红外光谱法研究重氮树脂自组装膜的光化学反应

将具有导电功能的聚(4-羧酸钠苯基)乙炔阴离子(PCPA)与具有生物活性的DNA聚阴离子交替与重氮树脂聚阳离子(DR)进行自组装,可以得到层重复单元为DR／DNA／DR／PCPA的三夹层聚电解质自组装膜。重氮树脂聚阳离子在紫外光照射下可与聚阴离子发生光化学反应,使层与层之间的离子键连接转化为共价键连接,从而制备稳定的纳米级超薄膜。本文用红外光谱法对此类聚电解质自组装膜的光化学反应过程进行了研究。     

Conformational energetics of interpolyelectrolyte complexation between ι-carrageenan and poly(methylaminophosphazene) measured by high-sensitivity differential scanning calorimetry

The interaction of poly(methylaminophosphazene) hydrochloride (PMAP·HCl) of varying degrees of ionization (f) with the potassium salt of ι-carrageenan was studied by high-sensitivity differential scanning calorimetry at a KCl concentration of 0.15 M, which is included for the purpose of stabilizing the helix conformation of the polysaccharide up to 55 °C. The conditions of strong (pH 3.8, I = 0.15), moderate (pH 7.4, I = 0.15), and weak (pH 7.4, I = 0.25) electrostatic interactions of the polyelectrolytes were considered. The thermodynamic parameters of the helix-coil transition of ι-carrageenan were determined as a function of the polycation/polyanion ratio. We show that the interpolyelectrolyte reaction between PMAP·HCl and ι-carrageenan results in a complete unfolding of the polysaccharide helix under conditions of strong electrostatic interaction and increases its stability under conditions of medium and weak electrostatic interactions. The formation of stoichiometric PMAP-carrageenan interpolyelectrolyte complexes proceeded via a cooperative mechanism at pH 3.8 (f = 0.5) and pH 7.4 (f = 0.2) at an ionic strength of 0.15. In contrast, the complexation at pH 7.4 and an ionic strength of 0.25 could be considered to be a consecutive competitive binding of charged units of poly(methylaminophosphazene) to the oppositely charged polysaccharide matrix in the helix or coil conformation. Binding constants of the polycation to the helix and coil forms of ι-carrageenan were estimated. They revealed a preferential binding of the polycation to the helix form of the polysaccharide.     

分子复合法制备新型聚合物驱油剂CMC/P(AM-DMDAAC)

通过具有互补结构的阴离子聚合物羧甲基纤维素(CMC)与阳离子聚合物聚(丙烯酰胺-二甲基二烯丙基氯化铵)[P(AM-DMDAAC)]间的聚电解质分子复合作用,制备了分子复合型CMC/P(AM-DMDAAC)新型驱油剂.电导率测定及紫外光谱分析结果表明,CMC与P(AM-DMDAAC)可以在水相通过库仑力形成均相聚电解质复合溶液.由于分子复合形成的独特超分子结构,复合溶液粘度显著增加,分别为组分聚合物溶液的5.2倍和9.0倍,在高温和高剪切环境中的粘度保持能力也明显优于其组分聚合物.     

Magnetic DNA vector constructed from PDMAEMA polycation and PEGylated brush-type polyanion with cross-linkable shell

A novel magnetic-responsive complex composed of polycation, DNA, and polyanion has been constructed via electrostatic interaction. The magnetic nanoparticles (MNPs) were first coated with a polycation, poly[2-(dimethylamino)ethyl methacrylate] end-capped with cholesterol moiety (Chol-PDMAEMA(30)), and then binded with DNA through electrostatic interaction; the complexes were further interacted with the brush-type polyanion, namely poly[poly(ethylene glycol)methyl ether methacrylate]-block-poly[methacrylic acid carrying partial mercapto groups] (PPEGMA-b-PMAA(SH)). The resulting magnetic particle/DNA/polyion complexes could be stabilized by oxidizing the mercapto groups to form cross-linking shell with bridging disulfide (S-S) between PPEGMA-b-PMAA(SH) molecular chains. The interactions among DNA, Chol-PDMAEMA coated MNPs, and PPEGMA-b-PMAA(SH) were studied by agarose gel retardation assay. The complexes were fully characterized by means of zeta potential, transmission electron microscopy (TEM), dynamic light scattering (DLS) measurements, cytotoxicity assay, antinonspecific protein adsorption, and in vitro transfection tests. All these results indicate that this kind of magnetic-responsive complex has potential applications for gene vector.     

