The Synthesis of Special Block Copolymers Using a Reaction Calorimeter

Summary : The paper provides experimental results about an easy and versatile method to produce amphiphilic block copolymers, block copolymer particles, and even inorganic – polymeric nano-composites via aqueous heterophase polymerization. Special emphasis is placed on the morphology and colloidal properties of some non-ionic di- and triblock copolymer particles with poly(ethylene glycol) of 10⁶ g/mol molecular weight as hydrophilic block as well as di-stimuli-responsive block copolymers containing both a poly(N-isopropyl acrylamide) and a poly(ionic liquid) block.     

Development of PEG-PLA/PLGA microparticles for pulmonary drug delivery prepared by a novel emulsification technique assisted with amphiphilic block copolymers

We developed a novel "spray dry-based" method for preparing surface-modified particle via "block copolymer-assisted" emulsification/evaporation for pulmonary drug delivery. The method included three steps: (1) o/w emulsion containing both hydrophobic polymers and amphiphilic block copolymers was obtained by emulsification of water and a polymer-containing organic solvent, (2) the o/w emulsion was misted with a nebulizer, and (3) the emulsion mists were dried by a heater. In this way, the hydrophobic polymers and the hydrophobic part of the amphiphilic block copolymers gradually tangled during the evaporation of organic solvents from the o/w emulsion. Consequently, the hydrophilic polymer chain was introduced on the particle surface. The particle surface can be easily modified although there are no reactive groups in the hydrophobic polymer molecules. We successfully obtained dry PEG-PLA/PLGA microparticles by controlling the weight ratio of the block copolymer and the hydrophobic polymer. The introduction of PEG to the particle surface involves an increase in the Zeta potential of the particles. Interestingly, the "dimpled" microparticles having a diameter of approximately 2 μm were obtained. The "dimpled" microparticles can serve as drug carriers for pulmonary drug delivery, because the particles have a large surface area. We expect that this novel surface-modification technique will enable efficient fabrication of particles in drug delivery systems.     

The formation of hydrophobic inorganic nanoparticles in the presence of amphiphilic copolymers

The presented paper describes a novel procedure for the preparation of inorganic nanoparticles and their surface functionalization in situ dedicated to an application in technical polymers. Using an inverse emulsion technique and amphiphilic block or statistical copolymers as stabilizers, a broad variety of nanoparticles such as ZnO, CdS, MgCO₃, Ni, or Cu can be prepared. The amphiphilic polymers serve not only as surface active compounds in the emulsion but also to hydrophobize the inorganic particles as they remain adsorbed on the surface after the precipitation. As a consequence of the high degree of surface coverage by polymer chains, organic solvents are able to redisperse these particles in the aggregate free manner. The utilization of the block copolymers instead of statistical copolymers resulted in the formation of the particles, which were larger in size and possessed a much broader size distribution. The chemical nature of the adsorbed polymer layer on the particle surface is crucial to the preparation of polymer nanocomposites. The primary goal of this contribution is to demonstrate the universality of such a one-pot synthetic procedure, which was found to be relevant for industrial use.     

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.     

Water-dispersible, uniform nanospheres by heating-enabled micellization of amphiphilic block copolymers in polar solvents

Uniform nanospheres with tunable size down to 30 nm were prepared simply by heating amphiphilic block copolymers in polar solvents. Unlike reverse micelles prepared in nonpolar, oily solvents, these nanospheres have a hydrophilic surface, giving them good dispersibility in water. Furthermore, they are present as individual, separated, rigid particles upon casting from the solution other than continuous thin films of merged micelles cast from micellar solution in nonpolar solvents. These nanospheres were generated by a heating-enabled micellization process in which the affinity between the solvent and the polymer chains as well as the segmental mobility of both hydrophilic and hydrophobic blocks was enhanced, triggering the micellization of the glassy copolymers in polar solvents. This heating-enabled micellization produces purely well-defined nanospheres without interference of other morphologies. The micelle sizes and corona thickness are tunable mainly by changing the lengths of the hydrophobic and hydrophilic blocks, respectively. The heating-enabled micellization route for the preparation of polymeric nanospheres is extremely simple, and is particularly advantageous in producing rigid, micellar nanospheres from block copolymers with long glassy, hydrophobic blocks which are otherwise difficult to prepare with high efficiency and purity. Furthermore, encapsulation of hydrophobic molecules (e.g., dyes) into micelle cores could be integrated into the heating-enabled micellization, leading to a simple and effective process for dye-labeled nanoparticles and drug carriers.     

