Abstract
The structures of Ce4+ complexes that are active for DNA hydrolysis were determined for the first time by X-ray crystallography. The crystals were prepared from a 1:2 mixture of Ce(NH4)2(NO3)6 and dipicolinic acid (2,6-pyridinedicarboxylic acid). Depending on the recrystallization conditions, three types of crystals were obtained. Some of the Ce4+ ions in these complexes have enough coordinated water molecules that can directly and indirectly participate in the catalysis. The distances between the Ce4+ and the dipicolinate ligand are considerably shorter than those in the corresponding La3+ and Ce3+ complexes. On the other hand, the distances between the Ce4+ and its coordinated water are similar to those for the La3+ and Ce3+ complexes. In a proposed mechanism of DNA hydrolysis, the scissile phosphodiester linkage is notably activated by coordination to Ce4+ and attacked by the Ce4+-bound hydroxide. The process is further assisted by acid catalysis of Ce4+-bound water.
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This work was partially supported by a Grant-in-Aid for Scientific Research from the Ministry of Education, Culture, Sports, Science, and Technology, Japan.
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Katada, H., Seino, H., Mizobe, Y. et al. Crystal structure of Ce(IV)/dipicolinate complex as catalyst for DNA hydrolysis. J Biol Inorg Chem 13, 249–255 (2008). https://doi.org/10.1007/s00775-007-0315-x
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DOI: https://doi.org/10.1007/s00775-007-0315-x