Crystallization and coalescence of block copolymer micelles in semicrystalline block copolymer/amorphous homopolymer blends

Crystallization of two oxyethylene/oxybutylene block copolymers (E₇₆B₃₈ and E₁₅₅B₇₆) from micelles in block copolymer/amorphous homopolymer blends was studied by differential scanning calorimetry (DSC) and time-resolved small angle X-ray scattering (SAXS). Unlike the simultaneous crystallization and formation of superstructure in crystallization from an ordered structure, crystallization of block copolymer from micelles can be divided into two steps. The core of the micelles firstly crystallizes individually, with first-order crystallization kinetics and homogeneous nucleation mechanism. The SAXS revealed that crystallization-induced deformation occurs for the micelles, which strongly depends on microstructure of the block copolymers. For the shorter block copolymer E₇₆B₃₈, larger deformation induced by crystallization was observed, leading to coalescence of the micelles after crystallization, while for the longer block copolymer E₁₅₅B₇₆ the micelles show little deformation and the morphology of micelle is retained after crystallization.     

Sheddable micelles based on disulfide-linked hybrid PEG-polypeptide copolymer for intracellular drug delivery

A novel reduction-sensitive sheddable micelle based on disulfide-linked hybrid PEG-polypeptide mPEG-SS-Pleu was demonstrated for intracellular drug delivery. These micelles are composed of an mPEG shell and polypeptide core, characterized by FT-IR, ¹H NMR, fluorescence techniques, TEM, and DLS. Interestingly, they would undergo a fast sheddable process when encounter the reduction sensitive condition, indicated by the aggregation phenomena in the presence of DTT, a reduction agent, which could cleave the disulfide bond between the micellar core and shell and consequently leading to the aggregation of hydrophobic core. Cytotoxicity study revealed that copolymers in this system have good biocompatibility and their self-assembled micelles showed a high drug loading efficiency for DOX, a hydrophobic drug model, and released DOX quantitatively in response to the intracellular level of reducing potential. Cellular uptake experiments demonstrated that the fluorescently labeled micelles could be successfully internalized into human liver carcinoma HepG2 cells, evidenced by confocal laser scanning microscopy. Above results indicate that the copolymers may have great potential in drug delivery to achieve improved cancer therapy.     

Controlled organization of self-assembled rod-coil block copolymer micelles

Spherical micelles of a series of poly(styrene-block-(2,5-bis[4-methoxyphenyl]oxycarbonyl)styrene) (PS-b-PMPCS) rod-coil diblock copolymers in a selective solvent can organize into large mono-layered films with a well-ordered hexagonal packing of the spheres after solvent evaporation. Organized domains in the spherical micelle film were observed by transmission electron microscopy (TEM) and atomic force microscopy (AFM). The core-shell structure of the spherical micelle remained after solvent evaporation. The micelle diameter in the ordered film as observed by TEM and AFM agree. The size of the spherical micelles can be controlled by the length of PMPCS when the length of the PS is fixed. The sphere diameters were varied from several tens of nanometers to more than one hundred nanometers. Solutions of smaller micelle spheres formed less ordered films than those from larger micelle particles. Additionally, monolayer films of cylindrical worm-like micelles were also prepared. Those cylindrical micelles were observed to be end-capped by spherical micelles. The monolayer micelle film from the largest spherical micelles appeared red when observed in optical microscopy in the reflection mode. A broad adsorption peak with a maximum adsorption wavelength of 545 nm was observed via UV-Vis spectroscopy.     

Regular and irregular micelles formed by A LEL triblock copolymer in aqueous solution

Laser light scattering (LLS) techniques were used to characterize the micellization of poly(d,l-lactide)-poly(ethylene glycol)-poly(d,l-lactide) (LEL) triblock copolymer (MW 1K-2K-1K) in aqueous solution. We observed the existence of both thermodynamically stable flower-like micelles (regular micelles) and large, less soluble nanoparticles (irregular micelles) in dilute aqueous solutions with the same preparation procedure. Both kinds of micelles were found to co-exist with single copolymer chains. The initial copolymer concentration determines the nature of the micelles. The regular core-shell micelle formation follows a closed association mechanism, resulting in flower-like micelles. The hydrophobicity of a L unit is estimated as ∼0.5-0.6 B (polyoxybutylene) units from the micellization parameters, which is quite consistent with earlier estimations obtained from EL diblock copolymers.     

