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钌多吡啶配合物的合成及结合DNA的研究 总被引:25,自引:3,他引:25
合成了咪唑并[f]邻菲咯啉(IP)和2-苯基咪唑并[f]邻菲咯啉(PIP)两种新的配体及[Ru·(bp)2(IP)] ̄(2+)(简称b2IP)、[Ru(bpy)2(PIP)] ̄(2+)(简称b2PIP)、[Ru(phen)2(IP)] ̄(2+)(简称p2IP)和[Ru(phen)2(PIP)] ̄(2+)(简称p2PIP)4种新混配物。用电子吸收、稳态发光、圆二色谱研究了配合物与小牛胸腺DNA的结合情况。总的结合强度顺序为:b2IP<b2PIP≤p2IP<p2PIP,这与配体的平面大小、π电子扩展程度和疏水性顺序(bpy<<phen<IP<PIP)是一致的。证明了配合物与DNA存在插入结合。CD谱表明这种结合有对映体选择性. 相似文献
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一种新型含二茂铁基的多吡啶钌配合物与DNA的相互作用 总被引:2,自引:0,他引:2
利用金属配合物与DNA作用前后的光电性质变化探索大分子DNA的结构、构象、生物功能和作用机制之间的规律是无机化学前沿研究热点.Koepf等发现二氯二茂钛[(C6H5)2TiCl2]具有抗肿瘤活性,开创了金属茂类抗癌络合物研究的新领域,大量实验表明:金属茂类化合物不仅具有广泛的抗癌谱, 相似文献
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多吡啶钌配合物作为DNA结构探针的研究 总被引:13,自引:2,他引:13
本文对多吡啶钌配合物作为DNA荧光或结构探针的研究背景、研究技术及其特点、钌配合物与DNA的键合模式及其结合力大小的影响因素、钌配合物与DNA键合的异构选择性及不同键合速率、非放射性核酸标记及DNA分子光开关等方面进行了简要述评 相似文献
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多吡啶钌(Ⅱ)配合物的合成及其与RNA相互作用的光谱学研究 总被引:4,自引:0,他引:4
RNA是生物的重要组成物质 ,它参与蛋白质的生物合成 ,在基因的调控中起着重要的作用 ,并与一些疾病 ,如艾滋病等的诊断与治疗相关联 .与 DNA相比 ,RNA为单链 ,其戊糖为核糖 ,在碱基组成上没有胸腺嘧啶 ,取而代之的是结构十分相近的尿嘧啶 .RNA能自身回折 ,碱基在局部区域内象DN 相似文献
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新型钌(Ⅱ)多吡啶配合物与DNA作用的黏度法研究 总被引:5,自引:0,他引:5
用黏度法系统地研究了新型钌(Ⅱ)多吡啶配合物与DNA的相互作用.结果显示:在一定程度上增大配体的刚性平面,将增大钌(Ⅱ)多吡啶配合物插入DNA碱基对的能力,但当配体的刚性平面太大时,却又由于位阻作用而阻碍了配体对DNA的插入;能够使配体平面性增强的分子内氢键的形成,有利于配合物对DNA的插入作用;配体中引入较大体积的取代基而引起的配体芳环间的扭转,将导致钌(Ⅱ)多吡啶配合物只能“部分地”或“非经典地”插入DNA. 相似文献
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联吡啶钌(Ⅱ)配合物的合成、晶体结构及其在染料敏化太阳能电池中的应用 总被引:2,自引:0,他引:2
制备了一个多吡啶钌(Ⅱ)配合物[Ru(bipy)2(Pyap)](PF6)2 (1)(bipy=2,2′-联吡啶,Pyap=4-(2-吡啶亚甲氨基)-苯酚),研究了它在染料敏化太阳能电池中的应用,对它进行了元素分析、IR、 1H NMR、UV-Vis、PL、XRD、CV、IV等表征。将配合物1的水溶液自然蒸发,得到配合物[Ru(bipy)2(Pyap)](PF6)2·H2O (2)的晶体,我们测定了它的单晶结构,配合物2的晶体属单斜晶系,P21/c空间群。配合物1的乙腈溶液在410~490 nm处有较宽的对应于MLCT跃迁的紫外吸收峰。在波长为400 nm光的激发下,分别在436、463、490 nm处各出现了1个荧光发射峰。其CV曲线表明1有2对可逆的氧化还原峰,在-0.158 V处有1个不可逆的氧化峰。用配合物1作为光敏染料组装成电池,测得最大输出功率Pmax为0.025 mW,短路电流Isc为0.142 mA,开路电压Voc为402 mV,填充因子ff为0.444,光电转化效率η为0.025%。 相似文献
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设计合成含多个配位中心的多吡啶配体ODCIP (3,4-二氯基苯并咪唑并[4,5-f][1,10]邻菲咯啉)及其钌(II)多吡啶配合物[Ru(bpy)2ODCIP]2+. 运用元素分析、红外光谱、核磁谱和质谱对配体及配合物进行结构表征. 利用紫外吸收光谱、荧光光谱和粘度法研究了[Ru(bpy)2ODCIP]2+与DNA(脱氧核糖核酸)的作用机制、与Co2+配位后与DNA的作用机制及其荧光变化情况. 结果表明[Ru(bpy)2ODCIP]2+与DNA通过部分插入模式作用, [Ru(bpy)2ODCIP]2+与Co2+配位形成的双核配合物[Ru(bpy)2(ODCIP)Co]4+也能与DNA插入结合. 进一步利用稳态荧光发射光谱、荧光淬灭实验等方法研究了单核配合物[Ru(bpy)2ODCIP]2+和双核配合物[Ru(bpy)2(ODCIP)Co]4+的荧光性质. 相似文献
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Yu‐Ru Jhou Chien‐Hui Chiou Lin‐Kia Ni Li‐Chou Chen Yau‐Hung Chen Chien‐Chung Chen 《中国化学会会志》2012,59(9):1053-1057
