Polymerization-induced Self-assembly Research Articles

Molecular Alignment-Induced Chemically Patchy Uniaxial Nanoparticles and Their Applications in Anti-Counterfeiting and Self-Assembled Superstructures.

We report an unusual strategy for synthesizing patchy nanoparticles (NPs) by controlling the orientation of the molecules that form the NPs. This is realized by synchronous polymerization and crystallization of liquid crystal (LC) monomers during scalable precipitation polymerization. The resulting NPs are cylinders with highly uniform shapes and have only a single LC domain. The patchy properties originate from the discrepancy of surface chemical compositions on flat and side surfaces and can be switched on and off by solvent. Extra colloidal blocks can be grown onto the patches, resulting in highly uniform triblock patchy dumbbells, which have integrated optical properties, and as demonstrated, show triple-mode optical authentication in anti-counterfeiting labels or patterns. We also demonstrate that the triblock patchy cylinders are attractive building blocks for long LC rods or porous colloidal materials through polymerization-induced self-assembly.

Triggered Polymersome Fusion.

The contents of biological cells are retained within compartments formed of phospholipid membranes. The movement of material within and between cells is often mediated by the fusion of phospholipid membranes, which allows mixing of contents or excretion of material into the surrounding environment. Biological membrane fusion is a highly regulated process that is catalyzed by proteins and often triggered by cellular signaling. In contrast, the controlled fusion of polymer-based membranes is largely unexplored, despite the potential application of this process in nanomedicine, smart materials, and reagent trafficking. Here, we demonstrate triggered polymersome fusion. Out-of-equilibrium polymersomes were formed by ring-opening metathesis polymerization-induced self-assembly and persist until a specific chemical signal (pH change) triggers their fusion. Characterization of polymersomes was performed by a variety of techniques, including dynamic light scattering, dry-state/cryogenic-transmission electron microscopy, and small-angle X-ray scattering (SAXS). The fusion process was followed by time-resolved SAXS analysis. Developing elementary methods of communication between polymersomes, such as fusion, will prove essential for emulating life-like behaviors in synthetic nanotechnology.

Tunable Polymer Nanoreactors from RAFT Polymerization-Induced Self-Assembly: Fabrication of Nanostructured Carbon-Coated Anatase as Battery Anode Materials with Variable Morphology and Porosity.

We demonstrate a modular synthesis approach to yield mesoporous carbon-coated anatase (denoted as TiO2/C) nanostructures. Combining polymerization-induced self-assembly (PISA) and reversible addition-fragmentation chain-transfer (RAFT) dispersion polymerization enabled the fabrication of uniform core-shell polymeric nanoreactors with tunable morphologies. The nanoreactors comprised of a poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) shell and a poly(benzyl methacrylate) (PBzMA) core. We selected worm-like and vesicular morphologies to guide the nanostructuring of a TiO2 precursor, namely, titanium(IV) bis(ammonium lactato)dihydroxide (TALH). Subsequent carbonization yielded nanocrystalline anatase and simultaneously introduced a porous carbon framework, which also suppressed the crystal growth (∼5 nm crystallites). The as-prepared TiO2/C materials comprised of a porous structure, with large specific surface areas (>85 m2/g) and various carbon contents (20-30 wt %). As anode components in lithium-ion batteries, our TiO2/C nanomaterials improved the cycling stability, facilitated high overall capacities, and minimized the capacity loss compared to both their sans carbon and commercial anatase analogues.

Tunable Hierarchically Structured Meso-Macroporous Carbon Spheres from a Solvent-Mediated Polymerization-Induced Self-Assembly.

Herein, we report a versatile solvent-mediated polymerization-induced self-assembly (PISA) strategy to directly synthesize highly N-doped hierarchically porous structured carbon spheres with a tunable meso-macroporous configuration. The introduction of intermolecular hydrogen bonds is verified to enhance the interfacial interactions between block copolymers, oil droplets, and polyphenols. Moreover, the dominant hydrogen-bond-driven interactions can be systematically manipulated by selecting different cosolvent systems to generate diverse porous structures from the transformation of micellar and precursor co-assembly. Impressively, hierarchically structured meso-macroporous N-doped carbon spheres present simultaneously tunable sphere sizes and mesopores and macropores, ranging from 1.2 μm, 9/50 and 227 nm to 1.0 μm, 40, and 183 nm and 480, 24, and 95 nm. As a demonstration, dendritic-like N-doped hierarchically meso-macroporous carbon spheres manifest excellent enzyme-like activity, which is attributed to the continuous mass transport from the multiordered porosity. The current study provides a new platform for the synthesis of novel well-defined porous materials.

Polymerization-Induced Self-Assembly: An Emerging Tool for Generating Polymer-Based Biohybrid Nanostructures.

