Free electrophoresis of mixtures of poly(methacrylic acid) and 2-hydroxyethyl methacrylate-methacrylic acid copolymers

The method of free electrophoresis was used in an analysis of mixtures of poly(methacrylic acid) and copolymers of methacrylic acid with 2-hydroxyethyl methacrylate. The methacrylic acid content in the copolymers was 73.5, 48, 25, and 7.5 mole %. The effect of the potential gradient and ionic strength was examined, and conditions under which the individual components of the mixture can be electrophoretically separated were determined.     

Hypercoiled structures in aqueous solutions of 2-hydroxyethyl methacrylate-methacrylic acid copolymers at low metnacrylic acid content

The behavior of solutions of 2-hydroxyethyl methacrylate-methacrylic acid copolymers in aqueous 2–8M urea was investigated at temperatures ranging from 10 to 50°C at pH from 3 to 8. The molar fraction of methacrylic acid in the copolymer was 0.045 at most. The values of the intrinsic viscosity and Huggins coefficient were determined. Under these conditions, the poly-(2-hydroxyethyl methacrylate) molecules are in a hypercoiled state. In copolymers at a low degree of dissociation, the methacrylic acid units make the degree of coiling even higher, but in the dissociated state this degree is much lower. Hypercoiling is interpreted as a consequence of the association of hydrophobic groups in the molecule of copolymers.     

Amphiphilic polysilane-methacrylate block copolymers — Formation and interesting properties —

Several polysilane block copolymers have been prepared by the newly developed method, anionic polymerization of masked disilenes. Especially amphiphilic block copolymers of poly(1,1-dimethyl-2,2-dihexyldisilene) and poly methacrylate are focused. Poly(1,1-dimethyl-2,2-dihexyldisilene)-b-poly(2-hydroxyethyl methacrylate) (PMHS-b-PHEMA) is the first example of the amphiphilic polysilane copolymer that can form micelles in polar solvents. Poly(1,1-dimethyl-2,2-dihexyldisilene)-b-poly(methacrylic acid) (PMHS-b-PMAA) is more polar than (PMHS-b-PHEMA), soluble in water to form micelles. The cross-linking reaction of (PMHS-b-PMAA) with 1,10-diaza-4,7-dioxadecane and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride afforded the first shell cross-linked micelles (SCM) of polysilane. In addition to interesting properties, SCM is indicated to be able to form hollow sphere particles (hollow shell cross-linked micelles, HSCM) by a photochemical process. Reversible encapsulation of guest molecules by SCM and HSCM is demonstrated. Finally, SCM can be used as the template for the synthesis of metal nanoparticles, which may be used as catalysts.     

Tuning surface interactions to control shape and array behavior of diblock copolymer micelles on a silicon substrate

The micellar shape of liquid crystalline diblock copolymers, PEO_m-b-PMA(Az)_n, consisting of high surface energy components was controlled by tuning surface interactions. On a fluorinated surface, the diblock copolymers formed ordered arrays of spherical micelles consisting of PEO cores surrounded by PMA(Az) coronas. Gold ions could be doped into the PEO cores by immersion in a solution of the gold ion. The Au³⁺-doped micelles were subsequently etched and reduced by VUV radiation to form hexagonally ordered gold nanodots.     

Coil-globule transition in a realistic model of N-isopropylacrylamide: Numerical simulation

A number of homopolymers and copolymers are studied in numerical experiments with allowance for the realistic chemical structure of macromolecules. The method of molecular dynamics is used to determine the temperature of the coil-globule transition in a single macromolecule of N-isopropylacrylamide, as well as to study the coil-globule transition temperature in relation to the degree of fragmentation of N-isopropylacrylamide and methacrylic acid copolymers.     

Complex nanostructured materials from segmented copolymers prepared by ATRP

The development of new controlled/living radical polymerization processes, such as Atom Transfer Radical Polymerization (ATRP) and other techniques such as nitroxide mediated polymerization and degenerative transfer processes, including RAFT, opened the way to the use of radical polymerization for the synthesis of well-defined, complex functional nanostructures. The development of such nanostructures is primarily dependent on self-assembly of well-defined segmented copolymers. This article describes the fundamentals of ATRP, relevant to the synthesis of such systems. The self-assembly of block copolymers prepared by ATRP is illustrated by three examples. In the first, block copolymers of poly(butyl acrylate) with polyacrylonitrile phase separate, leading to spherical, cylindrical or lamellar morphologies, depending on the block copolymer composition. At a higher temperature, polyacrylonitrile block converts to nanostructured carbon clusters, whereas poly(butyl acrylate) block serves as a sacrificial block, aiding the development of designed nanostructures. In the second example, conductive nanoribbons of poly(n-hexylthiophene) surrounded by a matrix of organic polymers are formed from block copolymers prepared by ATRP. The third example describes an inorganic-organic hybrid system consisting of hard nanocolloidal silica particles (20 nm) grafted by ATRP with well-defined polystyrene-poly(benzyl acrylate) block copolymer chains (1000 chains per particle). Silica cores in this system are surrounded by a rigid polystyrene inner shell and softer polyacrylate outer shell. Received 9 July 2002 Published online: 11 March 2003     

