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.     

Molecular bottle brushes in a solution of semiflexible polyelectrolytes and block copolymers with an oppositely charged block: a molecular dynamics simulation

Using a coarse-grained model, we performed molecular dynamics simulations of the electrostatically driven self-assembly of strongly charged polyelectrolytes and diblock copolymers composed of oppositely charged and neutral blocks. Stoichiometric micelle-like complexes formed in a dilute solution represent cylindrical brushes whose conformation is determined by the linear charge density on the polyelectrolyte and by temperature. The core-shell morphology of the cylindrical brushes is proven. The core of these anisotropic micelles consists of an insoluble complex coacervate formed by the ionic chains and a shell made up of the neutral solvophilic blocks. As the concentration of macromolecules increases, the orientational ordering of ionic micelles takes place. The complexation can induce effective steric stiffening of the polyelectrolyte chains.     

Micellization through complexation of oppositely charged diblock copolymers: Effects of composition,polymer architecture,salt of different valency,and thermoresponsive block

The structural and electrical characteristics of polyelectrolyte complex micelles (PCMs) formed by mixing of oppositely charged double hydrophilic copolymers are studied by means of molecular dynamics simulations. In mixtures of linear diblock copolymers we found that the preferential aggregation number N_p of PCMs is a universal function of the ratio γ_± of the total positive to total negative charges of the mixture. The addition of divalent salts ions induces a secondary micellization. In mixtures of copolymers bearing a common neutral thermoresponsive block, micelles with contracted corona consisting of thermoresponsive blocks and complex polyelectrolyte core are formed at low salt concentration and temperature far away the biphasic regime. At high salt concentration and temperature in the biphasic regime, reversed micelles are obtained. In equimolar mixtures of linear copolymers with miktoarm stars we found that N_p of PCMs decreases as the number of charged branches of miktoarm copolymer increases. The shape of micelles progressively changes from spherical to worm-like with the increase of number of branches of miktoarm copolymers. Our findings are in full agreement with existing experimental and theoretical predictions and provides new and additional insights.     

Ionic micelles in solutions of polyelectrolytes and block copolymers with oppositely charged blocks: Computer simulation

Complexation in solutions of strongly charged polyelectrolytes and diblock copolymers composed of oppositely charged and neutral blocks were studied via the molecular dynamics method. Stoichiometric micellar complexes formed in a dilute solution represent cylindrical brushes whose conformation is determined by the linear charge density on the polyelectrolyte and by temperature. As the concentration of macromolecules increases, the orientational ordering of anisotropic ionic micelles takes place. The complexation can induce the stiffening of the polyelectrolyte chain.     

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.     

Core-Corona Micelles Formed by Self-Assembly of Random Copolymer and Homopolymer Mixtures: Dissipative Particle Dynamics Simulations

Dissipative particle dynamics simulation was applied to investigate the cooperative aggregation of amphiphilic random copolymer and homopolymer mixtures in selective solvents. The amphiphilic random copolymers were set to contain more hydrophilic segments. The effects of the contents of homopolymers, the chain length of amphiphilic random copolymers, the interaction parameters, as well as the simulation time, on the cooperative aggregation were systematically studied with dissipative particle dynamics simulation method. The results showed that core-corona micelles could be formed with the addition of homopolymers, where the homopolymers accumulate at the core and the amphiphilic random copolymers as the corona. This work demonstrated that the morphology and the size of the micelles could be tuned by the controlled addition of homopolymers in the process of self-assembly.     

From well‐defined diblock copolymers prepared by a versatile atom transfer radical polymerization method to supramolecular assemblies

