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.     

Controlled placement of polystyrene-grafted CdSe nanoparticles in self-assembled block copolymers

Surface functionalization of semiconductor CdSe nanoparticles has been achieved with polystyrene (PS) brushes by “grafting from” technique for further addition to a polystyrene-b-polybutadiene-b-polystyrene (SBS) block copolymer in order to obtain self-assembled composites. For modification of nanoparticle surface 3-glycidoxypropyltrimethoxysilane (GPS) was used at first for the later attachment of the 4,4′-azobis(4-cyanopentanoic acid) azo initiator. Fourier-transform infrared spectroscopy confirmed the presence of GPS and PS on the surface of nanoparticles. Atomic force microscopy was used for morphological characterization of SBS/CdSe nanocomposites. Modification of nanoparticles with PS brushes by radical polymerization improved their affinity with PS block and the dispersion of nanoparticles avoiding agglomeration. CdSe nanoparticle size was measured to be around 2 nm by the use of X-ray diffraction and UV–Vis techniques. Optical properties were characterized using fluorescence measurements.     

Organoboronium amphiphilic block copolymers

A new class of amphiphilic organometallic block copolymers with cationic organoboron pendant groups was developed. Selective replacement of one of the bromine substitutents on each boryl group of the block copolymer PSBBr₂‐b‐PS with an organometallic reagent ArM (ArM = 2,4,6‐trimethylphenyl copper, 4‐t‐butylphenyltrimethyl tin) followed by treatment with 2,2′‐bipyridine gave the novel block copolymers [ 3Ar ](Br)_n as light yellow solid materials that show good stability in air and moisture and high solubility in most organic solvents. Their structure and composition were confirmed by multinuclear NMR, GPC, and elemental analysis. Highly regular micellar aggregates form in block‐selective solvents (e.g., MeOH, toluene) as demonstrated by ¹H NMR, dynamic light scattering, and transmission electron microscopy. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6612–6618, 2009     

Preparation of non‐spherical particles from amphiphilic block copolymers

Simple self‐assembly techniques to fabricate non‐spherical polymer particles, where surface composition and shape can be tuned through temperature and the choice of non‐solvents was developed. A series of amphiphilic polystyrene‐b‐poly(2‐ethyl‐2‐oxazoline) block copolymers were prepared and through solvent exchange techniques using varying non‐solvent composition a range of non‐spherical particles were formed. Faceted phase separated particles approximately 300 nm in diameter were obtained when self‐assembled from tetrahydrofuran (THF) into water compared with unique large multivesicular particles of 1200 nm size being obtained when assembled from THF into ethanol (EtOH). A range of intermediate structures were also prepared from a three part solvent system THF/water/EtOH. These techniques present new tools to engineer the self‐assembly of non‐spherical polymer particles. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 750–757     

Nanoreactors based on self-assembled amphiphilic diblock copolymers for the preparation of ZnO nanoparticles

A self-assembled diblock copolymer containing styrene (S), methyl methacrylate and a certain percentage of hydrophilic segment of poly(methacrylic acid) (i.e., poly(styrene)-block-poly(methyl methacrylate/methacrylic acid) was synthesized via the ATRP method in two steps. This was followed by a partial hydrolysis of the methyl ester linkages of the methyl methacrylate block under acidic conditions. The resultant block copolymer had a narrow molecular weight dispersity (Р< 1.3) and was characterized using FT-IR and Raman spectroscopy as well as size exclusion chromatography. The block copolymer was used as a nanoreactor for inorganic nanoparticles (ZnO). The incorporation of a single source precursor, such as ZnCl₂, into the self-assembled copolymer matrix and the conversion into ZnO nanostructures was carried out in the liquid phase using wet chemical processing techniques. We report the synthesis and characterization of nanocomposites with dual characteristics due to the functionalities incorporated into the matrix. The optical properties were determined by UV–Vis and fluorescence, the crystallinity was studied using X-ray diffraction, and the thermal stability and studies of the cyclic voltammetry were obtained by thermogravimetric analyzes and potentiodynamic electrochemical measurements, respectively. The structural, topographical and morphological characterizations of the ZnO composite in relation to the precursor block copolymer were analyzed via scanning electron microscopy, transmission electron microscopy and atomic force microscopy.     

