Synthesis and Self-Assembly Behaviors of Four-Arm Star Block Copolymers Poly(ϵ-caprolactone)-b-poly(2- (diethylamino) ethyl methacrylate)) in Aqueous Solution

Four-arm star block polymers consisting of hydrophobic poly(?-caprolactone) (PCL) block and hydrophilic poly(2-(diethylamino) ethyl methacrylate)) (PDEAEMA) block were successfully synthesized by ring opening polymerization (ROP) and atom transfer radical polymerization (ATRP). Chain lengths of PDEAEMA segments were varied to obtain a series of star copolymers with different hydrophilic/hydrophobic ratio, which were desired for self-assembly study. Dynamic light scattering (DLS) and transmission electron microscopic (TEM) were used to study their self-assembly behavior. In the PBS solution with different pH value, the star polymers formed micelles or nanoparticles. Furthermore, the morphologies of the micelles were also pH-dependent. Critical micelle concentrations of star copolymers changed from 5.0 to 17.5 mg/L with the increase of hydrophilic block length or the pH decrease. Moreover, a steady increase was found on the micelles diameters when the pH decreased from 7.0 to 3.0. The low CMC value and slight changes on micelle diameter indicated that the micelle remained stable under the changing external stimulus.     

化学酶法合成五嵌段聚合物及其自组装行为的研究

用酶促开环聚合与ATRP方法相结合,制备了聚甲基丙烯酸六氟丁酯-聚己内酯-聚乙二醇-聚己内酯-聚甲基丙烯酸六氟丁酯(PHFMA-b-PCL-b-PEG-b-PCL-b-PHFMA)五嵌段聚合物.首先用Novozym e 435作为催化剂合成了聚己内酯-聚乙二醇-聚己内酯三嵌段聚合物,然后通过端基官能化法合成了大分子引发剂,并用其引发甲基丙烯酸六氟丁酯(HFMA)的ATRP反应,合成了五嵌段聚合物.通过核磁和GPC证明了大分子引发剂和五嵌段共聚物的结构,五嵌段共聚物的GPC分析表明这种合成方法的可行.共聚物胶束的直径和大小通过动态光散射方法和原子力显微镜测试,五嵌段共聚物在水中的的自组装行为也被研究.结果证明胶束是球形,其平均直径为77 nm.聚合物在四氢呋喃中的浓度对聚合物的聚集形貌有很大的影响.     

Multicompartment micelles from hyperbranched star-block copolymers containing polycations and fluoropolymer segment

In this Article, we have investigated the self-assembly of a series of amphiphilic hyperbranched star-block copolymers to form multicompartment micelles in acidic aqueous solution (pH 3.0) or in a dimethylformamide/water (pH 3.0) mixture. These hyperbranched star-block copolymers were prepared via oxyanion-initiated polymerization process, using hydroxyl-terminated hyperbranched poly[3-ethyl-3-(hydroxymethyl)oxetane] (HP) as a macroinitiator precursor with multi-reactive sites. It was turned into oxyanion end-capped macroinitiator through the reaction with potassium hydride, and followed by a sequential addition of 2-(N,N-dimethylamino)ethyl methacrylate (DMAEMA) and 2,2,3,3,4,4,5,5-octafluoropentyl methacrylate (OFPMA). The resultant HP-star-PDMAEMA-b-POFPMA copolymers were characterized via 1H NMR, 19F NMR, and gel permeation chromatography (GPC). The analyses of transmission electron microscopy (TEM), dynamic light scattering (DLS), and microelectrophoresis confirmed that these copolymers could directly self-organize into supramolecular multicompartment micelles with different diameters, depending on the length of the PDMAEMA segment, which can be protonated in acidic aqueous medium. The measurement of the zeta potential gave further evidence of the aggregating structures for the multicompartment micelles.     

Rod-sphere transition in polybutadiene-poly(L-lysine) block copolymer assemblies

This paper describes the synthesis and characterization of poly(butadiene)m-poly(L-lysine)n (m-n = 107-200, 107-100, and 60-50) block copolymers. The polymers are prepared in a two-step process whereby amine-terminated polybutadiene is used to initiate the ring-opening polymerization of the epsilon-benzyloxycarbonyl L-lysine N-carboxyanhydride. After deprotection, the self-assembly of the block copolymers in aqueous media were studied using dynamic light scattering, transmission electron microscopy, and circular dichroism spectroscopy. These block copolymers were found to form either spherical micelles or rod-like micelles at high pH depending on the composition of the block copolymer. As the pH is decreased, the micelles swell due to charge-charge repulsions between corona chains and from the helix-coil transition of the polypeptide block. The two systems that form rod-like micelles at high pH also exhibit a pH-induced rod-sphere transition at low pH. This transition was verified from Kratky analysis of the static light scattering data and via CONTIN analysis of the dynamic light scattering data, which shows a bimodal distribution in particle sizes.     

