posted on 2022-01-21, 00:44authored byJun Guo, Danyu Wang, Evangelia Pantatosaki, Huihui Kuang, George K. Papadopoulos, Michael Tsapatsis, Efrosini Kokkoli
A DNA-based artificial
metalloenzyme (ArM) consisting of a copper(II)
complex of 4,4′-dimethyl-2,2′-bipyridine (dmbipy-Cu)
bound to double-stranded DNA (dsDNA) as short as 8 base pairs with
only 2 contiguous central pairs (G for guanine and C for cytosine)
catalyzes the highly enantioselective Diels–Alder reaction,
Michael addition, and Friedel–Crafts alkylation in water. Molecular
simulations indicate that these minimal sequences provide a single
site where dmbipy-Cu is groove-bound and able to function as an enantioselective
catalyst. Enantioselective preference inverts when d-DNA
is replaced with l-DNA. When the DNA is conjugated to a hydrophobic
tail, the obtained ArMs exhibit enantioselective performance in a
methanol–water mixture superior to that of non-amphiphilic
dsDNA, and dsDNA-amphiphiles with more complex G•C-rich sequences.