Femtosecond transient absorption spectroscopy of copper(II)-curcumin complexes. 2012

Mandy H M Leung, and Duc-Truc Pham, and Stephen F Lincoln, and Tak W Kee
Department of Chemistry, University of Adelaide, Adelaide, South Australia 5005, Australia.

Ligand-metal interaction between curcumin and Cu(II) in methanol and sodium dodecyl sulfate (SDS) micelles was investigated using fluorescence spectroscopy and transient absorption spectroscopy. The Cu(II) ion exhibits a high efficiency in quenching the fluorescence of curcumin. By quantifying fluorescence quenching as a function of Cu(II) concentration, the complexation constants, K(1) and K(2), for the formation of the 1 : 1 and 1 : 2 Cu(II)-curcumin complexes, [Cu(II)-Cur](+) and [Cu(II)-Cur(2)], have been determined. In methanol, K(1) and K(2) are (1.33 ± 0.47) × 10(8) M(-1) and (6.79 ± 1.77) × 10(5) M(-1), respectively, whereas those in SDS micelles are (9.90 ± 1.68) × 10(5) M(-1) and (1.70 ± 0.48) × 10(6) M(-1), respectively. The transient absorption spectra of curcumin and the Cu(II)-curcumin complexes from 520 nm to 700 nm show a combination of stimulated emission and excited state absorption (ESA). However, the transient absorption signal at 500 nm corresponds to ESA exclusively. For curcumin, the ESA kinetics exhibit two rising components with time constants of 0.9 ps and 8.2 ps in methanol, and 0.5 ps and 2.5 ps in SDS micelles, which are consistent with solvation dynamics of excited state curcumin in these media. In addition, the ESA kinetics show a decay component with a time constant of 125 ps in methanol and 64 ps in SDS micelles, reflecting the excited state intramolecular hydrogen atom transfer of curcumin in these media. The ESA kinetics of the Cu(II)-curcumin complexes exhibit a sharp rise and a fast decay with a time constant of approximately 1 ps in both media due to the strong interaction between Cu(II) and curcumin.

UI MeSH Term Description Entries
D009942 Organometallic Compounds A class of compounds of the type R-M, where a C atom is joined directly to any other element except H, C, N, O, F, Cl, Br, I, or At. (Grant & Hackh's Chemical Dictionary, 5th ed) Metallo-Organic Compound,Metallo-Organic Compounds,Metalloorganic Compound,Organometallic Compound,Metalloorganic Compounds,Compound, Metallo-Organic,Compound, Metalloorganic,Compound, Organometallic,Compounds, Metallo-Organic,Compounds, Metalloorganic,Compounds, Organometallic,Metallo Organic Compound,Metallo Organic Compounds
D003300 Copper A heavy metal trace element with the atomic symbol Cu, atomic number 29, and atomic weight 63.55. Copper-63,Copper 63
D003474 Curcumin A yellow-orange dye obtained from tumeric, the powdered root of CURCUMA longa. It is used in the preparation of curcuma paper and the detection of boron. Curcumin appears to possess a spectrum of pharmacological properties, due primarily to its inhibitory effects on metabolic enzymes. 1,6-Heptadiene-3,5-dione, 1,7-bis(4-hydroxy-3-methoxyphenyl)-, (E,E)-,Curcumin Phytosome,Diferuloylmethane,Mervia,Turmeric Yellow,Phytosome, Curcumin,Yellow, Turmeric
D013050 Spectrometry, Fluorescence Measurement of the intensity and quality of fluorescence. Fluorescence Spectrophotometry,Fluorescence Spectroscopy,Spectrofluorometry,Fluorescence Spectrometry,Spectrophotometry, Fluorescence,Spectroscopy, Fluorescence
D013056 Spectrophotometry, Ultraviolet Determination of the spectra of ultraviolet absorption by specific molecules in gases or liquids, for example Cl2, SO2, NO2, CS2, ozone, mercury vapor, and various unsaturated compounds. (McGraw-Hill Dictionary of Scientific and Technical Terms, 4th ed) Ultraviolet Spectrophotometry
D013997 Time Factors Elements of limited time intervals, contributing to particular results or situations. Time Series,Factor, Time,Time Factor
D015394 Molecular Structure The location of the atoms, groups or ions relative to one another in a molecule, as well as the number, type and location of covalent bonds. Structure, Molecular,Molecular Structures,Structures, Molecular

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