Synthesis of self-assemble pH-responsive cyclodextrin block copolymer for sustained anticancer drug delivery

Well-defined p H-responsive poly(ε-caprolactone)-graft-β-cyclodextrin-graft-poly(2-(dimethylamino)ethylmethacrylate)-co-poly(ethylene glycol) methacrylate amphiphilic copolymers(PCL-g-β-CD-g-P(DMAEMA-co-PEGMA)) were synthesized using a combination of atom transfer radical polymerization(ATRP),ring opening polymerization(ROP) and "click" chemistry.Successful synthesis of polymers was confirmed by Fourier transform infrared spectroscopy(FTIR),proton nuclear magnetic resonance(1H-NMR),and gel permeation chromatography(GPC).Then,the polymers could selfassemble into micelles in aqueous solution,which was demonstrated by dynamic light scattering(DLS) and transmission electron microscopy(TEM).The p H-responsive self-assembly behavior of these copolymers in water was investigated at different p H values of 7.4 and 5.0 for controlled doxorubicin(DOX) release,and these results revealed that the release rate of DOX could be effectively controlled by altering the p H,and the release of drug loading efficiency(DLE) was up to 88%(W/W).CCK-8 assays showed that the copolymers had low toxicity and possessed good biodegradability and biocompatibility,whereas the DOX-loaded micelles remained with high cytotoxicity for He La cells.Moreover,confocal laser scanning microscopy(CLSM) images revealed that polymeric micelles could actively target the tumor site and the efficient intracellular DOX release from polymeric micelles toward the tumor cells further confirmed the anti-tumor effect.The DOX-loaded micelles could easily enter the cells and produce the desired pharmacological action and minimize the side effect of free DOX.These results successfully indicated that p H-responsive polymeric micelles could be potential hydrophobic drug delivery carriers for cancer targeting therapy with sustained release.     

Synthesis,self-assembly,and pH-responsive drug release of PHMEMA-PEG-PHMEMA ABA triblock copolymers

Abstract

A series of tertiary amine containing PHMEMA-PEG-PHMEMA ABA triblock copolymers were synthesized by atom transfer radical polymerization (ATRP) using bromine-capped poly(ethylene glycol) (Br-PEG-Br) and 2-(hexamethyleneimino)ethyl methacrylate (HMEMA) as macro-initiator and monomers, respectively. The chemical structures and molecular weights of triblock copolymers were characterized by ¹H NMR and gel permeation chromatography (GPC). The self-assembly behaviors of copolymers in different pH conditions were studied by dynamic light scattering (DLS) and transmission electron microscopy (TEM). Triblock copolymers self-assembled into micelles in water (pH 7.4) and the micelles disassembled at acidic pH (pH 5.0). Anticancer drug doxorubicin (DOX) was used as a drug model and physically encapsulated into polymeric micelles. The drug release of DOX-loaded polymeric micelles was pH-responsive; the drug-loaded micelles that had higher contents of tertiary amine in polymer pendant groups showed faster release speed. In addition, the drug-loaded micelles showed excellent inhibition efficacy against HeLa cells in vitro.     

Cylindrical micelles from the aqueous self-assembly of an amphiphilic poly(ethylene oxide)-b-poly(ferrocenylsilane) (PEO-b-PFS) block copolymer with a metallo-supramolecular linker at the block junction

A supramolecular AB diblock copolymer has been prepared by the sequential self-assembly of terpyridine end-functionalized polymer blocks by using Ru(III)/Ru(II) chemistry. By this synthetic strategy a hydrophobic poly(ferrocenylsilane) (PFS) was attached to a hydrophilic poly(ethylene oxide) (PEO) block to give an amphiphilic metallo-supramolecular diblock copolymer (PEO/PFS block ratio 6:1). This compound was used to form micelles in water that were characterized by a combination of dynamic and static light scattering, transmission electron microscopy, and atomic force microscopy. These complementary techniques showed that the copolymers investigated form rod-like micelles in water; the micelles have a constant diameter but are rather polydisperse in length, and light scattering measurements indicate that they are flexible. Crystallization of the PFS in these micelles was observed by differential scanning calorimetry, and is thought to be the key behind the formation of rod-like structures. The cylindrical micelles can be cleaved into smaller rods whenever the temperature of the solution is increased or they are exposed to ultrasound.     

