Synthesis and bioimmunological efficiency of poly(2-oxazolines) containing a free amino group

Novel amphiphilic copolymers on the basis of 2-oxazolines containing a free amino group were prepared. The copolymers were synthesized by the living cationic polymerization of 2-ethyl-2-oxazoline (ETOX) and 2-(4-aminophenyl)-2-oxazoline (APOX). The main goal of this work was the synthesis of water soluble polymer material with the defined number of functional groups necessary for the attachment of proteins and polysaccharides. A high concentration of free amino groups allows immobilization of various biosubstances, e.g. drugs, proteins or polysaccharides. Thermal properties have been studied with respect to the composition of the copolymers. Cytotoxicity and the bioimmunological efficiency of the selected copolymer were studied.     

In vitro bio-immunological and cytotoxicity studies of poly(2-oxazolines)

Poly(2-oxazolines) with varying alkyl chain lengths (e.g., methyl, ethyl, aryl) and molar masses have been tested for cell cytotoxicity in vitro. A standard 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay was used for the estimation of cell viability. Two monomers, 2-methyl-2-oxazoline and 2-ethyl-2-oxazoline, were found to provide polymers with non-cytotoxic properties. The dependence of cell viability on molar mass confirmed the expected trend; the viability increased with the higher molar mass of poly(2-ethyl-2-oxazoline) (PETOX), up to 15,000 g/mol. The results obtained for the polymers with aliphatic side chains were compared with the analogues that possessed an aromatic moiety. All results confirmed low cytotoxicity of the polymers prepared by cationic polymerization of 2-alkyl- and 2-aryl-2-oxazolines, which supports their utilization in biomedical applications. Fluorescence microscopy and steady-state fluorescence were used to observe pyrene-labeled polymer interactions with living cells. Polymer accumulated within the cells was found to be dependent on polymer concentration in media. The immunoefficiency of aromatic and aliphatic oxazoline polymers and copolymers was also studied. Phagocytic and metabolic activities of macrophages were used to assess the immunosuppressive effects of the selected copolymers for possible applications in drug delivery and immunobiology. Overall, the tested polymers demonstrated no significant influences on the cellular immunological parameters.     

In vitro study of partially hydrolyzed poly(2-ethyl-2-oxazolines) as materials for biomedical applications

Polymers based on 2-oxazoline, such as poly(2-ethyl-2-oxazolines) (PETOx), are considered to be a type of ‘pseudopeptide’ with the ability to form novel biomaterials. The hydrolysis of PETOx was carried out to evaluate its use in biomedical applications. In the present work, PETOx samples with a range of molar masses were prepared by living cationic polymerization. Hydrolysis was carried out at time intervals ranging from 15 to 180 min to prepare copolymers with different amounts of ethylene imine units. ¹H NMR spectroscopy was used to identify the structure of the hydrolyzed polymers. The dependence of in vitro cell viability on the degree of hydrolysis was determined using three different model cell lines, namely, mouse embryonic 3T3 fibroblasts, pancreatic βTC3 cells, and mouse lymphoid macrophages P388.D1. It was demonstrated that increasing the degree of hydrolysis decreased cell viability for all cell types. Fibroblast cells displayed the highest tolerance; additionally, the effect of polymer size showed no observable significance. Macrophage cells, immune system representatives, displayed the highest sensitivity to contact with hydrolyzed PETOx. The effect of polymer hydrolysis, polymer concentration and the incubation time on cell viability was experimentally observed. Confocal laser-scanning microscopy provided evidence of cellular uptake of pyrene-labeled (co)polymers.     

Electrospinning of poly (2-ethyl-2-oxazoline)

Poly (2-ethyl-2-oxazoline) (PEOZ) is one of the commercial members of a family of materials that have shown significant application potential in a large number of technological contexts, most of them related with biomedical problems where water-soluble polymer systems are highly desirable. Polymeric fibers with diameters in the 200–800 nm range of PEOZ were prepared by electrospinning of its water solutions. Processing and solution parameters effects on the morphology and the diameter of the fibers were investigated. SEM results showed that the polymer concentration and the applied voltage might be used as variables to control the morphology and the diameter of the electrospun fibers. Solutions of the same polymer in other two organic solvents (N,N-dimethylformamide (DMF) and tetrahydrofurane (THF)) were also processed by the same technique but without the promising results of the water solutions.     

