time-resolved epr investigation of oxygen and temperature effects on synthetic eumelanin时间分辨的epr对氧气和温度对真黑素合成的影响.pdfVIP

Spectroscopy 24 (2010) 289–295 289 DOI 10.3233/SPE-2010-0430 IOS Press Time-resolved EPR investigation of oxygen and temperature effects on synthetic eumelanin Fosca Conti a,∗, Lucia Panzella b , Alessandra Napolitano b , Marco d’Ischia b and Antonio Toffoletti a a Department of Chemical Sciences, University of Padova, Padova, Italy b Department of Organic Chemistry and Biochemistry, University of Naples Federico II, Naples, Italy Abstract. Synthetic eumelanin produced using 5,6-dihydroxyindole-2-carboxylic acid as precursor and H O /horseradish per- 2 2 oxidase as oxidative reagent, in form of dry powder, has been investigated under photoexcitation by TR-EPR spectroscopy. The formation of spin polarized radical pairs from triplet excited states of melanin has been observed both in absence and in presence of oxygen and has been followed as a function of the temperature in the range 140–290 K. The triplet mechanism explains the observed polarization pattern in net emission. In the presence of oxygen new radical pairs are formed by interaction of melanin with molecular oxygen. Keywords: Melanin, DHICA, EPR spectroscopy, radical pair, spin polarization, excited state, superoxide radical anion 1. Introduction Eumelanins are biopolymers which play a key role in the mammalian pigmentation system. In humans they are present in skin, hair and eyes and are responsible for the dark colours, in contrast to pheome- lanins which are responsible of the red–yellow pigmentation. Eumelanins derive biogenetically from tyrosine via the oxidative polymerization of 5,6-dihydroxyindoles [15]. Although studied extensively in the last decades, the eumelanin role has not been fully elucidated. One effective strategy for investigation is the use of Electron Param