Synthesis and properties of a novel methoxy poly(ethylene glycol)-modified galactosylated chitosan derivative

Chitosan and its derivatives are attractive non-viral vectors. To produce target-cell specificity and improve the solubility of chitosan, a novel chitosan derivative, modified with galactose and methoxy poly(ethylene glycol) (mPEG) was synthesized, and structure changes of chitosan and its derivatives were characterized. Compared to chitosan, the solution viscosity of the novel chitosan derivative drastically decreased. And, the degree of substitution (DS) of chitosan by galactose and mPEG were calculated as 0.09 and 0.30. The average diameter and zeta potential of mPEGylated galactosylated chitosan (GaC) nanoparticle containing VRMFat plasmid were 178 nm and +2.93 mV, suggesting suitable properties for gene delivery system. The gel electrophoresis confirmed that the plasmid DNA was remained completely by the mPEGylated GaC nanoparticle. And, the cytotoxic effect of mPEGylated GaC nanoparticles on human embryonic kidney (HEK 293) cells was negligible in comparison with that of control chitosans. Therefore, it is expected that the mPEGylated GaC will have the potential as a targeting gene delivery system for a further application. Tao Zhang and Dong Li equally contributed to this research.     

Experimental wound dressings of degradable PHA for skin defect repair

The present study reports construction of wound dressing materials from degradable natural polymers such as hydroxy derivatives of carboxylic acids (PHAs) and 3-hydroxybutyrate/4-hydroxybutyrate [P(3HB/4HB)] as copolymer. The developed polymer films and electrospun membranes were evaluated for its wound healing properties with Grafts—elastic nonwoven membranes carrying fibroblast cells derived from adipose tissue multipotent mesenchymal stem cells. The efficacy of nonwoven membranes of P(3HB/4HB) carrying the culture of allogenic fibroblasts was assessed against model skin defects in Wistar rats. The morphological, histological and molecular studies revealed the presence of fibroblasts on dressing materials which facilitated wound healing, vascularization and regeneration. Further it was also observed that cells secreted extracellular matrix proteins which formed a layer on the surface of membranes and promoted the migration of epidermal cells from the neighboring tissues surrounding the wound. The wounds under the P(3HB/4HB) membrane carrying cells healed 1.4 times faster than the wounds under the cell-free membrane and 3.5 times faster than the wounds healing under the eschar (control).The complete wound healing process was achieved at Day 14. Thus the study highlights the importance of nonwoven membranes developed from degradable P(3HB/4HB) polymers in reducing inflammation, enhancing angiogenic properties of skin and facilitating better wound healing process.     

Evaluation of electrospun fibrous scaffolds of poly(dl-lactide) and poly(ethylene glycol) for skin tissue engineering

This study is derived from the innate concerns of electrospun poly(DL-lactide) (PDLLA) fibers as tissue engineering scaffolds: hydrophobic surface, surface erosion and dimensional shrinkage, which are not favorable to trigger the initial adhesion and further growth and population of cells. Blending electrospinning of PDLLA and poly(ethylene glycol) (PEG) with different PEG contents was evaluated for optimal tissue engineering scaffolds. The surface hydrophilicity was improved, and the degradation patterns of PDLLA/PEG mats changed from surface erosion to bulk degradation with the increase in PEG contents. The dimensional shrinkage was alleviated through the formation of crystal regions of PEG in the fiber matrix. The PDLLA/PEG fibrous mats were slightly weakened with the increase in the PEG contents, but a significant decrease in the tensile strength could be found for those with PEG contents of over 40%. Human dermal fibroblasts (HDFs) interacted and integrated well with the surrounding fibers containing 20 and 30% PEG, which provided significantly better environment for biological activities of HDFs than electrospun PDLLA mats. It indicated that electrospun mats containing 30% PEG exhibited the most balanced properties, including moderately hydrophilic surface, minimal dimensional changes, adaptable bulk biodegradation pattern and enhancement of cell penetration and growth within fibrous mats.     

