存,并主要以trans-Ⅲ构型存在。此外,用凝胶电泳研究了配体与单核金属配合物对超螺旋pBR322质粒DNA切割活性;实验结果表明,配合物3在抗坏血酸存在的条件下具有核酸酶活性,而配体(L1),配合物1和配合物2在实验条件下,无论是氧化切割还是水解切割都显阴性。 相似文献
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以1,8-二甲基-1,4,8,11-四氮杂环十四烷为原料,以N,N′-二叔丁氧羰基-2-甲璜酰氧基-1,3-二氨基丙烷为烷基化试剂,合成了cyclam衍生物:1,8-二(N,N′-二叔丁氧羰基-1,3-二氨基异丙基)-4,11-二甲基-1,4,8,11-四氮杂环十四烷(L1);及其对应的系列单核金属配合物,Zn(L1)Cl2(1),Ni(L1)Cl2(2)和Cu(L1)Cl2(3);核磁结果表明,L1为C2对称结构,且cyclam环上每一个亚甲基碳上的2个氢化学不等价;利用2D[1H,15N]HSQC对比配体配位前后N-H化学位移的变化,确定配合物的结构是金属与配体cyclam环上的4个氮原子配位;利用变温核磁1H NMR和13C NMR,结合2D[1H,15N]HSQC核磁共振波谱表明,配合物1在溶液中主要以两种构型并存,并主要以trans-Ⅲ构型存在。此外,用凝胶电泳研究了配体与单核金属配合物对超螺旋p BR322质粒DNA切割活性;实验结果表明,配合物3在抗坏血酸存在的条件下具有核酸酶活性,而配体(L1),配合物1和配合物2在实验条件下,无论是氧化切割还是水解切割都显阴性。 相似文献
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硫代磷酸酯(PS)修饰的寡聚核苷酸被广泛应用于生物化学机制研究、生物医药和新材料等领域.硫代磷酸酯中心P原子的立体构型对于PS核酸的生化性质具有显著影响.因此,高效、高立体选择性地合成PS寡聚核苷酸在过去的30年中引起了广泛的关注.本文分类归纳了制备立体纯PS寡聚核苷酸的方法,重点总结了近10年来基于立体纯单体和手性催化剂进行立体控制合成PS寡聚核苷酸的重要进展,对不同合成方法的优缺点进行了对比分析,最后对立体纯PS寡聚核苷酸合成的前景进行了展望. 相似文献
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介绍了近几年来富勒烯金属包合物、富勒烯球体与金属键联形成的配合物、富勒烯有机衍生物与金属原子形成的配合物以及富勒烯-有机金属配合物形成的共晶的研究进展. 相似文献
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多核金属配合物模拟水解酶催化研究进展 总被引:5,自引:0,他引:5
对近年来双核及三核金属配合物作为水解酶模型催化水解反应的研究工作进行了综述,分别从模型物的设计要求、催化反应机理等方面进行了讨论,并对其今后的发展前景进行了展望。 相似文献
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New metal‐free DNA cleaving reagent 1 , 1,4,7‐triazacrown (TACN) both with aminoethyl, hydroxyethyl side arms and a planar anthraquinone linked by an alkyl (1,6‐hexamethylene) spacer has been synthesized and characterized by NMR and MS spectrometry. For comparison, the corresponding aminoethyl, hydroxyethyl triazacrown derivative 2 without the anthraquinone has also been synthesized. DNA‐binding properties via fluorescence and CD spectroscopy indicate that the binding affinity of 1 with DNA is much stronger than that of 2 . Agarose gel electrophoresis was used to assess plasmid pUC19 DNA cleavage. Kinetic data of DNA cleavage promoted by 1 , 2 and parent triazacrown (TACN) 3 under physiological condition give the 15‐fold and 234‐fold rate acceleration of compound 1 over 2 and parent triazacrown 3 . Radical scavenger inhibition study suggests that DNA cleavage promoted by 1 may be a non‐oxidative pathway through the transphosphorylation and then hydrolysis. The dramatic rate acceleration is due not only to the anthraquinone moiety of compound 1 intercalating into DNA base pairs via stacking interaction, but also the cooperative catalysis of the nucleophilic hydroxyl and the electrophilic ammonium group for the cleavage of phosphodiester of DNA. 相似文献
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The interaction of zinc(II) complex of N,N′‐bis(guanidinoethyl)‐2,6‐pyridinedicarboxamide (Gua) with DNA was studied by CD spectroscopy and agarose gel electrophoresis analysis. The results indicate that the DNA binding affinity of Zn2+‐Gua is stronger than that of Gua and the Zn2+‐Gua can promote the cleavage of phosphodiester bond of supercoiled DNA under a physiological condition, which is ~106 times higher than DNA natural degradation. The hydrolysis pathway was proposed as the possible mechanism for DNA cleavage promoted by the Zn2+‐ Gua. The acceleration is due to cooperative catalysis of the zinc cation center and the functional groups (bisguanidinium groups). 相似文献
