Hantzsch ester, a widely used base or electron-donor compound was found to act as a catalyst in the deaminative difluoroalkylation reaction utilizing Katritzky salts and difluoroenoxysilane as substrates, which represent...
A visible light promoted deaminative strategy for the difluoroalkylation reaction utilizing pyridinium activated aliphatic primary amines and difluoroenoxysilane as substrates have been developed. This protocol is characteriazed by its mild...
Deoxyribozymes can catalyze various types of reactions mostly with metal ions as their cofactors. Here we demonstrate that three copper compounds with thiosemicarbazide or semicarbazide ligands, are highly active cofactors of Cu2+‐dependent deoxyribozymes without any additional reagents. The maximum catalytic rate constant of the deoxyribozyme with dichloro(di‐thiosemicarbazide)copper as a cofactor is ∼25‐fold faster than Cu2+ cofactor under the same reaction condition. Using a variety of spectroscopies, electrochemistry, and mutagenesis, we demonstrate that both the three‐dimensional structure and redox potential of the copper center of the cofactors are essential to the catalysis of deoxyribozymes. The cofactor interacts with the enzyme‐substrate complex forming a ternary enzyme‐substrate‐cofactor complex, which is confirmed by changing the structure of the enzyme‐substrate complex through varying the temperature, or mutating the active site of the enzyme and conserved site of the substrate. The result suggests that Cu2+‐dependent deoxyribozyme requires a well‐defined active site to carry out the catalysis proficiently.
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