Temperature-triggered micellization of block copolymers on an ionic liquid surface

In situ neutron reflectivity was used to study thermally induced structural changes of the lamellae-forming polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) block copolymer thin films floating on the surface of an ionic liquid (IL). The IL, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, is a nonsolvent for PS and a temperature-tunable solvent for P2VP, and, as such, micellization can be induced at the air-IL interface by changing the temperature. Transmission electron microscopy and scanning force microscopy were used to investigate the resultant morphologies of the micellar films. It was found that highly ordered nanostructures consisting of spherical micelles with a PS core surrounded by a P2VP corona were produced. In addition, bilayer films of PS homopolymer on top of a PS-b-P2VP layer also underwent micellization with increasing temperature but the micellization was strongly dependent on the thickness of the PS and PS-b-P2VP layers.     

Microenvironment in the corona region of triblock copolymer micelles: temperature dependent solvation and rotational relaxation dynamics of coumarin dyes

Dynamic Stokes' shift and fluorescence anisotropy measurements using coumarin-153 (C153) and coumarin-151 (C151) as the fluorescence probes have been carried out in aqueous poly(ethylene oxide)20-poly(propylene oxide)70-poly(ethylene oxide)20 (P123) and poly(ethylene oxide)100-poly(propylene oxide)70-poly(ethylene oxide)100 (F127) block copolymer micelles with an aim to understand the water structures and dynamics in the micellar corona region. It has been established that the probes reside in the micellar corona region. It is indicated that the corona regions of P123 and F127 micelles are relatively less hydrated than the Palisade layers of neutral micelles like Triton-X-100 and Brij-35. From the appraisal of total Stokes' shift values for the probes in the two block copolymer micelles, it is inferred that the F127 micelle is more hydrated than the P123 micelle. It is observed that the dynamic Stokes' shift values for both of the probes remain more or less similar at all the temperatures studied in the P123 micelle. For C153 in F127, however, the observed Stokes' shift is seen to decrease quite sharply with temperature, though it remains quite similar for C151. Moreover, the fraction of the unobserved initial dynamic Stokes' shift is appreciably higher for both the probes in the F127 micelle compared to that in P123. Over the studied temperature range of 293-313 K, the spectral shift correlation function is described adequately by a bi-exponential function. Rotational relaxation times for C153 in both the micelles show a kind of transition at around 303 K. These results have been rationalized assuming collapse of the poly(ethylene oxide) (PEO) blocks and formation of water clusters in the corona region due to dehydration of poly(ethylene oxide) blocks with an increase in temperature. A dissimilar probe location has been inferred for the differences in the results with C153 and C151 probes in F127. Comparison of the microviscosity and the hydration of the block copolymer micelles has also been made with those of the other commonly used neutral micelles, for a better understanding of the results in the block copolymer micelles.     

Temperature tunable micellization of polystyrene-block-poly(2-vinylpyridine) at Si-ionic liquid interface

Highly ordered and stable micelles formed from both symmetric and asymmetric block copolymers of polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) at the Si-ionic liquid (IL) interface have been investigated by scanning force microscopy (SFM) and transmission electron microscopy (TEM). The 1-butyl-3-methylimidazolium trifluoromethanesulfonate IL, a selective and temperature-tunable solvent for the P2VP block, was used and gave rise to block copolymer micelles having different morphologies that strongly depended on the annealing temperature. The effects of film thickness, molecular weight of block copolymers, and experimental conditions, such as preannealing, rinsing, and substrate properties, on the morphologies of block copolymer micelles were also studied. In addition, spherical micelles consisting of PS core and P2VP shell could also be obtained by core-corona inversion by annealing the as-coated micellar film in the IL at high temperatures. The possible mechanism for micelle formation is discussed.     