The synthesis of well‐defined diblock copolymers by atom transfer radical polymerization (ATRP) was explored in detail for the development of new colloidal carriers. The ATRP technique allowed the preparation of diblock copolymers of poly(ethylene glycol) (PEG) (number‐average molecular weight: 2000) and ionic or nonionizable hydrophobic segments. Using monofunctionalized PEG macroinitiator, ionizable and hydrophobic monomers were polymerized to obtain the diblock copolymers. This polymerization method provided good control over molecular weights and molecular weight distributions, with monomer conversions as high as 98%. Moreover, the copolymerization of hydrophobic and ionizable monomers using the PEG macroinitiator made it possible to modulate the physicochemical properties of the resulting polymers in solution. Depending on the length and nature of the hydrophobic segment, the nonionic copolymers could self‐assemble in water into nanoparticles or polymeric micelles. For example, the copolymers having a short hydrophobic block (5 < degree of polymerization < 9) formed polymeric micelles in aqueous solution, with an apparent critical association concentration between 2 and 20 mg/L. The interchain association of PEG‐based polymethacrylic acid derivatives was found to be pH‐dependent and occurred at low pH. The amphiphilic and nonionic copolymers could be suitable for the solubilization and delivery of water‐insoluble drugs, whereas the ionic diblock copolymers offer promising characteristics for the delivery of electrostatically charged compounds (e.g., DNA) through the formation of polyion complex micelles. Thus, ATRP represents a promising technique for the design of new multiblock copolymers in drug delivery. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3861–3874, 2001     

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.     

Mixed micelles of oppositely charged poly(N‐isopropylacrylamide) diblock copolymers

Mixed micelle formation between two oppositely charged diblock copolymers that have a common thermosensitive nonionic block of poly(N‐isopropylacrylamide) (PNIPAAM) has been studied. The block copolymer mixed solutions were investigated under equimolar charge conditions as a function of both temperature and total polymer concentrations by turbidimetry, differential scanning calorimetry, two‐dimensional proton nuclear magnetic nuclear Overhauser effect spectroscopy (2D ¹H NMR NOESY), dynamic light scattering, and small angle X‐ray scattering measurements. Well‐defined and electroneutral cylindrical micelles were formed with a radius and a length of about 3 nm and 35 nm, respectively. In the micelles, the charged blocks built up a core, which was surrounded by a corona of PNIPAAM chains. The 2D ¹H NMR NOESY experiments showed that a minor block mixing occurred between the core blocks and the PNIPAAM blocks. By approaching the lower critical solution temperature of PNIPAAM, the PNIPAAM chains collapsed, which induced aggregation of the micelles. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1457–1469     

Probing solubilization sites in block copolymer micelles using fluorescence quenching

The solubilization sites provided by micelles formed by a diblock copolymer with one neutral hydrophobic block, polystyrene, and one charged hydrophilic block, poly(acrylic acid) or poly(methacrylic acid), have been studied by fluorescence quenching of pyrene by polar and nonpolar quenchers. Pyrene solubilized into these micelles is distributed between the inner corona and the micelle core. The fraction of pyrene residing in the inner corona is almost unity for star micelles, where the corona-forming blocks are larger than the core-forming blocks, and around 0.5 for crew-cut micelles where the opposite situation prevails. The kinetics of the quenching process depends on the pyrene location, i.e. is static in the micelle core, and largely dynamic in the inner corona at low quencher concentration. The rate constants for fluorescence quenching by nitromethane are shown to increase with increasing pH.     

Oil-in-water microemulsions stabilized by charged diblock copolymers

We present here oil-in-water microemulsions stabilized by charged diblock copolymers alone, along with their structural characterization by small-angle neutron scattering measurements. They consist of swollen spherical micelles containing small amounts of oil in their core, which is surrounded by a corona of stretched polyelectrolyte chains. Structural changes, including core size variations, are evidenced when using a cosurfactant, or upon addition of salt, through a contraction of the charged corona. Attempts to relate the micellar structure to the individual copolymer characteristics are also presented, and show that the size of the hydrophobic block mainly determines that of the micelles.     

