Pyranopterin dithiolene distortions relevant to electron transfer in xanthine oxidase/dehydrogenase.
Pyranopterin dithiolene distortions relevant to electron transfer in xanthine oxidase/dehydrogenase.
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DOI：
10.1021/ic500873y
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发表时间：
2014-07-21
影响因子：
4.6
通讯作者：
Kirk, Martin L.
中科院分区：
文献类型：
--
作者：
Dong, Chao;Yang, Jing;Lehnkuehler, Silke;Kirk, Martin L.
还原底物4-硫代鲁马嗪和2，4-二硫代鲁马嗪已被用于与黄嘌呤氧化酶（XO）和黄嘌呤脱氢酶形成MoIV产物复合物。这些MoIV-产物络合物在光谱的近红外区域中显示出强烈的金属-配体电荷转移（MLCT）带。光泵浦到这个MLCT带产生共振拉曼光谱的Mo网站是没有贡献的高度吸收的FAD和2Fe 2S簇的蛋白质。共振拉曼光谱揭示了结合产物的面内弯曲模式和低频钼二硫杂环戊烯和吡喃蝶呤二硫杂环戊烯振动模式。这项工作提供了敏锐的洞察力的作用，吡喃蝶呤二硫杂环戊烯的电子转移反应。还原底物4-硫代鲁马嗪和2，4-二硫代鲁马嗪在黄嘌呤氧化酶（XO）和黄嘌呤脱氢酶（XDH）中形成MoIV产物复合物。MoIV-产物络合物在光谱的近红外（NIR）区域中吸收。光泵到这个近红外金属配体的电荷转移带揭示了平面内的弯曲模式的绑定产品，除了低频钼二硫杂环戊烯和吡喃蝶呤二硫杂环戊烯（吡喃蝶呤ditholene）的振动模式。这项工作提供了深入了解如何pyranopterin ditholene耦合到氧化还原变化在钼网站和如何pyranopterin ditholene功能作为一个电子转移管道在XO/XDH的氧化半反应。
The reducing substrates 4-thiolumazine and 2,4-dithiolumazine have been used to form MoIV-product complexes with xanthine oxidase (XO) and xanthine dehydrogenase. These MoIV-product complexes display an intense metal-to-ligand charge-transfer (MLCT) band in the near-infrared region of the spectrum. Optical pumping into this MLCT band yields resonance Raman spectra of the Mo site that are devoid of contributions from the highly absorbing FAD and 2Fe2S clusters in the protein. The resonance Raman spectra reveal in-plane bending modes of the bound product and low-frequency molybdenum dithiolene and pyranopterin dithiolene vibrational modes. This work provides keen insight into the role of the pyranopterin dithiolene in electron-transfer reactivity. The reducing substrates 4-thiolumazine and 2,4-dithiolumazine have been used to form MoIV-product complexes in xanthine oxidase (XO) and xanthine dehydrogenase (XDH). The MoIV-product complexes absorb in the near-infrared (NIR) region of the spectrum. Optical pumping into this NIR metal-to-ligand charge-transfer band reveals in-plane bending modes of the bound product in addition to low-frequency molybdenum dithiolene and pyranopterin dithiolene (pyranopterin ditholene) vibrational modes. The work provides insight into how pyranopterin ditholene is coupled to redox changes at the Mo site and how pyranopterin ditholene functions as an electron-transfer conduit in the oxidative half-reaction of XO/XDH.
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影响因子：
62.1
作者：
Hille, Russ;Hall, James;Basu, Partha
通讯作者：
Basu, Partha
影响因子：
4.6
作者：
Inscore, FE;McNaughton, R;Kirk, ML
通讯作者：
Kirk, ML
影响因子：
5.7
作者：
Truglio, JJ;Theis, K;Kisker, C
通讯作者：
Kisker, C
影响因子：
5.7
作者：
Kloer, Daniel P.;Hagel, Corina;Schulz, Georg E.
通讯作者：
Schulz, Georg E.
影响因子：
15
作者：
QIU, D;KILPATRICK, LT;SPIRO, TG
通讯作者：
SPIRO, TG