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cite in ref. 1"},{"key":"CIT0006","unstructured":"Ce(IV) complexes are also active for DNA hydrolysis"},{"key":"CIT0006a","doi-asserted-by":"publisher","DOI":"10.1039\/cc9960000105"},{"key":"CIT0006b","doi-asserted-by":"publisher","DOI":"10.1039\/p19960002623"},{"key":"CIT0006c","doi-asserted-by":"publisher","DOI":"10.1246\/cl.2000.356"},{"key":"CIT0006d","doi-asserted-by":"publisher","DOI":"10.1021\/ja0010103"},{"key":"CIT0006f","doi-asserted-by":"publisher","DOI":"10.1021\/ja0210998"},{"key":"CIT0006g","unstructured":"references cite in ref. 1"},{"key":"CIT0007","unstructured":"Catalysis by Ce(IV) for cAMP hydrolysis"},{"key":"CIT0007a","doi-asserted-by":"publisher","DOI":"10.1039\/C39920001707"},{"key":"CIT0007b","doi-asserted-by":"publisher","DOI":"10.1039\/C39940001755"},{"key":"CIT0007c","doi-asserted-by":"publisher","DOI":"10.1021\/ja990686z"},{"key":"CIT0008","doi-asserted-by":"publisher","DOI":"10.1039\/a701481c"},{"key":"CIT0009","unstructured":"In place of using Ce(IV) salts, catalytically active species can be formed by oxidizing Ce(III) ions with molecular oxygen (refs 5b and d). Molecular oxygen is not required for the catalytic process, and thus the DNA hydrolysis by Ce(IV) salts is efficient even in its absence (ref. 5b)"},{"key":"CIT0010","unstructured":"Lanthanide(III) ions hydrolyze the phosphate esters other than cAMP and DNA"},{"key":"CIT0010a","doi-asserted-by":"publisher","DOI":"10.1039\/c39900000714"},{"key":"CIT0010b","doi-asserted-by":"publisher","DOI":"10.1021\/ja00096a055"},{"key":"CIT0010c","doi-asserted-by":"publisher","DOI":"10.1039\/c39950002431"},{"key":"CIT0010d","doi-asserted-by":"publisher","DOI":"10.1093\/oxfordjournals.jbchem.a021765"},{"key":"CIT0011","doi-asserted-by":"publisher","DOI":"10.1063\/1.123036"},{"key":"CIT0012","doi-asserted-by":"publisher","DOI":"10.1063\/1.116104"},{"key":"CIT0013","unstructured":"Base ,  C. F.   Jr.  and \n                     Mesmer ,  R. E.  1976. The Hydrolysis of Cations, 138\u2013146. New York: John Wiley & Sons."},{"key":"CIT0014","unstructured":"The half-life of cAMP is only 9 min, corresponding to more than 1013-fold acceleration with respect to non-catalyzed reaction"},{"key":"CIT0015","unstructured":"The ratio of adenosine 3\u2032-monophosphate to its 5\u2032-monophosphate was about 10:1. The P-O(5\u2032) linkage was preferentially cleaved"},{"key":"CIT0016","unstructured":"These kinetic analyses were performed on the assumption that only one species of Ce(IV) is responsible for the hydrolytic reaction. The possibility that the combination of Ce(IV)-derived species is active for the reaction can not be completely ruled out. However, all the results presented here point to the overwhelming contribution of the proposed species to the catalysis"},{"key":"CIT0017","unstructured":"InFigure 3, water molecules are omitted because of clarity"},{"key":"CIT0018","unstructured":"This mechanism is different from that proposed for the catalysis by CeCl3\/O2combination in ref. 5d, although both involve dinuclear Ce(IV) species. In the previously proposed mechanism, the two Ce(IV) ions in the cluster are bridged by -O-O- group, which is derived from molecular oxygen, and this group is the nucleophile for the reaction. Thus, molecular oxygen is inevitable for the catalysis. In the present mechanism, however, the metal-bound hydroxide as the nucleophile comes from water. Consistently, no molecular oxygen is required for the hydrolysis of cAMP and DNA by Ce(NH4)2(NO3)6(see ref. 9)"},{"key":"CIT0019","unstructured":"If the reaction were involving nucleophilic attack by external hydroxide ion in the reaction mixtures, the reaction rate at pH 7 should be as 105times as large as that at pH 2. 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