Synthesis of pH-responsive polysilane with polyelectrolyte side chains through γ-ray-induced graft polymerization

Polysilanes with polyelectrolyte side chains are synthesized by two methods utilizing γ-ray-induced grafting and the pH responsiveness for one of those polymers is revealed mainly by investigating interfacial behavior of its monolayer at the air/water interface. In the first synthetic method, poly(methyl acrylate) is grafted onto poly(methyl-n-propylsilane) (PMPrS) through γ-ray-induced grafting, and then the PMA chains are hydrolyzed to poly(acrylic acid) resulting in the yield of ca. 97%. Thus PMPrS with polyelectrolyte side chains is successfully synthesized by the graft chain hydrolysis. The other method is the direct grafting of electrolyte monomers. Poly(methacrylic acid)-grafted PMPrS (PMPrS-g-PMAA) can be obtained through γ-ray-induced grafting of methacrylic acid monomers onto PMPrS chains, which shows the effectiveness of radiation grafting for the synthesis of polyelectrolyte graft copolymers. PMPrS-g-PMAA exhibits pH responsive behavior. In addition to the pH-dependence of water solubility, interfacial behavior also depends on the pH. Langmuir monolayers of PMPrS-g-PMAA exhibit different surface pressure-area isotherms according to the grafting yield and the pH of the subphase water. This result suggests that radiation modification is useful for fabricating polysilane-based ordered materials responsive to outer stimuli.     

Diphilic Macromolecular Brushes with a Polyimide Backbone and Poly(methacrylic acid) Blocks in Side Chains

Novel macromolecular brushes with a polyimide backbone and diphilic diblock copolymer side chains consisting of a hydrophilic block of poly(methacrylic acid) adjacent to the backbone and the outer hydrophobic block of poly(methyl methacrylate) are synthesized. The synthesis includes the grafting of poly(tert-butyl methacrylate) to the polyimide chain followed by the polymerization of methyl methacrylate on the graft copolyimide as a branched multicenter macroinitiator. Brushes with diphilic side chains are obtained via the acidic hydrolysis of ester groups in the first block of side chains. The grafting polymerization of methacrylates is performed according to the “grafting from” approach by the method of pseudoliving atom transfer radical polymerization using two methodologies of polymerization activated by either copper- or iron-containing complexes. Conditions providing the controlled regime of the polymerization processes under study are found, and pathways for the targeted regulation of the degree of polymerization of methacrylate blocks and their grafting density are determined. As is shown by dynamic light scattering and transmission electron microscopy, the macromolecules of brushes with diphilic side chains form in ethanol homotypic, obviously spherical, supramolecular micellar structures with hydrodynamic radii in the range from 40 to 120 nm depending on the length and grafting density of the two blocks in diphilic side chains.     

Covalent immobilization of chitosan on surfaces with anchoring layers of poly(glycidyl methacrylate) and maleic anhydride copolymers

The method for producing chitosan coatings on solid surfaces with anchoring layers of poly(glycidyl methacrylate) and maleic anhydride copolymers has been proposed. It is shown that, owing to a high reactivity of epoxy and anhydride groups, the efficiency of immobilization and the stability of the coatings are considerably higher than those prepared by the conventional method of chitosan grafting onto the surface modified by poly(acrylic acid). The properties of chitosan coatings are examined via atomic force microscopy, X-ray photoelectron spectroscopy, ellipsometry, and electrokinetic measurements. Depending on the anchoring layer used, the total thickness of the coatings is 6–16 nm with an rms roughness less than 1.2 nm, while the isoelectric points of the surfaces modified with chitosan are located in the pH range 5–6.     

Protein and buffer transport through anionically grafted nylon membranes

Microporous nylon 6,6 membranes were modified by grafting poly(2-acrylamido-2-methyl propane sulfonic acid (poly(AMPSA)) on the membrane surface. The poly(AMPSA) grafting on the membrane surface was confirmed by spectroscopic characterization. Several measures of the microfiltration membrane porosity indicated that the morphology was not significantly affected by the grafting procedure. Buffer fluxes through the modified membrane were very sensitive to the solution ionic strength (I) and also to the solution pH. The order of magnitude variation in buffer fluxes at different ionic strengths can be explained by charge-shielding of the poly(AMPSA) chains; at low I values, the poly(AMPSA) chains experience mutual repulsion, swell and hinder transport through the pores. Conversely, as I increases, charge-shielding allows the poly(AMPSA) chains to take a more compact conformation. The flux and rejection behavior during the protein (BSA) transport was consistent with this hypothesis and was also dependent on protein-membrane electrostatic interactions.     

