DNA-metal composites as bioinspired catalysts in chemical reactions

[Display omitted] •The comprehensive review article about DNA-based biocatalysts with a focus on the type of metals used in the composite structure.•Focuses on the development of metal catalysts based on DNA as a natural building block.•Advanced catalysts in various chemical asymmetric transformations.•Provides deeper comprehension of the factors that contribute to the selective binding of metal ions in DNAzymes, which can broaden the scope of organic chemistry and lead to the creation of valuable DNA-metal catalysts.•Develops the knowledge on how chirality is achieved and the effect of interactions between DNA and metallic cofactors on enantioselectivity. Since the initial discovery of DNAzymes, DNA-scaffold catalytic platform has undergone extensive exploration, and its applications have continuously expanded due to rapid advancements in biotechnology and molecular biology. Thespecialchirality of DNA and its helical structure havepermittedtheadvancementof a multitude of disparate asymmetric chemical reactions. The concept refers to the introduction of an achiral metal within a double-stranded DNA helix, thereby generating a crucial chiral microenvironment that facilitates the preferential formation of a specific enantiomer of a given product. Contemporary efforts toward uncovering modern reactivities have coincided with a desire to comprehend the underlying mechanisms through which chirality is conferred, as well as the implications of interactions between DNA and metallic cofactors on selectivity. In this manner, the present review provides a systematic overview of DNA-metal composites as bioinspired catalytic platforms, and categorizes the bio-catalytic scaffolds with respect to the metal ions utilized in the catalyst preparation process. The metallic cofactor binding mode to DNA template and its effect on the structure of DNA during the chemical transformations have been discussed. Last but not least, by representing a total outline of the field, this study highlights the complicated relationship between the architecture of the asymmetric bio-inorganic framework and its catalytic performance in chemical transformations, and also, current challenges and future perspectives in the field of DNA-scaffold catalysts will be discussed.