Surface modification of poly(ethylene terephthalate) by plasma polymerization of poly(ethylene glycol)

Poly(ethylene glycol) (PEG) was ‘polymerized’ onto poly(ethylene terephthalate) (PET) surface by radio frequency (RF) plasma polymerization of PEG (average molecular weight 200 Da) at a monomer vapour partial pressure of 10 Pa. Thin films strongly adherent onto PET could be produced by this method. The modified surface was characterized by infra red (IR) spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), cross-cut test, contact angle measurements and static platelet adhesion studies. The modified surface, believed to be extensively cross-linked, however showed all the chemical characteristics of PEG. The surface was found to be highly hydrophilic as evidenced by an interfacial free energy of about 0.7 dynes/cm. AFM studies showed that the surface of the modified PET became smooth by the plasma polymerized deposition. Static platelet adhesion studies using platelet rich plasma (PRP) showed considerably reduced adhesion of platelets onto the modified surface by SEM. Plasma ‘polymerization’ of a polymer such as PEG onto substrates may be a novel and interesting strategy to prepare PEG-like surfaces on a variety of substrates since the technique allows the formation of thin, pin-hole free, strongly adherent films on a variety of substrates.     

Impact compressibility of a poly(ethylene glycol)-based nanocomposite fluid

The behavior of a poly(ethylene glycol)-based nanocomposite shear thickening fluid (STF) under impact loading conditions has been experimentally studied using the Kolsky method and related techniques. The dependence of the pressure in the STF on the volume strain magnitude has been determined. It is established that the radial and axial components of the stress tensor almost coincide, which shows that the material behaves like an incompressible liquid. The character of the stress-strain curves (hysteresis) indicates that the STF is characterized by some energy dissipation in the load-unload cycle.     

交联壳聚糖共混膜醇水混合液分离性能研究

研究了醇水混合液体系在经交联的聚乙二醇／壳聚糖共混膜中的渗透蒸发分离性能．讨论了共混膜组成、料液浓度和温度、膜下侧压力等对渗透蒸发性能的影响．结果发现聚乙二醇的掺入能大大提高壳聚糖膜的渗透通量，但分离因子降低．当料液乙醇质量分数为８０％时，渗透通量及分离因子都随温度的升高而增加．料液中加入少量ＺｒＯＣｌ２能把分离因子从原来的８．８提高到７４．同时发现膜下游侧压力不仅仅影响渗透组分在膜表面的蒸发，还影响整个渗透蒸发传质过程．     

pH dependent hydrolysis and drug release behavior of chitosan/poly(ethylene glycol) polymer network microspheres

Semi-interpenetrating polymer network (IPN) microspheres of chitosan and poly(ethylene glycol) PEG were prepared for controlled release of drugs. A new method for the chemical crosslinking of chitosan microspheres containing isoniazid (INH) as a model drug is proposed and evaluated. The method consists of the exposure of microspheres to the vapor of crosslinking agent that act in gaseous phase under mild conditions. The structural analysis of the microspheres was carried out by FTIR-analysis. The swelling behavior, hydrolytic degradation, structural changes of the microspheres and loading capacity (LC) of the microspheres for INH were investigated. The prepared microspheres have shown 93% drug loading capacity, which suggested that these semi-IPN microspheres are suitable for controlled release of drugs in an oral sustained delivery system. © 2001 Kluwer Academic Publishers     

Novel one-component polymeric benzophenone photoinitiator containing poly (ethylene glycol) as hydrogen donor

Benzophenone (BP) is a common initiator which is often used in the UV-curing production and related fields. However, the shortcomings such as toxicity, odor, and migration always limit the development of the traditional BP photoinitiator. Polymeric benzophenone photoinitiator (PEG-BP) was synthesized basing on polyethylene glycol (PEG), succinic anhydride, 4-hydroxybenzophenone and epichlorohydrin. The structure of PEG-BP was characterized by IR and ¹H NMR. The radiation absorption of PEG-BP was detected by UV spectrophotometer with the maximum absorption wavelength at 283 nm in acetonitrile solvent, undergone significant redshift corresponding to small molecule photoinitiator BP, thus enhanced the photosensitive efficiency of UV-curing system in the long wavelength region. Besides, PEG-BP has better water solubility than BP, thus could be used in both oil and aqueous solution. The obvious advantage of this initiator was the elimination of amine based hydrogen donors and to provide alternative hydrogen donors with easily availability and non-toxicity. The effects of molecular weights of PEG-BP, photoinitiator concentration, UV-radiation intensity and different monomers on photopolymerization kinetics were investigated in detail. The synthesized polymeric photoinitiators are attractive to be used as type II photoinitiators.     

