期刊
JOURNAL OF MATERIALS CHEMISTRY B
卷 11, 期 30, 页码 7117-7125出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/d3tb00780d
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In this study, a nucleotide-Cu2+ complex capable of catalyzing ortho-hydroxylation reactions resembling those of minimalistic monooxygenases was synthesized and investigated. Experimental and theoretical findings revealed that the catalyst formed a ternary complex intermediate with H2O2 and tyramine substrates through weak interactions, leading to the ortho-hydroxylation of tyramine. Moreover, the Cu2+ bound to nucleotides or oligonucleotides exhibited thermophilic catalytic properties.
The de novo design of artificial biocatalysts with enzyme-like active sites and catalytic functions has long been an attractive yet challenging goal. In this study, we present a nucleotide-Cu2+ complex, synthesized through a one-pot approach, capable of catalyzing ortho-hydroxylation reactions resembling those of minimalist monooxygenases. Both experimental and theoretical findings demonstrate that the catalyst, in which Cu2+ coordinates with both the nucleobase and phosphate moieties, forms a ternary-complex intermediate with H2O2 and tyramine substrates through multiple weak interactions. The subsequent electron transfer and hydrogen (or proton) transfer steps lead to the ortho-hydroxylation of tyramine, where the single copper center exhibits a similar function to natural dicopper sites. Moreover, Cu2+ bound to nucleotides or oligonucleotides exhibits thermophilic catalytic properties within the temperature range of 25 & DEG;C to 75 & DEG;C, while native enzymes are fully deactivated above 35 & DEG;C. This study may provide insights for the future design of oxidase-mimetic catalysts and serve as a guide for the design of primitive metallocentre-dependent enzymes.
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