Patchy Wormlike Micelles with Tailored Functionality by Crystallization-Driven Self-Assembly: A Versatile Platform for Mesostructured Hybrid Materials

Abstract

One-dimensional patchy nanostructures are interesting materials due to their excellent interfacial activity and their potential use as carrier for functional nanoparticles. Up to now only wormlike crystalline-core micelles (wCCMs) with a nonfunctional patchy PS/PMMA corona were accessible using crystallization-driven self-assembly (CDSA) of polystyrene-block-polyethylene-block-poly­(methyl methacrylate) (SEM) triblock terpolymers. Here, we present a facile approach toward functional, patchy wCCMs, bearing tertiary amino groups in one of the surface patches. The corona forming PMMA block of a SEM triblock terpolymer was functionalized by amidation with different N,N-dialkyl­ethylene­diamines in a polymer analogous fashion. The CDSA of the functionalized triblock terpolymers in THF was found to strongly depend on the polarity/solubility of the amidated PMMA block. The lower the polarity of the amidated PMMA block (increased solubility), the higher is the accessible degree of functionalization upon which defined, well-dispersed wCCMs are formed. Interestingly, also the structure of the patchy corona can be tuned by the composition/chemistry of the functional patch, giving rise to spherical patches for R = methyl, ethyl and rectangular patches for R = isopropyl. Patchy wCCMs were successfully used as template for the selective incorporation of Au nanoparticles within the amidated corona patches, showing their potential as versatile platform for the construction of functional, mesostructured hybrid materials.

Understanding the CDSA of poly(lactide) containing triblock copolymers

“…[15][16][17][18] The size and morphology of the assemblies can be precisely adjusted with the instruction of a seed-growth methodology. [19][20][21][22] Various functional groups have also been incorporated, including fluorescent marking, 23 metal nanoparticle incorporation 24 and photo-responsibility, 25 demonstrating a diverse range of potential uses within drug delivery processes. 26 As a semi-crystalline polymer, PLLA is renowned for its outstanding biocompatibility and biodegradability, which allows use in bio-relevant applications.…”

Bottom‐Up Meets Top‐Down: Patchy Hybrid Nonwovens as an Efficient Catalysis Platform

“…The patchy wCCMs were produced by crystallization-driven selfassembly (CDSA, "bottom-up"), which is aversatile method for the formation of well-defined cylindrical micelles. [15,16] ThePSpatches guarantee agood adhesion of the wCCMs to the PS core fiber,and the functional corona patches with the diisopropylamino groups were tailored for efficient AuNP binding.I nt he next step,t he patchy nonwovens were loaded with preformed citrate-stabilized AuNPs by af acile dipping method (Scheme 1B). [14] In this work, patchy wCCMs with as emicrystalline polyethylene (PE) core and Scheme 1.…”

“…[17] Thed iscoloration of the aqueous AuNP dispersion and the corresponding red-purple color of the patchy nonwoven indicate successful loading with the AuNPs. [16] We assume that the strong binding of the AuNPs to the patchy nonwovens is mainly due to replacement of the citrate ligands by the multidentate,a mino-group containing patches,a sunder the employed conditions (AuNP dispersion shows ap Ho f8 ), electrostatic interactions might be neglected as the amino groups in the functional patches are uncharged. [16] We assume that the strong binding of the AuNPs to the patchy nonwovens is mainly due to replacement of the citrate ligands by the multidentate,a mino-group containing patches,a sunder the employed conditions (AuNP dispersion shows ap Ho f8 ), electrostatic interactions might be neglected as the amino groups in the functional patches are uncharged.…”

Functional Macromolecular Systems: Kinetic Pathways to Obtain Tailored Structures

“…Crystallization from dilute solution can direct the self‐assembly of block copolymers, as was shown for diblock copolymers . Patchy wormlike structures were obtained from triblock terpolymers with a crystallizable middle block ( Figure ) . Crystallization‐induced self‐assembly of block copolymers from solutions has been shown to be a versatile tool to design one‐dimensional micellar structures and also block‐like structures can be prepared by using this type of supramolecular polymerization …”