Poly(ethylene glycol) enhanced dehydrochlorination of poly(vinyl chloride)

Poly(ethylene glycol) (PEG), an environment-friendly reaction medium, has been adopted to accelerate the dehydrochlorination of poly(vinyl chloride) (PVC). Experimental results demonstrated that at 210 degrees C for 1h the dechlorination degree was as high as 74.2% for PVC/PEG, while for PVC only 50.0%. Moreover, from thermogravimetric analysis, it was found that for PVC/PEG the decomposition of PVC corresponding to the dehydrochlorination stage shifted to lower temperatures compared with that of pure PVC, suggesting some interactions exist between PEG and PVC that caused the faster dehydrochlorination rate. In addition, during this process, no waste byproducts such as KCl have been produced, and satisfactory recyclability of PEG (10 cycles) has been obtained.     

Grafting of poly(ethylene glycol) onto poly(acrylic acid)-coated glass for a protein-resistant surface

The surface of solid glass supports for samples in optical microscopy and for biosensors needs to be protein-resistant. A coating of a poly(ethylene glycol) monomethyl ether (mPEG) on the surface of the glass is one promising method for preventing the nonspecific adsorption of proteins. In this study, we have developed a novel technique for achieving an optimal coverage of a glass surface with mPEG to prevent protein adhesion. A clean glass substrate previously treated with (3-aminopropyl)dimethylethoxysilane (APDMES) was treated sequentially with poly(acrylic acid) and subsequently a primary amine derivative of mPEG in the presence of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide. The resultant glass surface was demonstrated to be highly protein-resistant, and the adsorption of bovine serum albumin decreased to only a few percentage points of that on a glass surface treated with APDMES alone. Furthermore, to extend the present method, we also prepared a glass substrate on which biotinylated poly(ethylene glycol) was cografted with mPEG, and biotinylated myosin subfragment-1 (biotin-S1) was subsequently immobilized on this substrate by biotin/avidin chemistry. Actin filaments were observed to glide on the biotin-S1-coated glass surface in the presence of ATP, and thus, the method is capable of immobilizing the protein specifically without any loss in its biological function.     

Synthesis of flower-like CuS nanostructured microspheres using poly(ethylene glycol) 200 as solvent

CuS flower-like microspheres with the diameter of about 3-4 microm constructed by nanoflakes with thickness of about 30-40 nm have been successfully synthesized by a simple wet chemical method. In this reaction system, Poly(ethylene glycol) 200 (PEG 200) was used as solvent, CuCl2 2H2O as cuprum source, and thioacetamide (TAA) as sulfur source. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and high-resolution transmission electron microscopy (HRTEM) in detail. The XRD patterns revealed that the products were pure hexagonal phase of CuS. Experiments with various parameters indicated that the reaction temperature and molar ratio of CuCl2 2H2O to thioacetamide had strong effects on the sizes and morphologies of CuS crystals. A possible growth mechanism on the formation of CuS microspheres was proposed. The PEG 200 acted as solvent, complexing agent, and soft template in this synthesis. Furthermore, optical studies of the products including UV-Vis absorption spectrum and photoluminescence spectrum have also been carried out.     

Electron-beam-initiated polymerization of poly(ethylene glycol)-based wood impregnants

