Complexes of lysozyme with sodium (sulfamate‐carboxylate)isoprene/ethylene oxide double hydrophilic block copolymers

Complexes between sodium (sulfamate‐carboxylate)isoprene/ethylene oxide double hydrophilic block copolymers and lysozyme, a globular protein, were formed in aqueous solutions, at pH 7, because of electrostatic interactions between the anionic groups of the polyelectrolyte block of the copolymers and the cationic groups of lysozyme. The structure of the complexes was investigated as a function of the anionic/cationic charge ratio of the two components in solution and ionic strength by static, dynamic, and electrophoretic light scattering, atomic force microscopy, and fluorescence spectroscopy. The mass and size of the micellar‐like complexes depend on the mixing ratio and the molecular characteristics (molecular weight, composition, and architecture) of the copolymer used. Complexation persists at 0.15M NaCl, the value for physiological saline, as a result of additional hydrophobic interactions between the copolymers and the enzyme. Fluorescence spectroscopy measurements indicate that the secondary structure of lysozyme does not change substantially after complex formation. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 509–520, 2007     

Electrostatic complexation of a double hydrophilic block polyelectrolyte and proteins of different molecular shape

The electrostatic complexation between the polyelectrolyte block of the novel double hydrophilic copolymer quaternized poly(3,5‐bis(dimethylaminomethylene) hydroxystyrene)‐b‐poly(ethylene oxide) (QNPHOS‐PEO) and proteins of different molecular shape, that is globular bovine serum albumin (BSA) or rod‐like bovine fibrinogen (FBG), is investigated by means of dynamic, static, and electrophoretic light scattering, as well as analytical ultracentrifugation measurements. The solution behavior, structure, and properties of the formed complexes at pH 7 and 0.01 M ionic strength, as a function of the protein concentration in the solution (or equivalently the charge ratio of the two components), depend on the protein concentration and molecular characteristics. Moreover, the structure of the complexes is greatly influenced by the intrinsic structure of the block polyelectrolyte, which forms rather loose multichain aggregates, due to hydrophobic interactions. A direct correlation between the stability of the preformed complexes against the increase of the solution ionic strength and their structure is established. Finally, the spectroscopic structural investigation of both complexed proteins reveals no signs of protein denaturation upon complexation. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1515–1529     

Characterization of polymer materials by scattering techniques,with applications to block copolymers

The application of six techniques—static and dynamic light scattering, small-angle neutron and X-ray scattering, neutron and X-ray reflectivity—to the characterization of polymer materials is summarized. Emphasis is placed on the similarities and differences among the various techniques, and on recent advances in experimental practice. Twelve examples from the recent literature are described, most of which concern block copolymers. A brief introduction to block copolymer properties is also provided.     

Light scattering study of solubilization of organic molecules by block copolymer micelles in aqueous media

Block copolymers, when dissolved in a selective solvent, form spherical micelles. These micelles can selectively solubilize organic molecules otherwise insoluble in the pure solvent. In this study, we report solubilization of organic molecules by styrene-methacrylic acid block copolymer micelles in aqueous buffers. A light scattering technique was developed to determine the extent of micellar solubilization. Our results indicate that the extent of micellar solubilization depends on the chemical nature of organic molecules, specifically, on the interactions between the organic compound and polystyrene. A thermodynamic model has been developed to describe micellar solubilization. The theoretical calculation agrees reasonably well with the experimental results for two micellar samples examined. ©1995 John Wiley & Sons, Inc.     

