短DNA序列及其两亲分子上的局部对映选择性催化位点。
A Localized Enantioselective Catalytic Site on Short DNA Sequences and Their Amphiphiles.
作者信息
Guo Jun, Wang Danyu, Pantatosaki Evangelia, Kuang Huihui, Papadopoulos George K, Tsapatsis Michael, Kokkoli Efrosini
机构信息
Institute for NanoBioTechnology, Johns Hopkins University, Baltimore, Maryland 21218, United States.
Department of Chemical and Biomolecular Engineering, Johns Hopkins University, Baltimore, Maryland 21218, United States.
出版信息
JACS Au. 2022 Jan 20;2(2):483-491. doi: 10.1021/jacsau.1c00513. eCollection 2022 Feb 28.
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.
一种基于DNA的人工金属酶（ArM），它由4,4'-二甲基-2,2'-联吡啶（dmbipy-Cu）的铜（II）配合物与仅8个碱基对且只有2个相邻中心对（鸟嘌呤为G，胞嘧啶为C）的双链DNA（dsDNA）结合而成，可在水中催化高度对映选择性的狄尔斯-阿尔德反应、迈克尔加成反应和傅克烷基化反应。分子模拟表明，这些最短序列提供了一个单一位点，dmbipy-Cu在该位点与沟槽结合并能够作为对映选择性催化剂发挥作用。当d-DNA被l-DNA取代时，对映选择性偏好会发生反转。当DNA与疏水尾缀合时，所得到的ArMs在甲醇-水混合物中的对映选择性性能优于非两亲性dsDNA以及具有更复杂富含G•C序列的dsDNA两亲物。
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