Zhou Yuze, Lei Jiaying, Peng Jing, Ye Tengling, Wang Yumeng, Huang Ruipeng, Zhang Yubo, Ren Yonghui, Zhou Yuhong, Tang Dongyan
School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001, China; State Key Laboratory of Advanced Welding and Joining, Harbin Institute of Technology, Harbin 150001, China.
School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001, China.
J Colloid Interface Sci. 2025 Jan 15;678(Pt B):1-10. doi: 10.1016/j.jcis.2024.08.261. Epub 2024 Sep 1.
Stimuli-responsive poly(N-vinylcaprolactam) (PVCL)-based microgels, which could response to small external environmental changes, have attracted great interests in the fields of biomedicine and nanotechnology. However, the preparation of such microgels meets severe challenge due to their low incorporation efficiency and thermoresponsivity passivation. To address these issues, we select 3-(tert-butoxycarbonyl)-N-vinylcaprolactam (TBVCL), a carboxyl-functionalized VCL derivative, as a comonomer to develop pH/temperature dual-responsive microgels. TBVCL, with a structure similar to VCL, enhances incorporation efficiency and colloidal stability, while reducing thermoresponsivity passivation. The volume phase transition temperature (VPTT) of the microgels can be adjusted over a broad range (19.0-49.5 °C). Notably, the radial swelling ratios of the microgels can be modulated by pH, achieving a maximum swelling ratio of 3. The distinct changes in dissolution-precipitation behavior under different temperatures or pH conditions make these microgels suitable for applications such as smart windows and sensors. Furthermore, this novel approach for fabricating microgels with pH-tunable phase-transition temperatures demonstrates significant potential for the controlled release of nanoparticles (e.g., drugs, catalysts, and quantum dots) and the development of smart nanocrystal-polymer composite sensors.
对微小外部环境变化有响应的基于聚(N-乙烯基己内酰胺)(PVCL)的微凝胶在生物医学和纳米技术领域引起了极大的兴趣。然而,由于其低掺入效率和热响应钝化,此类微凝胶的制备面临严峻挑战。为解决这些问题,我们选择3-(叔丁氧羰基)-N-乙烯基己内酰胺(TBVCL),一种羧基官能化的VCL衍生物,作为共聚单体来制备pH/温度双响应微凝胶。TBVCL结构与VCL相似,提高了掺入效率和胶体稳定性,同时降低了热响应钝化。微凝胶的体积相变温度(VPTT)可在较宽范围内(19.0 - 49.5°C)调节。值得注意的是,微凝胶的径向溶胀率可通过pH调节,最大溶胀率达到3。在不同温度或pH条件下溶解 - 沉淀行为的明显变化使这些微凝胶适用于智能窗户和传感器等应用。此外,这种制备具有pH可调相变温度的微凝胶的新方法在纳米颗粒(如药物、催化剂和量子点)的控释以及智能纳米晶体 - 聚合物复合传感器的开发方面显示出巨大潜力。