Polymer micelles with hydrophobic core and ionic amphiphilic corona. 2. Starlike distribution of charged and nonpolar blocks in corona

Mixed polymer micelles with hydrophobic polystyrene (PS) core and ionic amphiphilic poly(4-vinylpyridine)/poly(N-ethyl-4-vinylpyridinium bromide) corona (P4VP/PEVP) spontaneously self-assembled from mixtures of PS-b-PEVP and PS-b-P4VP macromolecules in dimethylformamide/methanol/water selective solvent. The fraction of PEVP units in corona was β = [PEVP]/([PEVP] + [P4VP]) = 0.05-1.0. Micelles were transferred into pure water via dialysis technique and pH was adjusted to 9, where P4VP blocks are insoluble. Structural characteristics of micelles as a function of corona composition β were investigated. Methods of dynamic and static light scattering, electrophoretic mobility measurements, sedimentation velocity, transmission electron microscopy, and UV spectrophotometry were applied. Spherical morphology with core (PS)-shell (P4VP)-corona (PEVP) organization was postulated. Micelles demonstrated a remarkable inflection in structural characteristics near β ～ 0.5-0.7. Above this region, aggregation number (m), core and corona radii of mixed micelles coincided with those of individual PS-b-PEVP micelles. When β decreased below 0.5, dramatic growth of aggregation number was observed, accompanied by growth in micelle size and stretching PEVP chains. At β below 0.2, dispersions of mixed micelles were unstable and easily precipitated upon addition of NaCl. Scaling relationships between micelle characteristics and β were obtained via minimization the micelle free energy, taking into account electrostatic, osmotic, volume, and surface contributions. Theoretical estimations predicted dramatic influence of β on aggregation number, m ～ β(-3). This result is in general agreement with experimental data and confirms the correctness of the core-shell-corona model. The inflection in micelle characteristics entails drastic changes in micelle dispersion stability in the presence of oppositely charged polymeric (sodium polymethacrylate) or amphiphilic (sodium dodecyl sulfate) complexing agents.     

Dynamics of solvent and rotational relaxation of coumarin-153 in room-temperature ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate confined in poly(oxyethylene glycol) ethers containing micelles

We have investigated solvent and rotational relaxation of coumarin 153 (C-153) in room-temperature ionic liquid (RTILs) 1-butyl-3-methyl-imidazolium tetrafluoroborate ([bmim][BF(4)]) and the ionic liquid confined in alkyl poly(oxyethylene glycol) ethers containing micelles. We have used octaethylene glycol monotetradecyl ether (C(14)E(8)) and octaethylene glycol monododecyl ether (C(12)E(8)) as surfactants. In the [bmim][BF(4)]-C(14)E(8) micelle, we have observed only a 22% increase in solvation time compared to neat [bmim][BF(4)], whereas in the [bmim][BF(4)]-C(12)E(8) system, we have observed approximately 57% increase in average solvation time due to micelle formation. However, the slowing down in solvation time on going from neat RTIL to RTIL-confined micelles is much smaller compared to that on going from water to water confined micellar aggregates. The 22-57% increase in solvation time is attributed to the slowing down of collective motions of cations and anions in micelles. The rotational relaxation times become faster in both the micelles compare to neat [bmim][BF(4)].     

Dependence of size and morphology on shear flow for PS-based amphiphilic block copolymer micelles in aqueous solution

This contribution focuses on the impact of shear flow on size and nanostructure of PS-based amphiphilic block copolymer (BC) micelles by varying the stirring rate and copolymer composition.The results show that the vesicles formed from diblock copolymer (di-BC) of PS-b-PAA remain with vesicular morphology,although the average size decreases,with the increase of stirring rate.However,the multi-compartment micelles (MCMs) formed from tri-block copolymer (tri-BC) of PS-b-P2VP-b-PEO are quite intricate,in which the copolymer first self-assembles into spheres,then to clusters,to large compound micelles (LCMs),and finally back to spheres,as stirring rate increases from 100 r/min to 2200 r/min.Formation mechanism studies manifest that vesicles form simultaneously as water is added to the di-BC solution,termed as direct-assembly,and remain with vesicular structure in the flowing process.While for the PS-b-P2VP-b-PEO copolymer,spherical micelles at initial stage can further assemble into clusters and LCMs,termed as second-assembly,due to the speeding-up-aggregation of the favorable stirring.As a result,an invert V-relationship between tri-BC micelle dimension and stirring rate is observed in contrast to the non-linear decreasing curve of di-BC vesicles.It is by investigating these various amphiphilic BCs that the understanding of shear dependence of size and morphology of micelles is improved from self-assembly to second-assembly process.     