Synthesis,self‐assembly and adsorption of PEO–PLA block copolymers onto colloidal polystyrene

A series of amphiphilic block copolymers composed of poly(ethylene oxide) and poly(lactide) were synthesized and their solution properties studied using static and dynamic light scattering. These materials self‐assemble in aqueous media with the hydrodynamic radius increasing with increasing hydrophobic fraction in the copolymer. To ascertain the potential for use of these materials as degradable coatings in delivery applications, block copolymers of varying compositions were adsorbed onto a series of colloidal polystyrene particles with varying radii, and the thickness of the adsorbed layer was determined from changes in the hydrodynamic size. The adlayer thicknesses ranged from 3 to 14 nm with varying block copolymer compositions, and colloid radii. The trends fit well with theoretical models for adlayer thickness, with the exception of the smallest colloids. In these systems, we propose that the colloids may become encapsulated into the block copolymer assembly. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 244–252, 2008     

Novel double hydrophilic block copolymers based on poly(p‐hydroxystyrene) derivatives and poly(ethylene oxide)

The synthesis of three series of double hydrophilic block copolymers (DHBCs), consisting of poly(ethylene oxide) as the neutral water soluble block and a second polyelectrolyte block of variable chemistry, is described. The synthetic scheme involves the anionic polymerization of poly(p‐tert‐butoxystyrene‐b‐ethylene oxide) (PtBOS‐PEO) amphiphilic block copolymer precursors followed by the acidic hydrolysis of the hydrophobic poly(p‐tert‐butoxystyrene) (PtBOS) block to an annealed anionic polyelectrolyte poly(p‐hydroxystyrene) (PHOS) block. The PHOS block was subsequently transformed into a high charge density annealed cationic polyelectrolyte namely poly[3,5‐bis(dimethylaminomethylene) hydroxystyrene] (NPHOS), via aminomethylation. Finally, the NPHOS block was transformed into a quenched polyelectrolyte, namely quaternized poly[3,5‐bis(dimethylaminomethylene) hydroxystyrene] (QNPHOS) block by reaction with CH₃I. The solution properties of the different series of the above block polyelectrolyte copolymers have been investigated using static, dynamic and electrophoretic light scattering, turbidimetry, and fluorescence spectroscopy. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5790–5799, 2007     

Double hydrophilic block copolymers of sodium(2‐sulfamate‐3‐carboxylate)isoprene and ethylene oxide

Poly(sodium(2‐sulfamate‐3‐carboxylate)isoprene)‐b‐poly(ethylene oxide) and poly(ethylene oxide)‐b‐poly(sodium(2‐sulfamate‐1‐carboxylate)isoprene)‐b‐poly(ethylene oxide) double hydrophilic block copolymers were prepared by selective post polymerization reaction of the polyisoprene block, of poly(isoprene‐b‐ethylene oxide) diblocks or poly(ethylene oxide‐b‐isoprene‐b‐ethylene oxide) triblock precursors, with N‐chlorosulfonyl isocyanate. The precursors were synthesized by anionic polymerization high vacuum techniques and had narrow molecular weight distributions and predictable molecular weights and compositions. The resulting double hydrophilic block copolymers were characterized by FTIR and potentiometric titrations in terms of the incorporated functional groups. Their properties in aqueous solutions were studied by viscometry and dynamic light scattering. The latter techniques revealed a complex dilute solution behavior of the novel block copolymers, resulting from the polyelectrolyte character of the functionalized PI block and showing a dependence on solution ionic strength and pH. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 606–613, 2006     

Synthesis and characteristic of double hydrophilic block copolymer with amine pendant chains

Novel double hydrophilic block copolymers with amine pendant chains were synthesized by polymerization of 4-vinyl benzylamine hydrochloric salt using 4,4′-azo-bis[4-cyanopentanoate poly（ethylene glycol） ester] as macroazoinitiator. The structures of the copolymers were characterized by ^1H NMR, FTIR spectra and acid-base titration, GPC-MALS techniques.     

Thermoresponsive polymersome from a double hydrophilic block copolymer

The article describes synthesis and thermally triggered self‐assembly of a Poly (ethylene oxide)‐block‐poly (N‐insopropylacrylamide) (PEO‐b‐PNIPAm) in aqueous medium. At rt, the polymer remains as unimer, however, at lower critical solution temperature (LCST) of PNIPAm (32 °C), it forms a rather large undefined aggregate which at slightly elevated temperature (～40 °C) converges to well defined polymersome structure (Critical aggregation concentration = 0.45 mg/mL) with hydrodynamic diameter of 40–50 nm. By lowering the temperature, initial swelling of the compact vesicle followed by reversible disassembly to unimer was noticed. The polymersome exhibits encapsulation ability to a hydrophilic dye Calcein which can be spontaneously released by lowering the temperature below cloud point. Likewise a hydrophobic dye namely 8‐Anilino‐1‐naphthalenesulfonic acid (ANS) can also be encapsulated and released by thermal trigger. Detail photoluminescence studies reveal ANS dye can be used as a generalized probe molecule for detecting LCST of a thermoresponsive polymer by “fluorescence on” above LCST even by cursory observation. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2444–2451     

