Metal Complex Systems of Novel Spectroscopic Significance with Applications to Biochemical Probing

化学探针（报告分子），它能够检测自组装介质中的生物系统，如脂质双层，细胞表面糖链，和核酸已被调查的敏化光谱响应在这种微环境的存在下。在金属络合物系统中发现了适合于此功能的物理过程;（I）近红外（NIR）光吸收（低能电子跃迁）和（II）室温磷光。(I-a)已经发现，疏水环境，如表面活性剂胶束、人工脂质双层和脂质体，强烈增强Ni、Pd和Pt离子的平面1，2-二氨基苯螯合物的MR吸收（730 nm - 850 nm，λ =（5-13）x10^4 M^<-1>cm^<-1>）。(I-b)本文从影响水溶液结构的因素出发，对这种疏水性环境识别的机理进行了探讨，并添加了结构促进剂、结构破坏剂、 关于我们 和疏水性水合破坏剂。加入尿素（一种强疏水性水化破坏剂），与脂质体介质一样，极大地增强了MIR吸收。这表明识别依赖于这些螯合探针附近的水结构，而不是负责感兴趣的介质的亲脂性。（II-a）来自Pt（II）-7-碘-5-磺基-8-羟基喹啉螯合物（ex. 475 nm，em. 630 rim），特别是在正十二烷基-β-D-麦芽糖苷胶束溶液中。这种糖基表面活性剂胶束的增强与生物学研究中必要的糖链识别应用有关。（II-b）合成了具有较大π电子体系的4-羟基吖啶，以提高其发光灵敏度。Pt（II）螯合物也是磷光性的（例如，396 nm，em. 448rim）。小牛胸腺DNA对该螯合物的发光也有类似的增强作用，表明该螯合物能够与DNA分子发生嵌插作用。少

Chemical probes (reporter molecules) which are capable of detecting self-assembly media in biological systems such as lipid bilayers, cell-surface sugar-chains, and nucleic acids have been investigated in terms of the sensitized spectroscopic response in the presence of such microenvironment. The photophysical processes amenable to this function are found in metal-complex systems ; (I) near-infrared (NIR) light absorption(low energy electronic transition) and (II) room-temperature phosphorescence.(I-a) It has been found that the hydrophobic environment, such as surfactant micelles, artificial lipid bilayers, and liposomes strongly enhances the MR absorption (730 nm - 850 nm, epsilon=(5-13)x10^4 M^<-1> cm^<-1>) of planar1 , 2-diaminobenzene chelates of Ni, Pd, and Pt ions.(I-b) The mechanistic investigation of this hydrophobic environment recognition has been made in terms of factors affecting solution structure of water with several additives of structure-promoters, structure-breakers, … More and hydrophobic hydration breakers. The addition of urea, a strong hydrophobic hydration breaker, gives rise to the great enhancement of the MIR absorption as the liposome medium does. This suggests that the recognition depends upon the water-structure in the close vicinity of these chelate probes, rather than being responsible for the lipophilicity of the media of interest.(II-a) The room-temperature phosphorescence from Pt(II) - 7-iodo-5-sulfo-8-quinolinol chelate (ex. 475 nm, em. 630 rim) is strongly facilitated in particular in n-dodecyl-beta-D-maltoside micellar solutions. This enhancement in such sugar-based surfactant micelles is interesting in relation with the applications tosugar-chain recognition necessary in biological studies.(II-b) 4-Hydroxyacridine possessing larger pi-electron system has been synthesized for the benefit of the greater luminescence sensitivity. The Pt(II) chelate is also phosphorescent (ex. 396 nm, em. 448rim) in the above sugar-based micelles. Calf thymus DNA gives the similar enhancement effect on the luminescence of the chelate, which indicates that the chelate can afford to report the intercalation interaction with DNA molecules. Less