4.8 Article

Novel Aggregation-Enhanced PEC Photosensitizer Based on Electrostatic Linkage of Ionic Liquid with Protoporphyrin IX for Ultrasensitive Detection of Molt-4 Cells

Journal

ANALYTICAL CHEMISTRY
Volume 94, Issue 8, Pages 3708-3717

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.analchem.1c05578

Keywords

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Funding

  1. Natural Science Foundation of Zhejiang Province [LQ19B050004]
  2. Open Research Fund of Key Laboratory of the Ministry of Education for Advanced Catalysis Materials (Zhejiang Normal University)
  3. National Natural Science Foundation of China [31970173]

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In this study, an aggregation-enhanced PEC photosensitizer PPIX-[BMIm] was prepared by electrostatic bonding, and its PEC performance in a binary solvent of water and DMSO was studied. A label-free PEC cytosensor was built using PPIX-[BMIm], which showed a wide linear range and low limit of detection for detecting leukemia cells.
Nowadays, aggregation quenching of most organic photosensitizers in aqueous media seriously restricts analytical andbiomedical applications of photoelectrochemical (PEC) sensors. In this work, an aggregation-enhanced PEC photosensitizer wasprepared 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 dimethylsulfoxide (DMSO, good solvent), while the PEC signals displayed a 44.1-fold enhancement in a water (poor solvent)/DMSO binarysolvent with a water fraction (fw) of 90%. Such PEC-enhanced mechanism was critically studied by electrochemistry and densityfunctional theory (DFT) calculation in some detail. Afterward, a label-free PEC cytosensor was built for ultrasensitive bioassay ofacute lymphoblastic leukemia (molt-4) cells by electrodepositing Au nanoparticles (Au NPs) on the PPIX-[BMIm] aggregates andsequential assembly of protein tyrosine kinase (PTK) aptamer DNA (aptDNA). The resultant cytosensor showed a wide linear range(300 to 3x105cells mL-1) with a limit of detection (LOD) as low as 63 cells mL-1. The aggregation-enhanced PEC performanceoffers a valuable and practical pathway for synthesis of advanced organic photosensitizer to explore its PEC applications in earlydiagnosis of tumors.

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