Carbon monoxide and nitrogen monoxide ligand dynamics in synthetic heme and heme-copper complex systems.

Carbon monoxide and nitrogen monoxide ligand dynamics in synthetic heme and heme-copper complex systems.
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DOI:
10.1021/ja906172c
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发表时间:
2009-10-07
影响因子:
15
通讯作者:
Karlin, Kenneth D.
Karlin, Kenneth D.
中科院分区:
化学1区
文献类型:
--
作者:
Lucas, Heather R.;Meyer, Gerald J.;Karlin, Kenneth D.

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采用瞬态吸收激光闪光光解方法,研究了一氧化氮(·NO)和一氧化碳(CO)在铁-铜间的迁移,发现了一种前所未有的现象.使用1:1血红素/铜组分体系,其由六配位亚铁物质F8 FeII(CO)(DCIM)或F8 FeII(NO)(thf){F8 =四(2,6-二氟苯基)卟啉(2-); DCIM = 1,5-二环己基咪唑; thf =四氢呋喃}和三齿配位的两种配体-铜(I)-络合物{BzL;(苄基)双(2-吡啶基甲基)胺}和四齿配位的两种配体-铜(I)-络合物{PyL;三(2-吡啶基甲基)胺}组成。结果表明,较低的亲和力NO结合铜(I)与CO和较高的速率NO结合血红素与CO。事实上,后者的事件已被观察到在细胞色素c氧化酶aa 3。
Intermolecular nitrogen monoxide (•NO) and carbon monoxide (CO) transfer from iron-to-copper and back, a phenomenon not seen before, has been accomplished by employing transient absorbance laser flash photolytic methods. A 1:1 heme/copper component system was utilized that consisted of a six-coordinate ferrous species, F8FeII(CO)(DCIM) or F8FeII(NO)(thf) {F8 = tetrakis(2,6-difluorophenyl)porphyrinate(2-); DCIM = 1,5-dicyclohexyl imidazole; thf = tetrahydrofuran}, and two ligand-copper(I)-complexes of tridentate {BzL; (benzyl)bis(2-pyridylmethyl)amine} and tetradentate coordination {PyL; tris(2-pyridylmethyl)amine}. The results suggest a lower affinity for NO binding to copper(I) versus CO and a higher rate for NO binding to heme versus CO. In fact, the latter event has been observed in cytochrome c oxidase aa3.
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