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11.
Microperoxidase 11 was adsorbed on Au(111) from basic aqueous solutions containing pure heme peptide and co-added stoichiometric amounts of exogenous neutral and ionic ligands. The addition of small molecules to MP11 produced different aggregate structures that were easily differentiated by STM. In the absence of a complexing agent, the MP-11 formed large clusters of metallopeptide molecules on the gold surface. With neutral imidazole in solution the MP11 aggregated into regular elongated structures (nano-épis) on the substrate. When S(2-) is used as coupling agent, single heme peptide molecules are isolated with identifiable porphyrin ring and substructure in the peptide chain. 相似文献
12.
Davydov R Satterlee JD Fujii H Sauer-Masarwa A Busch DH Hoffman BM 《Journal of the American Chemical Society》2003,125(52):16340-16346
Cryoreduction of the [FeO2]6 (n = 6 is the number of electrons in 3d orbitals on Fe and pi* orbitals on O2) dioxygen-bound ferroheme through irradiation at 77 K generates an [FeO2]7 reduced oxy-heme. Numerous investigations have examined [FeO2]7 centers that have been characterized as peroxo-ferric centers, denoted [FeO2]per7, in which a ferriheme binds a dianionic peroxo-ligand. The generation of such an intermediate can be understood heuristically if the [FeO2]6 parent is viewed as a superoxo-ferric center and the injected electron localizes on the O-O moiety. We here report EPR/ENDOR experiments which show quite different properties for the [FeO2]7 centers produced by cryoreduction of monomeric oxy-hemoglobin (oxy-GMH3) from Glycera dibranchiata, which is unlike mammalian "globins" in having a leucine in place of the distal histidine; of frozen aprotic solutions of oxy-ferrous octaethyl porphyrin; and of the oxy-ferrous complex of the heme model, cyclidene. These [FeO2]7 centers are characterized as "superoxo-ferrous" centers ([FeO2]sup7), with nearly unit spin density localized on a superoxo moiety which is end-on coordinated to a low-spin ferrous ion. This assignment is based on their g tensors and 17O hyperfine couplings, which are characteristic of the superoxide ion coordinated to a diamagnetic metal ion, and on the absence of detectable ENDOR signals either from the in-plane 14N ligands or from an exchangeable H-bond proton. Such a center would arise if the electron that adds to the [FeO2]6 superoxo-ferric parent localizes on the Fe ion, to make a superoxo-ferrous moiety. Upon annealing to T > 150 K, the [FeO2]sup7 species converts to peroxo/hydroperoxo-ferric ([FeO2H]7) intermediates. These experiments suggest that the primary reduction product is [FeO2]sup7 and that the internal redox transition to [FeO2]per7/[FeO2H]7 states is driven at least in part by H-bonding/proton donation by the environment. 相似文献
13.
临界电流密度Jc是影响高温超导体在强电领域应用的一个重要参数,在实际应用中,特别在外加磁场下,临界电流密度与超导材料的磁通钉扎性质密切相关.因此,磁通钉扎一直是高温超导体研究中的一个重要领域.由于高温超导体磁通钉扎力密度Fp的标度律存在,本文根据D.Dew-Hughes总结的钉扎力函数,主要存在两种主要作用类型(正常相和△K).我们将D.Dew-HugBes给出的钉扎力密度Fp标度函数改进为一个简化的具有物理意义的函数表达式.结合文献中已有的实验数据,我们对YBcO进行了计算机模拟,确定了它的磁通钉扎类型,模拟的研究结果与实际情况比较吻合. 相似文献