Functionalization of magnetic nanoparticles with dendritic-linear-brush-like triblock copolymers and their drug release properties

Novel water-soluble dendritic-linear-brush-like triblock copolymer polyamidoamine-b-poly(2-(dimethylamino)ethyl methacrylate)-b-poly(poly(ethylene glycol) methyl ether methacrylate) (PAMAM-b-PDMAEMA-b-PPEGMA)-grafted superparamagnetic iron oxide nanoparticles (SPIONs) were successfully prepared via a two-step copper-mediated atom transfer radical polymerization (ATRP) method. The macroinitiators were immobilized on the surface of Fe(3)O(4) nanoparticles via effective ligand exchange of oleic acid with the propargyl focal point PAMAM-typed dendron (generation 2.0, denoted as propargyl-D(2.0)) containing four carboxyl acid end groups, following a click reaction with 2'-azidoethyl-2-bromoisobutylate (AEBIB). PDMAEMA and PPEGMA were grown gradually from nanoparticle surfaces using the "grafting from" approach, which rendered the SPIONs soluble in water and reversed aggregation. To the best of our knowledge, this is the first report that describes the functionalization of magnetic nanoparticles with dendritic-linear-brush-like triblock copolymers. The modified nanoparticles were systematically studied via TEM, FT-IR, DLS, XRD, NMR, TGA, and magnetization measurements. DLS measurement confirmed that the obtained dendritic-linear-brush-like triblock copolymer-grafted SPIONs had a uniform hydrodynamic particle size of average diameter less than 30 nm. The dendritic-linear-brush-like triblock copolymer-grafted SPIONs possessed excellent biocompatibility by methyl tetrazolium (MTT) assays against NIH3T3 cells and hemolysis assays with rabbit erythrocytes. Furthermore, an anticancer drug, doxorubicin (Dox), was used as a model drug and loaded into the dendritic-linear-brush-like triblock copolymer-grafted SPIONs, and subsequently, the drug releases were performed in phosphoric acid buffer solution pH = 4.7, 7.4, or 11.0 at 37 °C. The results verify that the dendritic-linear-brush-like triblock copolymer-grafted SPIONs possess pH-responsive drug release behavior. The Dox dose of the loaded and free drug required for 50% cellular growth inhibition was 2.72 and 0.72 μm/mL, respectively, according to MTT assay against a Hella cell line in vitro. Therefore, on the basis of its biocompatibility and drug release effect, the modified SPION could provide a charming opportunity to design some excellent drug delivery systems for therapeutic applications.     

Transition metal nanoparticles protected by amphiphilic block copolymers as tailored catalyst systems

 Several stable palladium, platinum, silver, and gold colloids were prepared by reducing the corresponding metal precursors in the presence of protective amphiphilic block copolymers. Some palladium and platinum precursors with different hydrophobicities, namely palladium chloride PdCl₂, palladium acetate Pd (CH₃COO)₂, hexachloroplatinic acid H₂PtCl₆, and platinum acetylacetonate Pt (CH₃COCH=C(O–)CH₃)₂, have been used in order to investigate differences in their catalytic activity. The polymers investigated for their ability to stabilize such transition metal colloids were polystyrene-b-poly(ethylene oxide) and polystyrene-b-poly(methacrylic acid). The metal particle sizes and morphologies were determined by transmission electron microscopy and found to be in the M28.8nnanometer range. The catalytic activity of the palladium and platinum colloids was tested by the hydrogenation of cyclohexene as a model reaction. The protected palladium and platinum nanoparticles were found to be catalytically active, and final conversions up to 100% cyclohexane could be obtained. Depending on the choice of polymer block types and lengths, the precursor type, and the reduction method, different nanoparticle morphologies and catalytic activities could be obtained. These novel catalytically active metal–polymer systems are thus promising candidates for the development of tailored catalyst systems. Received: 10 June 1996 Accepted: 30 October 1996     

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.     

Facile and versatile strategy to prepare magnetic molecularly imprinted particles based on the coassembly of magnetic nanoparticles and amphiphilic random copolymers

Magnetic molecularly imprinted polymer nanoparticles for bisphenol A were prepared by coassembling magnetic nanoparticles and amphiphilic random copolymers. Under optimized conditions, bisphenol A as template molecules, magnetic molecularly imprinted polymer particles with regular morphology, small size, good monodispersity, and high content of OA‐Fe₃O₄ were prepared by the coassembly method using P(MMA‐co‐MAA) with monomer ratio of 9:1. These magnetic molecularly imprinted polymer particles could be rapidly collected by an external magnet within 1 min. The saturated adsorption capacity of the magnetic molecularly imprinted polymer for bisphenol A was 201.5 mg/g, and the imprinting factor was 2.5. The separation factors for bisphenol A to β‐estradiol, estriol, and diethylstilbestrol was 3.1, 2.9, and 3.7, respectively. Unlike assembling amphiphilic copolymer in the selective solvent, the coassembly process was simple and rapid. Therefore, the present work provided a facile and versatile approach to construct magnetic molecularly imprinted polymer nanoparticles under mild conditions.     