重氮树脂型聚离子复合物

高分子化合物沿分子链(主链和侧链)排列多量可离解基团(每个链节可有1～2个)称聚电解质或聚离子^[1]。聚电解质在水中可离解成两部分,若离解后,聚合物链带负电荷,称聚阴离子电解质或聚负离子;若带正电荷,称聚阳离子电解质或聚正离子。     

Water-soluble interpolyelectrolyte complexes of polyisobutylene-block-poly(methacrylic acid) micelles: formation and properties

We report on interpolyelectrolyte complexes (IPECs) formed by micelles of ionic amphiphilic diblock copolymers with polyisobutylene (PIB) and poly(sodium methacrylate) (PMANa) blocks interacting with quaternized poly(4-vinylpyridine) (P4VPQ). The interpolyelectrolyte complexation was followed by turbidimetry and small angle neutron scattering (SANS). The data obtained by means of a combination of SANS, dynamic light scattering (DLS), and cryogenic transmission electron microscopy (cryo-TEM) provide evidence on the core-shell-corona structure of the complex species with the shell assembled from fragments of electrostatically bound PMANa and quaternized P4VPQ fragments, original PIBx-b-PMAAy micelles apparently playing a lyophilizing part. The complex formation is followed by potentiometric titration as well. This process is initially kinetically controlled. In the second step larger aggregates rearrange in favor of smaller complexes with core-shell-corona structure, which are thermodynamically more stable. An increase in ionic strength of the solution results in dissociation of the complex species as proven by SANS and analytical ultracentrifugation (AUC). This process begins at the certain threshold ionic strength and proceeds via a salt-induced gradual release of chains of the cationic polyectrolyte from the complex species.     

Binding of anthraquinone dyes by polyion complexes consisting of a piperidinium cationic polymer and various polyanions in aqueous solution

The extent of binding of 1-amino-4-alkylaminoanthraquinone-2-sulfonates (alkyl?methyl, ethyl, propyl, and butyl), which have different chemical structures from methyl orange derivatives, by polyion complexes consisting of a piperidinium cationic polymer and various polyanions such as sodium poly acrylate, poly methacrylate, poly styrenesulfonate, carboxymethylcellulose, and dextran sulfate, was measured in an aqueous solution. The effect of alkyl group of the anthraquinone dye on the binding behavior was investigated. Also, the resultant binding characteristics were compared with those previously observed with methyl orange and its homologs. These polyion complexes exhibited very strong binding affinity toward the anthraquinone dye. The polyion complex of the polycation and sodium poly styrenesulfonate bound the dye noncooperatively and the binding process was athermal. The first binding constant accompanying the binding is of the order of 10⁵–10⁶. In contrast, the polyion complexes composed of the polycation and the other polyanions exhibited strong cooperative binding and the binding process was exothermic. The possible mode of binding is discussed.     

Ternary complex formation in aqueous solution between a beta-cyclodextrin polymer, a cationic surfactant and DNA

Polyelectrolyte complexes have been elaborated by mixing in water neutral poly(beta-CD), a cationic surfactant (DTAC) and herring sperm DNA fragments. The driving forces for the poly(beta-CD)/DTAC/DNA association in aqueous solution are, on the one hand, reversible inclusion interactions between the CD cavities of poly(beta-CD) and the alkyl group of DTAC, leading to the formation of a polycation and, on the other hand, electrostatic interactions between the opposite charges of the cationic surfactant and anionic DNA. Viscometry and SANS have been used to prove the occurrence of such ternary complexes in dilute aqueous solutions.     