Synthesis of double hydrophilic graft copolymer containing poly(ethylene glycol) and poly(methacrylic acid) side chains via successive ATRP

A well‐defined double hydrophilic graft copolymer, with polyacrylate as backbone, hydrophilic poly(ethylene glycol) and poly(methacrylic acid) as side chains, was synthesized via successive atom transfer radical polymerization followed by the selective hydrolysis of poly(methoxymethyl methacrylate) side chains. The grafting‐through strategy was first used to prepare poly[poly(ethylene glycol) methyl ether acrylate] comb copolymer. The obtained comb copolymer was transformed into macroinitiator by reacting with lithium diisopropylamine and 2‐bromopropionyl chloride. Afterwards, grafting‐from route was employed for the synthesis of poly[poly(ethylene glycol) methyl ether acrylate]‐g‐poly(methoxymethyl methacrylate) amphiphilic graft copolymer. The molecular weight distribution of this amphiphilic graft copolymer was narrow. Poly(methoxymethyl methacrylate) side chains were connected to polyacrylate backbone through stable C? C bonds instead of ester connections. The final product, poly[poly(ethylene glycol) methyl ether acrylate]‐g‐poly(methacrylate acid), was obtained by selective hydrolysis of poly(methoxymethyl methacrylate) side chains under mild conditions without affecting the polyacrylate backbone. This double hydrophilic graft copolymer was found be stimuli‐responsive to pH and ionic strength. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4056–4069, 2008     

Design of Well‐Defined Monofunctionalized Poly(3‐hexylthiophene)s: Toward the Synthesis of Semiconducting Graft Copolymers

The post‐functionalization of poly(3‐hexylthiophene) (P3HT) via various synthetic routes is reported. Well‐defined and monofunctionalized ω‐thiol‐terminated P3HT, ω‐carboxylic acid‐terminated P3HT, ω‐acrylate‐terminated P3HT, and ω‐methacrylate‐terminated P3HT are obtained in high yields through a straightforward procedure. From those, different novel P3HT‐based graft copolymers are synthesized following two routes: “grafting onto” and “grafting through” (macromonomer polymerization) methods. The synthesis of three types of graft copolymers is described. Each one has “rod” P3HT‐grafted side chains on a “coil” main chain, which can be polyisoprene, poly(vinyl alcohol), or poly(butyl acrylate). Each copolymer is characterized by size‐exclusion chromatography and NMR.     

Gas transport in surface‐modified low‐density polyethylene films with acrylic acid as a grafting agent

The modification of polyethylene by the grafting of poly(acrylic acid) onto the surface of one of the faces of low‐density polyethylene films with UV radiation is reported. The transport of oxygen, nitrogen, carbon monoxide, carbon dioxide, methane, ethane, ethylene, propane, and argon across surface‐modified films containing 3.7% poly(acrylic acid) has been investigated at several temperatures. The layer of poly(acrylic acid) grafted onto the surface of one of the faces of the films reduces the permeability coefficient of the gases by a factor of about 1/6. The sharp drop in the gas permeability as a result of the poly(acrylic acid) layer may arise either from the formation of ordered structures of the grafted chains or from the development of highly crosslinked structures. The values of the polymer–gas enthalpic interaction parameter for the modified film are higher than those for the unmodified one. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2828–2840, 2006     

Chitosan-graft-poly(L-glutamic acid) Hybrid Material and Its Self-assembly

Chitosan-graft-poly(L-glutamic acid)(CS-g-PGA) copolymer was successfully synthesized by grafting polymerization of γ-benzyl-L-glutamate N-carboxyanhydride onto the modified chitosan chains. The self-assembly behavior of such a CS-g-PGA amphiphilic copolymer was studied. The results show that spherical nanoparticles have been formed. The size of CS-g-PGA nanoparticles is found to be controlled by the grafting ratio of PGA. These bio-based polysaccharide/polypeptide hybrid nanoparticles with controllable size may have great potential application in biomedical fields, such as drug delivery systems.     

