Wang Guangtong, Tang Bohan, Liu Yang, Gao Qingyu, Wang Zhiqiang, Zhang Xi
Key Lab of Organic Optoelectronics & Molecular Engineering , Department of Chemistry , Tsinghua University , Haidian District , Beijing 100084 , China . Email:
School of Chemical Engineering and Technology , China University of Mining & Technology , Xuzhou , Jiangsu 221116 , China.
Chem Sci. 2016 Feb 1;7(2):1151-1155. doi: 10.1039/c5sc03907j. Epub 2015 Oct 28.
Dissipative self-assembly is a challenging but attractive field of supramolecular science, because it generally concerns complex systems but is more close to the self-assembly of living bodies. In this article, we realized dissipative self-assembly by coupling a supra-amphiphile with a chemical oscillator. The supra-amphiphile was fabricated with iodine and a double hydrophilic block copolymer containing PEG segments, as the non-covalent interaction between PEG and iodine could turn PEG hydrophobic, leading to the formation of the supra-amphiphile. The self-assembly and disassembly of the supra-amphiphile could be controlled by varying the concentration of iodine. Therefore, the dissipative self-assembly of the supra-amphiphile was realized when it was coupled with the IO-NHOH-OH chemical oscillator, which was able to produce iodine periodically. Meanwhile, the kinetic data of the self-assembly and disassembly of the supra-amphiphile could be estimated by the theoretical simulation of the chemical oscillations. This line of research promotes the self-assembly of supra-amphiphiles one step forward from thermodynamic statics to a dissipative system, and also suggests a new strategy to investigate the kinetics of stimuli-responsive molecular self-assembly.
耗散自组装是超分子科学中一个具有挑战性但颇具吸引力的领域，因为它通常涉及复杂系统，但更接近于生命体的自组装。在本文中，我们通过将超两亲体与化学振荡器耦合实现了耗散自组装。超两亲体由碘和含聚乙二醇（PEG）链段的双亲水嵌段共聚物制备而成，由于PEG与碘之间的非共价相互作用可使PEG变为疏水的，从而导致超两亲体的形成。超两亲体的自组装和解组装可通过改变碘的浓度来控制。因此，当超两亲体与能够周期性产生碘的IO-NHOH-OH化学振荡器耦合时，实现了超两亲体的耗散自组装。同时，超两亲体自组装和解组装的动力学数据可通过化学振荡的理论模拟来估算。这一系列研究将超两亲体的自组装从热力学静态向前推进到耗散系统迈出了一步，也为研究刺激响应性分子自组装的动力学提出了一种新策略。
