Fission of giant vesicles accompanied by hydrophobic chain growth through polymerization-induced self-assembly

In order to clarify the formation mechanisms of micrometer-sized spherical vesicles through the polymerization-induced self-assembly of amphiphilic poly(methacrylic acid)-block-poly(methyl methacrylate-random-methacrylic acid), PMAA-b-P(MMA-r-MAA), the nitroxide-mediated photocontrolled/living radical polymerization initiated by a PMAA end-capped with 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl was performed in an aqueous methanol solution. The polymerization proceeded in a living manner during the self-assembly. The vesicles produced during the early stage of the polymerization were not completely spherical and had dents and very small holes on their surface. As the hydrophobic P(MMA-r-MAA) block chains grew by the polymerization, the contorted vesicles were changed into half-sized elliptical vesicles accompanied by enlargement of the dents and holes. The vesicles were finally transformed into much smaller spherical vesicles by further growth of the hydrophobic chains. The mechanisms of the vesicles by fission involved the outside separation by the expansion of the dents and holes on the surface and the inside separation by budding.     

Formation of polymer vesicles by liquid crystal amphiphilic block copolymers

We report the formation of polymer vesicles (or polymersomes) by a new class of amphiphilic block copolymers in which the hydrophobic block is a side-on nematic liquid crystal polymer. Two series of these block copolymers, named PEG-b-PA444 and PEG-b-PMAazo444, with different hydrophilic/hydrophobic ratios were synthesized and characterized in detail. Polymersomes and nanotubes were formed by adding water into a solution of copolymers in dioxane. Polymersomes in water were finally obtained by dialyzing the resulting mixture against water. These self-assemblies have been studied by classical TEM and cryo-TEM. For the PEG-b-PA444 series, polymersomes were observed for hydrophilic/hydrophobic ratios ranging from 40/60 to 19/81. For PEG-b-PMAazo444 series, polymersomes were observed for hydrophilic/hydrophobic ratios ranging from 26/74 to 18/82. For a PEG-b-PA444 sample with hydrophilic/hydrophobic ratio equal to 25/75, a tubular morphology with tube diameter of typically 100 nm and tube length of up to 10 mum was also observed together with polymersomes during addition of water into the polymer solution in dioxane.     

Self-assembly and morphology control of new L-glutamic acid-based amphiphilic random copolymers: giant vesicles, vesicles, spheres, and honeycomb film

New amphiphilic random copolymers containing hydrophobic dodecyl (C12) chain and hydrophilic L-glutamic acid were synthesized, and their self-assembly in solution as well as on the solid surfaces was investigated. The self-assembly behavior of these polymers are largely dependent on their hydrophilic and hydrophobic balances. The copolymer with a more hydrophobic alkyl chain (～90%) self-assembled into giant vesicles with a diameter of several micrometers in a mixed solvent of ethanol and water. When the hydrophobic ratio decreased to ca. 76%, the polymer self-assembled into conventional vesicles with several hundred nanometers. The giant vesicles could be fused in certain conditions, while the conventional vesicles were stable. When the content of the hydrophilic part was further increased, no organized structures were formed. On the other hand, when the copolymer solutions were directly cast on solid substrates such as silicon plates, films with organized nanostructures could also be obtained, the morphology of which depended on solvent selection. When ethanol or methanol was used, spheres were obtained. When dichloromethane was used as the solvent, honeycomb-like morphologies were obtained. These results showed that through appropriate molecular design, random copolymer could self-assemble into various organized structures, which could be regulated through the hydrophobic/hydrophilic balance and the solvents.     

