Synthesis and characterization of hydrophobically modified poly(vinyl alcohol) hydrogel membrane

Hydrophobically modified poly(vinyl alcohol), [PVA] was synthesized by graft copolymerization of N-tertiary butyl acrylamide [NTBA] onto PVA by free radical polymerization. The incorporation of NTBA onto PVA chains was confirmed by elemental analysis, FT-IR and NMR spectroscopy. A series of graft copolymers with different contents of NTBA were prepared and membranes were casted from these copolymer solutions in dimethyl sulfoxide. The increase in hydrophobicity with an increase in NTBA content was investigated by contact angle measurements. The swelling behaviour of membranes as a function of temperature, hydrophobic content, annealing temperature and period was studied. Permeability of solutes through these membranes was investigated as a function of solute size, membrane hydrophobicity and temperature. The swelling behaviour of the copolymer membranes showed that the lower content of NTBA gives discontinuous volume transition with respect to temperature whereas, the presence of higher amounts of NTBA showed decreased swelling ratios with very little influence of temperature on the swelling. The permeabilities of solutes through these membranes were strongly dependent on the size of the solute, solution temperature and hydrophobicity of the membrane. The copolymer membranes were further characterized using DSC, DMA and XRD. The peak becomes broader as the NTBA content increases.     

Electrospun mat of thermal-treatment-induced nanocomposite hydrogel of polyvinyl alcohol and cerium oxide for biomedical applications

Hydrogels are one of the most thought-provoking formulations used widely for biomedical applications. In the present investigation, poly(vinyl) alcohol (PVA) and its cerium oxide (CO) composite-based hydrogels were prepared by the combination of electrospinning and thermal processing technique. The partial crosslinking, along with time-controlled heating (10 min), delivered PVA hydrogel. The mechanism was explained with Fourier-transform infrared spectroscopy analysis, where the hydroxyl group disappeared in long-duration (30 min) of heat treatment and they retain in lesser duration. The heat-treated PVA transformed from amorphous to crystalline, since the T_g of PVA disappeared in 30 min heat treatment, while the T_g increased to 85°C (10 min heat treatment) from 70°C in PVA, suggested the full and partial crystallinity. The swelling and porosity studies reveal the hydrogel formation of heat-treated PVA. Interestingly, CO reinforced PVA composites show better swelling with respect to heat-treated PVA. Furthermore, CO reinforced PVA hydrogel demonstrated better biocompatibility platelet adhesion and accelerated wound healing competence.     

Poly(vinyl alcohol) hydrogel fixation on poly(ethylene terephthalate) surface for biomedical application

A surface modification technique was developed for the covalent immobilization of poly(vinyl alcohol) (PVA) hydrogel onto poly(ethylene terephthalate) (PET) to improve the biocompatibility of the film. The PET film was first graft copolymerized with poly(ethylene glycol) monomethacrylate (PEGMA) in the presence of ethylene glycol dimethacrylate (EGDMA) as crosslinker, and then oxidized with a mixture of acetic anhydride (Ac₂O) and dimethyl sulfoxide (DMSO) to produce aldehyde groups on the PET surface. Finally, the prepared PVA solution was cast onto the film and covalently immobilized on the film through the reaction between the aldehyde groups on the PET film and the hydroxyl groups of PVA. The good attachment of the PVA layer to the PET film was confirmed by observing the cross-section of the PET-PVA film using scanning electron microscopy (SEM). Heparin was immobilized on the PVA layered PET using two different methods, physical entrapment and covalent bonding, to further improve the biocompatibility of the film. Attenuated total reflectance (ATR) FT-IR spectroscopy and X-ray photoelectron spectroscopy (XPS) were used to characterize the chemical composition of the surface modified films. The biocompatibility of the various surface modified PET films was evaluated using plasma recalcification time (PRT) and platelet adhesion.     

