Electrostatic Modification for Promotion of Flavin-Mediated Oxidation of a Probe for Flavin Detection
| Autor: | Kyungja Han, Jong-In Hong, Sohyeon Bae, Seong Keun Kim, Dong-Nam Lee, Ik-Soo Shin |
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| Rok vydání: | 2017 |
| Předmět: |
Static Electricity
Flavin mononucleotide chemistry.chemical_element Flavin group Zinc 010402 general chemistry Photochemistry 01 natural sciences Redox Catalysis chemistry.chemical_compound Electron transfer Coumarins Flavins Eosinophilia Organometallic Compounds Humans Moiety Amines Picolinic Acids chemistry.chemical_classification Flavin adenine dinucleotide 010405 organic chemistry Organic Chemistry Electrochemical Techniques General Chemistry Electron acceptor Flow Cytometry 0104 chemical sciences Eosinophils Kinetics Microscopy Fluorescence chemistry Thermodynamics Oxidation-Reduction |
| Zdroj: | Chemistry - A European Journal. 23:16078-16084 |
| ISSN: | 0947-6539 |
| DOI: | 10.1002/chem.201703466 |
| Popis: | Electrostatic effects on the redox photochemistry of synthetic probes (1, 2, and 1–Zn) are examined by adjusting the thermodynamic driving force of their oxidation reactions. The redox photochemistry was simply controlled by introducing a zinc binding site (2,2′-dipicolylamine (DPA)) on the coumarin moiety of probe 2. Zinc complexation produced a positively charged environment on the coumarin (1–Zn), which lowered the electron density of a nearby 9 H-xanthene ring, attenuating the auto-oxidation of 1–Zn by 45 % compared with that of probe 1 at 298 K. The positive net charge of 1–Zn also provided an attractive Coulombic force toward the phosphate of flavin mononucleotide and flavin adenine dinucleotide, which lowered the reduction potential of the electron acceptor (isoalloxazine) and improved intermolecular electron transfer from the 9 H-xanthene ring to isoalloxazine. The flavin-mediated oxidation rate of 1–Zn was increased to 1.5 times that of probe 2. Probe 1–Zn showed highly selective sensing behaviour toward flavins, producing an intense brightness (ϵΦF=2.80×103 m−1 cm−1) in the long-wavelength regions (λmax=588 nm) upon flavin-mediated oxidation. Furthermore, probes 1–Zn and 2 were successfully applied to eosinophil imaging and the differential diagnosis of eosinophilia; this demonstrates their use as diagnostic tools. |
| Databáze: | OpenAIRE |
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