无规共聚物自组装球形胶束表面亲水性的耗散粒子动力学模拟

建立了含不同亲疏水粒子比的双亲性无规共聚物粗粒化模型. 采用耗散粒子动力学方法模拟了两亲性无规共聚物选择性溶剂自组装球形胶束表面的亲水性能. 模拟结果表明, 无规共聚物在选择性溶剂中自组装得到实心球形胶束, 球形胶束表面的亲水性与聚合物链亲水粒子含量、溶剂的选择性有关. 随着聚合物链所含亲水粒子增加, 球形胶束表面的亲水性增强. 球形胶束表面的亲水性随着疏水粒子与溶剂粒子间的排斥参数增大而增强, 模拟结果与实验结论一致. 该模拟方法给出的胶束微结构信息可以为双亲无规共聚物分子设计及自组装双亲胶束制备提供一定的理论指导.     

Self‐assembly of di‐ and triblock PEG‐pentavaline amphiphiles

Nanoparticles formed from amphiphilic block copolymers can be used as drug delivery vehicles for hydrophilic therapeutics. Poly(ethylene glycol) (PEG)‐peptide copolymers were investigated for their self‐assembling properties and as consequent potential delivery systems. Mono‐ and dihydroxy PEGs were functionalized with a pentavaline sequence bearing Fmoc end groups. The molecular weight of the PEG component was varied to evaluate copolymer size and block number. These di‐ and tri‐block copolymers readily self‐assemble in aqueous solution with critical aggregation concentrations (CACs) of 0.46–16.29 μM. At concentrations above the CAC, copolymer solutions form spherical assemblies. Dynamic light scattering studies indicate these aggregates have a broad size distribution, with average diameters between 33 and 127 nm. The copolymers are comprised β‐conformations that are stable up to 80 °C, as observed by circular dichroism. This peptide secondary structure is retained in solutions up to 50% MeOH as well. The triblock copolymers proved to be the most stable, with copolymers synthesized from 10 kDa PEG having the most stable particles. Loading of carboxyfluorescein at 2–5 mol % shows that these copolymers have the potential to encapsulate hydrophilic drugs for delivery applications. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Dissipative particle dynamics simulations of toroidal structure formations of amphiphilic triblock copolymers

In this paper, the dynamic assembly of toroidal micelle structures of amphiphilic triblock copolymers in dilute solution has been investigated using dissipative particle dynamics simulations. The amphiphilic molecule is represented by a coarse-grained model, which contains hydrophilic and hydrophobic particles. Some microstructures of complex morphology having toroidal micelles have been observed in the simulations; the toroidal micelle formation is in accordance with the theoretical prediction of the toroidal structure in cylindrical micelle suspensions by Pochan et al. (Science 2004, 306, 94). These findings are very interesting, and these complex morphologies enrich our knowledge of the potential products obtained from the self-assembly of block copolymers.     

Polymer–TiO2 composite nanorattles via RAFT‐mediated emulsion polymerization

In this work, successful synthesis of polymer nanorattles containing titanium dioxide pigment particles in the centers of air voids is reported. The method used amphiphilic macro‐RAFT copolymers as stabilizers for pigment dispersion and the subsequent encapsulation of the pigment with polymer. The particles were first encapsulated by a water swellable hydrophilic layer, followed by a hard hydrophobic layer. Nanorattles were formed by swelling of hydrophilic polymer layers on the surface of the encapsulated pigment particles in a basic solution at elevated temperature. After swelling, the outer hard polymer shell was crosslinked to improve its strength. Air void sizes of the nanorattles were found to be controlled by swelling time, temperature, and the hydrophilic polymer layer thickness. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Double‐Hydrophilic Block Copolymers: Synthesis and Application as Novel Surfactants and Crystal Growth Modifiers