Synthesis and characterization of CdS quantum dots with carboxylic-functionalized poly (vinyl alcohol) for bioconjugation

In the present research it is reported the synthesis and characterization of CdS nanoparticles (NPs) prepared using carboxylic-functionalized poly (vinyl alcohol) (PVA) as the ligand via aqueous route at room temperature and ambient pressure. Different molar concentrations of carboxylic-PVA and PVA were investigated aiming at producing stable colloidal systems. Carboxylic-PVA was conjugated with BSA (bovine serum albumin) and used as capping ligand in the preparation of CdS nanocrystals. UV-visible spectroscopy, photoluminescence spectroscopy, and transmission electron microscopy were used to characterize the kinetics and the relative stability of polymer-capped CdS nanocrystals. The results have clearly indicated that the carboxylic-functionalized PVA was much more effective on nucleating and stabilizing colloidal CdS nanoparticles in aqueous suspensions compared to PVA. In addition, the CdS nanocrystals were obtained in the so-called “quantum-size confinement regime”, with the calculated average size below 4.0 nm and fluorescent activity. Thus, a novel simple route was successfully developed for synthesizing nanohybrids based on quantum dots and water-soluble chemically functionalized polymers with incorporated carboxylic moiety with the possibility of direct bioconjugation.     

Porous silicone hydrogel interpenetrating polymer networks prepared using a template method for biomedical use

Porous interpenetrating polymer networks (IPNs) of polydimethylsiloxane with hydrophilic components synthesized by radical homopolymerization and copolymerization of 2‐hydroxyethyl methacrylate (HEMA) and N,N‐dimethylacrylamide (DMAA) were obtained using a template method. Surface modification of CaCO₃ microsphere templates improved their dispersibility, leading to the realization of IPN films with an interconnected porous structure. Results showed that these porous IPN films exhibited higher swelling abilities, and thus better drug loading capabilities than the corresponding non‐porous films. In addition, IPNs comprised of DMAA exhibited higher swelling abilities and faster drug release rates than those of only HEMA. These silicone hydrogels were also tested for their cytotoxicity against L929 cells, confirming their non‐toxicity to cells and their potential use as materials for biomedical applications. Copyright © 2011 Society of Chemical Industry     

Nano-enabled poly(vinyl alcohol) based injectable bio-nanocomposite hydrogel scaffolds

We report development of poly(vinyl alcohol) (PVA)-based novel injectable hydrogel nanocomposite scaffolds. Nanocellulose (NC), synthesized from agricultural biomass, was used as reinforcement within PVA matrix. The hydrogels were formed using physical crosslinking process involving multiple freeze–thaw cycles. A range of bio-nanocomposite hydrogels were prepared with varying concentrations of NC. With increasing loading of NC, crystallinity was found to be increased, which could be attributed to nucleating effect and crystalline nature of nanofibrillar cellulose. Investigation of microstructural surface topology indicated reduced surface perturbations upon incorporation of NC. Fourier transform infrared spectroscopy studies further indicated presence of characteristic functional groups and possible interactions between PVA and NC. Enhanced structural integrity and dynamic stability of the bio-nanocomposite hydrogels were also confirmed by carrying out rheological investigations at different frequency, amplitude, temperature, and time sweeps. Further, the bio-nanocomposite hydrogels demonstrated excellent injectability and self-standing behavior, establishing the promising potential as injectable scaffolds. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48789.     

互穿网络敏感型聚氨酯水凝胶的合成与研究

以异佛尔酮二异氰酸酯（IPDI）、聚氧化丙烯二醇（PPG-220）、二羟甲基丙酸（DMPA）、蓖麻油（C0）等为主要原料,合成交联型水性聚氨酯乳液,在此乳液中加入丙烯酰胺、引发剂（KPS）,交联剂（BMA）进行自由基聚合,制备具有IPN结构的聚氨酯-聚丙烯酰胺（PU—PAAm）水凝胶。研究了（PU—PAAm）水凝胶溶胀率（SR）受pH值、温度（T）、交联剂用量等因素的影响。     

Facile preparation and characterization of poly(vinyl alcohol)/chitosan/graphene oxide biocomposite nanofibers

Poly(vinyl alcohol) (PVA)/chitosan (CS)/graphene oxide (GO) biocomposite nanofibers have been successfully prepared using aqueous solution by electrospinning. CS colloidal gel in 1% acetic acid can be changed to homogeneous solution by using electron beam irradiation (EBI). The uniform distributions of GO sheets in the nanofibers were investigated by field emission scanning electron microscopy (FESEM) and Raman spectroscopy. FESEM images illustrated that the spread single GO sheet embedding into nanofibers was formed via self-assembly of GO sheet and PVA/CS chains. And the average diameters of the biocomposite nanofibers decreased (200, 173, 160 and 123 nm) with increasing the contents of GO (0.05, 0.2, 0.4 and 0.6 wt%). Raman spectra verified the presence of GO in the biocomposite nanofibrous mats. The mechanical properties of as-prepared materials related with GO contents. It revealed that the highest tensile strength was 2.78 MPa, which was 25% higher than that of neat PVA/CS nanofibers. Antibacterial test demonstrated that the addition of GO to PVA/CS nanofiber had great ability to increase inhibition zone till 8.6 mm. Overall, these features of PVA/CS/GO nanofibers which were prepared by eco-friendly solvent can be a promising candidate material in tissue engineering, wound healing and drug delivery system.     

