Emission‐based sensing of cobalt (II) and vitamin B12 via a bis‐indole derivative

• Published in: Luminescence (Chichester, England) England), 2024-08, Vol.39 (8), p.e4863-n/a
• Main Authors: Mumcu, Taskin, Oncuoglu, Serkan, Hizliates, Cevher Gundogdu, Ertekin, Kadriye
• Format: Article
• Language: English
• Subjects: bis‐indole; Co (II); Co2; Cobalt; Cobalt - chemistry; Cobalt compounds; Cyanocobalamin; Dyes; Emission analysis; Emissions; Extinction coefficient; Fluorescence; Fluorescent Dyes - chemical synthesis; Fluorescent Dyes - chemistry; Fourier analysis; Fourier transforms; Indoles; Indoles - chemistry; Infrared analysis; Limit of Detection; Mass spectrometry; Mass spectroscopy; Molecular Structure; NMR; Nuclear magnetic resonance; Polymethyl methacrylate; Polymethylmethacrylate; Quenching; sensor; Spectrometry, Fluorescence; Stoichiometry; Tetrahydrofuran; Vit. B12; Vitamin B 12 - analysis; Vitamin B 12 - chemistry; Vitamin B12; Vitamins
• ISSN: 1522-7235; 1522-7243; 1522-7243
• DOI: 10.1002/bio.4863

In this study, a bis‐indole compound was synthesized, characterized by 1H NMR, Fourier transform infrared, and mass spectroscopic measurements and used as a selective and efficient probe for the spectrofluorimetric analysis of Co (II). The cobalt‐induced quenching in the emission maximum at 567 nm was considered as the analytical signal in calibration studies. When encapsulated in a polymethyl methacrylate (PMMA) matrix, the bis‐indole compound exhibited a limit of detection (LOD) of 3.60 × 10–11 M for Co (II). Vitamin B12, which contains a cobalt ion in the center of a corrin ring in its structure, was also successfully quantified using the same probe. The bis‐indole compound showed a linear response based on quenching for increasing concentrations of vitamin B12, partially mimicking the contracted tetrapyrrole ring found naturally in the center of vitamin B12. The LOD for vitamin B12 was found to be 76 nm. Promising photophysical properties of the proposed probe, including high molar extinction coefficient, considerable quantum yield (0.46 and 0.64 in tetrahydrofuran and PMMA, respectively), high Stoke's shift and satisfactory photostability, make it a good choice for fluorescence‐based Co (II) determination. The ML3‐type stoichiometry of the complex between the dye and cobalt was elucidated both by Job's method and by high‐resolution mass spectrometry (HR‐MS). In this study, a newly synthesized bis‐indole derivative has been successfully used in the analysis of both ionic cobalt and vitamin B12. The fluorescent bis‐indole ligand surrounds cobalt ions and acts similarly to the corrin ring in the structure of vitamin B12 in nature. The quenching of the emission band at 512 nm versus varying concentrations of cobalt can be used as an analytical signal in the assay.