Asymmetric morphology from an organic/organometallic block copolymer

Block copolymer self-assembly is a burgeoning subject in polymer and materials science driven by both fundamental and applied inspirations. Whereas the vast majority of block copolymer studies have focused on highly symmetric morphologies, here we report the first observation of an unusual asymmetric cylindrical phase in thick films of an organic/organometallic block copolymer, poly(styrene-block-ferrocenyldimethylsilane) (PS-b-PFS). Microscopy and X-ray scattering data establish the lack of symmetry in this structure and reveal an unusual 3-D network organization. Following selective removal of the PS matrix, the remaining nanoporous film has characteristics of potential value in separation applications such as substantial interconnection (mechanical strength), uniform pore size, and chemical and physical stability.     

Polymeric nanoparticles with tunable architecture formed by biocompatible star shaped block copolymer

An amphiphilic star shaped block copolymer, based on well known biocompatible components, was synthesized using branched poly(ε-caprolactone) as hydrophobic core and branched poly(ethyleneglycol) as hydrophilic corona. The composition of this macromolecule, based on two well differentiated blocks, conferred amphiphilic behavior to the whole system that acted as driving force for its self-assembling in aqueous media. Depending on the polymer concentration it was possible to obtain different architectures. The TEM micrographs permitted to follow the evolution of the system from single vesicles toward necklace entanglements. In this work, we discuss the mechanism that would be involved in the evolution of the system's morphology as a function of the block copolymer concentration. In addition, the proposed star shaped block copolymer presented good solubilizing properties that were used to disperse in water, poorly soluble molecules such as chlorine-carbazoles, which were used to investigate the suitability of the self-assembled nanostructures as drug nano-carriers.     

Polymeric nanoparticles,micelles and polymersomes from amphiphilic block copolymer

Block copolymers are made up of blocks of different polymerized monomers. Among the block copolymers, amphiphilic block copolymers can self-assemble to form nano-sized vehicles, such as micelles, nanoparticles, polymersomes, in aqueous or non-aqueous media. This review describes the synthesis, formation, and major applications of amphiphilic block copolymer and corresponding vehicles in order to provide an overview of the current features of functionalized block copolymers for drug delivery applications.     

Aggregate structure change induced by intramolecular helix-coil transition

Self-assembly behavior of poly(γ-benzyl l-glutamate)-graft-poly(ethylene glycol) (PBLG-g-PEG) in ethanol medium was studied by transmission electron microscopy (TEM), scanning electron microscopy (SEM), laser light scattering (LLS), and circular dichroism (CD). The experimental results revealed that the conformation change of the polypeptide graft copolymer exerts marked effect on its self-association behavior. Spindle-like micelles with polypeptide blocks aligned inside the cores are formed in ethanol solution without denaturant acid. When the denaturant acid is added, the rigid α-helix transforms to random coil, resulting in an aggregate structure change from the spindle-like micelle to large compound micelle. For the large compound micelles, the coiled polypeptide chains and PEG blocks pack randomly within the cores, surrounded by the PEG chains outside to stabilize the aggregates.     