Maximizing the grain growth rate during the disorder‐to‐order transition in block copolymer melts

The factors controlling grain growth during the disorder‐to‐order transition in a polystyrene‐block‐polyisoprene copolymer melt were studied with time‐resolved depolarized light scattering. The ordered phase consisted of hexagonally packed polyisoprene cylinders, and the order–disorder‐transition temperature of the block copolymer (T_ODT) was 132 ± 1 °C. Our objective was to identify the temperature at which the grain growth rate was maximized (T_max) and compare it with theoretical predictions. We conducted seeded grain growth experiments, which comprised two steps. In the first step, which lasted for 43 min, the sample was cooled from the disordered state to 124 °C. This resulted in the formation of a small number of ordered grains or seeds. This was followed by a second step in which the sample was heated to temperatures between 124 and 132 °C and the seeds grew with time. Our objective was to study grain growth at different temperatures starting from the same initial condition. The value of T_max obtained experimentally was 128 °C. The theoretically predicted value of T_max, based entirely on the rheological properties of the disordered sample and T_ODT, was also 128 °C. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2231–2242, 2001     

Miniemulsion polymerization of styrene with a block copolymer surfactant

A series of miniemulsion systems based on styrene/azobisisobutyronitrile in the presence of poly(methyl methacrylate‐b‐2‐(dimethylamino)ethyl methacrylate) as a surfactant and hexadecane (HD) as a cosurfactant were developed. For comparison, a series of pseudoconventional emulsions also were carried out with the same procedure used for the aforementioned series but without the cosurfactant (HD). Both the droplet size and shelf life were also measured. Experimental results indicate that it is possible to slow the effect of Ostwald ripening and thereby produce a stable miniemulsion with the block copolymer as the surfactant and HD as the cosurfactant. In addition, the extent to which varying the surfactant concentration and copolymer composition could affect both the polymer particle size during the polymerization and the polymerization rate was examined. Variation in the polymer particle sizes during polymerization indicates that droplet and aqueous (micellar or both homogeneous) nucleation occurs in the miniemulsion polymerization. With the same concentration of the surfactant used in the miniemulsion polymerization, the polymerization rates of systems with M₁₂B₃₆ are faster than those of systems with M₁₂B₁₂. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1818–1827, 2000     

Complexes of cationic block copolymer micelles with DNA: histone/DNA complex mimetics

The formation of complexes between cationic polymeric micelles of PS-b-PQ2VP amphiphilic block copolymers and DNA molecules in aqueous solutions is investigated at pH = 7. The physicochemical characteristics of the "polyplexes" at different DNA/polymer ratios were characterized in terms of mass, size and charge using static, dynamic and electrophoretic light scattering and AFM. The complexes are spherical and assume their maximum size and mass around the charge stoichiometric ratio. After addition of increased amounts of salt in the solutions, partial dissociation of the systems was observed. The present systems can be considered as mimetics of histone/DNA complexes formed under physiological conditions in living cells.     