Formation of copper sols via reduction of Cu2+ ions in solutions of cationic and anionic polyelectrolytes

Zero-valence copper sols are prepared at 20°C via the chemical reduction of Cu(II) ions in aqueous solutions of high-molecular-mass cationic and anionic polyelectrolytes [(poly(1,2-dimethyl-5-vinylpyridium methyl sulfate) and poly(sodium styrenesulfonate), respectively]. In both sols, metal nanoparticles are characterized by narrow size distribution, indicating the pseudomatrix mechanism of their formation; however, the diameter of spherical copper particles formed in the polycation solution (3–14 nm) is much smaller than that of particles formed in the solution of polyanion (10–30 nm). Causes of different sizes of metal nano-particles formed in solutions of polyelectrolytes with different chain charges are discussed in terms of the pseudomatrix mechanism of new phase synthesis in polymer solutions and classical electrocapillary theory.     

聚电解质与相反电荷表面活性剂的相互作用

通过透光度测定、电导滴定和粘度法考察了阳离子聚电解质聚苯乙烯 4 乙烯基吡啶硫酸甲酯盐与阴离子表面活性剂十二烷基硫酸钠 (SDS)的相互作用。研究表明 ,在表面活性剂未过量时 ,二者之间的静电作用占主导地位 ,并且当二者电荷总量相等时 ,生成的复合物沉淀最多 ;在表面活性剂过量后 ,复合物可部分溶解 ,溶解的原因是疏水相互作用。本文初步阐述了二者的作用机理     

New organoelement polyelectrolytes: Protonated poly(alkylaminophosphazenes)

The organoelement polymer bases poly(methylaminophosphazene) and pol(ethylaminophosphazene) have been synthesized by the solid-phase aminolysis of linear ultrahigh-molecular-weight poly(dichlorophosphazene) and characterized. The related cationic polyelectrolytes have been prepared in aqueous solutions in the presence of HCl. As exemplified by the interaction with sodium polystyrenesulfonate and sodium polyphosphate, the polymers form interpolyelectrolyte complexes with anionic polyelectrolytes.     

POLYCATION EFFECTS ON ELECTRONIC SPECTRA OF CONJUGATED POLYMERS IN PROGRAMMED ELECTROSTATIC ASSEMBLIES

A polysaccaride, chitosan, has been used to study polycation effects on electronic spectra of conjugated polymers in programmed electrostatic assemblies. Conjugated polyelectrolytes, poly[2-(3-thienyl)-ethanolhydroxycarbonylmethylurethane] (HPURET) and polydiacetylene from 5,7-dodecadiyn-1,12-bis-(hydroxycarbonylmethylurethane) (HP4BCMU), were assembled from aqueous solution alternately with the polycation, poly (diallydimethylammonium) chloride [PDADMAC], and with the polysaccharide cation, chitosan. Switching polycations did not significantly change the visible absorption spectra for HP4BCMU multilayers. The optical properties of the regiorandom polythiophene, HPURET, depend distinctly on the polycation and the pH of the solution, showing significant differences on visible absorption maxima of the assemblies ranging from 435 nm to 516 nm. After the assemblies were exposed to vapor of aqueous ammonia, they showed UV-vis maxima further red shifted and an enhanced emission intensity, compared to those of the original assemblies. A chitosan/HPURET complex was prepared as a precipitate from solution. Its visible absorption maximum is at 536 nm with a shoulder at 580 nm, reminiscent of regioregular poly(3-alkylthiophenes). This unusual sensitivity of conjugated polymers to polycations may have potential application in sensor devices.     

Effects of particle volume fraction on distortion of particle-arrayed structure during immobilization of colloidal crystals formed by poly(methyl methacrylate)-grafted silica in acetonitrile

Changes of particle array structure with particle volume fraction during immobilization of colloidal crystals, formed by poly(methyl methacrylate)-grafted silica in acetonitrile, were investigated. Immobilization of colloidal crystals formed in acetonitrile was carried out by two-step photo-radical copolymerization of methyl methacrylate and ethylene dimethacrylate to make organogel, followed by solidification after exchanging the solvent with methyl methacrylate. Crystallite size in colloidal crystals formed in acetonitrile was mostly unchanged with particle volume fraction in the range of 0.11–0.18, while the size and number of single crystals decreased during gelation. Disordering in particle array in immobilized colloidal crystals in gel and poly(methyl methacrylate) matrix was observed to decrease with increasing particle volume fraction less than 0.18 due to strong electrostatic repulsion between particles.     