Gas transport in surface grafted polypropylene films with poly(acrylic acid) chains

This work describes the grafting reaction of poly(acrylic acid) (PA) onto the surface of polypropylene (PP) films carried out with ultraviolet radiation, using benzophenone as photoinitiator and water as solvent. By increasing the reaction time, graft percentages of 3.5, 6.5, 12.9, 19.8, 29.4, and 36.0% were obtained. Micrographs of the modified films show that grafting exclusively occurs on the PP films surface. The values of the permeability coefficient of oxygen, nitrogen, carbon dioxide, carbon monoxide, argon, methane, ethane, ethylene, and propane across the grafted films undergo a sharp drop. The interpretation of the permeation results suggest that radicals created in the tertiary carbons of the grafted chains by effect of UV light or by chain transfer reactions may highly crosslink the PA grafted layer. A rigid layer involving both strong hydrogen bonding and chains crosslinking is formed at grafting percentages of 3.5% that strongly hinders gas permeation across that layer. Destruction of hydrogen bonding by partially replacing protons of acrylic acid residues by sodium/silver cations increases the permeability of the surface grafted films. Finally, the films permselectivity is hardly affected by the grafted layer. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2421–2431, 2007     

Synthesis of molecular brushes by "grafting onto" method: combination of ATRP and click reactions

Molecular brushes (densely grafted polymers or bottle-brush macromolecules) were synthesized by the "grafting onto" method via combination of atom transfer radical polymerization (ATRP) and "click" reactions. Linear poly(2-hydroxyethyl methacrylate) (PHEMA) polymers were synthesized first by ATRP. After esterification reactions between pentynoic acid and the hydroxyl side groups, polymeric backbones with alkynyl side groups on essentially every monomer unit (PHEMA-alkyne) were obtained. Five kinds of azido-terminated polymeric side chains (SCs) with different chemical compositions and molecular weights were used, including poly(ethylene glycol)-N3 (PEO-N3), polystyrene-N3, poly(n-butyl acrylate)-N3, and poly(n-butyl acrylate)-b-polystyrene-N3. All click coupling reactions between alkyne-containing polymeric backbones (PHEMA-alkyne) and azido-terminated polymeric SCs were completed within 3 h. The grafting density of the obtained molecular brushes was affected by several factors, including the molecular weights and the chemical structures of the linear SCs, as well as the initial molar ratio of linear chains to alkynyl groups. When linear polymers with "thinner" structure and lower molecular weight, e.g., PEO-N3 with Mn = 775 g/mol, were reacted with PHEMA-alkyne (degree of polymerization = 210) at a high molar ratio of linear chains to alkynyl groups in the backbone, the brush copolymers with the highest grafting density were obtained (Y(grafting) = 88%). This result indicates that the average number of SCs was ca. 186 per brush molecule and the average molecular weight of the brush molecules was ca. 190 kg/mol.     

羧甲基香菇多糖表面修饰的聚乳酸材料的表面性能研究

制备了香菇多糖羧甲基衍生物,再通过化学接枝方法利用共价键将羧甲基香菇多糖固定在氨基化聚乳酸基材表面,得到羧甲基香菇多糖化学接枝修饰的聚乳酸材料.此外,通过在氨基化聚乳酸基材表面进行羧甲基香菇多糖与壳聚糖的层层自组装,得到生物多糖层层自组装修饰的聚乳酸材料.采用扫描电子显微镜、水接触角测量仪、抗菌活性测试、溶血试验和血栓试验等方法对被修饰聚乳酸材料的表面性能和生物性能进行了分析和比较.结果表明采用2种表面修饰方法得到的羧甲基香菇多糖修饰的聚乳酸材料的亲水性、血液相容性以及对大肠杆菌抗菌活性得到改善.与化学接枝方法相比,经过羧甲基香菇多糖与壳聚糖层层自组装修饰的聚乳酸材料具有更好的亲水性、血液相容性和抗菌活性.     

Mechanical characteristics of films based on comb-shaped poly(amidoimides) with different contents of side chromophoric groups

For films based on poly(amidoimide) with a comb-shaped structure and long side chains, the specific features of the mechanical and thermomechanical behavior and their dependence on the concentration of the above chains are studied. With variation of the composition of the material, changes in the mechanical characteristics show a nonmonotonic character. Comparison of the results of mechanical tests and densimetric measurements allows certain conclusions to be drawn about the character of variations in the structural organization of films with an increase in the concentration of side fragments in macrochains. The role of plasticization in the behavior of the above materials during heating is demonstrated. The advantages of the practical use of the above phenomena for the optimization of the regimes of thermally stimulated polarization of films are discussed.     