一种光致变色水凝胶的合成与表征

合成了一种结合了螺吡喃(SP)的光致变色水凝胶,即N-乙烯基吡咯烷酮与N-异丙基丙烯酰胺共聚物水凝胶.红外光谱和溶胀实验的结果都表明,螺吡喃很好地结合进了水凝胶里.紫外-可见光谱的结果证明,合成的水凝胶具有光致变色特性,水凝胶对周期性交替的紫外光照射和黑暗条件的响应情况可以说明其光致变色的可回复性.从荧光显微镜照片可以...     

Novel semi-interpenetrated networks based on collagen-polyurethane-polysaccharides in hydrogel state for biomedical applications

The development of collagen hydrogels with tailored properties for improved applications in biomedicine represents an area of opportunity for materials science. The collagen can form semi-interpenetrated networks (semi-IPN) with various natural and/or synthetic polymers. This work aims the preparation of novel hydrogels generated from a collagen matrix cross-linked with polyurethane (PU), and the subsequent inclusion of polysaccharide chains to form semi-IPN systems with improved properties. The choice of polysaccharides for this purpose is related to their ability to modulate the biocompatibility and the antibacterial capacity in various biomedical strategies. The work contemplates to study the effect of the chemical structure of polysaccharide (hydroxyethylcellulose (HEC), hydroxypropylmethylcellulose (HPMC) or starch (Alm)) on the properties of these novel hydrogels. The results indicate that the semi-IPN hydrogels that include Alm exhibit the formation of stronger intermolecular interactions promoted by hydrogen bonds than HEC and HPMC, significantly improving the mechanical properties and their degradation rate in acidic, alkaline, and proteolytic media; also showing high capacity to inhibit the growth of E. colli. The semi-IPN hydrogels based on HEC and HPMC exhibit excellent improvement in both thermal and proteolytic degradation, compared with the collagen-PU matrix. On the other hand, this semi-IPN system does not present cytotoxic character for monocytes and fibroblasts growing for up to 48 h of culture. Therefore, these innovative 3D matrices will be excellent candidates with potential application in biomedical strategies such as wound healing dressings.     

Characterization of Poly(Vinyl Alcohol) and Poly(Vinyl Pyrrolidone) Co-polymer Blend Hydrogel Prepared by Application of Gamma Radiation

Hydrogel is prepared from a poly(vinyl pyrrolidone) (PVP) and poly(vinyl alcohol) (PVA) blend solution by gamma radiation with a ₆₀Co λ source at room temperature. Properties of the prepared hydrogel, such as gel fraction, gel strength swelling ratio, equilibrium water content, and water absorption in room temperature, were investigated. Blending hydrogel with PVP and PVA obviously increased the gel strength and decreased the swelling ratio of hydrogel. It was observed that the gel fraction increased while the swelling ratio and water content decreased with increased radiation dose, but gel strength increased up to a certain radiation dose and then decreased. The percentage of water absorption at room temperature increased with time but after a certain time it became steady and decreased with radiation dose.     

Electroresponsive behavior of 2‐hydroxypropyltrimethyl ammonium chloride chitosan/poly(vinyl alcohol) interpenetrating polymer network hydrogel

An interpenetrating polymer network hydrogel composed of 2‐hydroxypropyltrimethyl ammonium chloride chitosan and poly(vinyl alcohol) was prepared. Its swelling properties and electroresponsive behavior in aqueous NaCl solutions were studied. The results indicated that the water uptake ability of the hydrogel decreased with increasing ionic strength of aqueous NaCl solution. The Young's modulus, elongation at break and tensile strength of the hydrogel swollen in deionized water were 4.29 MPa, 76.5% and 3.26 MPa, respectively. The hydrogel swollen in the NaCl solution bent toward the anode under non‐contact direct current electric fields, and its bending speed and equilibrium strain increased with increasing applied voltage. The electroresponsive behavior of the hydrogel was also affected by the electrolyte concentration of external NaCl solution, and there was a critical ionic strength of 0.10 where the maximum equilibrium strain of the hydrogel occurred. By changing the direction of the applied potential cyclically, the hydrogel exhibited good reversible bending behavior. Copyright © 2011 Society of Chemical Industry     

