Pang Juan, Gao Ziyu, Tan Huaping, Mao Xincheng, Wang Huiming, Hu Xiaohong
School of Material Engineering, Jinling Institute of Technology, Nanjing, China.
Biomaterials for Organogenesis Laboratory, School of Materials Science and Engineering, Nanjing University of Science and Technology, Nanjing, China.
Front Chem. 2019 Feb 28;7:86. doi: 10.3389/fchem.2019.00086. eCollection 2019.
Azobenzene (AZO) has attracted increasing interest due to its reversible structural change upon a light stimulus. However, poor fatigue durability and the photobleaching phenomenon restricts its further application. Herein, the AZO domain as a pendent group, was incorporated into copolymers, which was synthesized by radical copolymerization in the research. Structure-properties of synthesized copolymer can be adjusted by monomer ratios. Emphatically, responsive properties of copolymer in different solutions were investigated. In the DMSO solution, copolymer exhibited effective structural change, stable rapid responsive time (1 min) upon UV light at room temperature, stable relative acceptable recovery time (100 min) upon white light at room temperature, and good fatigue resistance property. In an aqueous solution, even more controllable responsive properties and fatigue resistance properties for copolymer were verified by results. More pervasively, the recovery process could be controlled by light density and temperature. In order to clarify reasons for the difference between the AZO molecule and the AZO domain of copolymer, energy barrier or interactions between single atoms or even structural units was calculated using the density functional theory (DFT). Furthermore, the status of copolymer was characterized by dynamic light scattering (DLS) and transmission electron microscope (TEM). Finally, copolymer was further functionalized with bioactive protein (concanavalin, ConA) to reduce the cytotoxicity of the AZO molecule.
偶氮苯(AZO)因其在光刺激下的可逆结构变化而受到越来越多的关注。然而,较差的疲劳耐久性和光漂白现象限制了其进一步应用。在此,将作为侧基的偶氮苯域引入共聚物中,该共聚物是通过自由基共聚合成的。合成共聚物的结构性质可通过单体比例进行调节。重点研究了共聚物在不同溶液中的响应性能。在二甲基亚砜(DMSO)溶液中,共聚物表现出有效的结构变化,在室温下紫外光照射下具有稳定快速的响应时间(1分钟),在室温下白光照射下具有稳定且相对可接受的恢复时间(100分钟),以及良好的抗疲劳性能。在水溶液中,结果验证了共聚物具有更可控的响应性能和抗疲劳性能。更普遍地,恢复过程可由光密度和温度控制。为了阐明偶氮苯分子与共聚物的偶氮苯域之间差异的原因,使用密度泛函理论(DFT)计算了单个原子甚至结构单元之间的能垒或相互作用。此外,通过动态光散射(DLS)和透射电子显微镜(TEM)对共聚物的状态进行了表征。最后,用生物活性蛋白(伴刀豆球蛋白,ConA)对共聚物进行进一步功能化,以降低偶氮苯分子的细胞毒性。