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
(f
w) 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.