Multi-Stimuli-Triggered Shape Transformation of Polymeric Filaments Derived from Dynamic Covalent Block Copolymers

Using dynamic polymers to achieve the morphology transformation of polymeric assemblies under different conditions is challenging. Herein, we reported diversiform shape transformation of multi-responsive polymer filaments, which were self-assembled by a new kind of amphiphilic block copolymer (PVEG-PVEA) possessing dynamic and reversible acylhydrazone bonds through reacting benzaldehyde-containing block copolymers poly(vinylbenzaldehyde)-b-poly(N-(4-vinylbenzyl)-N,N-diethylamine) (PVBA-PVEA) with acylhydrazine-modified oligoethylene glycol. It was found that the resulting amphiphilic and dynamic PVEG-PVEA was capable of hierarchically self-assembling into intriguing core-branched filaments in aqueous solution. Notably, the features of acylhydrazone bonds and PVEA block endow the filaments with multi-responsiveness including acid, base, and temperature, leading to the multiple morphological transformations under such stimuli. Moreover, the core-branched filaments would further transform into polymeric braided bundles driven by hydrogen-bonding interactions of amide bonds. It is noteworthy that both core-branched filaments and braided bundles made from polymers are quite rare. These diversiform polymeric assemblies and their morphological evolution were characterized by TEM, Cryo-TEM, SEM, and DLS. Finally, we used PVBA-PVEA as a platform to facilely prepare functional polymers, such as glycopolymers via the reaction of amino-containing sugars and aldehyde groups. The obtained glycopolymers self-assembled into glycofibers for the biomimicry of glycans via binding with lectins. These findings not only are conducive to understanding of the stimulated shape change process of dynamic polymeric assemblies in water but also provide a new method for the facile fabrication of smart and functional polymeric assemblies for different potential applications, such as biomimicry and targeted drug nanocarriers or delivery vehicles.