Self-assembled film of poly(4-carboxyphenyl)acetylene and diazoresin and its photoelectric conversion property

A novel multilayer film was assembled from water-soluble poly(4-carboxyphenyl)acetylene sodium salt (PCPA) and diazoresin (DR) in aqueous solution via electrostatic attraction. Under UV irradiation, following the decomposition of the diazonium group between the adjacent interfaces of the multilayers, the ionic bonds of the self-assembled film convert to covalent bonds and the film becomes very stable toward electrolyte aqueous solutions. Thus, the photoelectric conversion property of PCPA-containing film can be measured in a conventional three-electrode photoelectrochemical cell, and 0.5 mol/l KCl solution can be used as the supporting electrolyte. The photocurrent spectroscopy response coincides with the absorption spectrum of the irradiated self-assembled film, which indicates that the irradiated DR/PCPA film is responsible for the photocurrent generation.     

Formation of Se0 Nanoparticles in an Aqueous Cationic Polyelectrolyte

The nanostructures formed by reduction of Se(IV) in the selenite-ascorbate redox system in an aqueous solution of supermacromolecular polycation, poly[trimethyl(methacryloyloxyethyl)ammonium] methyl sulfate, were studied by static and dynamic optical scattering and flow birefringence.     

HA/PDM自组装复合胶体粒子及其乳化性能

以阴离子天然大分子透明质酸(HA)和阳离子单体甲基丙烯酸二甲氨基乙酯(DM)组成带相反电荷的聚合物/单体复合体系, DM通过水相原位聚合可制备荷正电的聚甲基丙烯酸二甲氨基乙酯(PDM), PDM与HA间的静电作用可诱导两者在水溶液中进行自组装, 得到HA/PDM复合胶体粒子. 用傅里叶变换红外(FTIR)光谱仪对HA/PDM复合物结构进行了表征. 用动态激光光散射(DLS)研究了HA与PDM复合体系在水溶液中的自组装行为, 并表征了反应时间对HA/PDM复合胶体粒子粒径的影响. 利用透射电镜(TEM)表征了胶体粒子的形貌. 考察了溶液pH 对胶体粒子粒径及zeta 电位的影响, 并对胶体粒子的乳化性能进行初步探索. 结果表明:DM单体聚合前, 无HA/DM复合物聚集体形成; 而随着DM的逐步聚合, HA与PDM可通过静电作用逐渐组装形成球状HA/PDM复合胶体粒子, 其粒径随反应时间延长逐渐减小并趋于稳定. 同时, 该复合胶体粒子具有pH敏感性和乳化性, 乳化性能较纯HA和PDM有较大提高.     

Conformational changes of strong polycations in the presence of divalent counterions and their influence upon the flocculation efficiency

The interaction between strong polycations, which possess the ammonium quaternary centers attached to an acrylic macromolecular chain derived from poly(N,N-dimethylaminoethyl methacrylate) (polycations Q_x), and divalent counterions was investigated by viscometry and turbidimetry. Conformational changes of polycations were influenced by the polycation charge density, counterion nature (SO₄²⁻ or S₂O₈²⁻) and concentration. The morphology of the polycation layers deposited onto silicon wafers has been studied by tapping mode atomic force microscopy, a strong influence of the polycation and ammonium persulfate concentration on the surface topography being observed. The optimum flocculation concentration of polycation decreased and the flocculation window increased in the presence of S₂O₈²⁻, in the destabilization of kaolin model dispersion. Removal of Congo Red from aqueous solution by the complex system formed between polycations and divalent counterions was also investigated. The behavior of polycations Q_x in separation processes was compared with that of one polycation containing 95 mol% N,N-dimethyl-2-hydroxypropyleneammonium chloride units in the backbone (PCA₅).     

