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Spectroscopic Analysis of Apoferritin Associates with the Water-Soluble Porphyrins
Photochemistry and Photobiology ( IF 2.6 ) Pub Date : 2021-06-23 , DOI: 10.1111/php.13476 Hiroki Sakae 1
Photochemistry and Photobiology ( IF 2.6 ) Pub Date : 2021-06-23 , DOI: 10.1111/php.13476 Hiroki Sakae 1
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The association behavior of apoferritin species with the anionic porphyrins, 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (H2TPPS4−) and its zinc(II) complex (ZnTPPS4−), which are water-soluble even in acidic solutions, was investigated for the first time through UV–Vis absorption and fluorescence spectroscopy in order to evaluate a potential ability of apoferritin as a stimuli-responsive molecular capsule. The absorption maximum wavelengths of both porphyrins were redshifted and the fluorescence intensity decreased, indicating the effective association between apoferritin species and the porphyrins, although it depended on the pH adjustment procedure. At pH 2, the ZnTPPS4− associated with apoferritin subunits without demetallating and protonating, while the free base porphyrin formed the J-aggregate of the diprotonated species (H4TPPS2−)n, with extremely low fluorescence. As the concentration of apoferritin subunits increased, the H2TPPS4−-subunits associates were formed accompanied by recovering the fluorescence. The association stoichiometries of 1 or 2 subunits/porphyrin obtained under neutral and acidic conditions. The significantly large association constant of ZnTPPS4− as compared with that of H2TPPS4− indicated that the coordination to the zinc(II) center strongly contributes to the association in addition to the electrostatic interaction between apoferritin subunits and the porphyrin under acidic conditions.
中文翻译：
脱铁铁蛋白与水溶性卟啉的光谱分析
脱铁铁蛋白与阴离子卟啉 5,10,15,20-四(4-磺基苯基)卟啉 (H 2 TPPS 4− ) 及其锌 (II) 络合物 (ZnTPPS 4− ) 的缔合行为，它们是水-首次通过紫外-可见吸收和荧光光谱研究即使在酸性溶液中也可溶，以评估脱铁铁蛋白作为刺激响应分子胶囊的潜在能力。两种卟啉的最大吸收波长发生红移，荧光强度降低，表明脱铁铁蛋白与卟啉之间存在有效结合，尽管这取决于 pH 调节程序。在 pH 2 时，ZnTPPS 4−与脱铁铁蛋白亚基结合而没有去金属化和质子化，而游离碱卟啉形成双质子化物质 (H 4 TPPS 2- ) n的 J-聚集体，具有极低的荧光。随着脱铁铁蛋白亚基浓度的增加，H 2 TPPS 4- -亚基缔合物伴随着荧光的恢复而形成。在中性和酸性条件下获得的 1 或 2 个亚基/卟啉的缔合化学计量。与 H 2 TPPS 4-相比，ZnTPPS 4-的缔合常数显着大 表明除了在酸性条件下脱铁铁蛋白亚基与卟啉之间的静电相互作用之外，与锌（II）中心的配位对缔合有很大贡献。
更新日期：2021-06-23
中文翻译：
脱铁铁蛋白与水溶性卟啉的光谱分析
脱铁铁蛋白与阴离子卟啉 5,10,15,20-四(4-磺基苯基)卟啉 (H 2 TPPS 4− ) 及其锌 (II) 络合物 (ZnTPPS 4− ) 的缔合行为，它们是水-首次通过紫外-可见吸收和荧光光谱研究即使在酸性溶液中也可溶，以评估脱铁铁蛋白作为刺激响应分子胶囊的潜在能力。两种卟啉的最大吸收波长发生红移，荧光强度降低，表明脱铁铁蛋白与卟啉之间存在有效结合，尽管这取决于 pH 调节程序。在 pH 2 时，ZnTPPS 4−与脱铁铁蛋白亚基结合而没有去金属化和质子化，而游离碱卟啉形成双质子化物质 (H 4 TPPS 2- ) n的 J-聚集体，具有极低的荧光。随着脱铁铁蛋白亚基浓度的增加，H 2 TPPS 4- -亚基缔合物伴随着荧光的恢复而形成。在中性和酸性条件下获得的 1 或 2 个亚基/卟啉的缔合化学计量。与 H 2 TPPS 4-相比，ZnTPPS 4-的缔合常数显着大 表明除了在酸性条件下脱铁铁蛋白亚基与卟啉之间的静电相互作用之外，与锌（II）中心的配位对缔合有很大贡献。
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