Key Laboratory of Optic-electric Sensing and Analytical Chemistry for Life Science, MOE, Shandong Key Laboratory of Biochemical Analysis, College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Zhengzhou Rd. No. 53, Qingdao, 266042, PR China.
Key Laboratory of Optic-electric Sensing and Analytical Chemistry for Life Science, MOE, Shandong Key Laboratory of Biochemical Analysis, College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Zhengzhou Rd. No. 53, Qingdao, 266042, PR China.
Acta Biomater. 2021 Jul 1;128:143-149. doi: 10.1016/j.actbio.2021.04.039. Epub 2021 Apr 27.
Development of photoliquefiable solid-state biomaterials at room temperature would address scientific challenges in life science. However, external stimuli-induced phase transitions are difficult for some biomacromolecules based materials, due to the high rigidity of these biomolecules. In this present work, by delicate molecule design on azobenzene-type ammonium surfactants, two new types of DNA-surfactant materials are fabricated. At room temperature, these DNA materials show photoliquefaction of ionic crystals to isotropic liquids under UV light, and fast self-assembly from isotropic liquids back to crystals after ceasing UV light, under the assistance of azobenzene isomerization. To achieve this objective, the designed solid-state DNA materials should have melting points near room temperature and an immediate liquid crystal to isotropic liquid transition process just above the melting points, which highly depends on the stoichiometric charge ratio between DNA and surfactants. As proved by the successful self-healing tests, these DNA ionic crystals are good biomaterials with potential applications in biomedicine and life science. This work would provide a new strategy for designing anhydrous functional biomaterials at room temperature by using rigid biomacromolecules. STATEMENT OF SIGNIFICANCE: At room temperature, solid-state biomaterials with photoregulated crystal⇄isotropic liquid phase transition property are attractive functional materials in life science, considering the body temperature and living environment temperature of human beings. Although several kinds of anhydrous materials achieved isothermal photoresponsive phase transitions, the photoregulated phase transition of anhydrous biomacromolecules based materials has not been achieved at room temperature, due to the high rigidity of these biomolecules. In this work, by delicate molecule design on ammonium surfactants, we synthesized two kinds of anhydrous DNA-surfactants ionic crystals. These DNA materials show fast photoliquefaction under UV light and self-assembly after ceasing light, which affords excellent self-healing biomaterials. This work would provide a new strategy for designing anhydrous photoresponsive biomaterials by using rigid biomacromolecules.
室温下光致液态的固态生物材料的发展将解决生命科学中的科学挑战。然而，对于一些基于生物大分子的材料，由于这些生物大分子的刚性较高，外部刺激诱导的相转变是困难的。在本工作中，通过对吖啶型季铵盐表面活性剂的精细分子设计，制备了两种新型 DNA-表面活性剂材料。在室温下，这些 DNA 材料在紫外光照射下表现出离子晶体向各向同性液体的光致液化，并且在停止紫外光照射后，在吖啶异构化的辅助下，从各向同性液体快速自组装回晶体。为了实现这一目标，所设计的固态 DNA 材料的熔点应接近室温，并且在熔点以上具有立即从液晶向各向同性液体转变的过程，这高度依赖于 DNA 与表面活性剂之间的化学计量电荷比。正如自修复测试的成功所证明的那样，这些 DNA 离子晶体是具有潜在应用于生物医学和生命科学的良好生物材料。这项工作为利用刚性生物大分子设计室温下无水功能生物材料提供了一种新策略。
考虑到人体的体温和生活环境温度，具有光控晶体-各向同性液相转变性质的室温下固态生物材料是生命科学中极具吸引力的功能材料。尽管已经实现了几种无水材料的等温光响应相转变，但由于这些生物大分子的刚性较高，室温下无水生物大分子基材料的光控相转变尚未实现。在这项工作中，通过对季铵盐表面活性剂的精细分子设计，我们合成了两种无水 DNA-表面活性剂离子晶体。这些 DNA 材料在紫外光下表现出快速光致液化和光照停止后的自组装，提供了优异的自修复生物材料。这项工作为利用刚性生物大分子设计无水光响应生物材料提供了一种新策略。
