Polymerization-induced self-assembly of homopolymer and diblock copolymer using a binary mixture of small chain transfer agent (CTA) and macromolecular chain transfer agent (macro-CTA) is reported. With this system, homopolymer and diblock copolymer were formed and chain extended at the same time to form polymer nano-objects. The molar ratio of homopolymer and diblock copolymer had a significant effect on the morphology of the polymer nano-objects. Porous vesicles, porous nanospheres, and micron-sized particles with highly porous inner structure were prepared by this method. We expect that this method will greatly expand the promise of polymerization-induced self-assembly for the synthesis of a range of polymer nano-objects with unique morphologies.

High-throughput synthesis of well-defined polymer nano-objects has long been an attractive yet challenging topic in the area of polymer chemistry and material science. Herein, we report an enzyme-assisted photoinitiated polymerization-induced self-assembly (photo-PISA) approach to prepare well-defined AB diblock or ABC triblock copolymer nano-objects at room temperature in open vessels and multiwell plates. Kinetic studies indicated that the presence of glucose oxidase (GOx) endowed the polymerizations with excellent oxygen tolerance. Good control was maintained during the enzyme-assisted photo-PISA process. This method facilitates high-throughput PISA, allowing for the construction of a detailed phase diagram in a rather short time. We also demonstrate the potential bio-related application of this method by the successful encapsulation of horseradish peroxidase (HRP) and bovine serum albumin (BSA) into self-assembled polymer vesicles without compromising protein activities. This robust oxygen-tolerant PISA approach leads to unprecedented access to well-defined polymer nano-objects for nonexperts.

A poly(glycerol monomethacrylate) (PGMA) chain transfer agent is used for aqueous reversible addition–fragmentation chain transfer (RAFT) dispersion polymerization of 2-hydroxypropyl methacrylate (HPMA) via photoinitiation or thermal initiation. Kinetic studies showed that the rate of polymerization of photo-PISA was much faster than that of thermally initiated PISA, both at the homogeneous polymerization stage and the heterogeneous polymerization stage. The effect of light intensity on photo-PISA was investigated, which showed that increasing light intensity led to faster polymerization behavior. In virtue of the temperature-insensitive property of the photoinitiator, the sole effect of reaction temperature on PISA was studied in detail for the first time. Transmission electron microscopy (TEM) measurements indicated that higher reaction temperature facilitated the formation of higher order morphologies. Finally, a one-pot photoinitiated polymerization was conducted in water to prepare diblock copolymer nano-objects with different morphologies (spheres, worms, and vesicles).

We report a reversible addition–fragmentation chain transfer (RAFT) dispersion polymerization of styrene (St) and 4-vinylpyridine (4VP) in methanol/water at 70 °C. The polymerization was mediated by a binary mixture of S-1-dodecyl-S′-(α,α′-dimethyl-α′′-acetic acid) trithiocarbonate (DDMAT) and monomethoxy poly(ethylene glycol)-based macromolecular RAFT agent (mPEG45-DDMAT). By varying the molar ratio of [St]0/[4VP]0, polymer nano-objects of different morphologies (porous vesicles, large compound vesicles (LCVs), and lamellae) were formed. Transmission electron microscopy (TEM) observations demonstrated that LCVs were formed by further aggregation and reorganization of vesicles during the process. Effects of [mPEG45-DDMAT]/[DDMAT] molar ratio, methanol/water ratio, and degree of polymerization (DP) of the core-forming block on the assemblies were also studied in detail. Ag@mPEG45-P(St108-co-4VP24)/P(St108-co-4VP24) LCVs were prepared by in situ reduction of AgNO3, as confirmed by TEM and UV-vis measurements. The obtained Ag@mPEG45-P(St108-co-4VP24)/P(St108-co-4VP24) LCVs exhibited catalytic activity for the catalysis of methylene blue (MB) using NaBH4.

A series of well-defined all-acrylic poly(hydroxyethyl acrylate)-poly(isobornyl acrylate) (PHEA-PIBOA) diblock copolymer nano-objects were prepared by photoinitiated polymerization-induced self-assembly (photo-PISA) of isobornyl acrylate in ethanol/water at 40 °C using poly(hydroxyethyl acrylate)-based macromolecular chain transfer agents (macro-CTAs). Polymerizations proceeded rapidly upon exposure to visible light irradiation (λmax = 405 nm, 0.46 mW cm−2) with high monomer conversion being achieved within 30 min. Gel permeation chromatography (GPC) demonstrated that good control was maintained throughout the photo-PISA process, and the final block copolymers exhibited relatively low polydispersities (Mw/Mn ≤ 1.55). By virtue of the high Tg value of PIBOA, a diverse set of block copolymer nano-objects having different morphologies (e.g. spheres, worms, and vesicles) were prepared and characterized by conventional transmission electron microscopy (TEM). Two phase diagrams were constructed by varying the DP of the PIBOA block or monomer concentration or the DP of the PHEA macro-CTA. Worm-like micelles were prepared by monitoring the viscosity of the reaction mixture in a proof-of-concept experiment. Finally, poly(acrylic acid) (PAA) and poly(2-(dimethylamino)ethyl acrylate) (PDMAEA) macro-CTAs were also utilized to mediate the photo-PISA process, demonstrating the versatility of this method.

