Glyco-Platelets with Controlled Morphologies via Crystallization-Driven Self-Assembly and Their Shape-Dependent Interplay with Macrophages

Abstract

Two-dimensional (2D) materials are of great significance to the materials community for their high surface area and controllable surface properties. However, controlled preparation of 2D structures with biological functions and biodegradable features is considerably hard. In this work, we demonstrate that, by careful selection of building block structures and assembly conditions, the above obstacle can be overcome partially by crystallization-driven self-assembly (CDSA) from PLLA-based diblock glycopolymers. 1D glyco-cylinders and 2D diamond-shaped glyco-platelets with solid or hollow core were achieved, where the latter structures have not been reported in literatures so far. The glyco-platelets further demonstrated exciting macrophage activation efficiency with clear size effect compared to their 1D analogues, which indicated their possible potential in immunological applications.

Emerging applications for living crystallization-driven self-assembly

“…This has now been achieved for a variety of crystallizable core-forming blocks, such as PFDMS, 250,253,254 polycarbonate, 62 PDHF, 251 PCL, 169,255 PLLA, 252,[256][257][258] , PE, 70,72 OPV. 259 Watersoluble low dispersity triblock fiber-like comicelles with a PFDMS core have also been prepared by living CDSA.…”

“…255 In 2017, living CDSA was achieved in water for the first time with a PCL-based triblock terpolymer. 169 256 The size of 2D platelets comprising PLLA-b-PDMAEMA (PDMAEMA = poly(dimethylaminoethyl methacrylate)) with coronal quaternization has also been found to affect their inhibition of bacterial growth. 257 A detailed study found that small platelets have higher antibacterial activity compared to large platelets or spherical particles.…”

Evaluation of Self-Assembly Pathways to Control Crystallization-Driven Self-Assembly of a Semicrystalline P(VDF-co-HFP)-b-PEG-b-P(VDF-co-HFP) Triblock Copolymer

“…In 1966, Lotz et al first found that poly(ethylene glycol)- b -polystyrene (PEO- b -PS) block copolymers (BCP) could form square-shaped platelets through crystallization from ethyl benzene solutions [ 5 ]. Since then, the preparation of micelles from crystalline-coil BCPs by crystallization-driven self-assembly (CDSA) has been gaining momentum [ 4 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 ].…”

“…Cylinders and lamellar architectures are the most commonly observed morphologies [ 8 , 14 , 15 , 16 ]. However, modifying the interactions between the two blocks and the solvent, and the interplay between the crystallization of the core-forming block and the corona chain stretching, gives access to more complex structures that may incorporate desired properties [ 13 , 17 , 18 , 19 ]. In solvents able to solubilize both blocks, the BCP remains as unimers undergoing a slower crystallization process and can form larger defect-free crystals (platelets, for example) [ 13 , 20 , 21 ].…”

“…Interestingly, they were able to control the dimensions and dispersity of the self-assembled nanostructures [ 6 ]. Li et al have reported a poly( l -lactide)-based diblock glycopolymer that assembled into 1D cylinders and 2D diamond-shaped platelets [ 13 ]. Qiu et al reported the preparation of cylindrical micelles from poly(ferrocene dimethylsilane)- b -poly(dimethylsiloxane) (PFS- b -PDMS) BCPs.…”