Polymerization-induced self-assembly enables access to diverse highly ordered structures through kinetic and thermodynamic pathways.

Poly(N-2-(methacryloyloxy)ethyl pyrrolidone)-poly(benzyl methacrylate) diblock copolymer nano-objects via RAFT alcoholic dispersion polymerisation in ethanol

Latex templating using core-shell particles represents a unique opportunity to design mesoporous carbons with a high level of control on textural properties. This new class of organic colloid templates is synthesized by polymerization-induced self-assembly (PISA) in which a solvophilic poly(hydroxyethyl acrylate) (PHEA) homopolymer is chain extended with a solvophobic polystyrene (PS) via a photomediated reversible-addition-fragmentation-transfer (RAFT) polymerization. The resultant PHEA-b-PS diblock copolymer nanoparticles exhibit a PS core stabilized by a PHEA shell, with two blocks characterized by a low molecular weight dispersity (1.1-1.3) and an adjustable degree of polymerization (DP). The core-shell structured nanoparticles are used as soft template for the formation of mesostructured carbons from phloroglucinol and glyoxylic acid in methanol solution. A micro- and mesostructured cellular foam is obtained having uniform, interconnected, and narrowly distributed mesopores ranging between 15 and 30 nm in diameter, a specific surface area up to 719 m2 g-1, and a total pore volume of (0.4-1.3) cm3 g-1. The mesopore size can be controlled by adjusting the diameter of the PS core (16-29 nm), while the wall thickness can be tailored independently by varying the size of the solvated PHEA shell (5-25 nm). An increase of PHEA block's DP from 25 to 85 gradually extends the stabilizing shell dimension, thus increasing the wall thickness up to 10 nm, and causing the shift from interconnected to isolated mesopores. By comparison, much thinner walls (2-3 nm) are obtained with conventional latex templates such as polystyrene nanoparticles or colloidal silica. Decreasing PHEA DP to 17 induces the formation of copolymer vesicles that can be used as template to create mesoporous carbons with nonspherical mesopores.

Ice binding proteins modulate ice nucleation/growth and have huge (bio)technological potential. There are few synthetic materials that reproduce their function, and rational design is challenging due to the outstanding questions about the mechanisms of ice binding, including whether ice binding is essential to reproduce all their macroscopic properties. Here we report that nanoparticles obtained by polymerization-induced self-assembly (PISA) inhibit ice recrystallization (IRI) despite their constituent polymers having no apparent activity. Poly(ethylene glycol), poly(dimethylacrylamide), and poly(vinylpyrrolidone) coronas were all IRI-active when assembled into nanoparticles. Different core-forming blocks were also screened, revealing the core chemistry had no effect. These observations show ice binding domains are not essential for macroscopic IRI activity and suggest that the size, and crowding, of polymers may increase the IRI activity of “non-active” polymers. It was also discovered that poly(vinylpyrrolidone) particles had ice crystal shaping activity, indicating this polymer can engage ice crystal surfaces, even though on its own it does not show any appreciable ice recrystallization inhibition. Larger (vesicle) nanoparticles are shown to have higher ice recrystallization inhibition activity compared to smaller (sphere) particles, whereas ice nucleation activity was not found for any material. This shows that assembly into larger structures can increase IRI activity and that increasing the “size” of an IRI does not always lead to ice nucleation. This nanoparticle approach offers a platform toward ice-controlling soft materials and insight into how IRI activity scales with molecular size of additives.

In this work we constructed a detailed phase diagram for the solutions of ideal diblock-copolymers and compared such diagram with that obtained during polymerization-induced self-assembly (PISA); a wide range of polymer concentrations as well as chain compositions was studied. As the length of the solvophobic block nB increases (the length of the solvophilic block nA was fixed), the transition from spherical micelles to cylinders and further to vesicles (lamellae) occurs. We observed a rather wide transition region between the spherical and cylindrical morphology in which the system contains a mixture of spheres and short cylinders, which appear to be in dynamic equilibrium; the transition between the cylinders and vesicles was found to be rather sharp. Next, upon increasing the polymer concentration in the system, the transition region between the spheres and cylinders shifts towards lower nB/nA values; a similar shift but with less magnitude was observed for the transition between the cylinders and vesicles. Such behavior was attributed to the increased number of contacts between the micelles at higher polymer volume concentrations. We also found that the width of the stability region of the cylindrical micelles for small polymer volume concentrations is in good quantitative agreement with the predictions of analytical theory. The obtained phase diagram for PISA was similar to the case of presynthesized diblock copolymer; however, the positions of the transition lines for PISA are slightly shifted towards higher nB/nA values in comparison to the presynthesized diblock copolymers, which is more pronounced for the case of the cylinders-to-vesicles transition. We believe that the reason for such behavior is the polydispersity of the core-forming blocks: The presence of the short and long blocks being located at the micelle interface and in its center, respectively, helps to reduce the entropy losses due to the insoluble block stretching, which leads to the increased stability of more curved micelles.