Morphology of hybrid polystyrene-block-poly(ethylene oxide) micelles: analytical ultracentrifugation and SANS studies

Morphology and structure of aqueous block copolymer solutions based on polystyrene-block-poly(ethylene oxide) (PS-b-PEO) of two different compositions, a cationic surfactant, cetyl pyridinium chloride (CPC), and either platinic acid (H2PtCl6.6H2O) or Pt nanoparticles were studied using a combination of analytical ultracentrifugation (AUC), transmission electron microscopy (TEM), and small angle neutron scattering (SANS). These studies combining methods contributing supplemental and analogous structural information allowed us to comprehensively characterize the complex hybrid systems and to discover an isotope effect when H2O was replaced with D2O. In particular, TEM shows formation of both micelles and larger aggregates after incorporation of platinic acid, yet the amount of aggregates depends on the H2PtCl6.6H2O concentration. AUC reveals the presence of micelles and micellar clusters in the PS-b-PEO block copolymers solution and even larger (supermicellar) aggregates in hybrids (with CPC). Conversely, SANS applied to D2O solutions of the similar species indicates that micelles are spherical and no other micellar species are found in block copolymer solutions. To reconcile the SANS and AUC data, we carried out AUC examination of the corresponding D2O block copolymer solutions. These measurements demonstrate a pronounced isotope effect on micelle aggregation and micelle size, i.e., no micelle aggregation in D2O solutions, revealing good agreement of AUC and SANS data.     

Effects of block size of pluronic polymers on the water structure in the corona region and its effect on the electron transfer reactions

Effects of constituent block size of triblock copolymers on the nature of the water molecules in the corona region of their micelles have been investigated using time-resolved fluorescence measurements. The physical nature of the water molecules in the micellar corona region of the block copolymer, Pluronic F88 ([ethylene oxide (EO)]103-[propylene oxide (PO)]39-EO103), has been studied using a solubilized coumarin dye. Solvent reorientation time and rotational correlation time have been measured and compared with another block copolymer, Pluronic P123 (EO20-PO70-EO20), which has a different composition of the constituent PO and EO blocks. It is noted that due to the presence of larger number of EO blocks in F88 as compared with P123, the corona region of the former micelle is more hydrated than that of the latter. The solvent reorientation time and rotational correlation time are found to be relatively shorter for F88 as compared with P123. This indicates that the water molecules in the corona of the F88 micelle are more labile than those of P123, which is also supported from the estimated number of water molecules associated with each EO unit, measured from the size of each type of micelle and its aggregation number. To understand the effect of block size on the chemical reactions in these microheterogeneous media, electron transfer reactions have been carried out between different coumarin acceptors and N, N-dimethylaniline donor. The electron transfer results obtained in F88 micelles have been compared with those obtained in P123, and the results are rationalized on the basis of the relative hydration of the two triblock copolymer micelles.     

Sphere-to-rod transition of non-surface-active amphiphilic diblock copolymer micelles: a small-angle neutron scattering study