Interactions of amphiphilic block copolymers with lipid model membranes

Studies on interactions between amphiphilic block copolymers and lipid membranes have been focused traditionally on ABA triblock copolymers of poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide), widely due to their commercial availability. However, new architectures of amphiphilic block copolymer have been synthesized in recent years partially taking advantage of new polymerization techniques. This review focuses on amphiphilic block copolymers with potential biological activity and on model membrane systems used for studying interactions with such block copolymers. Experimental methods to study block copolymer–phospholipid interactions in Langmuir monolayers, liposomes, and planar bilayers are summarized. This work is intended to convey a better understanding of amphiphilic block copolymers used for in vitro and in vivo experiments in medicine and pharmacy. Recent developments and open questions are addressed.     

Internally self-assembled submicrometer emulsions stabilized with a charged polymer or with silica particles

Internally self-assembled submicrometer emulsions were stabilized by F127, by the charged diblock copolymer K151, by L300 particles, and by sodium dodecyl sulfate (SDS). The stabilization of all investigated internal phases and the impact of the stabilizer on them are discussed. The use of charged stabilizers results in a highly negative zeta potential of the emulsion droplets, which can be exploited as a means to control their adsorption onto charged surfaces. Small-angle X-ray scattering and dynamic light scattering were used to determine the internal structure and size of the emulsion droplets, respectively.     

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.     

Functionalization of monodisperse magnetic nanoparticles

We report a new strategy for the preparation of monodisperse, water-soluble magnetic nanoparticles. Oleic acid-stabilized magnetic nanocrystals were prepared by the organic synthesis route proposed by Sun et al. (J. Am. Chem. Soc. 2004, 126, 273.), with size control obtained via seeded-mediated growth. The oleic groups initially present on the nanoparticle surfaces were replaced via ligand exchange reactions with various capping agents bearing reactive hydroxyl moieties. These hydroxyl groups were (i) exploited to initiate ring opening polymerization (ROP) of polylactic acid from the nanoparticle surfaces and (ii) esterified by acylation to permit the addition of alkyl halide moieties to transform the nanoparticle surfaces into macroinitiators for atom transfer radical polymerization (ATRP). By appropriate selection of the ligand properties, the nanoparticle surfaces can be polymerized in various solvents, providing an opportunity for the growth of a wide variety of water-soluble polymers and polylectrolyte brushes (both cationic and anionic) from the nanoparticle surfaces. The nanoparticles were characterized by Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), electron microscopy, and light scattering. Light scattering measurements indicate that the nanoparticles are mostly present as individual nonclustered units in water. With pH-responsive polymers grown on the nanoparticle surfaces, reversible aggregation of nanoparticles could be induced by suitable swings in the pH between the stable and unstable regions.     

Anti-biofouling properties of comblike block copolymers with amphiphilic side chains

Surfaces of novel block copolymers with amphiphilic side chains were studied for their ability to influence the adhesion of marine organisms. The surface-active polymer, obtained by grafting fluorinated molecules with hydrophobic and hydrophilic blocks to a block copolymer precursor, showed interesting bioadhesion properties. Two different algal species, one of which adhered strongly to hydrophobic surfaces, and the other, to hydrophilic surfaces, showed notably weak adhesion to the amphiphilic surfaces. Both organisms are known to secrete adhesive macromolecules, with apparently different wetting characteristics, to attach to underwater surfaces. The ability of the amphiphilic surface to undergo an environment-dependent transformation in surface chemistry when in contact with the extracellular polymeric substances is a possible reason for its antifouling nature. Near-edge X-ray absorption fine structure spectroscopy (NEXAFS) was used, in a new approach based on angle-resolved X-ray photoelectron spectroscopy (XPS), to determine the variation in chemical composition within the top few nanometers of the surface and also to study the surface segregation of the amphiphilic block. A mathematical model to extract depth-profile information from the normalized NEXAFS partial electron yield is developed.     

Synthesis and characterization of thermoresponsive amphiphilic block copolymers incorporating a poly(ethylene oxide‐stat‐propylene oxide) block

Amphiphilic BuO‐(PEO‐stat‐PPO)‐block‐PLA‐OH diblock and MeO‐PEO‐block‐(PEO‐stat‐PPO)‐block‐PLA‐OH triblock copolymers incorporating thermoresponsive poly(ethylene oxide‐stat‐propylene oxide) (PEO‐stat‐PPO) blocks were prepared by ring‐opening polymerization of lactide (LA) initiated by macroinitiators formed from treating BuO‐(PEO‐stat‐PPO)‐OH and MeO‐PEO‐block‐(PEO‐stat‐PPO)‐OH with AlEt₃. MeO‐PEO‐block‐(PEO‐stat‐PPO)‐OH was prepared by coupling MeO‐PEO‐OH and HO‐(PEO‐stat‐PPO)‐OH, followed by chromatographic purification. The cloud points of 0.2% aqueous solutions are between 36 and 46 °C for the diblock copolymers that contain a 50 wt % EO thermoresponsive block and 78 °C for the triblock copolymer that contains a 75 wt % EO thermoresponsive block. Variable temperature ¹H NMR spectra recorded on D₂O solutions of the diblock copolymers display no PLA resonances below the cloud point and fairly sharp PLA resonances above the cloud point, suggesting that desolvation of the thermoresponsive block increases the miscibility of the two blocks. Preliminary characterization of the micelles formed in aqueous solutions of BuO‐(PEO‐stat‐PPO)‐block‐PLA‐OH conducted using laser scanning confocal microscopy and pulsed gradient spin echo NMR point to significant changes in the size of the micellar aggregates as a function of temperature. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5156–5167, 2005     

