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Effect of zinc cations on the kinetics of supramolecular assembly and the chirality of porphyrin J-aggregates

机译:锌阳离子对超分子组装动力学的影响及卟啉j-骨料的手性

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摘要

Dilute aqueous solutions of anionic meso-4-sulfonatophenyl-porphyrin (TPPS) extract zinc(ii) ions from glass or quartz surfaces at room temperature and efficiently form the corresponding metal complex (ZnTPPS). The partial or complete formation of ZnTPPS has been probed by UV/Vis spectroscopy and both static and time-resolved fluorescence. The source of zinc(ii) ions has been clearly identified through inductively coupled plasma optical emission spectrometry. The presence of increasing amounts of ZnTPPS slows down the rate of TPPS J-aggregate formation in acid solution. This influences the nucleation step and has a profound impact on the onset of chirality in these species. This evidence indicates the important role of this adventitious metal ion in the interpretation of various spectroscopic and kinetic data for the self-assembly of the TPPS porphyrin and provides some insights into controversial findings on their chirality. The use of this metal derivative as the starting compound for in situ formation of monomeric TPPS is suggested.
机译:阴离子内消旋-4-磺酸苯基卟啉的稀水溶液(TPPS)提取锌(II)由玻璃或在室温下的石英表面,并且有效地离子形成相应的金属配合物(ZnTPPS)。 ZnTPPS的部分或完全形成的已被探测通过UV / Vis光谱和静态和时间分辨荧光。锌的源(II)离子中已经明确通过电感耦合等离子体光学发射光谱法鉴定。增加ZnTPPS的量的存在减慢的TPPS J-聚集形成在酸性溶液中的速率。这会影响核步骤,并有手性的这些物种发作产生深远的影响。该证据表明这种不定的金属离子的各种光谱和动力学数据的自组装的TPPS卟啉的解释中的重要作用,并提供了一些见解对它们的手性争议的发现。在单体TPPS的原位形成,其用作起始化合物的本金属衍生物的建议。

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