Programmable selectivity of metal–imine bond coordination in subcomponent self-assembly of a primary amine based block copolymer

Xuejun Chen^a,Na Xu^a,Nan Li^b,Lican Lu^b,Yuanli Cai*^a(蔡远利),Ying Zhao*^c(赵莹)and Dujin Wang<sup>c

a</sup>Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, Department of Polymer Science and Engineering, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China.^bCollege of Chemistry, Xiangtan University, Xiangtan 411105, China^cBeijing National Laboratory for Molecular Sciences, Key Laboratory of Engineering Plastics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China

Soft Matter2013,9, 1885-1894.

We describe the programmable selectivity of intra-/inter-chain coordination in the subcomponent self-assembly of a primary amine based block copolymer. A well-defined poly(6-aminohexylmethacrylamide hydrochloride)-block-poly(N-2-hydroxypropylmethacrylamide) (PHPMA-b-PAHMA) was synthesizedviavisible light activated aqueous RAFT polymerisation at 25 °C. The conjugation of 2-hydroxy-5-methoxybenzaldehyde (HMBA) in the absence or presence of small fractions of the nickel ion complex was monitored using¹H NMR and UV spectroscopy. Subcomponent self-assembly and the programmable selectivity of intra-/inter-chain coordination were studied using dynamic light scattering and¹H NMR. The results demonstrated that the coordinated HMBA was much more reactive than the free HMBA, which promoted the collapse and hydrophobic association of polymer chains and thus brought about the autocatalysis of imine formation inside the collapsed “hot spots”. The polymer chains progressively assembled into narrowly-distributed nanoparticles on adding small fractions of Ni^II(HMBA)₂rather than autopoietically splitting into smaller ones, as observed on adding pure HMBA. More importantly, the diversity of subcomponent self-assembly and solubility of aggregates originated from the programmable selectivity of intra-/inter-chain coordination.

链接：http://pubs.rsc.org/en/content/articlelanding/2013/sm/c2sm26904j#!divAbstract