脱氧核糖核酸(DNA)水凝胶是一类独特的可编程,能够对复杂刺激做出反应的生物相容性材料,使它们在药物输送中有价值,分析物检测,细胞生长,和形状记忆材料。然而,文献中未经修饰的DNA水凝胶非常柔软,很少达到103Pa的储能模量,它们缺乏功能,限制其应用。这里,DNA/小分子基序,用于从未修饰的DNA产生坚硬的水凝胶,使用储能模量达到105Pa。基序由聚腺嘌呤和三聚氰酸之间的相互作用组成,三聚氰酸具有3-胸腺嘧啶样的表面,进入多显微镜超分子纤维。这些水凝胶的机械性能很容易调整,它们具有自愈性和触变性。它们集成了高密度的小,无毒分子,并简单地通过改变分子侧链来官能化。它们对三个独立的刺激作出反应,包括小分子刺激。这些刺激用于在水凝胶内整合和释放DNA线框和DNA折纸纳米结构。将水凝胶用作可注射的递送载体,在细胞中释放反义寡核苷酸,并提高其基因沉默功效。这项工作提供了可调,刺激反应,来自简单序列的异常坚硬的全DNA水凝胶,扩展这些材料的能力。
Deoxyribonucleic acid (DNA) hydrogels are a unique class of programmable, biocompatible materials able to respond to complex stimuli, making them valuable in drug delivery, analyte detection, cell growth, and shape-memory materials. However, unmodified DNA hydrogels in the literature are very soft, rarely reaching a storage modulus of 103 Pa, and they lack functionality, limiting their applications. Here, a DNA/small-molecule motif to create stiff hydrogels from unmodified DNA, reaching 105 Pa in storage modulus is used. The motif consists of an interaction between polyadenine and cyanuric acid-which has 3-thymine like faces-into multimicrometer supramolecular fibers. The mechanical properties of these hydrogels are readily tuned, they are self-healing and thixotropic. They integrate a high density of small, nontoxic molecules, and are functionalized simply by varying the molecule sidechain. They respond to three independent stimuli, including a small molecule stimulus. These stimuli are used to integrate and release DNA wireframe and DNA origami nanostructures within the hydrogel. The hydrogel is applied as an injectable delivery vector, releasing an antisense oligonucleotide in cells, and increasing its gene silencing efficacy. This work provides tunable, stimuli-responsive, exceptionally stiff all-DNA hydrogels from simple sequences, extending these materials\' capabilities.