Ascenzi Paolo, Ciaccio Chiara, Coletta Massimo
Department of Biology and Interdepartmental Laboratory for Electron Microscopy, University Roma Tre, Viale Guglielmo Marconi 446, I-00146 Roma, Italy.
Biochem Biophys Res Commun. 2007 Nov 30;363(4):931-6. doi: 10.1016/j.bbrc.2007.09.053. Epub 2007 Sep 24.
Peroxynitrite-mediated oxidation of ferrous nitrosylated myoglobin (Mb(II)-NO) involves the transient ferric nitrosylated species (Mb(III)-NO), followed by ()NO dissociation and formation of ferric myoglobin (Mb(III)). In contrast, peroxynitrite-mediated oxidation of ferrous oxygenated myoglobin (Mb(II)-O2) involves the transient ferrous deoxygenated and ferryl derivatives (Mb(II) and Mb(IV)O, respectively), followed by Mb(III) formation. Here, kinetics of peroxynitrite-mediated oxidation of ferrous carbonylated horse heart myoglobin (Mb(II)-CO) is reported. Values of the first-order rate constant for peroxynitrite-mediated oxidation of Mb(II)-CO (i.e., for Mb(III) formation) and of the first-order rate constant for CO dissociation from Mb(II)-CO (i.e., for Mb(II) formation) are h=(1.2+/-0.2)x10(-2)s(-1) and k(off(CO))=(1.4+/-0.2)x10(-2)s(-1), respectively, at pH 7.2 and 20.0 degrees C. The coincidence of values of h and k(off(CO)) indicates that CO dissociation represents the rate limiting step of peroxynitrite-mediated oxidation of Mb(II)-CO.
过氧亚硝酸盐介导的亚铁亚硝基化肌红蛋白(Mb(II)-NO)氧化涉及瞬态铁亚硝基化物种(Mb(III)-NO),随后是()NO解离并形成高铁肌红蛋白(Mb(III))。相比之下,过氧亚硝酸盐介导的亚铁氧合肌红蛋白(Mb(II)-O2)氧化涉及瞬态亚铁脱氧和高铁衍生物(分别为Mb(II)和Mb(IV)O),随后形成Mb(III)。在此,报道了过氧亚硝酸盐介导的亚铁羰基化马心肌红蛋白(Mb(II)-CO)氧化的动力学。在pH 7.2和20.0℃下,过氧亚硝酸盐介导的Mb(II)-CO氧化(即形成Mb(III))的一级速率常数和CO从Mb(II)-CO解离(即形成Mb(II))的一级速率常数分别为h=(1.2±0.2)x10(-2)s(-1)和k(off(CO))=(1.4±0.2)x10(-2)s(-1)。h和k(off(CO))值的吻合表明CO解离是过氧亚硝酸盐介导的Mb(II)-CO氧化速率的限制步骤。