Determination of Basicity of Core X and Terminal Y Lignds (X, Y = S and Se) of Reduced, Oxidized, and Super-Oxidized Forms of [Fe_4X_4(YAd)_4]~(2-) (Ad = 1-Admantyl) in Aqueous Solutions

Masami Nakamoto; Kenji Fukaishi; Tsuyoshi Tagata; Hide Kambayashi; Koji Tanaka

首页> 外文期刊>Bulletin of the Chemical Society of Japan >Determination of Basicity of Core X and Terminal Y Lignds (X, Y = S and Se) of Reduced, Oxidized, and Super-Oxidized Forms of [Fe_4X_4(YAd)_4]~(2-) (Ad = 1-Admantyl) in Aqueous Solutions

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Determination of Basicity of Core X and Terminal Y Lignds (X, Y = S and Se) of Reduced, Oxidized, and Super-Oxidized Forms of [Fe_4X_4(YAd)_4]~(2-) (Ad = 1-Admantyl) in Aqueous Solutions

机译：确定[Fe_4X_4（YAd）_4]〜（2-）（Ad = 1-Admantyl）中还原，氧化和超氧化形式的X核和Y末端木质素的碱度（X，Y = S和Se）水溶液

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A series of [Fe_4X_4(YAd)_4]~(2-) (X, Y=S, Se; Ad= 1-adamantly) were prepared as a model of high potential iron-sulfur proteins. Hydrolysis of the clusters was effectively depressed in aqueous ploy[2-(dimethylamino)hexanamide] (PDAN) solutions due to the enbedding effect in hydrophobic environment and/or inhibition of dissociation of the terminal ligand into the aqueous media. Cyclic voltammetry of those cluster in aqueous PDAH solutions showed pH-dependent redox phtentials of not only the [Fe_4X_4]~(+/2+) but also the [Fe_4X_4]~(2+/3+) (X=S and Se) couples, resulting from redox-linked protonation reactions of three oxidation states of [Fe_4X_4(YAd)_4]~(n-) (n=1-3). pk_a values of the reduced,oxidized, and super-oxidized forms of [Fe_4X_4(YAd)_4]~(2-) were determined by computer simulation of the pH dependent redox potentials. The basicity of the core X(X=S and Se) of three oxidation states of [Fe_4X_4(YAd)_4]~(n-) (n=1, 2, 3) was stronger than the terminal YAd (Y=Sand Se) ligands: in the case of the mono-protonated [Fe_4X_4(YAd)_4]~(3-) (H~+) and [Fe_4X_4(YAd)_4]~(2-) (H~+), basicity of the terminal YAd ligand of [Fe_4X_4(YAd)_4]~(2-) (H~+) becomes stronger than that of core X< although the core X of [Fe_4X_4(YAd)_4]~(3-) (H~+) still showed a stronger basicity than those of terminal YAd ligands.

机译：制备了一系列[Fe_4X_4（YAd）_4]〜（2-）（X，Y = S，Se; Ad = 1均匀地）作为高潜在铁硫蛋白的模型。由于在疏水环境中的包埋作用和/或抑制了末端配体解离到水性介质中，在聚[2-（二甲基氨基）己酰胺]（PDAN）水溶液中有效抑制了簇的水解。这些簇在PDAH水溶液中的循环伏安法显示，不仅[Fe_4X_4]〜（+ / 2+）而且[Fe_4X_4]〜（2 + / 3 +）（X = S和Se）依赖于pH的氧化还原电位偶合，是由[Fe_4X_4（YAd）_4]〜（n-）的三个氧化态的氧化还原连接的质子化反应产生的（n = 1-3）。通过计算机模拟pH依赖的氧化还原电位来确定[Fe_4X_4（YAd）_4]〜（2-）的还原，氧化和超氧化形式的pk_a值。 [Fe_4X_4（YAd）_4]〜（n-）（n = 1，2，3）的三个氧化态的核X（X = S和Se）的碱度强于末端YAd（Y = Sand Se ）配体：单质子化的[Fe_4X_4（YAd）_4]〜（3-）（H〜+）和[Fe_4X_4（YAd）_4]〜（2-）（H〜+）时，尽管[Fe_4X_4（YAd）_4]〜（3-）的核心X [[Fe_4X_4（YAd）_4]〜（2-）（H〜+）的末端YAd配体变得比核心X <强）仍显示出比末端YAd配体强的碱性。

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《Bulletin of the Chemical Society of Japan》 |1999年第3期|共8页
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Masami Nakamoto; Kenji Fukaishi; Tsuyoshi Tagata; Hide Kambayashi; Koji Tanaka;
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1. Determination of Basicity of Core X and Terminal Y Lignds (X, Y = S and Se) of Reduced, Oxidized, and Super-Oxidized Forms of [Fe_4X_4(YAd)_4]~(2-) (Ad = 1-Admantyl) in Aqueous Solutions [J] . Masami Nakamoto, Kenji Fukaishi, Tsuyoshi Tagata, Bulletin of the Chemical Society of Japan . 1999,第3期

机译：确定[Fe_4X_4（YAd）_4]〜（2-）（Ad = 1-Admantyl）中还原，氧化和超氧化形式的X核和Y末端木质素的碱度（X，Y = S和Se）水溶液
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KKT is a science wing that tries to solve human problems with a wider perspective aimed at solving problematic human behaviors (Plumb, Stewart, Dahl and Lundgren, 2009). It is seen that there is very little research about the new approach of ACT approach when the aiming country of our country is screened and it is thought that our country will contribute to the field of psychological counseling with the work done. In the scope of the research, experimental and control groups and preliminary test, post-test and follow-up measurements of 2x3 experimental design were used. The study's study group consists of a total of 24 (12 experimental and 12 control groups) university students studying in different departments and levels, continuing their education in the academic year of 2015-2016 in Ağrı province and İbrahim Chechen University in 2015-2016 academic year. The average age of participants in the experiment and control group is 20. 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Participants in the experimental and control groups; homogeneity test results for decision-style pre-test measurements indicate that the data are homogeneous. According to the results of the Mauchly Globalness Test, it has been determined that working supports the hypothesis. It was determined that there was no significant difference between the pre-test scores obtained from dependent decision-making style of experiment and control groups, but the test group showed lower mean scores at the significant level within the scores of post-test and follow-up tests. Therefore, it can be said that the ACT-oriented psychoeducation program applied to the experimental group reduces the dependent decision-making style scores from the decision style sub-dimensions and the psychoeducation program has a lasting effect. 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8. Formation of fine palladium particles from palladium sulfate aqueous solution by gamma-ray irradiation as observed by electronic absorption spectroscopy and dynamic light scattering [R] . Jonah, C. D. , Hatada, M. 1994

机译：通过电子吸收光谱和动态光散射观察，通过γ射线照射由硫酸钯水溶液形成细钯颗粒

Determination of Basicity of Core X and Terminal Y Lignds (X, Y = S and Se) of Reduced, Oxidized, and Super-Oxidized Forms of [Fe_4X_4(YAd)_4]~(2-) (Ad = 1-Admantyl) in Aqueous Solutions

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