The current study demonstrates that methacrylate and acrylate poly(ethylene glycol) (PEG) functional oligomers can be effectively impregnated into wood blocks, and cured efficiently to high conversions without catalyst by e-beam radiation, allowing for less susceptibility to leaching, and favorable properties including higher Brinell hardness values. PEG based monomers were chosen because there is a long history of this water-soluble monomer being able to penetrate the cell wall, thus bulking it and decreasing the uptake of water which further protects the wood from fungal attack. Diacrylate, dimethacrylate, and dihydroxyl functional PEG of M(w) 550-575, of concentrations 0, 30, 60, and 100 wt % in water, were vacuum pressure impregnated into Scots Pine blocks of 15 × 25 × 50 mm in an effort to bulk the cell wall. The samples were then irradiated and compared with nonirradiated samples. It was shown by IR, DSC that the acrylate polymers were fully cured to much higher conversions than can be reached with conventional methods. Leaching studies indicated a much lower amount of oligomer loss from the cured vinyl functional PEG chains in comparison to hydroxyl functional PEG indicating a high degree of fastening of the polymer in the wood. The Brinell hardness indicated a significant increase in hardness to hardwood levels in the modified samples compared to the samples of hydroxyl functional PEG and uncured vinyl PEG samples, which actually became softer than the untreated Scots Pine. By monitoring the dimensions of the sample it was found by weight percent gain calculations (WPG %) that water helps to swell the wood structure and allow better access of the oligomers into the cell wall. Further, the cure shrinkage of the wood samples demonstrated infiltration of the oligomers into the cell wall as this was not observed for methyl methacrylate which is well-documented to remain in the lumen. However, dimensional stability of the vinyl polymer modified blocks when placed in water was not observed to the same extent as PEG.     

Biocompatibility and biodegradation of poly(hydroxybutyrate)/poly(ethylene glycol) blend films

Using chloroform as co-solvent, a series of poly(3-hydroxybutyrate) (PHB) and polyethylene glycol (PEG) blend materials with different ratio ranging from 80 : 20 (wt %) to 20 : 80 (wt %) were prepared by solution blend. The blood-compatibility was evaluated by means of platelet clotting time test and exploring its morphological changes. The results showed that PEG played an important role in resisting platelet adhesion. With the increased addition of PEG, the clotting times became longer and the number of platelet adhesion decreased apparently. All platelets were in discrete state, no pseudopodium had been found and no collective phenomenon had been happened. The cell-compatibility was evaluated via Chinese Hamster Lung (CHL) fibroblast cultivation in vitro. The cells cultured on the matrix spread and proliferated well. With the increase of PEG content in the blend films, the number of live cells became more and more. These results indicated that PHB exhibited satisfying cell-compatibility and the addition of PEG also could improve the cell-compatibility of PHB. The biodegradation experiment indicated that the degradation of PHB/PEG was accelerated by enzyme in vitro and the blending of PEG was favorable to degradation.     

Nanostructured antifouling poly(ethylene glycol) films for silicon-based microsystems

The creation of antifouling surfaces is one of the major prerequisites for silicon-based micro-electrical-mechanical systems for biomedical and analytical applications (known as BioMEMS). Poly(ethylene glycol) (PEG), a water-soluble, nontoxic, and nonimmunogenic polymer has the unique ability to reduce nonspecific protein adsorption and cell adhesion and, therefore, is generally coupled with a wide variety of surfaces to improve their biocompatibility. To this end, we have analyzed PEG thin films of various grafting densities (i.e., number of PEG chains per unit area) coupled to silicon using a single-step PEG-silane coupling reaction scheme using variable-angle ellipsometry. Initial PEG concentration and coupling time were varied to attain different grafting densities. These data were theoretically analyzed to understand the phenomenon of PEG film formation. Furthermore, all the PEG films were evaluated for their ability to control biofouling using albumin and fibrinogen as the model proteins. PEG thin films formed by using higher PEG concentrations ( > or = 10 mM PEG) or coupling time ( > or = 1 h) demonstrated enhanced protein fouling resistance behavior. This analysis is expected to be useful to form PEG films of desired grafting density on silicon substrates for appropriate application.     

A new synthesis of lamellar-mesostructured silica by using poly(ethylene glycol) distearate as template

A lamellar-mesostructured silica has been synthesized by using poly(ethylene glycol) distearate as template in ethanol solution. Highly ordered lamellar mesostructure was confirmed by X-ray diffraction pattern, transmission electronic microscopy, and nitrogen adsorption-desorption isotherm. The material obtained in this work has a large interlayer distance, and good thermal and mechanical stabilities, which can favor the preparation of the in situ polymerized nanocomposites based on intercalation of polymers in the lamellar-mesostructured silica.