Syntheses of Water-Soluble Silver(II)-Phthalocyanines toward Optical Sensing for Thiol Detection
Syntheses of Water-Soluble Silver(II)-Phthalocyanines toward Optical Sensing for Thiol Detection
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水溶性银(II)-酞菁的合成用于硫醇检测的光学传感
DOI：
10.1021/acs.inorgchem.1c00567
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发表时间：
2021
影响因子：
4.6
通讯作者：
Sugimori Tamotsu
中科院分区：
文献类型：
--
作者：
Isago Hiroaki;Fujita Harumi;Nakai Suzuko;Sugimori Tamotsu
用Meerwein试剂季铵化四（4-吡啶硫基）酞菁银（II）的吡啶基，首次合成了四（4-（N-烷基吡啶硫基）酞菁银（II）四氟硼酸盐[Ag（tRpySpc）]（BF_4）_4（R = Me和Et），并通过电喷雾质谱、元素分析和吸收光谱进行了表征。虽然它们在水中强烈聚集，但适当的表面活性剂如聚乙二醇-单油基醚（n=约50; PEG 50）和十二烷基硫酸钠的存在有效地将它们解聚成单体物质。通过光吸收光谱、发射光谱和磁圆二色光谱研究了银酞菁及其聚集体在水溶液和非水溶液中的光谱性质。这些AgPc在室温下在PEG 50水溶液中与硫醇如半胱氨酸、谷胱甘肽、高半胱氨酸和2-硫烷基乙磺酸钠（甚至在0.01 mM的量级）快速反应以释放相应的大环配体H2 Pc，但不与没有巯基的其他氨基酸类似物反应。硫醇与AgPc的摩尔比已被确定为1：1。由于AgPcs在室温下基本上是无荧光的，而H2 Pcs发出强烈的红色荧光，因此AgPcs可以成为生物成像的有效硫醇传感器。
Water-soluble silver(II)–phthalocyanine complexes (AgPcs), tetrakis{4-(N-alkylpyridinium)thio}phthalocyaninato silver(II) tetrafluoroborate, [Ag(tRpySpc)](BF4)4, (R = Me and Et), have been synthesized for the first time by quaternization of pyridyl groups of tetrakis(4-pyridylthio)phthalocyaninato silver(II) by using Meerwein reagents and characterized by ESI-MS, elemental analyses, and optical absorption spectroscopy. Although they strongly aggregate in water, the presence of appropriate surfactants, such as polyethyleneglycol-monooleyl ether (n= approximately 50; PEG50) and sodium dodecyl sulfate, effectively disaggregates them to monomeric species. The spectral properties of the AgPcs and their aggregates in aqueous and nonaqueous solutions have been investigated by optical absorption, emission, and magnetic circular dichroism spectroscopy. These AgPcs rapidly react with thiols such as cysteine, glutathione, homocysteine, and sodium 2-sulfanylethanesulfonate (even on the order of 0.01 mM) in aqueous PEG50 solutions at room temperature to liberate the corresponding macrocyclic ligand, H2Pc, but not with the other amino-acid analogs without sulfhydryl groups. The molar ratio of thiol to AgPc has been determined to be 1:1. Since AgPcs are essentially nonfluorescent at room temperature, while H2Pcs emit intense red fluorescence, AgPcs can be a potent thiol-sensor toward bioimaging.