We report a room-temperature photoinitiated polymerization-induced self-assembly (photo-PISA) of 2-hydroxypropyl methacrylate (HPMA) in the presence of silica nanoparticles using a poly(ethylene glycol) methyl ether (mPEG) macromolecular chain transfer agent (macro-CTA). Hybrid vesicles loaded with silica nanoparticles were obtained by this one-pot approach. The solids content of the polymer vesicles can be up to 25% w/w. A control experiment was conducted to prove that free silica nanoparticles can be removed via centrifugation-redispersion. Finally, CO2-responsive hybrid vesicles were prepared by photo-PISA of HPMA and 2-(dimethylamino)ethyl methacrylate (DMAEMA). Silica nanoparticles were subsequently released from the vesicles via CO2 bubbling at room temperature.

The photoinitiated polymerization-induced self-assembly (photo-PISA) of 2-hydroxypropyl methacrylate (HPMA) is conducted in water by using poly(poly(ethylene glycol) methyl ether methacrylate) (PPEGMA) based macro-RAFT agents. Polymerizations were carried out at room temperature via exposure to visible light irradiation, and quantitative monomer conversions (>99%) were achieved within 30 min of visible light irradiation. A remarkably diverse set of complex morphologies (spheres, worms, and vesicles) have been prepared by aqueous photo-PISA under mild conditions (water medium, room temperature, and visible light). The morphology of nano-objects can be tuned by changing the reaction parameters (e.g. degree of polymerization, solids concentration), and two detailed phase diagrams were constructed. The polymerization can be activated or deactivated by a simple “ON/OFF” switch of the light source. A thermo-responsive behavior of PPEGMA14-PHPMA200 nanoparticles prepared at 15% w/w was investigated by changing the temperature from 25 °C to 4 °C.

We report a fast alcoholic photoinitiated polymerization-induced self-assembly (photo-PISA) formulation via photoinitiated RAFT dispersion polymerization of isobornyl acrylate (IBOA) in an ethanol/water mixture at 40 °C using a monomethoxy poly(ethylene glycol) (mPEG) based chain transfer agent. Polymerization proceeded rapidly via the exposure to visible light irradiation (405 nm, 0.5 mW/cm2), and high monomer conversion (>95%) was achieved within 30 min. Kinetic studies confirmed that good control was maintained during the photo-PISA process, and the polymerization can be activated or deactivated by light. Finally, we demonstrated that a diverse set of complex morphologies (spheres, worms, or vesicles) could be achieved by varying reaction parameters, and a phase diagram was constructed.

Herein we report an aqueous photoinitiated polymerization-induced self-assembly (photo-PISA) for the preparation of a remarkably diverse set of complex polymer nanoparticle morphologies (e.g., spheres, worms, and vesicles) at room temperature. Ultrafast polymerization rates were achieved, with near quantitative monomer conversion within 15 min of visible light irradiation. An important feature of the photo-PISA is that diblock copolymer vesicles can be prepared under mild conditions (room temperature, aqueous medium, visible light), which will be important for the preparation of functional vesicles loaded with biorelated species (e.g., proteins). As a proof of concept, silica nanoparticles and bovine serum albumin (BSA) were encapsulated in situ within vesicles via the photo-PISA process.

•Four novel 2-arylethenyl-8-hydroxyquinoline Zn(II) complexes have been synthesized.•The aggregation behavior was investigated by 1H NMR, UV–vis and photoluminescence.•The photophysical properties can be tuned by introducing different substituents.A series of 2-arylethenyl-8-hydroxyquinoline ligands (A1–A4) with a trimethoxyphenyl, naphthyl, 2-fluoro-4-bromophenyl and anthracenyl group and their corresponding Zn(II) complexes (B1–B4) were synthesized and characterized by means of 1H NMR, ESI-MS, FT-IR and elemental analysis. A1 and A4 were characterized by single-crystal X-ray crystallography. The aggregation behavior of zinc salt and ligands in solution was investigated by several techniques, containing 1H NMR, UV–vis and photoluminescence (PL). The electronic nature and volume of arylethenyl substituents affect the absorption wavelength, the emission color, fluorescence lifetime, fluorescence quantum yield and thermostability of Zn(II) complexes. The experiments corroborated that the properties of Zinc(II) complexes can be tuned by introducing different functional substituents.Graphical abstract