Reversible addition-fragmentation chain transfer (RAFT) dispersion polymerization of benzyl methacrylate (BzMA) is utilized to prepare a series of poly(stearyl methacrylate)-poly(benzyl methacrylate) (PSMA-PBzMA) diblock copolymer nano-objects at 90 °C directly in mineral oil. Polymerization-induced self-assembly (PISA) occurs under these conditions, with the resulting nanoparticles exhibiting spherical, worm-like or vesicular morphologies when using a relatively short PSMA13 macromolecular chain transfer agent (macro-CTA), as confirmed by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) studies. Only kinetically-trapped spherical nanoparticles are obtained when using longer macro-CTAs (e.g. PSMA18 or PSMA31), with higher mean degrees of polymerization (DPs) for the PBzMA core-forming block simply producing progressively larger spheres. SAXS is used for the first time to monitor the various morphological transitions that occur in situ during the RAFT dispersion polymerization of BzMA when targeting either spheres or vesicles as the final copolymer morphology. This powerful characterization technique enables the evolution of particle diameter, mean aggregation number, number of copolymer chains per unit surface area (Sagg) and the distance between adjacent copolymer chains at the core-shell interface (dint) to be monitored as a function of monomer conversion for kinetically-trapped spheres. Moreover, the gradual evolution of copolymer morphology during PISA is confirmed unequivocally, with approximate 'lifetimes' assigned to the intermediate pure sphere and worm morphologies when targeting PSMA13-PBzMA150 vesicles. Within vesicle phase space, the membrane thickness (Tm) increases monotonically with PBzMA DP. Furthermore, a combination of dynamic light scattering (DLS), TEM and post mortem SAXS studies indicate that the lumen volume is reduced while the overall vesicle dimensions remain essentially constant. Thus the constrained vesicles grow inwards, as recently reported for an aqueous PISA formulation. This suggests a universal vesicle growth mechanism for all PISA formulations.

Polymerization-induced self-assembly (PISA) is an emerging industrially relevant technology, which allows the preparation of defined and predictable polymer self-assemblies with a wide range of morphologies. In recent years, interest has turned to photoinitiated PISA processes, which show markedly accelerated reaction kinetics and milder conditions, thereby making it an attractive alternative to thermally initiated PISA. Herein, we attempt to elucidate the differences between these two initiation methods using isothermally derived phase diagrams of a well-documented poly(ethylene glycol)-b-(2-hydroxypropyl methacrylate) (PEG-b-HPMA) PISA system. By studying the influence of the intensity of the light source used, as well as an investigation into the thermodynamically favorable morphologies, the factors dictating differences in the obtained morphologies when comparing photo- and thermally initiated PISA were explored. Our findings indicate that differences in a combination of both reaction kinetics and end group fidelity led to the observed discrepencies between the two techniques. We find that the loss of the end group in photoinitiated PISA drives the formation of higher order structures and that a morphological transition from worms to unilamellar vesicles could be induced by extended periods of light and heat irradiation. Our findings demonstrate that PISA of identical block copolymers by the two different initiation methods can lead to structures that are both chemically and morphologically distinct.

Liquid Crystalline Nanoparticles In article number 2506077, Guoxing Liao, LinGe Wang, and co-workers prepared spherical liquid crystalline nanoparticles using a liquid crystalline polymer as the core-forming block during polymerization-induced self-assembly. Further analysis confirmed the straight main-chain conformation of the core-forming block, which exhibits unique birefringence as lyotropic liquid crystal behaviour in nanoparticle formations under polarized optical microscopy.

