Yes / We report the crystallization-driven self-assembly of diblock copolymers bearing a poly(L-lactide) block into cylindrical micelles. Three different hydrophilic corona-forming blocks have been employed: poly(4-acryloyl morpholine) (P4AM), poly(ethylene oxide) (PEO) and poly(N,N-dimethylacrylamide) (PDMA). Optimization of the experimental conditions to improve the dispersities of the resultant cylinders through variation of the solvent ratio, the polymer concentration, and the addition speed of the selective solvent is reported. The last parameter has been shown to play a crucial role in the homogeneity of the initial solution, which leads to a pure cylindrical phase with a narrow distribution of length. The hydrophilic characters of the polymers have been shown to direct the length of the resultant cylinders, with the most hydrophilic corona block leading to the shortest cylinders. / EPSRC and the University of Warwick, the Swiss National Science Foundation - Early Postdoc Mobility fellowship (Grant no PBNEP2-142949 to A.P.B.). The Warwick Research Development Fund. Some items of equipment funded by Birmingham Science City: Innovative Uses for Advanced Materials in the Modern World (West Midlands Centre for Advanced Materials Project 2), with support from Advantage West Midlands (AWM) and part funded by the European Regional Development Fund (ERDF).

Yes / 2D materials such as graphene, LAPONITE® clays or molybdenum disulfide nanosheets are of extremely high interest to the materials community as a result of their high surface area and controllable surface properties. While several methods to access 2D inorganic materials are known, the investigation of 2D organic nanomaterials is less well developed on account of the lack of ready synthetic accessibility. Crystallization-driven self-assembly (CDSA) has become a powerful method to access a wide range of complex but precisely-defined nanostructures. The preparation of 2D structures, however, particularly those aimed towards biomedical applications, is limited, with few offering biocompatible and biodegradable characteristics as well as control over self-assembly in two dimensions. Herein, in contrast to conventional self-assembly rules, we show that the solubility of polylactide (PLLA)-based amphiphiles in alcohols results in unprecedented shape selectivity based on unimer solubility. We use log Poct analysis to drive solvent selection for the formation of large uniform 2D diamond-shaped platelets, up to several microns in size, using long, soluble coronal blocks. By contrast, less soluble PLLA-containing block copolymers yield cylindrical micelles and mixed morphologies. The methods developed in this work provide a simple and consistently reproducible protocol for the preparation of well-defined 2D organic nanomaterials, whose size and morphology are expected to facilitate potential applications in drug delivery, tissue engineering and in nanocomposites. / University of Warwick, Materials GRP, EPSRC, The Royal Society, ERC

Yes / Sequential ring-opening and reversible addition–fragmentation chain transfer (RAFT) polymerization was used to form a triblock copolymer of tetrahydropyran acrylate (THPA), 5-methyl-5-allyloxycarbonyl-1,3-dioxan-2-one (MAC) and L-lactide. Concurrent deprotection of the THPA block and crystallization-driven self-assembly (CDSA) was undertaken and allowed for the formation of cylindrical micelles bearing allyl handles in a short outer core segment. These handles were further functionalized by different thiols using photo-initiated thiol–ene radical reactions to demonstrate that the incorporation of an amorphous PMAC block within the core does not disrupt CDSA and can be used to load the cylindrical nanoparticles with cargo. / Royal Society (Great Britain), Engineering and Physical Sciences Research Council (EPSRC), European Research Council (ERC)