The combination of biomolecules and synthetic polymers provides an easy access to utilize advantages from both the synthetic world and nature. This is not only important for the development of novel innovative materials, but also promotes the application of biomolecules in various fields including medicine, catalysis, and water treatment, etc. Due to the rapid progress in synthesis strategies for polymer nanomaterials and deepened understanding of biomolecules' structures and functions, the construction of advanced polymer-based biohybrid nanostructures (PBBNs) becomes prospective and attainable. Polymerization-induced self-assembly (PISA), as an efficient and versatile technique in obtaining polymeric nano-objects at high concentrations, has demonstrated to be an attractive alternative to existing self-assembly procedures. Those advantages induce the focus on the fabrication of PBBNs via the PISA technique. In this review, current preparation strategies are illustrated based on the PISA technique for achieving various PBBNs, including grafting-from and grafting-through methods, as well as encapsulation of biomolecules during and subsequent to the PISA process. Finally, advantages and drawbacks are discussed in the fabrication of PBBNs via the PISA technique and obstacles are identified that need to be overcome to enable commercial application.

Recent advances in the solution self‐assembly of polypeptides

AbstractPolypeptides derived from amino acids bridge the synthetic polymers and proteins, and they have attracted continuous attention on their properties and functionalities. In the past decades, the self‐assembly behavior of polypeptides has been widely studied, and diversities of assembly nanostructures have been observed. In this perspective, we focus on the recent advances in the solution self‐assembly of polypeptides from two aspects. One is new type driving forces for the polypeptide self‐assembly, including liquid crystallization of polypeptides and conformation variation of helical polypeptides. Another is novel preparation methods for the polypeptide self‐assembly, including supramolecular polymerization, substrate‐mediated self‐assembly, and polymerization‐induced self‐assembly (PISA). In the end, we give a conclusion and outlook for the trends in the polypeptide solution self‐assembly.

Unimer Exchange Is not Necessary for Morphological Transitions in Polymerization-Induced Self-Assembly.

Polymerization-induced self-assembly (PISA) has established itself as a powerful and straightforward method to produce polymeric nano-objects of various morphologies in (aqueous) solution. Generally, spheres are formed in the early stages of polymerization that may evolve to higher order morphologies (worms or vesicles), as the solvophobic block grows during polymerization. Hitherto, the mechanisms involved in these morphological transitions during PISA are still not well understood. Combining a systematic study of a representative PISA system with rheological measurements, we demonstrate that-unexpectedly-unimer exchange is not necessary to form higher order morphologies during radical RAFT-mediated PISA. Instead, in the investigated aqueous PISA, the monomer present in the polymerization medium is responsible for the morphological transitions, even though it slows down unimer exchange.

Efficient Synthesis and PISA Behavior of Molecular Bottlebrush Block Copolymers via a Grafting-From Strategy through RAFT Dispersion Polymerization

Precise synthesis of molecular bottlebrushes (MBBs) with high yield via the grafting-from strategy using a reversible deactivation radical polymerization (RDRP) technique has remained elusive. Herein, the molecular bottlebrush block copolymers (MBB BCPs) with high yield and varying chemical compositions were synthesized via a polymerization-induced self-assembly (PISA)-assisted grafting-from strategy by reversible addition–fragmentation chain transfer (RAFT) dispersion polymerization. First, the poly(norbornene-g-poly(ethylene oxide))-b-poly(norbornene-g-chain transfer agent) [P(NB-g-PEG45)-b-P(NB-CTA)] BCPs with varied chemical compositions were synthesized by sequential ring-opening metathesis polymerization (ROMP) of norbornene PEG macromonomers (NB-PEG45) and norbornene chain transfer agent (NB-CTA) monomers. Subsequently, these P(NB-g-PEG45)m-b-P(NB-CTA)n BCPs were used as multifunctional macro-CTAs for the synthesis of MBB BCPs with a high yield (up to 80% styrene monomer conversion) and a low dispersity (Đ < 1.15) via a grafting-from strategy through RAFT dispersion polymerization. The PISA behaviors of these MBB BCPs were also investigated, and the results indicated that the MBB BCPs assemblies were transformed from spherical micelles into two-dimensional disk-like micelles because the rigidity of the PS MBB segment increased with the growth of PS side chains.

Polymerization-Induced Self-Assembly for Efficient Fabrication of Biomedical Nanoplatforms.

