光敏剂
化学
离子液体
原卟啉IX
四氟硼酸盐
溶剂
荧光
光电流
检出限
光动力疗法
猝灭(荧光)
水溶液
适体
组合化学
光化学
色谱法
有机化学
催化作用
物理
生物
量子力学
遗传学
光电子学
作者
Xiang Hu,Wang Ying,Zuping Xiong,Pei Song,Ai‐Jun Wang,Zhaosheng Qian,Pei-Xin Yuan,Tiejun Zhao,Jiu‐Ju Feng
标识
DOI:10.1021/acs.analchem.1c05578
摘要
Nowadays, aggregation quenching of most organic photosensitizers in aqueous media seriously restricts analytical and biomedical applications of photoelectrochemical (PEC) sensors. In this work, an aggregation-enhanced PEC photosensitizer was prepared by electrostatically bonding protoporphyrin IX (PPIX) with an ionic liquid of 1-butyl-3-methylimidazole tetrafluoroborate ([BMIm][BF4]), termed as PPIX-[BMIm] for clarity. The resultant PPIX-[BMIm] showed weak photocurrent in pure dimethyl sulfoxide (DMSO, good solvent), while the PEC signals displayed a 44.1-fold enhancement in a water (poor solvent)/DMSO binary solvent with a water fraction (fw) of 90%. Such PEC-enhanced mechanism was critically studied by electrochemistry and density functional theory (DFT) calculation in some detail. Afterward, a label-free PEC cytosensor was built for ultrasensitive bioassay of acute lymphoblastic leukemia (molt-4) cells by electrodepositing Au nanoparticles (Au NPs) on the PPIX-[BMIm] aggregates and sequential assembly of protein tyrosine kinase (PTK) aptamer DNA (aptDNA). The resultant cytosensor showed a wide linear range (300 to 3 × 105 cells mL–1) with a limit of detection (LOD) as low as 63 cells mL–1. The aggregation-enhanced PEC performance offers a valuable and practical pathway for synthesis of advanced organic photosensitizer to explore its PEC applications in early diagnosis of tumors.
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