Department of Chemical Sciences (formerly Applied Chemistry), University of Johannesburg, Johannesburg 2028, South Africa.
Centre for Nanomaterials Science Research, University of Johannesburg, Johannesburg 2028, South Africa.
Int J Nanomedicine. 2019 Aug 30;14:7065-7078. doi: 10.2147/IJN.S211959. eCollection 2019.
BACKGROUND: Metal-free, water-soluble and highly stable meso-tetra-(4-sulfonatophenyl) porphyrin (TPPS) has been studied for their singlet oxygen quantum yield. However, TPPS suffers from inherent shortcomings. To address these, TPPS was conjugated to ternary copper indium sulphide/ zinc sulphide (CuInS/ZnS) quantum dots (QDs). PURPOSE: We herein report for the first time the synthesis of TPPS-CuInS/ZnS QDs conjugate as an improved photosensitizer. METHODS: Water-soluble TPPS was synthesized from tetraphenylporphyrin (TPPH) after silica-gel purification. The CuInS/ZnS QDs were synthesized by hydrothermal method at a Cu:In ratio of 1:4. The porphyrin-QDs conjugate was formed via the daggling sulfonyl bond of the porphyrin and amine bond of the QDs. The effect of pH on the optical properties of TPPS was evaluated. The effect of Zn:Cu + In ratio on the ZnS shell passivation was examined to reduce structural defects on the as-synthesized QDs. RESULTS: Various spectroscopic techniques were used to confirm the successful conversion of the organic TPPH to water-soluble TPPS. The singlet oxygen generation evaluation shows an improved singlet oxygen quantum yield from 0.19 for the porphyrin (TPPS) alone to 0.69 after conjugation (CuInS/ZnS-TPPS) with an increase in the reaction rate constant (k (s-1)).
背景:无金属、水溶性且高度稳定的介孔四-(4-磺酸钠苯基)卟啉(TPPS)因其单线态氧量子产率而受到研究。然而,TPPS 存在固有缺陷。为了解决这些问题,将 TPPS 与三元铜铟硫化锌/锌硫化物(CuInS/ZnS)量子点(QDs)偶联。
目的:我们首次报道了 TPPS-CuInS/ZnS QD 缀合物作为一种改良光敏剂的合成。
方法:通过硅胶纯化从四苯基卟啉(TPPH)合成水溶性 TPPS。通过水热法在 Cu:In 比为 1:4 的条件下合成 CuInS/ZnS QDs。通过卟啉的 Daggling 磺酰基键与 QDs 的氨基键形成卟啉-QDs 缀合物。评估 pH 对 TPPS 光学性质的影响。考察 Zn:Cu+In 比对 ZnS 壳层钝化的影响,以减少合成 QDs 上的结构缺陷。
结果:使用各种光谱技术证实了有机 TPPH 成功转化为水溶性 TPPS。单线态氧生成评价表明,单线态氧量子产率从卟啉(TPPS)单独的 0.19 提高到偶联后的 0.69(CuInS/ZnS-TPPS),反应速率常数(k(s-1))增加。
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