Micellization behavior of amphiphilic diblock copolymers with strong acid groups, poly(hydrogenated isoprene)-block-poly(styrenesulfonate), was investigated by small-angle neutron scattering (SANS). We have reported previously (Kaewsaiha, P.; Matsumoto, K.; Matsuoka, H. Langmuir 2005, 21, 9938) that this strongly ionic amphiphilic diblock copolymer shows almost no surface activity but forms micelles in water. In this study, the size, shape, and internal structures of the micelles formed by these unique copolymers in aqueous solution were duly investigated. The SANS data were well described by the theoretical form factor of a core-shell model and the Pedersen core-corona model. The micellar shape strongly depends on the hydrophobic chain length of the block copolymer. The polymer with the shortest hydrophobic chain was suggested to form spherical micelles, whereas the scattering curves of the longer hydrophobic chain polymers showed a q-1 dependence, reflecting the formation of rodlike micelles. Furthermore, the addition of salt at high concentration also induced the sphere-to-rod transition in micellar shape as a result of the shielding effect of electrostatic repulsion. The corona thickness was almost constant up to the critical salt concentration (around 0.2 M) and then decreased with further increases in salt concentration, which is in qualitatively agreement with existing theories. The spherical/rodlike micelle ratio was also constant up to the critical salt concentration and then decreased. The micelle size and shape of this unique polymer could be described by the common concept of the packing parameter, but the anomalously stable nature of the micelle (up to 1 M NaCl) is a special characteristic.     

The Hybrids of Polystyrene-block-Poly(ethylene Oxide) Micelles and Sodium Dodecyl Sulfate in Aqueous Solutions: Interaction with Rh Ions and Rh Nanoparticle Formation

The interaction of amphiphilic block copolymer, polystyrene-block-poly(ethylene oxide) (PS-b-PEO), with anionic surfactant, sodium dodecyl sulfate (SDS), in aqueous media has been studied by sedimentation in ultracentrifuge. Three well-defined populations of hybrid aggregates corresponding to micelles, micellar clusters, and supermicellar aggregates were detected in the PS-b-PEO/SDS aqueous solutions at various rotation rates. Parameters of all the micellar aggregates were characterized depending on the SDS loading. An increase in the SDS loading was found to result in an increase in block copolymer/surfactant micelle size and weight at the SDS concentration of 0.8x10(-3) mol/L and in a slight decrease of both parameters at critical micelle concentration and at higher concentration. This decrease was caused by incorporation of SDS molecules in block copolymer micelles followed by charging the PS core and repulsion between similar charges. Using dichlorotetrapyridine rhodium(III)chloride hexahydrate ([Rh(Py)(4)Cl(2)]Clx6H(2)O), ion exchange of surfactant counterions in the hybrid PS-b-PEO/SDS system for Rh cations was carried out, which allowed saturating the micellar structures with Rh species. Subsequent reduction of the Rh-containing hybrid solutions with NaBH(4) resulted in the formation of Rh nanoparticles with a diameter of 2-3 nm mainly located in the block copolymer micellar aggregates. Copyright 2000 Academic Press.     

Control of the morphology of linear and cyclic PS-b-PI block copolymer micelles via PS addition

We have studied the effect of polystyrene (PS) homopolymer addition on the morphology of self-assembled block copolymer micelles made from linear or cyclic poly(styrene-b-isoprene), PS-b-PI, in a selective solvent for the PI block (heptane). Both copolymers have the same composition: the degree of polymerization is 290 for the PS block, and 110 for the PI block, and we focused on the influence of the addition of small amounts of PS homopolymer on the micellar morphology. For the copolymer concentrations considered, the linear copolymer self-organizes into spherical micelles while the cyclic copolymer forms cylindrical micelles. PS and PI chains constitute the core and the corona of these micelles, respectively, due to the different affinity of the blocks for heptane. Consequently, the PS homopolymer added is "solubilized" into the micellar core. Dynamic light scattering (DLS) data combined with atomic force microscopy (AFM) results show that the addition of PS homopolymer induces a drastic change in the micellar organization. Indeed, a morphological transition, from spheres to cylinders for the linear copolymer, and from cylinders to vesicles for the cyclic copolymer, is observed. These results highlight the fact that a small incorporation of PS homopolymer is clearly sufficient to modify the morphology (size and shape) of the micelles. This approach could be a key parameter for the design/control of micelles for specific applications in nanotechnology.     

