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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和卟啉J-聚集体手性的影响

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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:室温下,阴离子型内消旋-4-磺酰基苯基卟啉(TPPS)的稀水溶液可从玻璃或石英表面提取锌(ii)离子,并有效地形成相应的金属络合物(ZnTPPS)。 ZnTPPS的部分或全部形成已通过紫外/可见光谱以及静态和时间分辨荧光进行了探测。锌(ii)离子的来源已通过电感耦合等离子体光学发射光谱法明确鉴定。越来越多的ZnTPPS的存在减慢了在酸性溶液中TPPS J聚集体形成的速度。这会影响成核步骤,并对这些物种中手性的产生产生深远影响。该证据表明这种不定形金属离子在解释TPPS卟啉自组装的各种光谱和动力学数据中的重要作用,并提供了有关其手性的有争议发现的一些见解。建议使用该金属衍生物作为原位形成单体TPPS的起始化合物。

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