Novel fluorescent amphiphilic block copolymers: Controllable morphologies and size by self-assembly

New fluorescent amphiphilic copolymers polyacrylamide-b-poly(p-methacrylamido)acetophenone thiosemicarbazone (PAM-b-PMATC) were synthesized by atom transfer radical polymerization (ATRP) method. The structures of polymers were confirmed by ¹H NMR and gel permeation chromatography-multi-angle laser light scatting (GPC-MALLS). PAM-b-PMATC showed a broad emission peak about 388 nm excited at 318 nm in aqueous solution. The self-assembly behavior of PAM-b-PMATC in the binary mixture formamide/water was observed by transmission electron microscope (TEM). It indicated that PAM-b-PMATC-I and -II with the same PAM block self-assembled to vesicles and sunflower-like micelles. The water fraction in the mixture could control the size and thickness of vesicles. Vesicle size increased from 50 to 420 nm and vesicle thickness changed from 5 to 50 nm with water content ranging from 33 to 90 vol.%. In addition, the cytotoxicity in vitro of PAM-b-PMATC-I and its nanoparticles loaded with methotrexate (MTX) were evaluated by MTT assay.     

Giant vesicles prepared by nitroxide-mediated photo-controlled/living radical polymerization-induced self-assembly

Giant vesicles with several-micrometer diameters were prepared by self-assembly induced by the nitroxide-mediated photo-controlled/living radical polymerization. The random block copolymerization of methyl methacrylate (MMA) and methacrylic acid (MAA) were performed using poly(methacrylic acid) (PMAA) as the prepolymer in an aqueous methanol solution to produce a PMAA-block-poly(MMA-random-MAA) random block copolymer (PMAA-b-P(MMA-r-MAA)). PMAA₁₉₅-b-P(MMA_0.817-r-MAA_0.183)₂₂₄ formed spherical vesicles with a 4.74 μm diameter and 0.108 μm wall thickness. A differential scanning calorimetry analysis demonstrated that the vesicles had a bilayer structure consisting of a hydrophilic PMAA surface and hydrophobic P(MMA-r-MAA) interface. The wet vesicles before air-drying were flexible and easily transformed by stress, whereas the dry vesicles were fragile and cracked. The vesicles in the solution were dissociated into much smaller vesicles by increasing the temperature. They were also transformed by a further temperature increase into hollow fibers and finally into membranes retaining the bilayer structure.     

Synthesis and aggregation behaviour of amphiphilic block copolymers with random middle block

The effect of microstructure on the aggregation behaviour of symmetrical di- and triblock copolymers P(BMA)-b-P(MAA) and P(BMA)-b-P(BMA-co-MAA)-b-P(MAA) with a molecular weight of 40,000 g/mol was studied. The critical micelle concentration, hydrodynamic radius and morphology of the micelles were determined by fluorescence spectroscopy, dynamic light scattering and scanning force microscopy (SFM). Whereas no effect of the microstructure on the critical micelle concentration could be detected, the hydrodynamic radius decreased from di- to triblock copolymer from 53 to 36 nm. The decrease of about 32% corresponds to the length of the random middle block within the triblock copolymer so that the reduction in hydrodynamic radius was caused by a complete orientation of the random middle block at the core corona interface. Finally, the SFM investigation showed that dehydration of micelles on a substrate is accompanied by formation of a physisorbed monolayer with a thickness of 2 nm on which the micelles are deposited.     

Synthesizing amphiphilic block copolymers through macromolecular azo-coupling reaction

This communication reports a new approach to synthesize amphiphilic block copolymers. The copolymers with well-defined structures were synthesized by macromolecular azo-coupling reaction between the diazonium salt of aniline-functionalized PEG and the polymeric blocks with a terminal suitable for the azo-coupling reaction.     

Shell-crosslinked nanoparticles through self-assembly of thermoresponsive block copolymers by RAFT polymerization

A reversible addition-fragmentation chain transfer (RAFT) agent, the methyl-2-(n-butyltrithiocarbonyl)propanoate (MBTTCP) has shown to be efficient in controlling the polymerization of N,N-dimethylacrylamide (DMA), N-isopropylacrylamide (NIPAM) and N-acryloyloxysuccinimide (NAS). Two different strategies have been studied to synthesize block copolymers based on one PNIPAN block and the other a random copolymer of DMA and NAS. When a PNIPAM trithiocarbonate-terminated is used as macromolecular chain transfer agent for the polymerization of a mixture of NAS and DMA, well-defined P(NIPAM-b-(NAS-co-DMA)) block copolymers were obtained with a low polydispersity index. These thermoresponsive block copolymers dissolved in aqueous solution at 25 °C and self-assembled into micelles when the temperature was raised above the LCST of the PNIPAM block. The micelle shell containing NAS units was further crosslinked using a primary diamine in order to get shell-crosslinked nanoparticles. Upon cooling below the LCST of PNIPAM this structure may easily reorganize to form nanoparticles with a water filled hydrophilic core.     