Surface structure of stimuli-responsive polystyrene particles prepared by dispersion polymerization with a polystyrene/poly(l-lysine) block copolymer as a stabilizer

A block copolymer composed of polystyrene and poly(α-l-lysine hydrobromide) (PLL) segments was used as a stabilizer for dispersion polymerization of styrene in water–methanol medium to give narrowly-distributed polystyrene particles in the size range from 0.36 to 1.09 μm, on which the PLL segment was grafted with a surface density of 0.2–3.4 l-lysine residue/nm². We investigated effects of polymerization time, stabilizer concentration, segmental composition of the block copolymer, and composition of the medium on surface structure and particle size of the affording particles. Interestingly, we obtained an experimental evidence that the surface density of the PLL clearly depends on structural parameters of the stabilizer and various polymerization conditions. Based on the dependence, it was possible to control the surface density of the narrowly-distributed particles within the range between the minimum and the maximum density limits of the graft chain by changing the structure of the stabilizer and polymerization conditions. Conformation of the PLL, which underwent a helix–coil transformation with an increase in water composition of the medium, had a strong effect on the surface structure, the size, and property of the resulting particles. Further modification of the particle surface was possible by utilizing the amino groups in the PLL graft.     

Tailoring the morphology of self-assembled block copolymer hollow fiber membranes

Isoporous asymmetric polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) hollow fiber membranes were successfully made by a dry-jet wet spinning process. Well-defined nanometer-scale pores around 20–40 nm in diameter were tailored on the top surface of the fiber above a non-ordered macroporous layer by combining block copolymer self-assembly and non-solvent induced phase separation (SNIPS). Uniformity of the surface-assembled pores and fiber cross-section morphology was improved by adjusting the solution concentration, solvent composition as well as some important spinning parameters such as bore fluid flow rate, polymer solution flow rate and air gap distance between the spinneret and the precipitation bath. The formation of the well-organized self-assembled pores is a result of the interplay of fast relaxation of the shear-induced oriented block copolymer chains, the rapid evaporation of the solvent mixture on the outer surface and solvent extraction into the bore liquid on the lumen side, and gravity force during spinning. Structural features of the block copolymer solutions were investigated by small-angle X-ray scattering (SAXS) and rheological properties of the solutions were examined as well. The scattering patterns of the optimal solutions for membrane formation indicate a disordered phase which is very close to the disorder-order transition. The nanostructured surface and cross-section morphology of the membranes were characterized by scanning electron microscopy (SEM). The water flux of the membranes was measured and gas permeation was examined to test the pressure stability of the hollow fibers.     

Design and stabilization of block copolymer micelles via phenol-pyridine hydrogen-bonding interactions

A new approach for the preparation of block copolymer micelles in non-selective solvent is introduced. Phenol-pyridine hydrogen-bonding interactions are used for the first time to prepare core-shell micelles in non-selective solvents using block copolymers and bifunctional low-molecular-weight hydrogen-bonding crosslinkers. Poly(styrene-b-4-vinylphenol)/Bis-pyridyl ethane and poly(styrene-b-4-vinylpyridine)/Bisphenol A were investigated as micelle formation due to phenol-pyridine hydrogen bond crosslinking. The influence of several factors such as temperature, concentration, solvent and pH in micellization-demicellization process was analyzed by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), dynamic light scattering (DLS) and atomic force microscopy (AFM). This method opens new possibilities to the generation of block copolymer micelles in non-selective solvents.     

The effect of block lengths on micelle structure in blends of styrene-isoprene diblock copolymer and poly(vinyl methyl ether)

The micellar structure of styrene-isoprene diblock copolymer and poly(vinyl methyl ether) blends was investigated by using small-angle X-ray scattering and transmission electron microscopy techniques. In order to determine the effect of styrene block length on the formation of micellar structure, three sets of diblock copolymers, with near-identical isoprene block molecular weights, but with different styrene block lengths were studied. With modeling based on the polydisperse Percus-Yevick hard sphere fluid model, the structural parameters characterizing the micelles were determined as a function of copolymer concentrations, temperature, and copolymer block lengths. The core radius was found to decrease on increasing the length of styrene block. The degree of swelling of the corona by PVME increased steadily with increasing the styrene block length.     