Amphiphilic copolymers can self-assemble into nano-objects in aqueous solution. However, the self-assembly process is usually performed in a diluted solution (<1 wt%), which greatly limits scale-up production and further biomedical applications. With recent development of controlled polymerization techniques, polymerization-induced self-assembly (PISA) has emerged as an efficient approach for facile fabrication of nano-sized structures with a high concentration as high as 50 wt%. In this review, after the introduction, various polymerization method-mediated PISAs that include nitroxide-mediated polymerization-mediated PISA (NMP-PISA), reversible addition-fragmentation chain transfer polymerization-mediated PISA (RAFT-PISA), atom transfer radical polymerization-mediated PISA (ATRP-PISA), and ring-opening polymerization-mediated PISA (ROP-PISA) are discussed carefully. Afterward, recent biomedical applications of PISA are illustrated from the following aspects, i.e., bioimaging, disease treatment, biocatalysis, and antimicrobial. In the end, current achievements and future perspectives of PISA are given. It is envisioned that PISA strategy can bring great chance for future design and construction of functional nano-vehicles.

Bimodal nanolatexes prepared via polymerization-induced self-assembly: losing control in a controlled manner

In this paper we demonstrate the potential advantages of reproducible bimodal nanolatexes prepared by the combination of reversible addition–fragmentation chain-transfer (RAFT) polymerization with polymerization-induced self-assembly (PISA).

Efficient preparation of polyoxometalate-junctional cross-linking hybrid nanocomposites by polymerization-induced self-assembly.

We reported a facile method for the preparation of POM-polymer hybrids in one-pot via polymerization-induced self-assembly. Polyoxometalate macroanions were complexed with cations to prepare cross-linking agents. RAFT dispersion polymerization was conducted in the presence of the cross-linking agent. The hybrid nanoparticles can be used as nanoreactors for the photocatalytic synthesis of Au nanoparticles.

3D printable, thermo-responsive, self-healing, graphene oxide containing self-assembled hydrogels formed from block copolymer wormlike micelles.

Graphene oxide (GO) containing block copolymer nanocomposite hydrogels formed from poly(glycerol monomethacrylate-block-hydroxypropyl methacrylate) (PGMA-PHPMA) wormlike micelles were prepared by either mixing GO and copolymer at low temperature or via in situ reversible addition-fragmentation chain-transfer (RAFT) polymerisation-induced self-assembly (PISA) of HPMA in the presence of a PGMA macromolecular chain-transfer agent and GO flakes. Hydrogels containing 15-25% w/w copolymer and 0 and 8% w/w GO, based on copolymer, were investigated and the maximum gel strength measured was ∼33 kPa for a 25% w/w copolymer gel prepared by in situ polymerisation and containing 2% w/w GO based on copolymer. This gel strength represents a fifteen-fold increase over the same copolymer gel without the addition of GO. The nanocomposite gels were found to recover efficiently after the application of high shear, with up to 98% healing efficiency within seconds. These gels are also 3D printable, self-healing, adhesive and temperature responsive on cooling and re-heating. The observed properties were both GO and copolymer concentration dependent, and tensile testing demonstrated that the nanocomposite gels had higher moduli, elongation at break and toughness than gels prepared without GO.

Visible label-free detection of bacterial DNA using flocculation of sterically stabilised cationic latexes.

The current gold standard diagnostic for bacterial infections is the use of culture, which can be time consuming and can take up to five days for results to be reported. There is therefore an unmet clinical need for a rapid and label free alternative. This paper demonstrates a method of detecting the presence of amplified DNA from bacterial samples using a sterically-stabilised, cationic polymer latex and widely available equipment, providing an accessible alternative DNA detection technique. If DNA is present in a sample, successful amplification by polymerase chain-reaction (PCR) results in the amplified DNA inducing flocculation of the polymer latex followed by rapid sedimentation. This results in a visible and obvious change from a milky-white dispersion to a precipitated latex with a colourless and transparent supernatant, thus giving a clear visual indication of the presence or absence of amplified DNA. Specifically, the response of four polymer latexes with different morphologies to the addition of amplified bacterial DNA was investigated. Cationic latexes flocculated rapidly whereas non-ionic and anionic latexes did not, as judged by eye, disc centrifuge photosedimentometry (DCP), and UV-visible spectrophotometry. The stability of several cationic latexes with different morphologies in typical PCR reagents was investigated. It was found that unwanted flocculation occurred for a latex with a non-ionic core and a cationic corona (poly[2-vinyl pyridine-b-benzyl methacrylate], prepared by polymerisation-induced self-assembly) whereas a ∼700 nm PEGMA-stabilised P2VP latex (non-ionic stabiliser, cationic core), prepared by emulsion polymerisation remained stable. The sensitivity and rate of sedimentation of the PEGMA-stabilised P2VP latex was demonstrated by varying the sequence length and concentration of amplified DNA from Pseudomonas aeruginosa using universal bacterial primers. DNA concentrations as low as 0.78 ng μl-1 could readily be detected within 30 minutes from the addition of amplified DNA to the latex. Furthermore, the specificity of this method was demonstrated by showing a negative result occurs (no flocculation of the latex) when PCR product from a fungal (Candida albicans) sample using bacterial primers was added to the latex.