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Zhen Li Zhao Wei Feng Xu Yin Huan Li Tian Jian Lu Yong Mei Chen Gui Jiang Zhou 《Macromolecular rapid communications》2012,33(14):1191-1196
Novel phosphorescent hydrogels have been explored by immobilizing an IrIII metal complex into the matrices of hydrogels. FTIR spectra demonstrate that the IrIII–PNaAMPS hydrogel is achieved by irreversible incorporation of positively charged [Ir(ppy)2(dmbpy)]Cl (ppy = 2‐phenylpyrine, dmbpy = 4,4′‐dimethyl‐2,2′‐bipyridine) into negatively charged poly(2‐acrylamido‐2‐methylpropane sulfonic acid sodium) (PNaAMPS) hydrogel via electrostatic interaction. The photoluminescent spectra indicate that the IrIII–PNaAMPS hydrogel exhibits stable phosphorescence. In vitro cultivation of human retinal pigment epithelial cells demonstrates the cytocompatibility of the IrIII–PNaAMPS hydrogel. This work herein represents a facile pathway for fabrication of phosphorescent hydrogels. 相似文献
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高能量密度、大容量、高工作电压、低成本、环境友好的二次电池是未来储能电池技术的发展方向。高比能的镁离子电池(MIBs)是以镁或镁合金为负极的二次电池,是一种重要的有望用于电动汽车的新型绿色储能电池。镁离子电池发展缓慢的主要问题是镁离子在正极材料中扩散速度慢。因此,本文综述了五类晶体结构的镁-过渡金属复合物类型(包括一维隧道结构、二维层状结构、三维尖晶石结构、三维NASICON结构、三维橄榄石结构)、制备方法、电化学性能等,还阐述了镁离子在固体中扩散行为及提高扩散速度的措施,最后展望了镁离子电池正极材料镁-过渡金属复合物的重要研究方向。寻找高电压(大于3 V)、高比能量、高可逆性的正极材料和与其匹配的电解液是实现镁离子电池第三次突破的关键。我们希望本文有利于更深入地了解镁离子电池正极材料,促进镁离子电池的发展。 相似文献
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C. Allen Chang Tamar E. Woodhouse Qihui Wu Ceshing Sheu Katherine McManus 《中国化学会会志》1988,35(4):253-260
Substitution-inert metal complexes, [Co(edda)(H2O)2]+, (Co(edda)(en)]+, [Co(edda)(dmen)]+, [Co(en)2-(gly)]2+, [Co(en)2(acac)]2+, and [Co(trien)(gly)]2+ in their nitrate salt solutions are used as eluents in nonsuppressed cation chromatography (where edda = ethylenediamine-N,N′-diacetic acid, en = ethylenediamine, dmen = N,N′-dime-thylethylenediamine, gly = glycine, acac = acetylacetone, and trien = triethylenetetraamine). It is found that all the mono- and di-valent charged complexes can be used to separate alkali and alkaline earth metal cations, respectively. The separations for monovalent cations are sometimes comparable to those using ultrapure HNO3 solutions. However, the divalent Ca2+ and Sr2+ ions cannot be resolved using the metal complex eluents. On the other hand, a selected, direct non-suppressed IC separation of zinc(II) and cadmium(II) ions is demonstrated for the first time using a substitution-inert metal complex eluent and a conductivity detector. Comparisons of these eluents with those reported previously, i. e. HNO3 and ethylenediammonium salt solution are made and explanations are proposed to account for the different selectivities observed where possible. The future development of this technique is also briefly discussed. 相似文献