Polymer vesicles formed by amphiphilic diblock copolymers containing a thermotropic liquid crystalline polymer block

New amphiphilic diblock copolymers composed of poly(ethylene glycol) and a thermotropic liquid crystalline polymer have been synthesized and demonstrated to form well-defined unilamellar vesicles in water by cryo-electron microscopy.     

Aggregation and self-assembly of amphiphilic block copolymers in aqueous dispersions of carbon nanotubes

The self-assembly (SA) of amphiphilic block copolymers (poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)) was investigated in dispersions of single-walled and multiwalled carbon nanotubes (SWNT and MWNT, respectively) as a function of temperature. Differential scanning calorimetry (DSC) was used for characterization of the thermal behavior of the combined polymers-nanostructures system, and spin-probe electron paramagnetic resonance (EPR) was employed for probing the local dynamic and polarity of the polymer chains in the presence of nanostructures. It was found that SWNT and MWNT modify the temperature, enthalpy, and dynamic behavior of polymer SA. In particular, SWNT were found to increase the cooperativity of aggregating chains and dominate aggregate dynamics. MWNT reduced the cooperativity, while colloidal carbon black additives, studied for comparison, did not show similar effects. The experimental observations are consistent with the suggestion that dimensional matching between the characteristic radius of the solvated polymer chains and the dimensions of additives dominate polymer SA in the hybrid system.     

Morphology transformation of micrometre-sized giant vesicles based on physical conditions for photopolymerisation-induced self-assembly

The physical conditions to vary the morphology of vesicles formed by amphiphilic poly(methacrylic acid)-block-poly(methyl methacrylate-random-methacrylic acid) were determined for the self-assembly induced by the nitroxide-mediated photocontrolled/living radical polymerisation performed in an aqueous methanol solution. The copolymer produced micrometre-sized spherical vesicles in the solution with a 30 wt% water content. The vesicles were transformed into a film-like morphology by decreasing the water content, whereas they were changed into nanometre-sized spherical vesicles by increasing it. The concentration of the growing polymer chain also varied the morphology. Large spherical vesicles formed at a low concentration were transformed into much smaller vesicles, followed by rod-like vesicles as a result of increasing the concentration. Furthermore, the stirring speed during the polymerisation-induced self-assembly dominated the morphology. Large elliptical vesicles produced at a low stirring speed changed into spherical vesicles, but decreased the size as the speed increased.     

功能性两亲嵌段共聚物的研究进展

功能性两亲嵌段共聚物因自身独特的性质而在靶向输送、控制释放、分子识别等领域得到广泛的应用.本文对这类嵌段共聚物的合成方法、其胶束的形成机理、制备形式、表征手段以及一些常见的具有光学活性的两亲嵌段共聚物及其应用进行了综述.     

Hydrophobic energy estimation for giant vesicle formation by amphiphilic poly(methacrylic acid)-block-poly(alkyl methacrylate-random-mathacrylic acid) random block copolymers

The self-assembly induced by the photocontrolled/living radical polymerization mediated by 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl was performed for amphiphilic poly(methacrylic acid)-block-poly(alkyl methacrylate-random-methacrylic acid) containing ethyl, n-propyl, and n-butyl methacrylates in order to control the morphology based on the hydrophobic-hydrophilic balance. The morphology transformation from films to spherical vesicles via the transition was well-controlled by adjusting the ratio of the alkyl methacrylate unit to the methacrylic acid in the hydrophobic random copolymer block. The copolymers formed the respective morphologies at different ratios dependent on the alkyl chain length of the methacrylates; the ratio for the formation of the respective morphologies decreased as the alkyl chain length increased. The hydrophobic energy estimation of these copolymers demonstrated that the respective morphologies had definite hydrophobic energies independent of the alkyl chain length, indicating that the morphologies were determined only by the hydrophobic magnitude of the random copolymer block.     

