Emerging applications for living crystallization-driven self-assembly

Abstract

The use of crystallization as a tool to control the self-assembly of polymeric and molecular amphiphiles in solution is attracting growing attention for the creation of non-spherical nanoparticles and more...

Block copolymer solution self‐assembly: Recent advances, emerging trends, and applications

“…The majority of nanoassemblies of this category originate from BCPs with at least one crystallizable block that usually serves as the micellar core. Therefore, the term “crystallization‐driven self‐assembly” (CDSA) was introduced to describe the formation of BCP micelles where crystallization plays a key role in the determination of the micellar morphology 5,21–24 …”

“…Therefore, the term "crystallization-driven self-assembly" (CDSA) was introduced to describe the formation of BCP micelles where crystallization plays a key role in the determination of the micellar morphology. 5,[21][22][23][24] One of the most comprehensive collective work in this field belongs to Manners and Winnik et al, who have thoroughly studied the self-assembly of BCPs with the metal-containing poly(ferrocenyldimethylsilane) (PFDMS or PFS) [25][26][27] or the regioregular semiconducting poly(3-hexylthiophene) (P3HT) [28][29][30] polymers as the crystallizable core-forming blocks that led to cylindrical/ "fiber-like" micelles. Moreover, this group were the first to report on the elongation of these pre-existing micelles upon further addition of unimer chains via an epitaxial growth process, since the exposed crystalline faces at each micelle core terminus are available for subsequent polymer crystallization, thus establishing the notion of "living" CDSA.…”

Patchy Micelles with a Crystalline Core: Self-Assembly Concepts, Properties, and Applications

“…Consequently, the self-assembly of such BCPs, bearing crystallizable blocks, is termed crystallization-driven self-assembly (CDSA) [ 1 , 62 , 63 ]. This field was pioneered by studies on poly(ferrocenyl dimethylsilane) (PFS)-containing BCPs and is gaining increasing importance for the preparation of well-defined 1D and two-dimensional (2D) assemblies, especially since the discovery of living CDSA ( Figure 2 ) [ 63 , 64 , 65 , 66 , 67 ]. Analogous to the living polymerization of monomers, CDSA can proceed in a living manner, employing small micellar fragments as seeds ( Figure 2 a: seeded growth) for the addition of unimers (molecularly dissolved BCPs with a crystallizable block).…”

“…Centrosymmetric and non-centrosymmetric block co-micelles are accessible, and give rise to broad structural complexity [ 79 ]. In particular, the introduction of fluorescent corona blocks marks an important step in the development of block co-micelles, since this enables the formation of barcode and RGB micelles ( Figure 3 b) [ 67 , 77 , 122 ]. Up to that point, the fabrication of cylindrical nanomaterials with precise, color-tunable compartments of predictable length and number was challenging.…”

“…( d ) Schematic depiction of the formation of B–A–B triblock co-micelles with patchy outer corona blocks, starting from SES wCCMs as seed micelles and subsequent living CDSA of SEM unimers in THF (left) and corresponding TEM image of patchy block co-micelles (scale bar: 100 nm). ( a ) Reproduced from [ 79 ] with permission of the American Association for the Advancement of Science (AAAS), ( b ) reproduced from [ 67 ] with permission of the Royal Society of Chemistry (RSC), ( c ) reproduced from [ 105 ], and ( d ) reproduced from [ 68 ] with permission of ACS.…”