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首页> 外文期刊>Biochemistry >Electron Exchange between Fe(II)-Horse Spleen Ferritin and Co(III)/Mn(III) Reconstituted Horse Spleen and Azotobacter vinelandii Ferritins
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Electron Exchange between Fe(II)-Horse Spleen Ferritin and Co(III)/Mn(III) Reconstituted Horse Spleen and Azotobacter vinelandii Ferritins

机译:铁(II)-马脾铁蛋白与Co(III)/ Mn(III)重构的马脾和葡萄固氮铁蛋白之间的电子交换

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Azotobacter vinelandii bacterioferritin (AvBF) containing 800-1500 Co or Mn atoms as Co-(III) and Mn(III) oxyhydroxide cores (Co-AvBF,Mn-AvBF) was synthesized by the same procedure used previously for horse spleen ferritin (HoSF).The kinetics of reduction of Co-AvBF and Mn-AvBF by ascorbic acid are first-order in each reactant.The rate constant for the reduction of Mn-AvBF (8.52 M~(-1) min~(-1)) is ~12 times larger than that for Co-AvBF (0.72 M~(-1) min~(-1)),which is consistent with a previous observation that Mn-HoSF is reduced approx 10-fold faster than Co-HoSF [Zhang,B.et al.(2005) Inorg.Chem.44,3738-3745].The rates of reduction of M-AvBF (M = Co and Mn) are more than twice that for the reduction of the corresponding M-HoSF.HoSF containing reduced Fe(II) cores (Fe(II)-HoSF),prepared by methyl viologen and CO,also reduces M-HoSF and M-AvBF species,with both cores remaining within ferritin,suggesting that electrons transfer through the ferritin shell.Electron transfer from Fe(II)-HoSF to Co-AvBF occurs at a rate approx 3 times faster than that to Co-HoSF,indicating that the Co cores in AvBF are more accessible to reduction than the Co cores in HoSF.The presence of nonconductive (SiO_2) or conductive (gold) surfaces known to bind ferritins enhances the rate of electron transfer.A more than approx 4-fold increase in the apparent reaction rate is observed in the presence of gold.Although both surfaces (SiO_2 and gold) enhance reaction by providing binding sites for molecular interaction,results show that ferritins with different mineral cores bound to a gold surface transfer electrons through the gold substrate so that direct contact of the reacting molecules is not required.
机译:采用与以前用于马脾铁蛋白(HoSF)相同的方法合成了800-1500个Co或Mn原子作为Co-(III)和Mn(III)羟基氧化物核心(Co-AvBF,Mn-AvBF)的葡萄固氮菌铁蛋白(AvBF)在每种反应物中,抗坏血酸还原Co-AvBF和Mn-AvBF的动力学是一阶的.Mn-AvBF的还原速率常数为(8.52 M〜(-1)min〜(-1))。比Co-AvBF(0.72 M〜(-1)min〜(-1))大12倍,这与以前的观察结果一致,即Mn-HoSF的还原速度比Co-HoSF快10倍[ Zhang,B.et al。(2005)Inorg.Chem.44,3738-3745] .M-AvBF的还原速率(M = Co和Mn)是相应的M-HoSF还原速率的两倍以上。 。由甲基紫精和一氧化碳制备的含有减少的Fe(II)核(Fe(II)-HoSF)的HoSF也会还原M-HoSF和M-AvBF物质,两个核都保留在铁蛋白中,这表明电子通过铁蛋白传递从Fe(II)-HoS转移电子F到Co-AvBF的发生速度比Co-HoSF快3倍,表明AvBF中的Co核比HoSF中的Co核更易还原。存在非导电(SiO_2)或导电(金)已知与铁蛋白结合的表面可提高电子转移速率。在金存在下,表观反应速率可提高约4倍以上。尽管两个表面(SiO_2和金)均通过提供分子的结合位点来增强反应相互作用结果表明,结合到金表面的具有不同矿物质核的铁蛋白通过金基质转移电子,因此不需要反应分子直接接触。

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