Loading and release of small hydrophobic molecules in multilayer films based on amphiphilic polysaccharides

We report on the loading and release behaviors of polyelectrolyte multilayers based on hydrophobically modified carboxymethylpullulan (CMP) derivatives and poly(ethyleneimine) (PEI) toward hydrophobic dye. The dye-loaded films are obtained according to two different protocols: (i) the postdiffusion approach, which involves the diffusion of the dye within preassembled self-assemblies, and (ii) the precomplexation method, which requires the formation of a water-soluble amphiphilic CMP derivative-dye complex before the multilayer buildup. In both cases, we provide clear evidence for the entrapment of the dye in hydrophobic nanoreservoirs resulting from the aggregation of decyl pendent groups grafted on CMP chains. We show that the loading capacity of the multilayers, as well as their release behavior, can be tuned by varying the grafting degree of CMP chains. Moreover, we demonstrate the possibility to trigger the subsequent release of the loaded dye molecules by varying the composition of the surrounding solution.     

Development,Validation, and Performance of Chitosan‐Based Coatings Using Catechol Coupling

The use of long‐lasting polymer coatings on biodevice surfaces has been investigated to improve material–tissue interaction, minimize adverse effects, and enhance their functionality. Natural polymers, especially chitosan, are of particular interest due to their excellent biological properties, such as biocompatibility, non‐toxicity, and antimicrobial properties. One way to produce chitosan coating is by covalent grafting with catechol molecules such as dopamine, caffeic acid, and tannic acid, resulting in an attachment ten times stronger than that of simple physisorption. Caffeic acid presents an advantage over dopamine because it allows direct chitosan grafting, due to its terminal carboxylic acid group, without the need of a linking arm, as employed in the dopamine approach. In this study, the grafting of chitosan using caffeic acid, over surfaces or in solution, is compared with dopamine grafting using poly(ethylene glycol) as a linking arm. The following coating properties are observed; covering and homogeneity are assessed by X‐ray photoelectron spectroscopy and atomic force microscopy analyses, hydrophilicity with contact angle measurements, stability with aging tests, anticorrosion behavior, and coating non‐toxicity. Results show that grafting using caffeic acid/chitosan in solution over a metallic surface may be advantageous, compared to traditional dopamine coating.     

壳聚糖不饱和羧酸盐聚集行为的研究

以半干法制备了一系列壳聚糖不饱和羧酸盐--壳聚糖水杨酸盐(a1)、壳聚糖苯甲酸盐(a2)、壳聚糖肉桂酸盐(a3)壳聚糖丙烯酸盐(a4)和壳聚糖衣康酸盐(a5).用红外光谱和紫外光谱表征了该产品的结构,以凯氏定氮法测定了羧酸的结合量.结果表明壳聚糖和不饱和羧酸盐是通过壳聚糖上的氨基和羧酸中的羧基发生了成盐反应,羧酸的结合...     

Growth and structure of surface-initiated poly(n-alkylnorbornene) films

We report the surface-initiated growth of poly(alkylnorbornene) films via ring-opening metathesis polymerization (ROMP). The films are grown by exposure of a vinyl-terminated self-assembled monolayer (SAM) on gold to Grubbs first-generation catalyst and the subsequent exposure to an alkylnorbornene monomer. We investigate the influence of alkyl side chains on the structure, barrier, surface properties, and the growth kinetics of surface-initiated ROMP-type poly(norbornene) films. Rate constants for film growth are estimated for the comparison of monomer reactivity. The rate constant for film growth decreases by 3 orders of magnitude from norbornene to decylnorbornene, indicating a strong effect of chain length on initiation and/or propagation rates. Reflectance-absorption infrared spectroscopy is used to show the molecular level packing within the poly(alkylnorbornene) films is disrupted by the alkyl side chains. Tapping-mode atomic force microscopy is used to show that norbornene, butylnorbornene, and hexylnorbornene polymerize from the surface to form dense coatings, whereas decylnorbornene polymerizes to form isolated polymer clusters. The methyl terminus of the alkyl side chains increases the hydrophobicity of the poly(alkylnorbornene) films (thetaA(H2O) = 109-114 degrees) beyond that of a typical poly(norbornene) film (thetaA(H2O) approximately 106 degrees). The additional hydrophobicity throughout the film correlates with superior resistances against redox probes (Rf approximately 105 Omega.cm2) for poly(hexylnorbornene) when compared to polynorbornene (Rf approximately 104 Omega.cm2). The resistance of the poly(decylnorbornene) film (Rf approximately 102 Omega.cm2) is consistent with its nonuniform, cluster-like morphology.     