Synthesis and characterization of conducting poly (1-aminonaphthalene), poly (2-aminonaphthalene) and poly (aniline-co-1-aminonaphthalene)

Poly (1&2)-aminonaphthalene and poly (aniline-co-1-aminonaphthalene) have been synthesized in high yields by chemical oxidative polymerization method. The polymers are soluble in polar solvents such as DMSO, NMP etc. In PNA-2 as head-to-tail coupling cannot occur, the electrical conductivity is lower than PNA-1. The copolymer exhibits distinct morphology, higher viscosity, characteristic exciton peak, appreciable thermal stability and electrical conductivity compared to PNA-1.     

Thermal analysis of poly(2-hydroxyethyl methacrylate) (pHEMA) hydrogels

The influence of water on the physical properties of a hydrogel is important for understanding natural tissues and in designing synthetic materials to replace them. In this study, poly (2-hydroxyethyl methacrylate) (pHEMA) was used as a model system to understand how water interacts with the polymer of a hydrogel. Thermal analysis methods (thermogravimetric analysis coupled to mass spectrometry and differential scanning calorimetry) were used to determine: (i) the total water content of pHEMA gels; (ii) how this water was lost during heating; (iii) the relationship between water content of the gel and its glass transition temperature; and (iv) the behavior of the water in the gel on cooling. Previous researchers have invoked various models to describe the organization of water in a hydrogel. In this study, the simplest model which could explain all of the results from the different thermal analysis techniques was one which consisted of three classes of water: (i) hydration water in close proximity to the polymer; (ii) interstitial water in regions or cavities surrounded by polymer chains; and (iii) bulk water.     

iCVD growth of poly(N-vinylimidazole) and poly(N-vinylimidazole-co-N-vinylpyrrolidone)

The imidazole group plays an important role in α-chymotrypsin catalysis, metal-ion complexation, counterion or dye binding. Poly(N-vinylimidazole), PVI, is also a good model polymer interacting with neutral salts. The poly(N-vinylimidazole-co-N-vinylpyrrolidone) copolymer P(VI-co-VP), can be used to produce highly functionalized polymers.PVI and P(VI-co-VP) thins films were achieved via initiated chemical vapor deposition (iCVD), a solvent-free process to form films under mild conditions. The polymerization was initiated by hot wire heated tert-butyl peroxide (TBPO). The chemical structure and compositions of the polymers were analyzed using FTIR and XPS. The growth rate of PVI as a function of the pressure inside the iCVD reactor was measured to be 1 nm/h mTorr. The XPS results show that the functional groups were retained in the polymer deposited. For the P(VI-co-VP) deposition, there are more VI groups found in the co-polymer chain even when the reacting monomers were fed in the same ratio.     

Deformation and transformation mechanisms of poly(vinylidene fluoride) (PVF2)

The deformation process and the accompanyingα→β phase transformation of poly(vinylidene fluoride), drawn at 82 to 90 and 130° C, has been characterized by electron microscopy and X-ray and electron diffraction. Micronecking occurs at both draw temperatures, fibrils and mosaic blocks being drawn off the edges of the micronecks. The degree of phase transformation, at the same elongation, is dependent on the draw temperature; at 130° C the majority of the sample remains in theα phase at the natural draw ratio. The phase transformation at both draw temperatures accompanies the transformation from lamellar (block) structure to fibril.     

Reinforcement of elastomeric poly(dimethylsiloxane) by glassy poly(diphenylsiloxane)

Some novel approaches were taken to provide the improvements in mechanical properties that are almost always necessary to prepare a commercially useful elastomer from poly(dimethylsiloxane) (PDMS) [-Si(CH₃)₂O-]. The reinforcement was provided by poly(diphenylsiloxane) (PDPS) [-Si(C₆H₅)₂O-], a hard glassy polymer, which was introduced into the PDMS by two rather different techniques. In the first, the PDPS was prepared separately by condensation polymerization of diphenylsilanediol and then solution-blended into the PDMS. In the second, it was generated by in situ polymerization of the same monomer absorbed into the PDMS network. The resulting materials were characterized by scanning electron microscopy and by stress-strain isotherms in elongation. At least under some conditions both techniques were found to be successful, leading to increases in ultimate strength by a factor of two or more.     