新型线状-树枝状两亲嵌段共聚物的合成

本文设计合成了一系列由不同链长的聚丙烯酸(PAA)为亲水嵌段和不同代数聚苄醚树枝体(Dendr.PBE)为疏水嵌段的杂化共聚物(PAA-Dendr.PBE)。     

ATRP synthesis and association properties of thermoresponsive anionic block copolymers

Thermosensitive anionic block copolymers of sodium 2‐acrylamido‐2‐methylpropanesulfonate (AMPS) and N‐isopropylacrylamide (NIPAAM) with different block lengths were prepared by atom transfer radical polymerization (ATRP). Controlled polymerization was achieved by using ethyl 2‐chloropropionate (ECP) as initiator and CuCl/CuCl₂/tris(2‐dimethylaminoethyl)amine (Me₆TREN) catalytic system in DMF:water 50:50 (v/v) mixtures at 20 °C. Blocks lengths ranging from 36 to 98 repeating units were obtained. The association properties in aqueous solutions at different NaCl ionic strengths were studied as a function of temperature and polymer concentration by dynamic light scattering, fluorescence spectroscopy, and energy‐filtered transmission electron microscopy. The block copolymers with a higher pNIPAAM/pAMPS ratio formed spherical core‐shell type micelles independently of the ionic strength. The block copolymers with lower pNIPAAM/pAMPS ratio formed core‐shell type micelles at high ionic strength. Larger particles were observed at low ionic strength, which could be due to the formation of vesicles or compound micelles/micellar clusters. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4830–4842, 2008     

P(OEGMA-co-LMA) hyperbranched amphiphilic copolymers as self-assembled nanocarriers

We report on the synthesis of novel amphiphilic hyperbranched copolymers, namely Hyperbranched-[poly (ethylene glycol) methyl ether methacrylate-co-lauryl methacrylate] (H-[P(OEGMA-co-LMA)]), obtained by reversible addition-fragmentation chain transfer (RAFT) polymerization utilizing the divinyl monomer, ethylene glycol dimethacrylate (EGDMA) as the branching agent. Molecular characterization by size exclusion chromatography (SEC) and proton nuclear magnetic resonance (¹H-NMR) spectroscopy indicated the success of the polymerization. The self-assembly behavior in aqueous media was investigated by light scattering techniques and fluorescence spectroscopy. The hyperbranched copolymers form multimolecular aggregates of nanoscale dimensions with a low critical aggregation concentration. In addition, the model hydrophobic drug, curcumin (CUR), known also for its intrinsic fluorescence properties, was used in order to investigate the H-[P(OEGMA-co-LMA)] copolymers drug encapsulation ability. Curcumin is successfully loaded into the polymeric nanoparticles, as confirmed by dynamic light scattering and UV–Vis spectroscopy. Interestingly, curcumin hydrophobic interactions with the hyperbranched copolymers result in more well-defined co-assembled nanostructures, in terms of size and size distribution. The mixed copolymer-CUR nano-assemblies consist of small size nanoparticles (<100 nm) which exhibit relatively high size uniformity, colloidal stability and fluorescent properties. Overall, results signify that the biocompatible H-[P(OEGMA-co-LMA)] nanostructures could potentially serve as nanocarrier systems for drug delivery and bio-imaging applications.     

Facile fabrication of amphiphilic gold nanoparticles with V-shaped brushes from block copolymers with a trithiocarbonate group as the junction

Amphiphilic gold nanoparticles grafted with V-shaped brushes (Au-V-brushes) were prepared by grafting a polystyrene-b-poly(ethylene oxide) (PS-b-PEO) block copolymer with a trithiocarbonate group as the junction to the Au surface. The obtained Au-V-brushes were subjected to solubility test and UV-vis, FT-IR, TEM and DLS characterizations. It is found that the Au-V-brushes are soluble in both water and organic solvents. In the common solvent DMF, the size of the Au-V-brushes is about 17 nm, whereas in selective solvents (toluene and water) aggregates of 70-90 nm are formed. Phase transfer of the Au-V-brushes from the water phase into the toluene phase occurs upon addition of Na(2)SO(4) into water and the Au-V-brushes can also transfer from the toluene phase to the interface of toluene and water phases after addition of citric acid in the water phase.