Generation of High-Spin Iron(I) in a Protein Environment Using Cryoreduction

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• 作者：Roman M. Davydov ; Matthew P. McLaughlin ; Eckhard Bill ; Brian M. Hoffman ; Patrick L. Holland
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：July 1, 2013
• 年：2013
• 卷：52
• 期：13
• 页码：7323-7325
• 全文大小：193K
• 年卷期：v.52,no.13(July 1, 2013)
• ISSN：1520-510X

文摘

High-spin Fe¹⁺ sites are potentially important in iron鈥搒ulfur proteins but are rare in synthetic compounds and unknown in metalloproteins. Here, we demonstrate a spectroscopically characterized example of high-spin non-heme Fe¹⁺ in a protein environment. Cryoreduction of Fe²⁺-substituted azurin at 77 K with ⁶⁰Co 纬 radiation generates a new species with a S = ³/₂ (high-spin) Fe¹⁺ center having D > 0 and E/D 0.25. This transient species is stable in a glycerol鈥搘ater glass only up to 170 K. A combination of electron paramagnetic resonance and M枚ssbauer spectroscopies provides a powerful means of identifying a transient high-spin Fe¹⁺ site in a protein scaffold.