Effect of the processes of orientation of nonlinear optical fragments of a side chain in comb-shaped polymers of the methacrylic series on the second-harmonic generation in thin films

New comblike copolymers of methacrylic acid esters with an optically nonlinear chromophore—a derivative of the 4′-(4-nitrobenzylideneamino)phenol—in a side chain were obtained. Processes of forced orientation of nonlinear optical chromophores covalently bonded with the main chains in an electric field and the effects of the conditions of orientation on the nonlinear second-order optical activity of the polymer films were studied in some detail. The existence of a correlation between the chemical structure and the composition of the copolymers with the magnitude and the stability of the surface electron potential of the corresponding films was shown. It was established that a maximum extent of orientation of chromophores in the bulk of the polymer and, as a consequence, a high intensity of the second-harmonic signal were achieved when the thickness of the region of the uniform electric field maximally approached the thickness of the sample.     

Direct opal-like structures consisting of monodisperse polymer particles and synthesis of the related inverse structures

Three-dimensional periodic solid-state film structures with a face-centered cubic lattice and a high degree of perfection have been prepared from monodisperse particles of styrene copolymers with methacrylic acid. It has been shown that these structures can be successfully used not only as model objects for studying specific features of light propagation in photonic crystals but also as templates for synthesizing inverse opal-like structures. The influence of the degree of hydrophilization of the surface layer of polymer particles forming a polymer template and the template synthesis conditions on the quality of an inverse opal-like TiO₂-based structure has been analyzed.     

Third harmonic generation in copolymer films with optically nonlinear N-substituted 4-nitroazobenzene in the side and main polymer chains

The third-order nonlinear optical susceptibility χ⁽³⁾(3ω; ω, ω, ω) of two types of copolymer films containing optically nonlinear N-substituted nitroazobenzene in the side (methacrylic series copolymers) and main (copolyimidoamido esters) polymer chains is investigated using the third harmonic generation method at a wavelength of 1.064 μm. __________ Translated from Fizika Tverdogo Tela, Vol. 44, No. 2, 2002, pp. 379–382. Original Russian Text Copyright ? 2002 by Lebedeva, Loretsyan, Ivanova, Romashkova, Lukoshkin, Kudryavtsev.     

Dielectric properties and conductivity of styrene-methacrylic acid copolymers and partially neutralized salts

Dielectric and conductivity measurements have been carried out on styrene-methacrylic acid copolymers and their salts in the glass transition region, stressing the comparison of polymers neutralized to different extents. A simple monomer-dimer equilibrium between carboxylic acid groups is applicable to the pure acid polymers, which explains the increase of both the glass transition temperature and of the dielectric strength with concentration of methacrylic acid. The dielectric data indicate that very few sodium carboxylate groups can dissolve in the matrix of the pure salt, whereas the presence of carboxylic acid groups in partly neutralized polymers enhances the dissolution of the salt groups in the matrix. Considerable differences are observed between the partly neutralized polymer and the blend consisting of pure acid and pure salt copolymers, which suggests that exchange of cations between acid and salt groups is quite slow even at high temperatures. The conductivity of the ionomers appears to be related to the diffusion of carriers through the matrix.     

Triblock copolyampholytes from 5-(N,N-dimethylamino)isoprene, styrene, and methacrylic acid: Synthesis and solution properties

ABC triblock copolymers of the type poly[5-(N,N-dimethylamino)isoprene]-block-polystyrene-block-poly(tert-butyl methacrylate) (AiST) were synthesized and hydrolyzed to yield poly[5-(N,N-dimethylamino)isoprene]-block-polystyrene-block-poly(methacrylic acid) (AiSA) triblock copolyampholytes. Due to a complex solubility behavior the solution properties of these materials had to be investigated in THF/water solvent mixtures. Potentiometric titrations of AiSA triblock copolyampholytes showed two inflection points with the A block being deprotonated prior to the Ai hydrochloride block thus forming a polyzwitterion at the isoelectric point (iep). The aggregation behavior was studied by dynamic light scattering (DLS) and freeze-fracture/transmission electron microscopy (TEM). Large vesicular structures with almost pH-independent radii were observed. Received 15 March 2000     

Copolyacrylates with phenylalanine and anthracene entities prepared by ATRP and microwave irradiation

