Department of Chemical Sciences and Technologies, University of Rome Tor Vergata, Via della Ricerca Scientifica, 00133, Rome, Italy.
Department of Chemical Sciences, University of Padua, Via Marzolo 1, 35131, Padua, Italy.
Chemistry. 2023 May 26;29(30):e202300394. doi: 10.1002/chem.202300394. Epub 2023 Apr 19.
We demonstrate here a strategy that allows the programmable and autonomous reorganization of self-assembled DNA polymers using redox chemistry. We have rationally designed different DNA monomers (tiles) that can co-assemble into tubular structures. The tiles can be orthogonally activated/deactivated with disulfide-linked DNA fuel strands that are degraded over time upon reduction because of the presence of a reducing agent in the system. The concentration of the disulfide fuels determines the activation kinetics of each DNA tile, which controls the degree of order/disorder in the formed co-polymer. The disulfide-reduction pathway can be employed together with enzymatic fuel-degradation pathways providing an additional level of control in the re-organization of DNA structures. Taking advantage of the different pH-sensitivities of disulfide-thiol and enzymatic reactions, we show that we can control the order in DNA-based co-polymers as a function of pH.
在这里，我们展示了一种使用氧化还原化学实现自组装 DNA 聚合物可编程和自主重组的策略。我们合理设计了不同的 DNA 单体（瓦片），它们可以共同组装成管状结构。瓦片可以通过带有二硫键的 DNA 燃料链进行正交激活/失活，这些燃料链随着时间的推移在系统中存在还原剂的情况下被降解。二硫键燃料的浓度决定了每个 DNA 瓦片的激活动力学，从而控制形成的共聚物的有序/无序程度。二硫键还原途径可以与酶促燃料降解途径一起使用，为 DNA 结构的重组提供额外的控制水平。利用二硫键-巯基和酶反应的不同 pH 敏感性，我们表明我们可以根据 pH 控制基于 DNA 的共聚物中的有序性。