Preparation of polymer nanoparticle-based complex coacervate hydrogels using polymerisation-induced self-assembly derived nanogels.

This paper reports a generic method to prepare polymer nanoparticle-based complex coacervate (PNCC) hydrogels by employing rationally designed nanogels synthesised by reversible addition-fragmentation chain-transfer (RAFT)-mediated polymerisation-induced self-assembly (PISA). Specifically, a poly(potassium 3-sulfopropyl methacrylate) (PKSPMA) macromolecular chain-transfer agent (macro-CTA) was synthesised via RAFT solution polymerisation followed by chain-extension with a statistical copolymer of benzyl methacrylate (BzMA) and methacrylic acid (MAA) at pH 2. Thus, pH-responsive nanoparticles (NPs) comprising a hydrophobic polyacid core-forming block and a sulfonate-functional stabiliser block were formed. With the introduction of methacrylic acid into the core of the NPs, they become swollen with increasing pH, as judged by dynamic light scattering (DLS), indicating nanogel-type behaviour. PNCC hydrogels were prepared by simply mixing the PISA-derived nanogels and cationic branched polyethyleneimine (bPEI) at 20% w/w. In the absence of MAA in the core of the NPs, gel formation was not observed. The mass ratio between the nanogels and bPEI affected resulting hydrogel strength and a mixture of bPEI and PKSPMA68-P(BzMA0.6-stat-MAA0.4)300 NPs with a mass ratio of 0.14 at pH ∼7 resulted in a hydrogel with a storage modulus of approximately 2000 Pa, as determined by oscillatory rheology. This PNCC hydrogel was shear-thinning and injectable, with recovery of gel strength occurring rapidly after the removal of shear.

Colloidal crystals of monodisperse fluoro-nanoparticles by aqueous polymerization-induced self-assembly.

Here, we prepared monodisperse fluorinated nanospheres with the diameter regulated from 100 to 200 nm and PDI of the diameter lower than 0.05 via polymerization-induced self-assembly (PISA). Mono/multilayered 2D and large-scale ordered 3D lattices were formed by solvent evaporation-induced colloidal self-assembly. This work shows the promising application of PISA in colloidal self-assembly.

Morphological evolution of poly(glycerol monomethacrylate)-stat-glycine–phenylalanine–phenylalanine–methacrylamide-b-poly(2-hydroxypropylmethacrylate) (P(GMA-stat-(MAm-GFF))-b-PHPMA) block copolymer nano-objects via polymerization-induced self-assembly

Here we report a study on the reversible addition–fragmentation chain transfer (RAFT) polymerization-induced self-assembly (PISA) of self-assembling peptide-containing diblock copolymers.

Preparation of polymeric vesicles with tertiary amine and epoxy functional groups via polymerization-induced self-assembly

Polymeric vesicles with tertiary amine and epoxy functional groups were fabricated via the reversible addition-fragmentation chain transfer (RAFT) dispersion polymerization of 2-(diisopropylamino) ethyl methacrylate (DIPEMA) and glycidyl methacrylate (GlyMA) in an ethanol-water mixture by using poly (ethylene oxide)-4-(4-Cyanopentanoic acid) dithiobenzoate (mPEG45-CPADB) as the macro-chain-transfer agent (macro-CTA). Biocompatible polymer mPEG45 with molecular weight of 2000 and 4-(4-Cyanopentanoic acid) dithiobenzoate (CPADB) were used for the macro-CTA synthesizing via the esterification reaction. Investigation of the degree of polymerization (DP) of the hydrophobic block P(DIPEMA-co-GlyMA) and the solid content indicated that both have significant effect on the particle morphology and particle diameter. 1H NMR and FTIR analysis indicated the existing of tertiary amine and epoxy functional groups on the produced vesicles.

Continuous synthesis of block copolymer nanoparticlesviatelescoped RAFT solution and dispersion polymerisation in a miniature CSTR cascade

Miniaturised continuous-flow reactors offer an economical and scalable route to explore the synthesis of block copolymersviaRAFT mediated polymerisation-induced self-assembly (PISA).

Aqueous RAFT polymerization-induced self-assembly (PISA): amphiphilic macroRAFT self-assembly vs. monomer droplet nucleation (miniemulsion polymerization)

The effect of monomer droplet size on the particle formation mechanism in aqueous heterogeneous polymerization using a hydrophilic macroRAFT agent has been investigated.

Heterobimetallic block copolymers with a combined main-chain/side-chain topology.

We report for the first time the synthesis of heterobimetallic block copolymers with a combined main-chain/side-chain topology. The photophysical, electrochemical, and thermal properties and ring-opening metathesis polymerization-induced crystallization-driven self-assembly (ROMPI-CDSA) behavior of these polymers can be significantly modulated by switching the metal identity.