Grafting epoxy-modified hydrophilic polymers onto poly(dimethylsiloxane) microfluidic chip to resist nonspecific protein adsorption

In order to achieve a simple covalent hydrophilic polymer coating on poly(dimethylsiloxane) (PDMS) microfluidic chip, epoxy modified hydrophilic polymers were synthesized in aqueous solution with a persulfate radical initiation system, and crosslinked onto PDMS pretreated by oxygen plasma and silanized with 3-aminopropyl-triethoxysilanes (APTES). Glycidyl methacrylate (GMA) was copolymerized with acrylamide (poly(AAM-co-GMA)) or dimethylacrylamide (poly(DAM-co-GMA)), and graft polymerized with polyvinylpyrrolidone (PVP-g-GMA) or polyvinylalcohol (PVA-g-GMA). The epoxy groups in the polymers were determined by UV spectra after derivation with benzylamine. Reflection absorption infrared spectroscopy (RAIRS) confirmed covalent grafting of GMA-modified polymers onto PDMS surface. Electroosmotic flow (EOF) in the polymer grafted microchannel was strongly suppressed within the range pH 3-11. Surface adsorption of lysozyme and bovine serum albumin (BSA) was reduced to less than 10% relative to that on the native PDMS surface. On the GMA-modified polymer coated PDMS microchip, basic proteins, peptides, and sodium dodecyl sulfate (SDS) denatured proteins were separated successfully.     

Competing reactions in anionic gel-poly(propylene imine) dendrimer-surfactant ternary systems

Competitive interactions in ternary systems including a lightly crosslinked polyanionic hydrogel, a protonated Astramol? poly(propylene imine) dendrimer (of first to fifth generation), and an ionic surfactant were studied. It was found that the direction of the substitution reactions in systems containing cationic surfactants depends on the length of the aliphatic radical in the surfactant molecule as well as on the dendrimer generation number. Depending on these parameters, the interpolyelectrolyte complex formed by the network polyanion and the cationic dendrimer is either capable or incapable of sorbing surfactant cations from aqueous solutions, thereby transforming into the network polyanion-cationic surfactant complex with the release of dendrimers to the surrounding solution. It was shown that the substitution reaction in systems containing anionic surfactants leads to the formation of a polyanionic gel reinforced by particles of the dendrimer-anionic surfactant complex.     

A New Protocol for Ash Wood Modification: Synthesis of Hydrophobic and Antibacterial Brushes from the Wood Surface

The article presents the modification of ash wood via surface initiated activators regenerated by electron transfer atom transfer radical polymerization mediated by elemental silver (Ag⁰ SI-ARGET ATRP) at a diminished catalyst concentration. Ash wood is functionalized with poly(methyl methacrylate) (PMMA) and poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) to yield wood grafted with PMMA-b-PDMAEMA-Br copolymers with hydrophobic and antibacterial properties. Fourier transform infrared (FT-IR) spectroscopy confirmed the covalent incorporation of functional ATRP initiation sites and polymer chains into the wood structure. The polymerization kinetics was followed by the analysis of the polymer grown in solution from the sacrificial initiator by proton nuclear magnetic resonance (¹H NMR) and gel permeation chromatography (GPC). The polymer layer covalently attached to the wood surface was observed by scanning electron microscopy (SEM). The hydrophobic properties of hybrid materials were confirmed by water contact angle measurements. Water and sodium chloride salt aqueous solution uptake tests confirmed a significant improvement in resistance to the absorption of wood samples after modification with polymers. Antibacterial tests revealed that wood-QPDMAEMA-Br, as well as wood-PMMA-b-QPDMAEMA-Br, exhibited higher antibacterial activity against Gram-positive bacteria (Staphylococcus aureus) in comparison with Gram-negative bacteria (Escherichia coli). The paper presents an economic concept with ecological aspects of improving wood properties, which gives great opportunities to use the proposed approach in the production of functional hybrid materials for industry and high quality sports equipment, and in furniture production.