Abstract
In the present work we report the structure and the spectroscopic characterization of a new fluorescent 3-hydroxy-4-pyridinone ligand D-3,4-HPO. The synthesis of the compound was performed in two steps, which involve the reaction of the commercially available fluorophore dansyl chloride with a 3-hydroxy-4-pyridinone chelating unit and further deprotection. The new fluorescent chelator was characterized in the solid state by single-crystal X-ray diffraction and in solution by NMR, MS, absorption and fluorescence spectroscopies. The analysis of the variation of the absorption spectrum with pH allowed the determination of four pK a values (pK a1 = 3.50, pK a2 = 4.50, pK a3 = 9.60, pK a4 = 10.20) and establishment of the corresponding distribution diagram. The study of the fluorescence properties of the ligand show that in the pH range between 4 and 9 the fluorescence intensity is constant and has its maximum value thus allowing its further use at physiological pH values. The interaction of the ligand with copper(II) was accessed by fluorescence spectroscopy in MOPS buffer and the results show that the presence of copper(II) quenches the fluorescence of the ligand in ca 94 % at a ligand: metal ratio of 2:1. The latter result is consistent with the formation of a copper(II) complex with the bidentate ligand, as confirmed by the EPR spectroscopy.
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Acknowledgments
This work received financial support from the European Union (FEDER funds through COMPETE) and National Funds (FCT, Fundação para a Ciência e Tecnologia), under the Partnership Agreement PT2020 through projects NORTE-07-0162-FEDER-000048 UID/QUI/50006/2013 (LAQV/REQUIMTE), and UID/Multi/04378/2013 (UCIBIO/REQUIMTE). The NMR spectrometers are part of the National NMR Network and were purchased within the framework of the National Program for Scientific Re-equipment, contract REDE/1517/RMN/2005, with funds from POCI 2010 (FEDER) and FCT. The authors are greatly indebted to all financing sources. A.L. also thank FCT her grant (SFRH/BPD/85793/2012).
We also thank Dr. Ribeiro, David S. M. and Dr. Santos, Joao L. M. from LAQV, REQUIMTE, FFUP for measurements of absolute photoluminescence quantum yields.
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Leite, A., Silva, A.M.G., Coutinho, C. et al. Design of a Water Soluble Fluorescent 3-Hydroxy-4-Pyridinone Ligand Active at Physiological pH Values. J Fluoresc 26, 1773–1785 (2016). https://doi.org/10.1007/s10895-016-1869-1
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DOI: https://doi.org/10.1007/s10895-016-1869-1