Self-assembly of charged amphiphilic diblock copolymers with insoluble blocks of decreasing hydrophobicity: from kinetically frozen colloids to macrosurfactants

We have investigated the self-assembly properties in aqueous solution of amphiphilic diblock copolymers with insoluble blocks of different hydrophobicity and demonstrated that the condition to obtain dynamic micelles is to design samples with insoluble blocks of low enough hydrophobicity. We focus here on results with new water-soluble amphiphilic diblock copolymers poly(diethyleneglycol ethylether acrylate)-b-poly(acrylic acid), or PDEGA-b-PAA. The physical characteristics of PDEGA-b-PAA micelles at high ionization have been determined by small angle neutron scattering (SANS). We show that PDEGA-b-PAA samples form micelles at thermodynamic equilibrium. The critical micelle concentrations (CMCs) decrease strongly with ionic strength and temperature due to a solvent quality decrease for, respectively, the corona and the core. This behavior of reversible aggregation is remarkable as compared to the behavior of kinetically frozen aggregation that has been widely observed with samples of similar architecture and different hydrophobic blocks, for example, poly(styrene)-b-poly(acrylic acid), PS-b-PAA, and poly(butyl acrylate)-b-poly(acrylic acid), PBA-b-PAA. We have measured the interfacial tension between water and the homopolymers PDEGA and PBA at, respectively, 3 and 20 mN/m at room temperature, which permits one to estimate the energy cost to extract a unimer from a micelle. The results are consistent with a micelle association that is fast for PDEGA-b-PAA and kinetically frozen PBA-b-PAA. Hence, PDEGA-b-PAA samples form a new system of synthetic charged macrosurfactant with unique properties of fast dynamic association, tunable charge, and water solubility even at temperatures and NaCl concentrations as high as 65 °C and 1 M.     

Temperature-dependent micellar structures in poly(styrene-b-isoprene) diblock copolymer solutions near the critical micelle temperature

The temperature dependence of the micelle structures formed by poly(styrene-b-isoprene) (SI) diblock copolymers in the selective solvents diethyl phthalate (DEP) and tetradecane (C14), which are selective for the PS and PI blocks, respectively, have been investigated by small angle neutron scattering (SANS). Two nearly symmetric SI diblock copolymers, one with a perdeuterated PS block and the other with a perdeuterated PI block, were examined in both DEP and C14. The SANS scattering length density of the solvent was matched closely to either the core or the corona block. The resulting core and corona contrast data were fitted with a detailed model developed by Pedersen and co-workers. The fits provide quantitative information on micellar characteristics such as aggregation number, core size, overall size, solvent fraction in the core, and corona thickness. As temperature increases, the solvent selectivity decreases, leading to substantial solvent swelling of the core and a decrease in the aggregation number and core size. Both core and corona chains are able to relax their conformations near the critical micelle temperature due to a decrease in the interfacial tension, even though the corona chains are always under good solvent conditions.     

Influence of a strong polyelectrolyte block on the formation and properties of polymer micelles with a mixed corona

Joint micellization of two amphiphilic diblock copolymers is studied by velocity sedimentation, transmission electron microscopy, electrophoretic mobility measurements, and static light scattering. One of the diblock copolymers is a strong polyelectrolyte (polystyrene-block-poly(N-ethyl-4-vinylpyridinium bromide)), while the second one is a weakly charged or uncharged copolymer (polystyrene-block-poly(acrylic acid) or polystyrene-block-poly(4-vinylpyridine)). It is shown that the mixing of the diblock copolymers in a selective aqueous-organic solvent (DMF-methanol-water) leads to the formation of joint (hybrid) micelles and that the composition of these micelles is close to the composition of the polymer mixture. Micelles consist of an insoluble polystyrene core and a mixed corona composed of blocks of a strong polyelectrolyte and a weakly charged or uncharged copolymer. Aqueous dispersions of mixed micelles are obtained with the use of the dialysis technique, the spherical morphology of the micelles is ascertained, and their three-layered structure is proposed. The nonlinear dependence of the molecular mass of micelles on their composition is found. The decisive effect of electrostatic repulsion between strong polyelectrolyte units on the thermodynamics of micellization and the dispersion stability and molecular-mass characteristics of the mixed micelles is demonstrated.     