Interaction of amphiphilic block copolymer micelles with surfactants

An out line and summary of literature studies on interactions between different types of amphiphilic copolymer micelles with surfactants has been given. This field of research is still emerging and it is difficult presently to make generalisations on the effects of surfactants on the copolymer association. The effects are found to be varied depending upon the nature and type of hydrophobic (hp) core and molecular architecture of the copolymers and the hydrocarbon chain length and head group of surfactants. The information available on limited studies shows that both anionic and cationic surfactants (in micellar or molecular form) equally interact strongly with the associated and unassociated forms of copolymers. The beginning of the interaction is typically displayed as critical aggregation concentration (CAC), which lies always below the critical micelle concentration of the respective surfactant. The surfactants first bind to the hydrophobic core of the copolymer micelles followed by their interaction with the hydrophilic (hl) corona parts. The extent of binding highly depends upon the nature, hydropobicity of the copolymer molecules, length of the hydrocarbon tail and nature of the head group of the surfactant. The micellization of poly(ethylene oxide) (PEO)–poly(propylene oxide) (PPO)–poly(ethylene oxide) was found to be suppressed by the added surfactants and at higher surfactant concentrations, the block copolymer micelles get completely demicellized. This effect was manifested itself in the melting of liquid crystalline phases in the high copolymer concentrations. However, no such destabilization was found for the micelles of polystyrene (PS)–poly(ethylene oxide) copolymers in water. On the contrary, the presence of micellar bound surfactant associates resulted in to large super micellar aggregates through induced intra micellar interactions. But with the change in the hydrophobic part from polystyrene to poly(butadiene) (PB) in the copolymer, the added surfactants not only reduced the micellar size but also transformed cylindrical micelles to spherical ones. The mixtures in general exhibited synergistic effects. So varied association responses were noted in the mixed solutions of surfactants and copolymers.     

Self-assembly of block copolymer micelles in an ionic liquid

Four amphiphilic poly((1,2-butadiene)-block-ethylene oxide) (PB-PEO) diblock copolymers were shown to aggregate strongly and form micelles in an ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF(6)]). The universal micellar structures (spherical micelle, wormlike micelle, and bilayered vesicle) were all accessed by varying the length of the corona block while holding the core block constant. The nanostructures of the PB-PEO micelles formed in an ionic liquid were directly visualized by cryogenic transmission electron microscopy (cryo-TEM). Detailed micelle structural information was extracted from both cryo-TEM and dynamic light scattering measurements, with excellent agreement between the two techniques. Compared to aqueous solutions of the same copolymers, [BMIM][PF(6)] solutions exhibit some distinct features, such as temperature-independent micellar morphologies between 25 and 100 degrees C. As in aqueous solutions, significant nonergodicity effects were also observed. This work demonstrates the flexibility of amphiphilic block copolymers for controlling nanostructure in an ionic liquid, with potential applications in many arenas.     

Formation of Core‐Shell‐Corona Micellar Complexes through Adsorption of Double Hydrophilic Diblock Copolymers into Core‐Shell Micelles

Summary: The complexation between polystyrene‐block‐poly(acrylic acid) (PS‐b‐PAA) micelles and poly(ethylene glycol)‐block‐poly(4‐vinyl pyridine) (PEG‐b‐P4VP) is studied, and a facile strategy is proposed to prepare core‐shell‐corona micellar complexes. Micellization of PS‐b‐PAA in ethanol forms spherical core‐shell micelles with PS block as core and PAA block as shell. When PEG‐b‐P4VP is added into the core‐shell micellar solution, the P4VP block is absorbed into the core‐shell micelles to form spherical core‐shell‐corona micellar complexes with the PS block as core, the combined PAA/P4VP blocks as shell and the PEG block as corona. A model is suggested to characterize the core‐shell‐corona micellar complexes.

Schematic formation of core‐shell‐corona (CSC) micellar complexes by adsorption of PEG‐b‐P4VP into core‐shell PS‐b‐PAA micelles.     