Synthesis of multicentered polyimide initiators for the preparation of regular graft copolymers via controlled radical polymerization

Multicentered initiators for the controlled (pseudoliving) radical polymerization are synthesized via polymer analog transformation of hydroxyl-containing polyimides based on o-aminophenols. Conditions providing variations in the degree of functionalization of polyimides by initiating 2-bromoisobutyrate groups are determined, and optimum conditions for the preparation of macroinitators containing the above groups in each repeat polyimide unit are found. Via the method of controlled radical polymerization with the atom transfer on multicentered macroinitiators in the presence of complexes of univalent copper halides, graft copolymers of poly(methylmethacrylate) on polyimide backbone are obtained. Molecular-mass characteristics of graft copolymers are studied via multiple-detection size-exclusion liquid chromatography. Preparation of graft copolymers (polymer brushes) with a homogeneous grafting density and a homogeneous length of side chains necessitates grafting of the side chain on the polyimide initiator, which contains initiating groups in each repeat unit.     

Degradable cellulose‐based polymer brushes with controlled grafting densities

Cellulose‐based polymer brushes with variable grafting densities and low dispersity were synthesized by grafting poly(n‐butyl acrylate) (PBA) side chains from cellulose‐derived backbones via ATRP. Esterification of commercially available cellulose acetate with 2‐bromoisobutyryl bromide (2‐BiBB) in NMP provided cellulose‐based macroinitiators averaging one initiation site per double glucose unit. ATRP macroinitiators averaging up to 6 initiation sites per repeating double glucose unit were prepared by acylation of microcrystalline cellulose (MCC) in LiCl/DMAc solvent system with 2‐BiBB. A series of linear macroinitiators with narrow MWD were obtained by fractional precipitation process. The content of initiating sites was determined by elemental analysis. (Meth)acrylate side chains were then grafted from the cellulose‐based macroinitiators. The prepared cellulose‐based polymer brushes showed tunable degradation rates dependent on grafting density of the brush, following two different degradation pathways, either cleavage of the main chain or detachment of the side chains. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2426–2435     

Biodegradable polyesters reinforced with surface-modified vegetable fibers

Flax fibers are investigated as reinforcing agents for biodegradable polyesters (Bionolle and poly(lactic acid) plasticized with 15 wt.-% of acetyltributyl citrate, p-PLLA). The composites are obtained either by high temperature compression molding fiber mats sandwiched between polymer films, or by batch mixing fibers with the molten polymer. Fibers in composites obtained by the latter method are much shorter (140-200 microm) than those of the mats (5,000 microm). Flax fibers are found to reinforce both p-PLLA and Bionolle (i.e. tensile modulus and strength increase) when composites based on fiber mats are investigated. Conversely, analogous composites obtained by batch mixing show poor mechanical properties. The observed behavior is attributed to the combined effect of fiber length and fiber-matrix adhesion. If flax fibers with a modified surface chemistry are used, the strength of short fiber composites is seen to improve significantly because the interface strengthens and load is more efficiently transferred. Appropriate surface modifications are performed by heterogeneous acylation reactions or by grafting poly(ethylene glycol) chains (PEG, molecular weight 350 and 750). The highest tensile strength of p-PLLA composites is reached when PEG-grafted flax fibers are used, whereas in the case of Bionolle the best performance is observed with acylated fibers.     

Molecular polyimide brushes as a novel membrane material for pervaporation processes

Samples of molecular polyimide brushes with poly(methyl methacrylate) side chains with substantially different grafting densities and lengths of side chains are obtained by the atom-transfer radical polymerization of methyl methacrylate using samples of polyimide multicenter macroinitiators with different contents of initiation groups. Strong homogeneous films suitable for use as diffusion membranes for pervaporation separations of liquid mixtures are cast from solutions of polyimide brushes in dimethylformamide. Investigations are performed for films of polyimide brushes with loosely grafted short side chains or densely grafted long side chains as well as for films of a polyimide identical in its chemical structure to the backbone of polyimide brushes. It is shown that all film membranes sorb water moderately and do not sorb isopropanol. For membranes made of the polyimide and the loosely grafted brush, which is close to the polyimide in its properties, the active sorption of acetonitrile is demonstrated. It is found that all membranes exhibit high selectivities for water upon pervaporation of water–isopropanol mixtures. In addition, membranes made of the brush with densely grafted side chains show high productivity.