Double‐hydrophilic block copolymers are a new class of amphiphilic molecules of rapidly increasing importance with unique and fascinating properties potentially connecting materials science, pharmacy, biochemistry and polymer science. Characteristic of these polymers is their application in aqueous environments and that amphiphilicity is just induced in the presence of a substrate or by temperature and pH changes, respectively. Their chemical structure may be tuned for a wide range of applications covering as different aspects as stabilization of colloids, crystal growth modification, induced micelle formation, polyelectrolyte complexing towards novel drug carrier systems. As the potential of this novel polymer class is relatively unexplored yet, it can be expected that more applications will arise due to the possibility to adapt the chemical structure to either the desired substrate in contact with water or the stimulus for the induction of structural changes. This review describes the synthetic strategies towards these AB block copolymers, as well as their applications.     

Microfluidic fabrication of monodisperse biocompatible and biodegradable polymersomes with controlled permeability

We describe a versatile technique for fabricating monodisperse polymersomes with biocompatible and biodegradable diblock copolymers for efficient encapsulation of actives. We use double emulsion as a template for the assembly of amphiphilic diblock copolymers into vesicle structures. These polymersomes can be used to encapsulate small hydrophilic solutes. When triggered by an osmotic shock, the polymersomes break and release the solutes, providing a simple and effective release mechanism. The technique can also be applied to diblock copolymers with different hydrophilic-to-hydrophobic block ratios, or mixtures of diblock copolymers and hydrophobic homopolymers. The ability to make polymer vesicles with copolymers of different block ratios and to incorporate different homopolymers into the polymersomes will allow the tuning of polymersome properties for specific technological applications.     

A new design for light-breakable polymer micelles

A new and general design strategy is presented for amphiphilic block copolymers whose micellar aggregates can be dissociated by light. A diblock copolymer composed of hydrophilic poly(ethylene oxide) (PEO) and a hydrophobic polymethacrylate bearing pyrene pendant groups (PPy) was synthesized using ATRP. Upon UV light irradiation of polymer micellar solutions, the photosolvolysis of pyrene moieties results in their detachment from the polymer and converts the hydrophobic PPy block into hydrophilic poly(methacrylic acid). This effect leads to complete dissociation of polymer micelles.     

Controlling Internal Pore Sizes in Bicontinuous Polymeric Nanospheres

Complex polymeric nanospheres were formed in water from comb‐like amphiphilic block copolymers. Their internal morphology was determined by three‐dimensional cryo‐electron tomographic analysis. Varying the polymer molecular weight (MW) and the hydrophilic block weight content allowed for fine control over the internal structure. Construction of a partial phase diagram allowed us to determine the criteria for the formation of bicontinuous polymer nanosphere (BPN), namely for copolymers with MW of up to 17 kDa and hydrophilic weight fractions of ≤0.25; and varying the organic solvent to water ratio used in their preparation allowed for control over nanosphere diameters from 70 to 460 nm. Significantly, altering the block copolymer hydrophilic–hydrophobic balance enabled control of the internal pore diameter of the BPNs from 10 to 19 nm.     

Formation of Vesicles from Amphiphilic Random Copolymers in Solution: A Dissipative Particle Dynamics Simulation Study

Five coarse-grained models were built for amphiphilic random copolymers. The self-assembly of amphiphilic random copolymers in selective solvent was investigated via dissipative particle dynamics simulations. The simulation results showed that the content of hydrophilic particles and the repulsive parameter between solvent and copolymer particles were two key factors of the vesicle formation. We report herein on how to control the self-assembled morphology evolution. The two mechanisms of vesicle formation from amphiphilic random copolymers are found through investigating the dynamic processes of vesicle formation, which is in accordance with the experiment and simulation results of amphiphilic block copolymer reported in the literature.      