Temperature- and pH-responsive self-assembly of poly(propylene oxide)-b-poly(lysine) block copolymers in aqueous solution

A series of poly(propylene oxide)-b-poly(L-lysine) (PPO-PK) block copolymers were synthesized using Huisgen's 1,3-dipolar cycloaddition, and the solution self-assembly was studied using transmission electron microscopy, circular dichroism spectroscopy, and dynamic and static light scattering techniques. In contrast to previous studies of poly(lysine)-based block copolymers, PPO-PK exhibits a significant shift in the pH associated with the helix-coil transition of the poly(lysine) block, potentially a result of decreased hydrophobicity in the core PPO block. Given the proximity of the lower critical solution temperature of the PPO block, these materials exhibit both pH and temperature-responsive (i.e., "schizophrenic") self-assembly, the latter of which was interpreted in terms of changes in the second osmotic virial coefficient. Finally, the vesicle morphology obtained from these polymers was studied for the propensity in drug encapsulation and passive release.     

Synthesis and supramolecular organization of amphiphilic diblock copolymers combining poly(N,N-dimethylamino-2-ethyl methacrylate) and poly(epsilon-caprolactone)

Well-defined poly(epsilon-caprolactone) (PCL)/poly(N,N-dimethylamino-2-ethyl methacrylate (PDMAEMA) diblock copolymers were synthesized, and their self-assembly was investigated as micelles both in aqueous solutions and in thin solid deposits. The synthetic approach combines controlled ring opening polymerization (ROP) of epsilon-caprolactone (CL) and atom transfer radical polymerization (ATRP) of N,N-dimethylamino-2-ethyl methacrylate (DMAEMA). Diblock copolymers were prepared by ROP of CL initiated by (Al(OiPr)3), followed by quantitative reaction of the PCL hydroxy end-groups with bromoisobutyryl bromide. The alpha-isopropyloxy omega-2-bromoisobutyrate poly(epsilon-caprolactone) (PCL-Br) obtained was used as a macroinitiator for the ATRP of DMAEMA. The molecular characterization of those diblock copolymers was performed by 1H NMR spectroscopy and gel permeation chromatography (GPC) analysis. The self-assembly of the copolymers into micellar aggregates in aqueous media was followed with dynamic light scattering (DLS), as a function of concentration and the pH. In parallel, the morphology of the solid deposits of those micelles was examined with atomic force microscopy (AFM).     

Bionanoparticles of amphiphilic copolymers polyacrylate bearing cholesterol and ascorbate for drug delivery

In this study, a series of amphiphilic polymers with poly(ascorbyl acrylate) (PAAA) as hydrophilic blocks and polyacrylate bearing side-chain cholesteryl mesogens (PCholDEGA) as hydrophobic blocks were prepared using a combination of four-step reactions consisting of two consecutive reversible addition-fragmentation chain transfer (RAFT), desulfurization, and hydrogenolysis under normal pressure. The thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) as well as wide-angle X-ray diffraction (WAXD) studies showed that the copolymers with PCholDEGA as major block had relatively high stability and clear isotropization temperature (T(i)). Small-angle X-ray diffraction (SAXD) investigation exhibited that the copolymers had bilayer smectic A structure. Their self-assembly behavior was monitored by turbidity change using UV-vis spectrometer, and the morphology and size of the nanoparticles via self-assembly were detected using transmission electron microscopy (TEM) and dynamic light scattering (DLS). The entrapment efficiency and loading capacity of these amphiphilic copolymers were investigated using nile red and drug molecule Ibuprofen. These polymeric micelles with PAAA shell extending into the aqueous solution and strong hydrophobic PCholDEGA core have potential abilities to act as promising nanovehicles with high loading and targeting delivery.     