Physicochemical properties of pH-controlled polyion complex (PIC) micelles of poly(acrylic acid)-based double hydrophilic block copolymers and various polyamines

The physicochemical properties of polyion complex (PIC) micelles were investigated in order to characterize the cores constituted of electrostatic complexes of two oppositely charged polyelectrolytes. The pH-sensitive micelles were obtained with double hydrophilic block copolymers containing a poly(acrylic acid) block linked to a modified poly(ethylene oxide) block and various polyamines (polylysine, linear and branched polyethyleneimine, polyvinylpyridine, and polyallylamine). The pH range of micellization in which both components are ionized was determined for each polyamine. The resulting PIC micelles were characterized using dynamic light scattering and small-angle X-ray scattering experiments (SAXS). The PIC micelles presented a core–corona nanostructure with variable polymer density contrasts between the core and the corona, as revealed by the analysis of the SAXS curves. It was shown that PIC micelle cores constituted by polyacrylate chains and polyamines were more or less dense depending on the nature of the polyamine. It was also determined that the density of the cores of the PIC micelles depended strongly on the nature of the polyamine. These homogeneous cores were surrounded by a large hairy corona of hydrated polyethylene oxide block chains. Auramine O (AO) was successfully entrapped in the PIC micelles, and its fluorescence properties were used to get more insight on the core properties. Fluorescence data confirmed that the cores of such micelles are quite compact and that their microviscosity depended on the nature of the polyamine. The results obtained on these core–shell micelles allow contemplating a wide range of applications in which the AO probe would be replaced by various cationic drugs or other similarly charged species to form drug nanocarriers or new functional nanodevices.     

Electrostatic self-assembly of neutral and polyelectrolyte block copolymers and oppositely charged surfactant

We investigated the phase behavior and the microscopic structure of the colloidal complexes constituted from neutral/polyelectrolyte diblock copolymers and oppositely charged surfactant by dynamic light scattering (DLS) and small-angle neutron scattering (SANS). The neutral block is poly(N-isopropylacrylamide) (PNIPAM), and the polyelectrolyte block is negatively charged poly(acrylic acid) (PAA). In aqueous solution with neutral pH, PAA behaves as a weak polyelectrolyte, whereas PNIPAM is neutral and in good-solvent condition at ambient temperature, but in poor-solvent condition above approximately 32 degrees C. This block copolymer, PNIPAM-b-PAA with a narrow polydispersity, is studied in aqueous solution with an anionic surfactant, dodecyltrimethylammonium bromide (DTAB). For a low surfactant-to-polymer charge ratio Z lower than the critical value ZC, the colloidal complexes are single DTAB micelles dressed by a few PNIPAM-b-PAA. Above ZC, the colloidal complexes form a core-shell microstructure. The core of the complex consists of densely packed DTA+ micelles, most likely connected between them by PAA blocks. The intermicellar distance of the DTA+ micelles is approximately 39 A, which is independent of the charge ratio Z as well as the temperature. The corona of the complex is constituted from the thermosensitive PNIPAM. At lower temperature the macroscopic phase separation is hindered by the swollen PNIPAM chains. Above the critical temperature TC, the PNIPAM corona collapses leading to hydrophobic aggregates of the colloidal complexes.     

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.     

Polyelectrolyte micelles in salt‐free solutions: Micelle size and electrostatic potential

The structural and electrical characteristics of polyelectrolyte micelles formed by diblock copolymers with one charged block and one solvophobic block are studied by the means of molecular dynamics simulations using the Primitive model at different Bjerrum lengths. The properties of interest are the mean aggregation number, the shape, the electrical potential as a function of the distance of the micelle's center of mass and the zeta potential. We found that for partially charged short A blocks the micelles’ mass distribution function is at least bimodal, indicating the coexistence of small and large micelles in agreement with theoretical and experimental findings. The zeta potential is not a monotonic function of the length of the charged block. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 924–934     

Controlled stacking of charged block copolymer micelles

Using poly(acrylic acid)-b-poly(methyl acrylate)-b-polystyrene (PAA-b-PMA-b-PS) triblock copolymers or a mixture of different molecular weight PAA-b-PS diblock copolymers, stacks of polymeric micellar assemblies, such as disks and Y-shaped cylinders, were formed through intermicellar interactions. Whereas micelles hierarchically stacked together, micellar interactions within the stack defined a uniform micelle geometry and size for up to micrometers in length. The kinetic pathway dependence and stability of the stacked assemblies were studied, and possible intermicellar interactions between micelles within the stacks are proposed.