Two‐Dimensional Supramolecular Polymerization of DNA Amphiphiles is Driven by Sequence‐Dependent DNA‐Chromophore Interactions
Two‐Dimensional Supramolecular Polymerization of DNA Amphiphiles is Driven by Sequence‐Dependent DNA‐Chromophore Interactions
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DNA 两亲物的二维超分子聚合是由序列 - 依赖性 DNA - 发色团相互作用驱动的
DOI：
10.1002/ange.202217814
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发表时间：
2023
影响因子：
--
通讯作者：
Sleiman, Hanadi F.
中科院分区：
文献类型：
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作者：
Ghufran Rafique, Muhammad;Remington, Jacob M.;Clark, Finley;Bai, Haochen;Toader, Violeta;Perepichka, Dmytro F.;Li, Jianing;Sleiman, Hanadi F.
由于缺乏将聚合物结构与途径机制和超分子形态联系起来的系统研究，限制了水溶性嵌段共聚物的二维(2D)组装。在这里，我们使用序列定义的三嵌段DNA两亲分子在水中进行自由站立的DNA纳米片的超分子聚合。我们对两亲性序列的系统调制显示，烷基链核形成了细胞膜状结构，远端的π堆积发色团折叠回来与纳米片表面的亲水DNA块相互作用。这种相互作用对于片状的形成是至关重要的，以手性“签名”为标志，并且对DNA序列敏感，其中纳米片状与混合序列形成，但不与均相多(胸腺嘧啶)序列形成。这项工作开启了使用单个DNA两亲性形成有序的双层样组件的可能性，用于细胞传感、核酸治疗递送和酶阵列。
Two‐dimensional (2D) assemblies of water‐soluble block copolymers have been limited by a dearth of systematic studies that relate polymer structure to pathway mechanism and supramolecular morphology. Here, we employ sequence‐defined triblock DNA amphiphiles for the supramolecular polymerization of free‐standing DNA nanosheets in water. Our systematic modulation of amphiphile sequence shows the alkyl chain core forming a cell membrane‐like structure and the distal π‐stacking chromophore block folding back to interact with the hydrophilic DNA block on the nanosheet surface. This interaction is crucial to sheet formation, marked by a chiral “signature”, and sensitive to DNA sequence, where nanosheets form with a mixed sequence, but not with a homogeneous poly(thymine) sequence. This work opens the possibility of forming well‐ordered, bilayer‐like assemblies using a single DNA amphiphile for applications in cell sensing, nucleic acid therapeutic delivery and enzyme arrays.