Length Control and Block-Type Architectures in Worm-like Micelles with Polyethylene Cores

We present evidence for "living"-like behavior in the crystallization-driven self-assembly of triblock copolymers with crystallizable polyethylene middle blocks into worm-like crystalline-core micelles (CCMs). A new method of seed production is introduced utilizing the selective self-assembly of the triblock copolymers into spherical CCMs in appropriate solvents. Seeded growth of triblock copolymer unimers from these spherical CCMs results in worm-like CCMs with narrow length distributions and mean lengths that depend linearly on the applied unimer-to-seed ratio. Depending on the applied triblock copolymer, polystyrene-block-polyethylene-block-polystyrene (SES) or polystyrene-block-polyethylene-block-poly(methyl methacrylate) (SEM), well-defined worm-like CCMs with a homogeneous or patch-like corona, respectively, can be produced. In a subsequent step, these worm-like CCMs can be used as seeds for the epitaxial growth of a different polyethylene containing triblock copolymer. In this manner, ABA-type triblock co-micelles containing blocks with a homogeneous polystyrene corona and those with a patch-like polystyrene/poly(methyl methacrylate) corona were prepared. While the epitaxial growth of SEM unimers from worm-like SES CCMs with a homogeneous corona yields triblock co-micelles almost quantitatively, the addition of SES unimers to patchy SEM wCCMs results in a mixture of ABA- and AB-type block co-micelles together with residual patchy wCCMs. Following reports on self-assembled block-type architectures from polymers containing core-forming polyferrocenylsilane blocks, these structures represent the first extension of the concept to block co-micelles from purely organic block copolymers.     

Comb-coil型聚(苯乙烯-异戊二烯)共聚物在正烷烃中的自组装

借助动态光散射(DLS)和原子力显微镜(AFM)研究了具有复杂结构的comb-coil型聚苯乙烯-异戊二烯嵌段共聚物(S-graft-I)-block-S在聚异戊二烯(PI)选择性溶剂正烷烃中的自组装行为. 结果表明comb-coil型分子在庚烷中形成球形胶束. 同时, 这些胶束的尺寸显示出独特的双分布现象. 除常见的PS-PI相分离机理外, 我们还提出一种comb-coil相分离机理. 这些双分布胶束的形成可能正是两种相分离机理共存的结果. 此外, 借助透射电镜(TEM)进一步研究了选择性、接枝度和接枝链长度对自组装行为的影响. 研究发现增加溶剂选择性或增加接枝链链长以及接枝度, 有利于两种尺寸的胶束的形成以及对应分布峰的完全分离.     

Characterization of layer-by-layer self-assembled multilayer films of diblock copolymer micelles

The in situ layer-by-layer (LbL) self-assembly of low Tg diblock copolymer micelles onto a flat silica substrate is reported. The copolymers used here were a cationic poly(2-(dimethylamino)ethyl methacrylate)-block-poly(2-(diethylamino)ethyl methacrylate) (50qPDMA-PDEA; 50q refers to a mean degree of quaternization of 50 mol % for the PDMA block) and zwitterionic poly(methacrylic acid)-block-poly(2-(diethylamino)ethyl methacrylate) (PMAA-PDEA), which has anionic character at pH 9. Alternate deposition of micelles formed by these two copolymers onto a silica substrate at pH 9 was examined. The in situ LbL buildup of the copolymer micelle films was monitored using zeta potential measurements, optical reflectometry, and a quartz crystal microbalance with dissipation monitoring (QCM-D). For a six layer deposition, complete charge reversal was observed after the addition of each layer. The OR data indicated clearly an increase in adsorbed mass with each additional micelle layer and suggest that some interdiffusion of copolymer chains between layers and/or an increase in the film roughness, and hence in the effective surface area of the micellar multilayers, must take place as the film is built up. QCM-D data indicated that the self-assembled micellar multilayers on a flat silica substrate undergo structural changes over a prolonged period. This is attributed to longer-term interdiffusion of the copolymer chains between the outer two layers after the initial adsorption of each layer is complete. The QCM-D data further suggest that the outer adsorbed layers adopt a progressively more extended conformation, particularly for the higher numbered layers. The morphology of each successive layer was characterized using in situ soft-contact atomic force microscopy, and micelle-like surface aggregates are clearly observed within each layer of the complex film, suggesting the persistence of aggregate structures throughout the multilayer structure.     

