TY  - JOUR
A1  - Dong, Chao
A1  - Yang, Jing
A1  - Lehnkuehler, Silke
A1  - Kirk, Martin L.
T1  - Pyranopterin dithiolene distortions relevant to electron transfer in xanthine oxidase/dehydrogenase
JF  - Inorganic chemistry
N2  - The reducing substrates 4-thiolumazine and 2,4-dithiolumazine have been used to form Mo-IV-product complexes with xanthine oxidase (XO) and xanthine dehydrogenase. These Mo-IV-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.
Y1  - 2014
U6  - https://doi.org/10.1021/ic500873y
SN  - 0020-1669
SN  - 1520-510X
VL  - 53
IS  - 14
SP  - 7077
EP  - 7079
PB  - American Chemical Society
CY  - Washington
ER  -