Morphological transitions in aggregates of thermosensitive poly(ethylene oxide)‐b‐poly(N‐isopropylacrylamide) block copolymers prepared via RAFT polymerization

Double hydrophilic poly(ethylene oxide)‐b‐poly(N‐isopropylacrylamide) (PEO‐b‐PNIPAM) block copolymers were synthesized via reversible addition‐fragmentation chain transfer (RAFT) polymerization, using a PEO‐based chain transfer agent (PEO‐CTA). The molecular structures of the copolymers were designed to be asymmetric with a short PEO block and long PNIPAM blocks. Temperature‐induced aggregation behavior of the block copolymers in dilute aqueous solutions was systematically investigated by a combination of static and dynamic light scattering. The effects of copolymer composition, concentration (C_p), and heating rate on the size, aggregation number, and morphology of the aggregates formed at temperatures above the LCST were studied. In slow heating processes, the aggregates formed by the copolymer having the longest PNIPAM block, were found to have the same morphology (spherical “crew‐cut” micelles) within the full range of C_p. Nevertheless, for the copolymer having the shortest PNIPAM block, the morphology of the aggregates showed a great dependence on C_p. Elongation of the aggregates from spherical to ellipsoidal or even cylindrical was observed. Moreover, vesicles were observed at the highest C_p investigated. Fast heating leads to different characteristics of the aggregates, including lower sizes and aggregation numbers, higher densities, and different morphologies. Thermodynamic and kinetic mechanisms were proposed to interpret these observations, including the competition between PNIPAM intrachain collapse and interchain aggregation. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4099–4110, 2009     

Synthesis of block copolymers by the transformation of cationic polymerization into reversible atom transfer radical polymerization

Azo-containing polytetrahydrofuran (PTHF) obtained by cationic polymerization was used as a macroinitiator in the reverse atom transfer radical polymerization (RATRP) of styrene and methyl acrylate in conjunction with CuCl₂/2,2′-bipyridine as a catalyst. Diblock PTHF–polystyrene and PTHF–poly(methyl acrylate) were obtained after a two-step process. In the first step of the reaction, stable chlorine-end-capped PTHF was formed with the thermolysis of azo-linked PTHF at 65–70 °C in the presence of the catalyst. Heating the system at temperatures of 100–110 °C started the polymerization of the second monomer, which resulted in the formation of block copolymers. The decomposition behavior of the azo-linked PTHF and the structure of the block copolymers were determined by ¹H NMR and gel permeation chromatography (GPC). Kinetic studies and GPC analyses further confirmed the controlled/living nature of the RATRP initiated by the polymeric radicals. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2199–2208, 2002     

Self‐assembly in solutions of block and random copolymers during metal nanoparticle formation

The self‐assembly behavior of poly(isoprene‐b‐acrylic acid) and poly(styrene‐b‐2‐vinylpyridine) amphiphilic block copolymers, as well as a poly(styrene‐r‐2‐vinylpyridine) amphiphilic random copolymer was investigated in slightly selective organic solvents (tetrahydrofuran and toluene) in the presence of Ag and Au ions and subsequently Ag, Au metal nanoparticles, by means of dynamic light scattering. In the range of concentrations studied the copolymers exist in the form of micelles with cores composed of acrylic acid and 2‐vinylpyridine segments in equilibrium with unimers. The addition of metal ions and their subsequent transformation to metal nanoparticles shifts the equilibrium in favor of the micelles. The concentration of the inorganic components has also a considerable effect on the size of the polymeric aggregates. A similar behavior is observed for the random copolymer. Attenuated total reflectance Fourier transform infrared spectroscopy (ATR‐FTIR), UV‐visible spectroscopy, and transmission electron microscopy (TEM) give valuable additional information on the nature of the interactions between the polymeric and inorganic components, as well as on the characteristics of the metal nanoparticles and the hybrid micelles formed in each case. The presented results have a direct relation to the synthesis of metal nanoparticles under confinement by utilization of copolymer nanoreactors and appropriate solution conditions. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1515–1524, 2008     

Synthesis and characterization of hydrophilic thermotropic block copolyetheresters