In this study, two amino acid copolymers containing anthracene incorporated either on the one end, poly(N-acryloyl-l-phenylalanine-co-methyl methacrylate)-1 or as pendant groups, poly-(N-acryloyl-l-phenylalanine-co-methyl methacrylate)-2 were prepared directly from N-acryloyl-l-phenylalanine (APhe) and methyl methacrylate (MMA) through atom transfer radical polymerization (ATRP) and microwave-assisted synthesis. In the first case, 9-(chloromethyl)anthracene was used as an ATRP-initiator to obtain a copolymer that contains amino acid sequences and anthracene end-capped units (0.03 molar fraction). Rapid synthesis of copolymer under microwave irradiation (250 W) in the presence of 1,1′-azobis(cyclohexanecarbonitrile) used as an initiator was followed of a functionalization of the formed copolymer with an anthracene derivative yielding copolyacrylate with pendant anthracene (0.02 molar fraction). The structure of the copolymers was verified by ¹H NMR, UV-Vis and FTIR spectroscopy, gel permeation chromatography (GPC), and fluorescence spectroscopy. The fluorescence quenching process of anthracene which exists in copolymers by FeCl₃, cobalt acetate, nitrobenzene, maleic anhydride, diethylaniline and nitromethane in DMF solutions shows that this involves an electron transfer between the excited state anthracene and the present transitional metal cations, more efficiently being FeCl₃ for poly-(APhe-co-MMA)-1 and cobalt acetate for the latter copolymer.     

Surface properties of ionomers based on styrene-b-acrylic acid copolymers obtained by copolymerization in emulsion

Surface properties of styrene-b-acrylic acid copolymers obtained in emulsion and suitable ionomers before and after UV-irradiation were studied by measurements of contact angles and FTIR-ATR spectroscopy.The research focused on the influence of different content of carboxylic acid groups in copolymers, of various types and contents of alkali metal salts in ionomers and of cesium acrylate or methacrylate in ionomers on hydrophilicity of the surfaces of these samples and the course of photodegradation in them.Hydrophilicity of initial copolymer surfaces was higher than this of polystyrene as a result of presence of carboxylic acid groups, which also made the surfaces of these copolymers more sensitive to UV-irradiation.Hydrophilicity of the surfaces of ionomers containing cesium acrylates depended on the content of cesium salt in the samples. The course of ionomer photooxidation was also dependent on the content of this salt.The surface of ionomer containing cesium methacrylate was more polar than this of ionomer containing cesium acrylate.Styrene-based ionomers containing 3.7 mol% of various alkali metal acrylates had less polar surfaces than initial copolymer and they were also more resistant to UV-irradiation in comparison to the initial copolymer.Copolymers obtained in emulsion and suitable ionomers had more polar surfaces and they were more sensitive to UV-light compared to copolymers obtained in bulk and their ionomers.     

Stable and pH-responsive core–shell nanoparticles based on HEC and PMAA networks via template copolymerization

Taking advantage of the specific hydrogen bonding interactions, stable and pH-responsive core–shell nanoparticles based on hydroxyethyl cellulose (HEC) and polymethacrylic acid (PMAA) networks, with a 〈D _h 〉 size ranging from 190 to 250 nm, can be efficiently prepared via facile one-step co-polymerization of methacrylic acid (MAA) and N,N′-methylenebisacrylamide (MBA) on HEC template in water. Using dynamic light scattering, electrophoretic light scattering, fluorescence spectrometry, thermo-gravimetric analysis, TEM, and AFM observations, the influence of crosslinker MBA as well as the reaction parameters were studied. The results show that after the introduction of crosslinker MBA, the nanoparticles became less compact; their size exhibited a smaller pH sensitivity, and their stability against pH value was improved greatly. Furthermore, the size, structure, and pH response of the nanoparticles can be adjusted via varying the reaction parameters: nanoparticles of smaller size, more compact structure, and higher swelling capacity were produced as pH value of the reaction medium increased or the HEC/MAA ratio decreased; while nanoparticles of smaller size, less compact structure and smaller swelling capacity were produced as the total feeding concentration increased.     

聚苯乙烯-聚丁二烯嵌段共聚物的固体NMR研究

采用我们前期发展的测定多相高聚物中界面相厚度及相区尺寸的NMR新方法对两种不同嵌段结构的聚苯乙烯-聚丁二烯嵌段共聚物进行了研究,并与关于界面相厚度的高分子物理理论结果进行对比. 该NMR方法采用偶极滤波-自旋扩散技术分别测定非界面相的柔性区与界面相中质子的百分含量,然后根据界面相与柔性相的几何关系计算界面相厚度. 研究结果表明这两种嵌段共聚物具有几乎相同的界面相厚度,该结果与Helfand等人关于多相高聚物中界面相厚度的自洽场理论预言基本符合.     