两亲嵌段共聚物的合成及其自组装研究进展

作者介绍了两亲嵌段共聚物的活性阴离子聚合、基团转移聚合、开环歧化聚合、活性阳离子聚合、活性／可控自由基聚合、缩聚法、嵌段共聚物化学改性法等合成方法,并对其自组装形成聚合物纳米胶束的制备方法、形成机理以及在药物控制释放领域的应用进行了综述,并对其未来发展趋势进行了展望。     

Encapsulation of inorganic nanoparticles into block copolymer micellar aggregates: Strategies and precise localization of nanoparticles

Precise assembly and localization of preformed inorganic nanoparticles (NPs) in block copolymer (BCP) assemblies are of great importance in realizing the formation of nano-hybrids with high performance. Properties of the nanocomposites depend not only on those of individual building blocks but also on their spatial organization at different length scales, demonstrating unique optical, electrical, and magnetic properties. With the aid of the BCPs, NPs can form a broader range of structures in the nanoscopically confined geometry. Thus, many studies have focused on the selective localization of NPs in BCP aggregates. In this paper, we will outline recent advances in the preparation strategies for precise localization of inorganic NPs into BCP micelles, including co-precipitation, supramolecular assembly, interfacial instabilities of emulsion droplets, heating–cooling, electrostatic interaction, and others. Manipulating the balance between enthalpic and entropic contributions provides one of the opportunities to precisely control the spatial distribution of NPs in BCPs assemblies. We will focus on the principles of precise control of dispersion and localization of the NPs in BCP micelles. Potential applications of the hybrid micelles will finally be discussed, followed by the summary and outlook of this emerging area.     

Removal of perylene from water using block copolymer nanospheres or micelles

Water-soluble nanospheres with poly(acrylic acid) (PAA) coronas were prepared from poly(2-cinnamoylethyl methacrylate)-block-PAA (PCEMA-b-PAA) and P(CEMA-ran-OEMA)-b-PAA, where “ran” denotes the random incorporation of 2-octanoylethyl methacrylate (OEMA) into the PCEMA block. These nanospheres and polystyrene-block-PAA micelles uptake perylene, a polycyclic aromatic hydrocarbon (PAH), from water. The nanospheres or micelles, with the sorbed perylene, are precipitated by CaCl₂. These nanospheres may be useful in concentrating PAHs present in trace amounts in water for chemical analysis or in the reclamation of water contaminated by PAHs. Investigated in this article are factors that govern the capacities of the nanospheres and micelles, and the critical calcium concentration for inducing nanosphere or micelle precipitation. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 397–408, 1998     

Synthesis of amphiphilic polyethylene-b-poly(l-glutamate) block copolymers with vastly different solubilities and their stimuli-responsive polymeric micelles in aqueous solution

This paper describes the synthesis, characterization, and self-assembly behavior of amphiphilic polyethylene-block-poly(l-glutamate) (PE-b-PGA) diblock copolymers. PE-b-PGA diblock copolymers were obtained by ring-opening polymerization (ROP) of γ-benzyl-l-glutamate-N-carboxyanhydride (BLG-NCA) using PE–COOCH(ⁱPr)NH₂ as a macroinitiator and subsequent deprotection of the benzylester groups. The self-assembly behaviors of the PE-b-PGA copolymers in water were studied as a function of pH and ionic strength by means of fluorescence spectroscopy, laser light scattering, UV-circular dichroism, and transmission electron microscopy. The size of the polymeric micelles decreases with a decreasing pH value even at high salt concentrations because the solvating PGA units can perform a coil-to-helix transition.     

Self-assembly of an A-B diblock copolymer blended with a C homopolymer and a C-D diblock copolymer through hydrogen bonding interaction