Polymerization-Induced Self-Assembly (PISA) for in situ drug encapsulation or drug conjugation in cancer application

It is well‐known that the self‐assembly of AB diblock copolymers in solution can produce various morphologies depending on the relative volume fraction of each block. Recently, polymerization‐induced self‐assembly (PISA) has become widely recognized as a powerful platform technology for the rational design and efficient synthesis of a wide range of block copolymer nano‐objects. In this study, PISA is used to prepare a new thermoresponsive poly(N‐(2‐hydroxypropyl) methacrylamide)‐poly(2‐hydroxypropyl methacrylate) [PHPMAC‐PHPMA] diblock copolymer. Remarkably, TEM, rheology and SAXS studies indicate that a single copolymer composition can form well‐defined spheres (4 °C), worms (22 °C) or vesicles (50 °C) in aqueous solution. Given that the two monomer repeat units have almost identical chemical structures, this system is particularly well‐suited to theoretical analysis. Self‐consistent mean field theory suggests this rich self‐assembly behavior is the result of the greater degree of hydration of the PHPMA block at lower temperature, which is in agreement with variable temperature 1H NMR studies.

The common spherical mesophases observed from chemically distinct compounds have promoted extensive studies of packing structures in soft-matter self-assemblies. Here, we present a new approach for controlling sphere-packing phases by modulating homologous copolymer chain configurations. To this end, three sets of sample pairs, compositionally asymmetric polydimethylsiloxane-b-poly(2,2,2-trifluoroethyl acrylate) (PDMS-b-PTFEA) diblock copolymers (diBCPs) and their homologues containing the corresponding triblock copolymer (triBCP), are synthesized via atom transfer radical polymerization and designed with the consistent volume fractions of the core-forming PTFEA block, fPTFEA = 0.20, 0.18, and 0.15. We identify the formation of C15 and hexagonally close-packed (HCP) phases in the triBCP-containing PDMS-b-PTFEAs, whereas the σ and C14 phases are formed in their diBCP analogues, respectively. These phase shifts into C15 and HCP, due to molecular configuration differences, reveal a significant yet unrealized role of chain configurations and the associated chain size effects in determining the stable sphere-packing phases in BCP systems.

Polymerization-induced self-assembly (PISA) is an efficient and versatile method to afford polymeric nano-objects with polymorphic morphologies. Compared to dispersion PISA syntheses based on soluble monomers, the vast majority of emulsion PISA formulations using insoluble monomers leads to kinetically-trapped spheres. Herein, we present aqueous emulsion PISA formulations generating worms and vesicles besides spheres. Two monomers with different butyl groups, n-butyl (nBHMA) and tert-butyl (tBHMA) α-hydroxymethyl acrylate, and thus possessing different water solubilities were synthesized via Baylis-Hillman reaction. Photoinitiated aqueous emulsion polymerizations of nBHMA and tBHMA employing poly(ethylene glycol) macromolecular chain transfer agents (macro-CTAs, PEG45-CTA, and PEG113-CTA) at 40 °C were systematically investigated to evaluate the effect of monomer structure and solubility on the morphology of the generated block copolymer nano-objects. Higher order morphologies including worms and vesicles were readily accessed for tBHMA, which has a higher water solubility than that of nBHMA. This study proves that plasticization of the core-forming block by water plays a key role in enhancing chain mobility required for morphological transition in emulsion PISA.

A morphological transition of poly(ethylene glycol)-block-polystyrene with polymerization-induced self-assembly guided by using cosolvents

RAFT dispersion copolymerization of styrene and N-methacryloxysuccinimide: Promoted morphology transition and post-polymerization cross-linking

Dialkylphosphonate-functionalized and phosphonic acid-functionalized macromolecular chain transfer agents (macro-CTAs) are utilized for the reversible addition–fragmentation chain transfer (RAFT) dispersion polymerization of benzyl methacrylate (BzMA) at 20% w/w solids in methanol at 64 °C. Spherical, worm-like, and vesicular nano-objects could each be generated through systematic variation of the mean degree of polymerization of the core-forming PBzMA block when using relatively short macro-CTAs. Construction of detailed phase diagrams is essential for the reproducible targeting of pure copolymer morphologies, which were characterized using transmission electron microscopy (TEM) and dynamic light scattering (DLS). For nano-objects prepared using the phosphonic acid-based macro-CTA, transfer from methanol to water leads to the development of anionic surface charge as a result of ionization of the stabilizer chains, but this does not adversely affect the copolymer morphology. Given the well-known strong affinity of phosphonic acid for calcium ions, selected nano-objects were evaluated for their in situ occlusion within growing CaCO3 crystals. Scanning electron microscopy (SEM) studies provide compelling evidence for the occlusion of both worm-like and vesicular phosphonic acid-based nano-objects and hence the production of a series of interesting new organic–inorganic nanocomposites.

Synthesis and micellar characterization of short block length methoxy poly(ethylene glycol)-block-poly(caprolactone) diblock copolymers