Formation of Stable and Monodispersive Polyion Complex Micelles in Aqueous Medium from Poly(L-lysine) And Poly(Ethylene Glycol)-Poly(Aspartic Acid) Block Copolymer

Abstract

In this study, the formation of polyion complex micelles from a pair of poly(L-lysine) homopolymers (P(Lys)) and poly(ethylene glycol)-poly(aspartic acid) block copolymers (PEG-P(Asp)) with varying chain length was demonstrated in aqueous medium. There exists the lower critical chain length in the charged segments of both P(Lys) and PEG-P(Asp) to form stable polyion complex micelles in nanometric scale. The scaled average characteristic line width (ΓTK²) was independent on the detection angles for all combinations, suggesting that the formed polyion complex micelles may have a spherical shape. Furthermore, the transitional diffusion coefficient (D_T) had no concentration dependence, indicating the micelle system was free from secondary aggregates (the cluster of micelles). It is of interest that the micellar size was almost constant (ca. 50 nm) regardless of the change in the chain length of the charged segments. Size distribution was extremely narrow, and the values of variance μ₂/Γ ²) were always less than 0.1. Laser-Doppler electrophoresis measurements revealed that the polyion complex micelles were electrically neutral, suggesting that the PEG corona surrounding the polyion complex core may contribute to their stable dispersion in an aqueous medium through steric repulsion of the tethered hydrophilic chain, in this case, PEG. This system was considerably stable against the change in ionic strength, and it maintained a constant diameter in the region below 0.4 M NaCl. However, they dissociated under high ionic strength condition as 0.6 M NaCl. The system may have potential utility to include charged peptides and nucleotides in the core, delivering these biologically useful substances into a target site in the body.     

Fabrication of functional nano-objects via self-assembly of nanostructured hybrid materials

A simple route to fabricate functional nano-objects via self-assembly of block copolymer-based hybrid materials is described. In water–toluene mixtures, spheres, rod-like morphologies, and ring-like morphologies as well as vesicles of metal loaded block copolymers micelles are fabricated. The concept is generic to realize different functionalities by incorporating various inorganic components (Au, Ag, Pt, Co…) into the block copolymer matrix. A mechanism describing the formation of micellar aggregates with different morphologies is presented based on a simple force balance approach. Moreover, the composition of the solvent mixture is modified to gain control over the morphology of micellar aggregates. It was found that swelling of the micelle core with a selective cosolvent is the driving force to induce morphology transitions from spherical to rod- and ring-like structures as well as vesicles. These nano-objects can be further used as building blocks to construct well-defined structures via self-assembly in spin coated thin films. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1642–1650, 2010     

Micelle density regulated by a reversible switch of protein secondary structure

Protein secondary structures may exhibit reversible transitions that occur in an abrupt and controllable manner. In this report, we demonstrate that such transitions may be utilized in the design of a "smart" protein micellar system, in which a stimulus-induced change in protein structure triggers a rapid change in micelle compacticity and size. Specifically, recombinant DNA methods were used to prepare a protein triblock copolymer containing a central hydrophilic block and two hydrophobic end blocks derived from elastin-mimetic peptide sequences. Below the copolymer inverse transition temperature (T(t)), dilute solutions of this amphiphilic protein formed monodispersed micelles in a narrow range of R(H) of approximately 100 nm. When the the temperature was raised above T(t), an abrupt increase in micelle internal density was observed with a concomitant reduction in micelle size. This reversible change in micelle compacticity was triggered by helix-to-sheet protein folding transition. Significantly, these protein polymer-based micelles, which are rapidly responsive to environmental stimuli, establish a new mechanism for the design of controlled drug delivery vehicles.     