In this study, we investigated the miscibility, phase behavior, and self-assembled nanostructures formed from the immiscible crystalline-amorphous diblock copolymer poly(?-caprolactone-b-4-vinyl pyridine) (PCL-b-P4VP, A-B) when blended with the homopolymer poly(vinyl phenol) (PVPh, C) and the diblock copolymer poly(vinyl phenol-b-styrene) (PVPh-b-PS, C-D). Long-range-ordered microphase separation was difficult to achieve in the PCL-b-P4VP/PVPh (A-B/C) blend system because PVPh interacted with both the P4VP and PCL blocks simultaneously through hydrogen bonding interactions. In contrast, we observed sharp, multiple orders of diffraction in the SAXS profiles of the PCL-b-P4VP/PVPh-b-PS (A-B/C-D) blend system, indicating that perfect microphase separation occurred because the incorporation of the PS block induced the PVPh block to hydrogen bond preferentially with the P4VP block. This simple A-B/C-D (PCL-b-P4VP/PVPh-b-PS) diblock copolymer mixture exhibited self-assembly behavior (a three-lamella phase) similar to that of a corresponding ABC triblock copolymer.     

Phase behaviors of bidisperse nanoparticle/block copolymer mixtures in dilute solutions

The complex microstructures of bidisperse nanoparticles/diblock copolymer mixtures in dilute solutions have been investigated by a theoretical approach which combines the self-consistent field theory (SCFT) and the density functional theory (DFT). Special attention is payed to the role played by the block ratio and the interaction parameters between each component in the mixture. It is shown that the conformational entropy of the polymer chains, the block ratio of the diblock copolymer, the chemical difference between two kinds of particles and the steric packing effect of the particles play important roles in determining the morphologies of the systems. It is found that with the increase of the block ratio, the mixture undergoes a morphological transition from compound micelles to spherelike micelles. The increase of chemical difference between the two kinds of particles can promote the formation of “a jujube set in a cake”. When the selectivity of the particles is changed, another type of micelle emerges. Specifically, in the case where the particles are nonselective to the A- and B-blocks, ordered structures from the phase separation between the two types of particles emerge inside the micelles formed by the amphiphilic diblock copolymers in solutions.     

Architecture of nanostructured polymers by segregated domain crosslinking of block‐graft copolymer micelles

Polystyrene‐block‐polyisoprene (PS‐block‐PI; high 3,4‐structure) diblock copolymer was prepared by living anionic polymerization. For transfer into a reactive intermediate, the hydroxylation of the double bonds of PI block was achieved by hydroboration, followed by oxidation. Esterification of the hydroxy‐derivative with stearoyl chloride or decanoyl chloride resulted in block‐graft copolymers composed of PS (flexible chain)‐grafted long alkane (stretched chains). After partial chloromethylation of PS block copolymer, photofunctional N,N‐diethyldithiocarbamate (DC) groups were introduced into such pendant sites by reaction with the corresponding sodium salt. We studied the self‐assemblies of photofunctional block‐graft copolymers in a selective solvent, such as heptane, and constructed nanostructured polymers by crosslinking PS cores under UV irradiation. © 2001 Society of Chemical Industry     

嵌段共聚物SBS／SIS的接枝改性研究

以SBS和SIS为基材,采用不同橡胶胶种、丙烯酸及其酯类单体进行接枝共聚合成胶粘剂。研究了 CSM(氯磺化聚乙烯)、A-90(氯丁橡胶)、NR(丁腈)等橡胶胶种对SBS／SIS与AA／BA／MMA／GDMA进行化学改性的影响,同时还探讨了N-MAM(N-羟甲基丙烯酰胺)、GDMA(二甲基丙烯酸乙二醇酯)、TMPTMA(三羟甲基丙烷甲基丙烯酸酯)、MAH(顺丁烯二酸酐)、VAc(醋酸乙烯)等单体对SBS／SIS、丁腈橡胶、氯丁橡胶为接枝母体进行化学改性的效果。结果表明:以SBS／SIS为基材,以氯丁橡胶(A-90)为接枝母体,用AA／BA／ MMA／环氧丙烯酸酯／MAH／N-MAM／GDMA／TMPTMA／VAc混合单体进行接枝改性制得的胶粘剂对极性材料帆布的粘附力较强;以SBS／SIS为复合基材,以丁腈橡胶为接枝母体,用AA／BA／MMA／TMPTMA混合单体接枝改性制得的胶粘剂对非极性材料PP片的粘接强度较高。