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Effect of UV irradiation on free radicals in synthetic melanin and melanin biopolymer from Sepia offi cinalis : EPR examination

Zdybel M., Pilawa B.

Nukleonika

2015

Vol. 60, No. 3, part 1

483--488

Free radicals in synthetic melanin and melanin from Sepia officinalis were studied by electron paramagnetic resonance (EPR) spectroscopy. The effect of time of ultraviolet (UV) irradiation on free radicals in these melanins was tested. The samples were exposed to UV during 15, 30, and 60 minutes. EPR spectra were measured with microwaves from an X-band (9.3 GHz) in the range of microwave power of 2.2–70 mW. The performed EPR examinations indicate that high concentrations (~1021–1022 spin/g) of o-semiquinone free radicals with g factors of 2.0039–2.0045 exist in all the tested samples. For nonirradiated samples, free radical concentration was higher in natural melanin than in synthetic melanin. UV irradiation caused the increase of free radical concentrations in synthetic melanin samples and this effect depends on the time of irradiation. The largest free radical formation in the both melanins was obtained for 60 min of UV irradiation. Free radical concentrations after the UV irradiation of melanins during 30 min were lower than during irradiation by 15 min, and probably this effect was the result of recombination of the radiatively formed free radicals. EPR lines of the tested samples broadened with increasing microwave power, so these lines were homogeneously broadened. The two types of melanins differed in the time of spin-lattice relaxation processes. Slower spin-lattice relaxation processes exist in melanin from Sepia officinalis than in synthetic melanin. UV irradiation did not change the time of spin-lattice relaxation processes in the tested melanins. The performed studies confirmed the usefulness of EPR spectroscopy in cosmetology and medicine.

Badania centrów paramagnetycznych melaniny z Sepia officinalis metodą EPR

Chodurek E., Czyżyk D., Pilawa B., Wilczyński S.

Engineering of Biomaterials

2009

Vol. 12, no. 86

28-32

Przeprowadzono badania właściwości paramagnetycznych biopolimeru melaninowego otrzymanego z Sepia officinalis z zastosowaniem spektroskopii elektronowego rezonansu paramagnetycznego na pasmo X (9,3 GHz). Biopolimer ten jest wykorzystywany w preparatach kosmetycznych. Analizowano kształt i parametry widm EPR centrów paramagnetycznych melaniny zarejestrowanych jako pierwsza pochodna absorpcji. Otrzymano wartości współczynnika rozszczepienia spektroskopowego g, amplitudy, intensywności integralnej i szerokości linii EPR. Wyznaczono koncentrację centrów paramagnetycznych w badanym biopolimerze melaninowym. Stwierdzono podobne widma EPR i właściwości centrów paramagnetycznych melaniny z Sepia officinalis oraz eumaleniny. Zależne od mocy mikrofalowej asymetryczne widma EPR wskazują na złożony charakter układu centrów paramagnetycznych w testowanym biopolimerze. Wykazano, że w melaninie z Sepia officinalis występują głównie o-semichinonowe wolne rodniki. Wolne procesy relaksacji spin-sieć zachodzą w analizowanej melaninie.

Paramagnetic properties of melanin biopolymer from Sepia officinalis were studied by the use of electron paramagnetic resonance spectroscopy (EPR) at X-band (9.3 GHz). This biopolymer is applied in cosmetics. Lineshape and parameters of first-derivative EPR spectra of melanin paramagnetic centers were analysed. g-Factor, amplitude, integral intensity, and linewidth of EPR spectra were obtained. Concentration of paramagnetic centers in melanin biopolymer was determined. EPR spectra of melanin from Sepia officinalis and properties of its paramagnetic centers are similar to those of eumelanin. Asymmetrical EPR spectra dependent on microwave power indicate that complex paramagnetic centers system is characteristic for the tested biopolymer. It was proved that mainly o-semiquinone free radicals exist in melanin from Sepia officinalis. Slow spin-lattice relaxation processes exist in the analysed melanin.