Preparation and characterization of ethanol-induced chitosan-glutaric anhydride hydrogel for biomedical applications

Here we report a novel, fast, and facile sythesis of chitosan-based hydrogels by ethanol directly inducing. In the present of ethanol, chitosan (CS) with glutaric anhydride (GA) could form hydrogels (CS-GA-Hs) just in few minutes. The results of ¹H NMR and FTIR confirmed N-acylation substitution of chitosan. Furthermore, the relative concentration of GA was also the critical parameter for formation and properties of CS-GA-Hs. When the concentration was 1.5, CS-GA-Hs showed the highest swelling (253.6%) and release degree (99.9%). The porous structure of CS-GA-Hs were observed by SEM and the pore size of the gels decreased from 500 to 200 μm, when the relative concentration of GA was changed from 1.5 to 4. And all the hydrogels were demonstrated a good mechanical properties. Additionally, the CS-GA-Hs showed in vitro antimicrobial activity against Staphylococcus aureus and Escherichia coli, and no cytotoxicity toward L929 mouse fibroblasts, meaning it has potential applications in biomedical fields.     

Synthesis and characterization of konjac glucomannan/poly(vinyl alcohol) interpenetrating polymer networks

Novel interpenetrating polymer networks (IPNs) coded as KP were synthesized successfully from poly(vinyl alcohol) (PVA) and konjac glucomannan (KGM) in the presence of glutaraldehyde as a crosslink agent. The transparent IPN films that were 40 μm thick were prepared by means of conventional solvent‐casting technique and dried at room temperature for 2 days. The structure and miscibility of the KP films were studied by Fourier transformed infrared spectra, scanning electron microscopy, differential scanning calorimetry, wide‐angle X‐ray diffraction, and ultraviolet visible spectroscopy (UV–Vis). The results indicated that strong intermolecular interaction caused by crosslink bonding between PVA and KGM occurred in the IPN films, resulting in wonderful miscibility when the reaction time is 4 h. The tensile strength, elongation at break, and moisture uptake was much higher than that of the pure PVA film, KGM film, and uncrosslinked blend films. In other words, the structure of IPN endowed the films with excellent performance, so the new material has promising applications to food package film and agricultural film because of its biodegradability. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2775–2780, 2004     

辐照法制备聚乙烯醇水凝胶研究进展

简要评述了聚乙烯醇水凝胶的制备方法,分析了各种方法的优点和缺点,介绍聚乙烯醇辐照交联的基本原理,并展望了辐射交联聚乙烯醇水凝胶研究及应用前景.     

Rheological characterization of a charged cationic hydrogel network across the gelation boundary

The in situ rheological behavior across the gelation threshold has been investigated for an affine network of a completely charged cationic monomer (3-acrylamidopropyl)-trimethylammonium chloride (APTMAC1) when it is crosslinked with a neutral crosslinker (N,N′-methylenebisacrylamide) to form a fully charged novel cationic hydrogel. The elastic moduli (G′) near the gel point (during the crosslinking or ‘curing’ process) show a power law dependence of the form G′(t)=ε^z, where ε=((t−t_c)/t_c) is the distance from the gel point (t_c). The critical exponent, z, for the hydrogel series investigated is estimated to be 1.5, slightly lower than the predictions based on percolation theory (z∼1.7-1.9). From the equilibrium (after the curing process) rheological measurements of a series of samples, it is inferred that there is a critical crosslinker mole percent (X_c) with respect to the monomer concentration, required to form a well-defined three-dimensional network with a solid-like behavior. The value of this X_c is found to be between 0.5 and 1%. The theoretically predicted value of X_c using the percolation theory (for the percolation of crosslinks, G₀(X)∝[|X−X_c|/X_c]^z) and the exponent estimated from the in situ measurements (z=1.5), is X_c∼0.6, which is in good agreement with the experiments. The results may have applicability in translating from bulk systems to the nanoscale in hydrogel design.     