聚乙二醇改性聚乳酸的合成与性能表征

以外消旋乳酸(D,L-LA)和不同数均分子量(Mn)的聚乙二醇(PEG)为原料,通过熔融缩聚法,合成了系列聚乳酸聚乙二醇(PLEG)。最佳工艺条件为:以(Sn(Oct)2)为催化剂,m(Sn(Oct)2)为0.8%,n(PEG)∶n(D,L-LA)=1∶600,聚合温度170℃,压力0.096 MPa条件下,反应8h。用特性粘度测试、FT-IR、XRD、接触角等对其进行表征,实验结果表明系列PLEG中PLEG-800接触角为63°,表明其亲水性能最好;PEG-800和乳酸共聚合成的PLEG的粘均分子量最大,可达48997,与PDLLA相比,结晶度有较大提高,亲水性得到改善。     

The characteristics and transfection efficiency of PEI modified by biodegradable poly(β-amino ester)

To improve the cytotoxicity of PEI25k and the transfection efficiency of poly(β-amino ester) with DNA, we synthesized a poly(β-amino ester), PEDP, bearing ester linkages in the backbone and tertiary amines in the backbone and side chain and prepared a binary mixture, PEDP–PEI25k, using physical blending meyhod. Both poly(β-amino ester) PEDP and binary mixture PEDP–PEI25k, readily self-assembled with plasmid DNA (pCMV-β gal) in a HEPES buffer, were characterized by dynamic light scattering. The results reveal that PEDP–PEI25k was able to self-assemble plasmid DNA into PEDP–PEI25k/DNA nano-complexes small enough to enter a cell through endocytosis. Titration studies were performed to determine the buffering capacities of PEDP and PEDP–PEI25k. The COS-7 cell viabilities in the presence of PEDP and PEDP–PEI25k were studied. At low mass ratio of PEDP/PEI25k (1/1), it is found that the transfection curve of PEDP–PEI25k/DNA bearing a maximum peak is similar to that of PEI25k/DNA. In addition, the PEDP–PEI25k/DNA complexes were able to transfect COS-7 cells in vitro with a high efficiency comparable to a well-known gene carrier PEI25k/DNA. The results indicate that binary mixture PEDP–PEI25k is an attractive cationic carrier for gene delivery and an interesting candidate for further study.     

Textural and tensile properties of thermo-responsive poly(2-(2-methoxyethoxy)ethyl methacrylate) hydrogel

Hydrogel dressings should be adhesive and elastic, while providing excellent functional and aesthetic features. Owing to weak intermolecular forces, various measures are undertaken to improve the hydrogel mechanical properties. Thermo-responsive poly(2-(2-methoxyethoxy)ethyl methacrylate) (poly(MEO₂MA)) hydrogel fabricated with different amounts of di(ethylene glycol) dimethacrylate (DEGDMA) cross-linker was characterised using texture profile analysis. More cross-linking sites incorporated within the hydrogel limit the swelling ability where 1.0 and 10?mol-% of DEGDMA swell by 8.03 and 1.92 times, at 5°C. Hydrogel textural and tensile property correlated with the cross-linker amount. Meanwhile, network structure disentanglement within swollen hydrogel reduced the force required for deformation. Thus, the swelling behaviour, textural and tensile properties were investigated to discern the possible biomedical applications suitable for this hydrogel.     

聚合物光伏电池材料MEH-PPV的超声合成及其表征

研究了聚[2甲氧基-5-(2'-乙基己氧基)对苯乙炔](MEH-PPV)的合成路线.采用超声合成法制备出无凝胶、完全可溶、高分子量的MEH-PPV.其教均分子量可达7.9×105,并通过红外光谱、核磁共振氢谱(1H-NMR)、拉曼光谱对产物进行了结构袁征.