Phase diagrams,mechanisms and unique characteristics of alternating-structured polymer self-assembly via simulations

Alternating-structured polymers(ASPs), like alternating copolymers, regular multiblock copolymers and polycondensates, are very important polymer structures with broad applications in photoelectric materials. However, their self-assembly behaviors,especially the self-assembly of alternating copolymers, have not been clearly studied up to now. Meanwhile, the unique characteristics therein have not been systematically disclosed yet by both experiments and theories. Herein, we have performed a systematic simulation study on the self-assembly of ASPs with two coil alternating segments in solution through dissipative particle dynamics(DPD) simulations. Several morphological phase diagrams were constructed as functions of different impact parameters. Diverse self-assemblies were observed, including spherical micelles, micelle networks, worm-like micelles, disklike micelles, multimicelle aggregates, bicontinuous micelles, vesicles, nanotubes and channelized micelles. Furthermore, a morphological evolutionary roadmap for all these self-assemblies was constructed, along with which the detailed molecular packing models and self-assembly mechanisms for each aggregate were disclosed. The ASPs were found to adopt a folded-chain mechanism in the self-assemblies. Finally, the unique characteristics for the self-assembly of alternating copolymers were revealed especially, including(1) ultra-fine and uniform feature sizes of the aggregates;(2) independence of self-assembled structures from molecular weight and molecular weight distribution;(3) ultra-small unimolecular aggregates. We believe the current work is beneficial for understanding the self-assembly of alternating structured polymers in solution and can serve as a guide for the further experiments.     

Synthesis and characterization of ABA‐type amphiphilic tri‐block copolymers through anionic polymerization using end functionalized poly(ethylene oxide) oligomers

ABA‐type amphiphilic tri‐block copolymers were successfully synthesized from poly(ethylene oxide) derivatives through anionic polymerization. When poly(styrene) anions were reacted with telechelic bromine‐terminated poly(ethylene oxide) ( 1 ) in 2:1 mole ratio, poly(styrene)‐b‐poly(ethylene oxide)‐b‐poly(styrene) tri‐block copolymers were formed. Similarly, stable telechelic carbanion‐terminated poly(ethylene oxide), prepared from 1,1‐diphenylethylene‐terminated poly (ethylene oxide) ( 2 ) and sec‐BuLi, was also used to polymerize styrene and methyl methacrylate separately, as a result, poly (styrene)‐b‐poly(ethylene oxide)‐b‐poly(styrene) and poly (methyl methacrylate)‐b‐poly(ethylene oxide)‐b‐poly(methyl methacrylate) tri‐block copolymers were formed respectively. All these tri‐block copolymers and poly(ethylene oxide) derivatives, 1 and 2 , were characterized by spectroscopic, calorimetric, and chromatographic techniques. Theoretical molecular weights of the tri‐block copolymers were found to be similar to the experimental molecular weights, and narrow polydispersity index was observed for all the tri‐block copolymers. Differential scanning calorimetric studies confirmed the presence of glass transition temperatures of poly(ethylene oxide), poly(styrene), and poly(methyl methacrylate) blocks in the tri‐block copolymers. Poly(styrene)‐b‐poly(ethylene oxide)‐b‐poly(styrene) tri‐block copolymers, prepared from polystyryl anion and 1 , were successfully used to prepare micelles, and according to the transmission electron microscopy and dynamic light scattering results, the micelles were spherical in shape with mean average diameter of 106 ± 5 nm. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Influence of the macromolecular architecture on the self-assembly of amphiphilic copolymers based on poly(N,N-dimethylamino-2-ethyl methacrylate) and poly(epsilon-caprolactone)

The self-assembly of amphiphilic copolymers consisting of poly( N, N-dimethylamino-2-ethyl methacrylate) (PDMAEMA) and poly(-caprolactone) (PCL) segments arranged in graft and linear diblock architectures was investigated in this work by means of dynamic light scattering (DLS) in aqueous solution and by atomic force microscopy (AFM) on thin deposits. The solid-state deposits of the micelles were generated by a "freeze-drying" technique that preserves the initial micelle morphology in solution. A comparison between the morphological properties of graft copolymers with corresponding diblock copolymers was established to demonstrate the effect of the copolymer architecture on the micelle structure and organization.     