Aggregates and hydrogels prepared by self-assembly of amphiphilic copolymers with surfactants

Mesoporous carbons containing cobalt nanoparticles are synthesized by tri-or quad-constituent self assembly of Pluronic F127, phenol-formaldehyde oligomer (resol), cobalt acetylacetonate (acac), and optionally tetraethyl orthosilicate (TEOS, optional). Upon pyrolysis in N₂ atmosphere, the resol provides sufficient carbon yield to maintain the ordered structure, while decomposition of the Co(acac) yields cobalt nanoparticles. To provide increased surface area, the dispersed silicate from condensation of TEOS can be etched after carbonization to yield micropores, Without silica templated micropores, the surface area decreases as the cobalt content increases, but there is a concurrent increase in the volume-average pore diameter (BHJ) and a dramatic increase in the adsorption capacity of methylene green with the equilibrium adsorption capacity from 2 to 90 mg/g with increasing Co content. Moreover, the surface area and pore size of mesoporous composites can be dramatically increased by addition of TEOS and subsequent etching. These composites exhibit extremely high adsorption capacity up to 1151 mg/g, which also increases with increases in the Co content. Additionally, the inclusion of cobalt nanoparticles provides magnetic separation from aqueous suspension. The in situ synthesis of the Co nanoparticles yields to a carbon shell that can partially protect the Co from leaching in acidic media; after 96 h in 2 M HCl, the powders remain magnetic.     

Vesicular self-assembly of comb-dendritic block copolymers

New amphiphilic comb-dendritic block copolymers were developed as building blocks that self-assemble into stable vesicular structures with narrow size distribution.     

Polymerization-induced self-assembly of metallo-polyelectrolyte block copolymers

Cobaltocenium-containing polyelectrolyte block copolymer nanoparticles were prepared via polymerization-induced self-assembly (PISA) using aqueous dispersion RAFT polymerization. The cationic steric stabilizer was a macromolecular chain-transfer agent (macro-CTA) based on poly(2-cobaltocenium amidoethyl methacrylate chloride) (PCoAEMACl), and the core-forming block was poly(2-hydroxypropyl methacrylate) (PHPMA). Stable cationic spherical nanoparticles were formed in aqueous solution with low dispersity without adding any salts. The chain extension of macro-CTA with HPMA was efficient and fast. The effects of block copolymer compositions, solid content, charge density, and addition of salts were studied. It was found that the degree of polymerization of both the stabilizer PCoAEMACl and the core-forming PHPMA had a strong influence on the size of nanoparticles. © 2019 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 77–83     

Non-ionic amphiphilic block copolymers by RAFT-polymerization and their self-organization

Water-soluble, amphiphilic diblock copolymers were synthesized by reversible addition fragmentation chain transfer polymerization. They consist of poly(butyl acrylate) as hydrophobic block with a low glass transition temperature and three different nonionic water-soluble blocks, namely, the classical hydrophilic block poly(dimethylacrylamide), the strongly hydrophilic poly(acryloyloxyethyl methylsulfoxide), and the thermally sensitive poly(N-acryloylpyrrolidine). Aqueous micellar solutions of the block copolymers were prepared and characterized by static and dynamic light scattering analysis (DLS and SLS). No critical micelle concentration could be detected. The micellization was thermodynamically favored, although kinetically slow, exhibiting a marked dependence on the preparation conditions. The polymers formed micelles with a hydrodynamic diameter from 20 to 100 nm, which were stable upon dilution. The micellar size was correlated with the composition of the block copolymers and their overall molar mass. The micelles formed with the two most hydrophilic blocks were particularly stable upon temperature cycles, whereas the thermally sensitive poly(N-acryloylpyrrolidine) block showed a temperature-induced precipitation. According to combined SLS and DLS analysis, the micelles exhibited an elongated shape such as rods or worms. It should be noted that the block copolymers with the most hydrophilic poly(sulfoxide) block formed inverse micelles in certain organic solvents.