A fluorescent polypyridyl ruthenium complex was successfully prepared using an amide bond linkage to link two rhodamine moieties through bipyridine groups. Although photo‐induced electron transfer (PET) quenched the fluorescent intensity, the quantum yield of the rhodamine‐modified Ru(II) complex was 0.17 in water, sufficient for observing the fluorophore behaviour in biological systems. The rhodaminemodified Ru(II) complex was found to inhibit the bacterial growth of E. coli. In vitro fluorescence images of human hepatoma cells (SK‐Hep1) showed that a fluorescent polypyridyl ruthenium complex not only supported the above observation but also preferably accumulated in the cytoplasmic region inside the cell. These observations suggest that in addition to strong Ru–DNA interactions, Ru‐protein interactions in the cytoplasmic regions are strong and are therefore important to the development of metallopharmaceuticals. 相似文献
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Dr. Anna Notaro Marta Jakubaszek Severin Koch Dr. Riccardo Rubbiani Dr. Orsolya Dömötör Dr. Éva A. Enyedy Mazzarine Dotou Dr. Fethi Bedioui Mickaël Tharaud Dr. Bruno Goud PD Dr. Stefano Ferrari Prof. Dr. Enzo Alessio Dr. Gilles Gasser 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(22):4997-5009
Cancer is one of the main causes of death worldwide. Chemotherapy, despite its severe side effects, is to date one of the leading strategies against cancer. Metal-based drugs present several potential advantages when compared to organic compounds and they have gained trust from the scientific community after the approval on the market of the drug cisplatin. Recently, we reported the ruthenium complex ([Ru(DIP)2(sq)](PF6) (where DIP is 4,7-diphenyl-1,10-phenantroline and sq is semiquinonate) with a remarkable potential as chemotherapeutic agent against cancer, both in vitro and in vivo. In this work, we analyse a structurally similar compound, namely [Ru(DIP)2(mal)](PF6), carrying the flavour-enhancing agent approved by the FDA, maltol (mal). To possess an FDA approved ligand is crucial for a complex, whose mechanism of action might include ligand exchange. Herein, we describe the synthesis and characterisation of [Ru(DIP)2(mal)](PF6), its stability in solutions and under conditions that resemble the physiological ones, and its in-depth biological investigation. Cytotoxicity tests on different cell lines in 2D model and on HeLa MultiCellular Tumour Spheroids (MCTS) demonstrated that our compound has higher activity than cisplatin, inspiring further tests. [Ru(DIP)2(mal)](PF6) was efficiently internalised by HeLa cells through a passive transport mechanism and severely affected the mitochondrial metabolism. 相似文献
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[Ru6(μ-O2CCH3)12(CH3OH)2(HCOO)2][Ru2(μ-O2CCH3)4(H2O)2](PF6)2.2H2O(Ru2(Ⅱ,Ⅲ)混合价)是通过二步反应合成的。首先Ru2(O2CCH3)4Cl在加热条件下与甲醇反应得到红棕色中间物,然后将该中间物在甲醇水(体积比7∶1)溶液中用Ag2SO4和NH4PF6进行脱氯配位反应得到此化合物。用元素分析、红外光谱、热重分析、循环伏安、X-衍射单晶结构分析等对其进行了表征。晶体结构表明,标题化合物的晶体属单斜晶系,空间群为P21/n,晶胞参数:a=0.85362(14)nm,b=1.19589(19)nm,c=3.6642(6)nm,β=92.316(3)°,Z=2,每个结构基元包含2个不同的配离子,其中[Ru2(μ-O2CCH3)4(H2O)2]+是1个双核钌配离子,[Ru6(μ-O2CCH3)12(CH3OH)2(HCOO)2]+是由另1个由甲醇配位、甲酸根桥连的六核钌配离子。2个独立的结构单元通过氢键形成三维超分子网络结构。采用循环伏安法对其电化学性质进行了表征,结果为一对准可逆的氧化还原峰,表明该配合物的中心金属二价钌原子Ru(Ⅱ)与三价钌原子Ru(Ⅲ)之间存在电子转移。 相似文献