Density functional theory for a primitive model of nanoparticle-block copolymer mixtures

Amphiphilic block copolymers provide useful templates for fabrication of nanostructured materials that are appealing for a wide variety of applications. The preparation of polymer-particle hybrid materials requires a good understanding of the chemical nature and topology of the amphiphilic molecules as well as their interactions with the embedded nanoparticles. This article reports a density functional theory (DFT) for a coarse-grained model of block copolymer-nanoparticle mixtures that is able to account for the properties of particles and copolymers within a self-consistent framework. It predicts various well-organized structures that can be effectively controlled by adjusting the polymer chain length and polymer-particle interactions. Illustrative examples based on relatively short chains suggest that, in qualitative agreement with experiments, large particles tend to be excluded from a polymer brush near a solid substrate, whereas smaller particles may be dissolved. The DFT is able to capture the dispersion of large particles in the microdomain of block copolymer that is energetically favorable, but localization of smaller particles at the microdomain interfaces.     

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.     

Amphiphilic block copolymers containing thermally degradable poly(phthalaldehyde) blocks

In this study, the preparation of a new class of amphiphilic block copolymers consisting of a poly(phthalaldehyde) (PPA) block and hydrophilic poly(alkylene oxide) blocks is described. PPA was prepared by ionic cyclopolymerization. A telechelic polymer block was prepared by endcapping of the PPA by a bifunctional reagent carrying isocyanate and isothiocyanate groups. As the second block, monoamino‐terminated poly(alkylene oxide)s (Surfonamines®, also known as Jeffamines®) were chosen. These polymers could be readily coupled to the PPA telechel and gave amphiphlic, mainly ABA‐type block copolymers. The PPA block of these products can be selectively depolymerized at moderate temperature. The block copolymers were characterized by dual‐detection size exclusion chromatography, and the defined and stepwise thermal decomposition of the two different block types were shown by thermogravimetric analysis. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1499–1509, 2009     

端氨基聚乙二醇-聚已内酯二嵌段共聚物的合成及其微球表面氨基和形态的调控

生物降解高分子作为一种重要的生物材料已经发展到第3代[1],实际应用的复杂性不仅要求高分子材料本身具有合适的降解性能、热性能、力学性能和加工性能等,而且还要求高分子材料具有能够刺激细胞生长、识别特定细胞等生物活性特征.高分子材料的这些生物活性主要是通过高分子材料     

Heterophase Polymerization as Synthetic Tool in Polymer Chemistry for Making Nanocomposites

Summary: The paper considers various possibilities to produce inorganic – polymeric nanocomposites via aqueous heterophase polymerization. Special emphasis is placed on strategies to synthesize nanocomposite particles via joint nucleation or joint polymerization. The former strategy is used to make composite particles with CaCO₃ as inorganic component. The strategy of joint polymerization takes advantage from the condition that aqueous heterophase polymerization is a convenient possibility to synthesize amphiphilic block copolymers. This method relies on the fact that polymeric radicals can survive in isolated latex particles that are stabilized by hydrophilic blocks. This strategy can be successfully applied to produce silica-containing block copolymer particles in a one-step procedure.     

Synthesis strategies and properties of smart amphiphilic networks

This paper briefly surveys recent developments in the field of amphiphilic networks (APN) which are a new class of crosslinked polymer systems consisting of covalently bonded hydrophobic and hydrophilic chain segments. The covalent bonds between immiscible hydrophobic and hydrophilic polymer chains prevent demixing and yield polymer networks with unique structure and properties. Telechelic macromonomers provide the basis for the first generation of APNs obtained by copolymerization of the macromonomer with selected low molecular weight monomers. Synthesis of a variety of APNs using methacrylate-telechelic polyisobutylene (PIB) macromonomers prepared by living carbocationic polymerization (LCCP) and quantitative chain end derivatization is reviewed. The second generation of PIB-based amphiphilic networks is prepared by crosslinking of well-defined hydroxy-telechelic PIB and partially deprotected silylated poly(2-hydroxyethyl methacrylate) (PHEMA) precursor chains. Other opportunities providing better structural control of APNs by crosslinking of functional amphiphilic block copolymers (or precursors) obtained by combining living carbocationic and anionic polymerizations are outlined as well. Properties of APNs, such as control of swellability by composition, pH-response of swelling, fast surface structure reorganization by contacting with solvent, morphology, sustained release of drugs and bio- and blood compatibility, are also summarized.