聚(L-丙氨酸-co-羟丙-L-谷氨酰胺)无规共聚物的两亲性及其胶束行为研究

采用丙氨酸作为疏水聚合单体,谷氨酸作为亲水聚合单体,一步开环聚合反应,合成了具有两亲性的聚氨基酸无规共聚物.利用IR,1H-NMR等方法对所合成的聚合物进行了详细的表征,结果表明两种单体都能够按照投料比参加聚合反应生成无规共聚物.对比聚丙氨酸-聚羟丙谷氨酰胺嵌段共聚物,探讨了无规共聚物与嵌段共聚物在两亲性及结构性质上的差异和特点.研究表明,聚(L-丙氨酸-co-羟丙-L-谷氨酰胺)无规共聚物与嵌段共聚物一样,具有两亲性,在水溶液中也能够形成胶束,但胶束尺寸较嵌段共聚物要小,胶束形态也不像嵌段共聚物是规整的球形.实验发现,亲疏水单体的比例对胶束的形成有很大影响,P(A10-co-HPG40)所制得的胶束分散最为均匀.所形成的胶束以疏水的聚丙氨酸为内核,亲水的聚羟丙谷氨酰胺为外壳.     

Stoichiometric polyelectrolyte complexes of ionic block copolymers and oppositely charged polyions

Micellization in dilute solutions of diblock copolymers with a polyelectrolyte and a hydrophilic nonionic blocks and oppositely charged polyions is studied using mean-field theory. In aqueous solutions the micelle core consists of the polyelectrolyte complex (PEC) while the corona is formed by hydrophilic blocks of the block copolymers. Describing PEC as a globule in the framework of the Lifshitz [Zh. Eksp. Teor. Fiz. 55, 2408 (1968)] globule theory we calculate the surface tension of the micellar core/solvent interface as a function of the polyion degree of ionization, solvent quality, and concentration of low-molecular-mass salt. The equilibrium aggregation number of starlike micelles formed by block copolymers and homopolymers of opposite charge at stoichiometric mixture compositions is found as a function of the system parameters. It is shown that micelles disintegrate upon addition of salt.     

Hybrid polyion complex micelles formed from double hydrophilic block copolymers and multivalent metal ions: size control and nanostructure

Hybrid polyion complex (HPIC) micelles are nanoaggregates obtained by complexation of multivalent metal ions by double hydrophilic block copolymers (DHBC). Solutions of DHBC such as the poly(acrylic acid)-block-poly(acrylamide) (PAA-b-PAM) or poly(acrylic acid)-block-poly(2-hydroxyethylacrylate) (PAA-b-PHEA), constituted of an ionizable complexing block and a neutral stabilizing block, were mixed with solutions of metal ions, which are either monoatomic ions or metal polycations, such as Al(3+), La(3+), or Al(13)(7+). The physicochemical properties of the HPIC micelles were investigated by small angle neutron scattering (SANS) and dynamic light scattering (DLS) as a function of the polymer block lengths and the nature of the cation. Mixtures of metal cations and asymmetric block copolymers with a complexing block smaller than the stabilizing block lead to the formation of stable colloidal HPIC micelles. The hydrodynamic radius of the HPIC micelles varies with the polymer molecular weight as M(0.6). In addition, the variation of R(h) of the HPIC micelle is stronger when the complexing block length is increased than when the neutral block length is increased. R(h) is highly sensitive to the polymer asymmetry degree (block weight ratio), and this is even more true when the polymer asymmetry degree goes down to values close to 3. SANS experiments reveal that HPIC micelles exhibit a well-defined core-corona nanostructure; the core is formed by the insoluble dense poly(acrylate)/metal cation complex, and the diffuse corona is constituted of swollen neutral polymer chains. The scattering curves were modeled by an analytical function of the form factor; the fitting parameters of the Pedersen's model provide information on the core size, the corona thickness, and the aggregation number of the micelles. For a given metal ion, the micelle core radius increases as the PAA block length. The radius of gyration of the micelle is very close to the value of the core radius, while it varies very weakly with the neutral block length. Nevertheless, the radius of gyration of the micelle is highly dependent on the asymmetry degree of the polymer: if the neutral block length increases in a large extent, the micelle radius of gyration decreases due to a decrease of the micelle aggregation number. The variation of the R(g)/R(h) ratio as a function of the polymer block lengths confirms the nanostructure associating a dense spherical core and a diffuse corona. Finally, the high stability of HPIC micelles with increasing concentration is the result of the nature of the coordination complex bonds in the micelle core.