The block copolyetheresters with a hard segment of poly (hexamethylene p,p′-bibenzoate) and a soft segment of poly (ethylene oxide) were prepared by melt polycondensation of dimethyl-p,p′-bibenzoate, 1,6-hexanediol, and polyethylene glycol (PEG) with molecular weights of 400, 1000, 2000, or 4000. These block copolyetheresters were characterized by intrinsic viscosity, GPC, FT-IR, ¹H-NMR, and water absorption. The thermotropic liquid crystalline properties were investigated by DSC, polarized microscope, and x-ray diffraction. The block copolyetheresters exhibit smectic liquid crystallinity due to the polyester segment. The transitions are dependent on the molar content and the molecular weight of PEG used. The block copolyetheresters show high water absorption due to the hydrophilic nature of the poly (ethylene oxide) segment. The water absorption increases with increasing PEG content. As the molecular weight of PEG increases, the water absorption increases significantly. The results indicate that the water absorption of the poly (ethylene oxide) segment in the block copolymers is affected by the presence of polyester segments. © 1995 John Wiley & Sons, Inc.     

Effect of Hydrophilic/Hydrophobic Block Ratio and Temperature on the Surface and Associative Properties of Oxyethylene and Oxybutylene Diblock Copolymers in Aqueous Media

Recent development in dispersion science and technology demands block copolymers with a variable block length and composition. To highlight that purpose, the surface active, associative, colloidal, and thermodynamic behavior of three diblock copolymers having different hydrophilic to hydrophobic ratio is reported here. Using surface tension and light scattering measurements, the micellization and adsorption behavior of polyoxyethylene and polyoxybutylene diblock copolymers of the type E_mB_n have been analyzed. Critical micelle concentration (CMC) and related thermodynamic parameters like free energy (ΔG_mic), enthalpy (ΔH_mic), and entropy (ΔS_mic) of micellization were calculated from CMC value using the closed association model. Likewise, the surface active parameters, like surface excess concentration (Γ₂), area per molecule (A₂), and thermodynamic parameters such as free energy (ΔG_ads), enthalpy (ΔH_ads), and entropy (ΔS_ads) of adsorption of polymer at the air/water interface, were also calculated at various temperatures. Static and dynamic light scattering techniques were employed for the determination of the weight-average molar (M_w), association number (N_w), polymer–water interaction (A₂), and micellar size in terms of hydrodynamic radii (R_h) of copolymer micelles. The effect of block length and solution temperature on the surface and micellar properties of these copolymers was also investigated.     

End group polarity and block symmetry effects on cloud point and hydrodynamic diameter of thermoresponsive block copolymers

Thermoresponsive block copolymers are of interest for delivery vehicles in the body. Often an interior domain is designed for the active agent and the exterior domain provides stability in the bloodstream, and may carry a targeting ligand. There is still much to learn about how block sequence and chain end identity affect micelle structure, size, and cloud points. Here, hydrophilic oligo(ethylene glycol) methyl ether acrylate and more hydrophobic di(ethylene glycol) methyl ether methacrylate monomers were polymerized to give amphiphilic block copolymers with amphiphilic chain ends. The block sequence and chain end identity were both controlled by appropriate choice of RAFT chain transfer agents to study the effect of ‘matched’ and ‘mismatched’ chain end polarity with amphiphilic block sequence. The affect of matching or mismatching chain end polarity and block sequence was studied on the hydrodynamic diameter, cloud point, and temperature range of the chain collapse on linear di‐ and triblock copolymers and star diblock polymers. The affects of matching or mismatching chain end polarity were significant with linear diblock copolymers but more complex with triblock and star copolymers. Explanations of these results may help guide others in designing thermoresponsive block copolymers. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2838–2848     

Method of determining the absolute molecular weight from gel permeation chromatograms for star‐shaped styrenic block copolymers

A gel permeation chromatography (GPC) calculation method has been developed to determine the absolute molecular weight of a star‐shaped styrenic block copolymer with GPC–ultraviolet/refractive index calibrated with linear polystyrene standards. To illustrate the simplicity of this method, we have synthesized nearly monodisperse, multiple‐arm model polymers either by linking living polymeric arms with multifunctional silicon halide or by oligomerizing the p‐chloromethylstyrene‐terminated polystyrene macromonomers. The good agreement between the absolute molecular weight determined with this calculation method and that actually measured with a multi‐angle laser light scattering device has corroborated the validity of the calculation method. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 976–983, 2003