Brush-type amphiphilic diblock copolymers from "living"/controlled radical polymerizations and their aggregation behavior

Two brush-type amphiphilic diblock copolymers, poly(poly(ethylene glycol)methyl ether methacrylate-block-polystyrene) (P(PEGMA)-b-PS) and poly(glycidyl methacrylate)-block-poly(poly(ethylene glycol)methyl ether methacrylate) (P(GMA)-b-P(PEGMA)) were synthesized, respectively, via consecutive atom-transfer radical polymerizations (ATRPs) and reversible addition-fragmentation chain-transfer (RAFT) polymerizations. The diblock copolymers were characterized by gel permeation chromatography (GPC), (1)H nuclear magnetic resonance (NMR) spectroscopy, and FT-IR spectroscopy. The aggregation behavior of the two amphiphilic diblock copolymers in water was also studied. Scanning electron and transmission electron microscopic images revealed that spherical micelles (40-80 nm in diameter) from self-assembly of the P(PEGMA)-b-PS copolymers and wormlike micelles (60-120 nm in length and 20-30 nm in diameter) from self-assembly of the P(GMA)-b-P(PEGMA) copolymers were prevalent. The spherical P(PEGMA)-b-PS micelles could self-assemble gradually into giant aggregates of several micrometers in diameter.     

Amphiphilic Block Copolymer Micelles for Gene Delivery

Gene therapy is a promising method to treat acquired and inherited diseases by introducing exogenous genes into specific recipient cells. Polymeric micelles with different nanoscopic morphologies and properties hold great promise for gene delivery system. Conventional cationic polymers, poly(ethyleneimine)(PEI), poly(L-lysine)(PLL), poly(2-dimethyla-minoethyl methacrylate)(PDMAEMA) and novel cationic polymers poly(2-oxazoline)s(POxs), have been incorporated into block copolymers and decorated with targeting moieties to enhance transfection efficiency. In order to minimize cytotoxicity, nonionic block copolymer micelles are utilized to load gene through hydrophilic and hydrophobic interactions or covalent conjugations, recently. From our perspective, properties(shape, size, and mechanical stiffness, etc.) of block copolymer micelles may significantly affect cytotoxicity, transfection efficiency, circulation time, and load capacity of gene vectors in vivo and in vitro. This review briefly sums up recent efforts in cationic and nonionic amphiphilic polymeric micelles for gene delivery.     

Supramolecular self-assembly of conjugated diblock copolymers

This paper describes the synthesis and characterization of a novel series of copolymers with different lengths of oligo(phenylene vinylene) (OPV) as the rod block, and poly(propylene oxide) as the coil block. Detailed characterization by means of transmission electron microscopy (TEM), atomic force microscopy (AFM), and small-angle neutron scattering (SANS) revealed the strong tendency of these copolymers to self-assemble into cylindrical micelles in solution and as-casted films on a nanometer scale. These micelles have a cylindrical OPV core surrounded by a poly(propylene glycol) (PPG) corona and readily align with each other to form parallel packed structures when mica is used as the substrate. A packing model has been proposed for these cylindrical micelles.     

Synthesis and characterisation of new shell cross-linked micelles with amine-functional coronas

Shell cross-linked (SCL) micelles with amine-functional coronas have been constructed in aqueous solution by exploiting the micellar self-assembly of new thermo-responsive ABC triblock copolymers. These copolymers were prepared via atom transfer radical polymerisation (ATRP) in convenient one-pot syntheses and comprised a thermo-responsive core-forming poly(propylene oxide) [PPO] block, a cross-linkable central poly(glycerol monomethacrylate) [GMA] block and an amine-functional outer block based on either poly(2-(dimethylamino)ethyl methacrylate) [DMA] or poly([2-(methacryloyloxy)ethyl]trimethyl ammonium chloride) [QDMA]. DMF GPC analysis indicated an M_n of 17,700 and an M_w/M_n of 1.46 for the PPO-PGMA-PDMA triblock copolymer. The DMA residues of the PPO-PGMA-PDMA triblock copolymer were reacted with methyl iodide to prepare copolymers with differing degrees of quaternisation. Each triblock copolymer dissolved molecularly in aqueous solution at 5 °C and formed micelles with amine-functional coronas above a critical micelle temperature (CMT) of around 12 °C, which corresponded closely to the cloud point of the PPO macro-initiator. Cross-linking of the GMA residues in the inner shell using divinyl sulfone produced SCL micelles that remained intact at 5 °C, i.e. below the cloud point of the core-forming PPO block. Aqueous electrophoresis studies confirmed that these SCL micelles had considerable cationic surface charge, as expected. The cationic SCL micelles were adsorbed onto a near-monodisperse anionic silica sol, which was used as a model colloidal substrate. Thermogravimetric analyses indicated SCL micelle mass loadings of 6.1-15.5 wt.%, depending on the initial micelle concentration. Aqueous electrophoresis studies confirmed that surface charge reversal occurred on adsorption of the SCL micelles and scanning electron microscopy studies revealed the presence of SCL micelles on the silica particles.