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通过分子设计,将带有-OH端基的钌(Ⅱ)联吡啶配合物[Ru(bpy)2L]PF6{L=希夫碱4-[(N甲-基-N羟-乙基)氨基]苯甲醛缩肼基硫代甲酸甲酯}与甲苯-2,4异-氰酸酯、丙烯酸羟乙酯发生共聚合反应,合成了新的侧链型聚氨酯高分子钌聚合物(4)。4的结构经红外光谱和差热分析表征。 相似文献
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用紫外-可见吸收光谱和荧光光谱滴定、稳态荧光淬灭和反向盐滴定实验研究了双核钌(II)配合物[(bpy)2Ru(ebipcH2)Ru(bpy)2](ClO4)4 {bpy=2,2'-联吡啶; ebipcH2=N-乙基-4,7-二(咪唑-[4,5-f]-(1,10-邻菲啰啉)-2-基)咔唑}与酵母RNA 的相互作用. 结果表明该双核配合物以插入方式与酵母RNA 作用, 在生理盐浓度下(≈150 mmol/L NaCl)该配合物与RNA 的相互作用明显强于DNA. 相似文献
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用紫外-可见吸收光谱和荧光光谱滴定、稳态荧光淬灭和反向盐滴定实验研究了双核钌(II)配合物[(bpy)2Ru(ebipcH2)Ru(bpy)2](ClO4)4 {bpy=2,2'-联吡啶; ebipcH2=N-乙基-4,7-二(咪唑-[4,5-f]-(1,10-邻菲啰啉)-2-基)咔唑}与酵母RNA的相互作用. 结果表明该双核配合物以插入方式与酵母RNA作用, 在生理盐浓度下(≈150 mmol/L NaCl)该配合物与RNA的相互作用明显强于DNA. 相似文献
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Veronica Marin Elisabeth Holder Michael A. R. Meier Richard Hoogenboom Ulrich S. Schubert 《Macromolecular rapid communications》2004,25(7):793-798
Summary: An amino‐functionalized bipyridine ligand was prepared in order to serve as a bridging unit to an activated low‐molecular‐weight monomethyl ether of poly(ethylene glycol) (PEG). Coordination of a ruthenium(II ) phenantroline precursor onto the formed PEG‐containing bipyridine ligand yielded a metal‐containing polymer which shows interesting properties for solar cell applications.
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Prof. Kristof Van Hecke Dr. Thomas Cardinaels Dr. Peter Nockemann Jeroen Jacobs Louis Vanpraet Prof. Tatjana N. Parac‐Vogt Prof. Rik Van Deun Prof. Koen Binnemans Prof. Luc Van Meervelt 《Angewandte Chemie (International ed. in English)》2014,53(34):8959-8962
Evolution can increase the complexity of matter by self‐organization into helical architectures, the best example being the DNA double helix. One common aspect, apparently shared by most of these architectures, is the presence of covalent bonds within the helix backbone. Here, we report the unprecedented crystal structures of a metal complex that self‐organizes into a continuous double helical structure, assembled by non‐covalent building blocks. Built up solely by weak stacking interactions, this alternating tread stairs‐like double helical assembly mimics the DNA double helix structure. Starting from a racemic mixture in aqueous solution, the ruthenium(II) polypyridyl complex forms two polymorphic structures of a left‐handed double helical assembly of only the Λ‐enantiomer. The stacking of the helices is different in both polymorphs: a crossed woodpile structure versus a parallel columnar stacking. 相似文献