Aggregating block copolymers as model systems to study polymer brush dynamics

Summary A-B block copolymers in a selective solvent—good for the B-species and bad for the A-species—form micellar aggregates with a compact A-core with a corona (brush) of B ?hairs? reaching into the solvent. Whereas polystyrene(PS)-polyisoprene(PI) in decane forms spherical micelles with a PS core of about 10 nm radius, polyethylene(PE)-polyethylenepropylene(PEP) forms micellar platelets, the shape of which is goverend by the habitus of PE crystallites forming the core. These planar aggregates have large (several hundred nanometers) lateral extension and a core thickness in the range of 10 nm. Both systems are model systems for polymer brushes, either on a spherical surface or planar. Neutron spin-echo experiments allow for the investigation of the dynamics of the brushes which reflects their viscoelastic properties. Results of neutron small-angle and spin-echo investigations are reported. The brush dynamics is explained using a model based on an idea of de Gennes describing the brush properties in terms of scaling relations for osmotic pressure and viscosity of a semi-dilute solution with inhomogeneous density. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Study of photooxidation of styrene-butadiene copolymers by surface pressure measurements at the air-water interface

Block and random copolymers of butadiene and styrene as well as polybutadiene and polystyrene homopolymers have been investigated with respect to their monolayer properties and photooxidation behavior. Whereas polystyrene and block copolymers of styrene and butadiene form stable monolayers, polybutadienes and random copolymers do not interact with the aqueous subphase. The monolayer properties of block copolymers with different styrene content indicate that polybutadiene also contributes to the surface pressure. Photo-oxidation of random and block copolymers of styrene and butadiene leads to a significant enhancement in surface pressure of the monolayers due to the generation of groups which can effectively interact with the aqueous surface. FTIR spectral studies show the formation of carbonyl, hydroxyl, and hydroperoxyl groups in the polymers on photooxidation. A comparison of the pressure-area isotherms of random and block copolymers oxidized in solution indicates that there is an energy transfer from butadiene to styrene units in the case of random copolymers, resulting in a protective effect of butadiene units from oxidation. In addition, in the monolayers of oxidized block copolymers, a phase transition occurs which is attributed to the extrusion of polystyrene blocks from the monolayer. The surface pressure-area isotherms and the rates of photooxidation are strongly dependent on the microstructure of polybutadiene as well as on whether oxidation is performed in solution or at the oxygen-water interface.     

Multilayer dielectric cylindrical mirrors based on omnidirectional reflection from a one-dimensional photonic crystal

A multilayer dielectric cylindrical mirror (MDCM) based on the one-dimensional omnidirectional reflection of a photonic crystal is presented. In this case, the refractive indices of the two materials are 1.6 (polystyrene) and 4.6 (tellurium), and the corresponding optimized thicknesses are 0.75a and 0.25a. A very high reflectance over a wide frequency range is observed. In this case, a is the lattice constant of the photonic crystal. In this band, the MDCM has good reflection and focal properties. Therefore, it is feasible to use the MDCM for integrated waveguide devices. As an example, an etched diffraction grating demultiplexer based on the MDCM is also proposed. Both the operational principle and design of the device are introduced. This provides a method for designing compact integrated waveguide devices.     

Self-assemblies of magnetic nanoparticles and di-block copolymers: Magnetic micelles and vesicles

Magnetic nanocomposites are obtained by the self-assembly in water of polypeptide-based di-block copolymers polybutadiene-b-poly(glutamic acid) combined with hydrophobic γ-Fe₂O₃ nanoparticles. These hybrid supramolecular objects are either—(3D) spherical micelles filled with a hydrophobic ferrofluid at a concentration as high as 45 vol% or—hollow vesicles with a (2D) magnetic membrane. In this last case, the organic amphiphile copolymers are able to confine the hydrophobic nanoparticles within the thin layer of polybutadiene blocks. We probe these objects by atomic force microscopy, by small-angle neutron scattering (SANS) and by light scattering. Furthermore, anisotropic SANS data bring the experimental evidence of the capability to modify the shape of the mineralized membranes in response to a magnetic field intensity as low as 290 G.     

Design of a compact polarization splitter based on the dual-elliptical-core photonic crystal fiber

We propose a compact polarization splitter based on dual-elliptical-core photonic crystal fiber. Two elliptical cores are introduced to increase the difference of effective index between x-polarized and y-polarized mode and three elliptical modulation air holes are used to control the power transfer between the two cores. By optimizing the structure parameters, the length of the polarization splitter is distinctly shortened. Numerical results demonstrate that the compact splitter has the length of 775 μm and up to 50 dB extinction ratio at the central wavelength of 1.55 μm. The corresponding bandwidth of 32 nm could be achieved from the wavelength of 1.534–1.566 μm with the extinction ratio over 20 dB