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This article presents an overview of the latest key developments and research activities in the area of cylindrical polymer brushes (CPBs), also known as ‘molecular bottlebrushes’. CPBs consist of a polymer backbone containing polymer side chains that cause the backbone to extend and adopt a worm-like conformation. The extent of backbone stretching and the aspect ratio of CPBs is determined by the...
An amphiphilic diblock-copolymer consisting of poly(3-hexylthiophene) and poly(4-vinylpyridine) has been synthesized and self-assembled from mixed selective solvents of tetrahydrofuran and methanol to produce nanostructures having photoluminescence spanning from the blue to the red. The emission decay times of the nanostructures have been found to increase with the fraction of methanol, suggesting...
Novel amphiphilic poly(2-oxazoline)s bearing l-prolinamide moieties at the alkyl side-chain termini were designed and synthesized by a bottom-up protocol. These polymers formed micelle-type assemblies with a size of 10–30 nm in water, in which the majority of prolinamide active groups was tucked into the hydrophobic inner core. As a nanoreactor, the micellar systems were successfully applied to the...
S-layer recrystallization is part of, at least, two major scientific and technological challenges: a model system to study 2-D polymer crystal formation and a bottom-up approach to build biomimetic and functional interfaces. In particular, the self-assembly process of the bacterial surface layer protein (SbpA) might be influenced by two different interactions: protein/substrate and protein/protein...
The detailed knowledge of the structure and dynamics in molecular level is very relevant for our understanding of the conductivity mechanism of solid state polymer electrolytes. In this work, we have synthesized two conductive β-CD-polyether/Li+ inclusion crystals, which both have the channel-like structure formed by the β-CDs, but differ by the chemical nature of the assembled polymer chains. 1H,...
Surface modification of graphene oxide has been performed using diamine moieties with varying chain length and subsequently chemically grafted with long chain polyurethane for wrapping up of graphene sheet with large polymer chains. Functionalization of graphene and its subsequent grafting have been verified through spectroscopic measurements like NMR, FTIR and UV–visible spectroscopy and the uniform...
A series of well-defined amphiphilic polymethylene-b-poly(ethylene glycol) (PM-b-PEG) diblock copolymers, with different hydrophobic chain length, were synthesized by combining Diels-Alder reaction with polyhomologation. The successful synthetic procedure was confirmed by size-exclusion chromatography (SEC) and 1H NMR spectroscopy. These block copolymers self-assembled into spherical micelles in aqueous...
This paper reports a systematic study on a series of supramolecular polyurethanes that possess microphase separated morphologies which afford elastic materials at room temperature. Combinations of urea and/or urethane linkers in addition to a phenyl spacer have been used to study the effect of the rigidity of the hard end group segments as well as the hydrogen bonding capability of the urethane-urea...
The synthesis of polystyrene-block-poly[2-(N-morpholino)ethyl methacrylate] (PS-b-PMEMA) as a new highly amphiphilic and multiple stimuli-responsive block copolymer is presented. To achieve high molecular weights far beyond 100 kDa in a highly controlled manner (dispersities < 1.1), a synthetic route via sequential combination of anionic polymerization for the PS block and reversible addition–fragmentation...
Asymmetric poly(isoprene-b-styrene-b-4-vinylpyridine) (ISV) block copolymer membranes fabricated via self-assembly and non-solvent induced phase separation (SNIPS) process have drawn significant attention due to the simple processing method and the generation of high-quality isoporous ultrafiltration membranes. With the present study on SNIPS membrane substructure, we systematically varied membrane...
Block copolymer micelles and vesicles are mostly prepared by the solvent mixing method, where the block copolymer is first dissolved in a common solvent for both blocks, which is then mixed with a selective solvent, mostly water, to induce self-assembly into the desired structure. Using a combination of microfluidic flow-focusing and capillary interdiffusion experiments combined with in-situ small-angle...
The understanding of glycopolymer-based nanostructures formation and their lectin binding properties are of great interest to the development of drug delivery systems and other biological applications. Herein, glycosylated polypeptides were synthesized from a clickable poly(l-lysine)-b-poly(benzyl-l-glutamate) copolypeptide, obtained by a sequential ring opening polymerization. The clickable poly(l-lysine)...
Block copolymers microphase separate into a variety of bulk morphologies that serve as scaffolds, templates, masks and source for polymeric nano-particles. While supramolecular additives are common to complex within diblock copolymers to modify the morphology, the subtle effects of complexation on ABC triblock terpolymer morphologies are less explored. Here, we describe the manipulation of polystyrene-block-poly(4-vinylpyridine)-block-poly(tert-butyl...
The combination of block copolymer templating with electrostatic self-assembly provides a simple and robust method for creating nano-patterned polyelectrolyte multilayers over large areas. The deposition of the first polyelectrolyte layer provides important insights on the initial stages of multilayer buildup. Here, we focus on two-dimensionally confined “dots” patterns afforded by block copolymer...
Two Y-shaped molecules combining two dissimilar (hydrophilic and hydrophobic) units with a reactive triethoxysilane moiety were synthesized by Michael addition reaction of (aminopropyl)triethoxysilane with 2-hydroxyethyl acrylate (HEA), followed by the addition of 2,2,2-trifluoroethyl acrylate (TFEA) or 1H,1H,5H-octafluoropentyl acrylate (OFPA). Hydrolytic condensations of the Y-shaped triethoxysilane...
Formulating an analytical theory, we study phase separation of a polyelectrolyte solution under poor solvent condition confined in three types of finite geometric spaces: slab, cylinder, and sphere. Divided by a Lifshitz line, bulk polyelectrolyte solution undergoes either micro- or macro-phase separation. Confinement effects for both scenarios are studied. Composition fluctuations inducing phase...
A “grafting onto” approach based on two different controlled ring-opening polymerization (ROP) techniques is developed to synthesize polytyrosine-graft-poly(2-ethyl-2-oxazoline) (PTyr-g-PEtOx) copolymer conjugates of varying main backbone and pendent chain lengths. This approach consists of syntheses of propargyl functionalized polytyrosine (PTyr-O-Pr) by ROP of tyrosine N-carboxyanhydride and azide...
A diverse nanostructure, key to property alteration, has been observed by the insertion of two dimensional nanoparticles through in-situ polymerization. Self-assembly at the molecular level has been revealed starting from nanoscale to observable microscale in thermoplastic polyurethane using alicyclic diisocyanate and how the self-assembly behaviour changes in presence of nanoparticle. Varying dispersion...
A series of azo polyurethanes bearing push-pull type azo chromophores was synthesized by post-polymerization azo-coupling reactions between a polyurethane precursor and diazonium salts of different aniline derivatives, respectively. Colloidal spheres with narrow size distributions were obtained by aggregation of these azo polyurethanes in DMF-H2O mixed solvents, which were induced by slowly increasing...
A water-soluble amphiphilic peptide-poly (1-vinylimidazole) [Boc-Cys (PVim)-Trp-OMe] bioconjugate is synthesized by ‘grafting from’ technique based on thiol-mediated radical polymerization. The attachment of fluorescein isothiocyanate (FITC) at the N-terminus of the peptide moiety of the bioconjugate results in the generation of fluorescent bioconjugate [FITC-Cys (PVim)-Trp-OMe]. MALDI-TOF-MS analysis...
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