Investigation on the interpenetrating polymer networks (ipns) of polyvinyl alcohol and poly(N-vinyl pyrrolidone) hydrogel and its in vitro bioassessment

Poly(vinyl alcohol) (PVA) and poly(N-vinyl pyrrolidone) (PVP) composite hydrogel with interpenetrating polymer networks (IPNs) was prepared by in situ polymerization and compared with pure PVA hydrogel. The prepared IPN hydrogel was characterized by infrared spectroscopy (IR), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy. The mechanical property and cell culture were also tested. The results show that PVP can chemically bond with PVA and form uniform blend hydrogel. The content of PVP can affect the structure, crystallinity, glass transition temperature (T_g), and mechanical property of the hydrogel. The T_g of the PVA hydrogel is 2.7°C while the T_g of the IPN hydrogel is −37°C. The IPN hydrogel has lower glass transition temperature, corresponding to better elastic properties, and has better mechanical performance on stretch and compression than PVA hydrogel. The crystallinity (X_c) of PVA hydrogel and IPN hydrogel is 65.3 and 26.3%, respectively. The DMA curves and XPS analysis suggest that PVA and PVP are well miscible on a molecular level in the IPN hydrogel. The cell proliferation trend demonstrates that the addition of PVP has a positive influence on the cell growth and the IPN hydrogel may be used as a promising biomaterial for artificial cartilage substitute. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of diethanolamine-impregnated cross-linked polyvinylalcohol/glutaraldehyde membranes for CO2/CH4 separation

In this research, the cross-linking of diethanolamine (DEA) impregnated poly(vinyl alcohol) (PVA) on polytetrafluoroethylene (PTFE) by glutaraldehyde (GA) with different blend compositions (GA/PVA: 0.5, 1, 3, 5, 7 ratio%) was performed in the absence of an acid catalyst and organic solvents in order to avoid any interference in CO₂ facilitation reaction with DEA. The fabricated membranes were characterized by differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) and scanning electron microscopy (SEM). Furthermore, the effects of cross-linking agent content, feed pressure and composition as well as stability on CO₂/CH₄ transport properties were investigated in both pure and mixed gas experiments. The cross-linked membranes showed reasonable CO₂/CH₄ permselectivities in comparison with uncross-linked membranes. The best-yield CO₂-selective membranes (DEA-PVA/GA(1 wt%)/PTFE) represented the best CO₂/CH₄ selectivity of 91.13 and 665 for pure and mixed gas experiments, respectively.     

Bending behaviour of electroresponsive poly(vinyl alcohol)/poly(acrylic acid) semi‐interpenetrating network hydrogel fibres under an electric stimulus

Poly(vinyl alcohol) (PVA) and poly(acrylic acid) (PAA) composite fibres were prepared via solution spinning and subsequently, semi‐interpenetrating networks (SIPN) were obtained by crosslinking the fibres with glutaraldehyde. The hydrogel fibres exhibited bending behaviour under DC electric stimulation. The effects of a number of factors have been systematically studied, including the PAA content within the network, electric voltage imposed across the fibre, the fibre diameter, concentration of the crosslinking agent, pH and ionic strength of the bath solution. Our experimental results show a stable reversibility of bending behaviour under the applied electric field. The degree of bending at equilibrium and the bending speed of the hydrogel fibre increased with the intensity of the applied electric voltage and the PAA content having negatively charged ionic groups within the SIPN. The electroresponsive behaviour of the present SIPN hydrogel fibre was also affected by the aforementioned extrinsic factors. These observations are interpreted in terms of fibre stiffness, fixed charge density and swelling pressure, which depend on the hydrogel equilibrium states in different pH and ionic environments together with the electrochemical reactions under DC electric field. © 2002 Society of Chemical Industry     

室温交联PVA水凝胶的制备与性能研究

以环氧氯丙烷为交联剂,采用室温化学交联法制备了聚乙烯醇(PVA)水凝胶,研究了交联温度和交联时间对PVA溶胀性能和力学性能的影响,借助差示扫描量热法(DSC)和扫描电子显微镜(SEM)对PVA水凝胶进行分析表征。结果表明,当交联时间为3d且交联温度为50℃时PVA水凝胶的综合性能最佳。PVA的玻璃化转变温度为-54.50℃,PVA水凝胶中包含有自由水、束缚水和非冷冻水。