Plasma protein adsorption pattern and tissue-implant reaction of poly(vinyl alcohol)/carboxymethyl-chitosan blend films

Various poly(vinyl alcohol)/carboxymethyl-chitosan (PVA/CMCS) blend films were prepared by a mechanical blending method and characterized by SEM for their surface and cross-section morphologies. It indicated that blending high CMCS content in PVA plastic led to a rough surface and loose structure. Bovine serum albumin (BSA) and bovine fibrinogen (BFG) were chosen as representative plasma proteins to carry out adsorption tests. Equilibrium adsorption amount of proteins onto the blends decreased with the increase of CMCS content in film matrix, and BSA was more easily adsorbed onto the films than BFG in the same conditions. The blend films also exhibited different trends for BSA and BFG adsorption when pH of the media changed, but maximum adsorption approximately occurred at the isoelectric point of proteins. Moreover, increasing the ionic strength would always decrease the adsorptions of protein onto the films. In animal experiments, it was found that incorporation of CMCS and PVA gave a lower tissue reaction than pure PVA films when they were subcutaneously implanted in Wistar rats. After two weeks subcutaneous implantation, surfaces of PVA became wrinkled and cracked; however, the blend implants exhibited a alveolate porous microstructure.     

Mechanical properties and biocompatibility of soluble eggshell membrane protein/poly(vinyl alcohol) blend films

Poly(vinyl alcohol) (PVA) has been blended with soluble eggshell membrane protein (SEP) to improve the mechanical properties of SEP film that is brittle. Tensile strength and elongation-at-break increase with increasing amount of PVA. When the SEP/PVA proportion is 1:1, a strong and flexible film is obtained, having a tensile strength of 22.7 MPa and elongation-at-break of 106%. Although scanning electron microscopy observation of the freeze-fractured cross-section shows microphase separation, interaction between SEP and PVA exists, as revealed by FT-IR. NIH3T3 cell culture demonstrates that SEP/PVA blend films with up to 50% of PVA show biocompatibility comparable to pure SEP film.     

Cell-compatible properties of calcium carbonates and hydroxyapatite deposited on ultrathin poly(vinyl alcohol)-coated polyethylene films

Poly(vinyl alcohol) (PVA) was coated onto polyethylene (PE) films by a repetitive adsorption and drying process, and then the PVA-coated PE films were alternately immersed into aqueous solutions of Ca²⁺ and CO^2- ₃ ions (alternate soaking cycles), to deposit calcium carbonate (CaCO₃) onto the films. The PVA coating was essential for the CaCO₃ deposition. The amount of CaCO₃ deposited increased with an increasing number of cycles. Scanning electron microscopic observations and attenuated total reflection spectra revealed the presence of both calcite and aragonite as the crystal structures of CaCO₃ on the film. L929 fibroblast cells adhered and proliferated on these CaCO₃-deposited PE films, as well as the hydroxyapatite-coated PE films previously prepared. It was found that the PVAcoating and the subsequent deposition of calcium salts on certain films facilitated cell compatibility.     

Mechanical properties and biocompatibility of soluble eggshell membrane protein/poly(vinyl alcohol) blend films

Poly(vinyl alcohol) (PVA) has been blended with soluble eggshell membrane protein (SEP) to improve the mechanical properties of SEP film that is brittle. Tensile strength and elongation-at-break increase with increasing amount of PVA. When the SEP/PVA proportion is 1:1, a strong and flexible film is obtained, having a tensile strength of 22.7 MPa and elongation-at-break of 106%. Although scanning electron microscopy observation of the freeze-fractured cross-section shows microphase separation, interaction between SEP and PVA exists, as revealed by FT-IR. NIH3T3 cell culture demonstrates that SEP/PVA blend films with up to 50% of PVA show biocompatibility comparable to pure SEP film.     

Multiphase blends from poly(L-lactide) and poly(methyl mathacrylate)

Melt processing of poly(L-lactide) (PLLA) and poly(methyl methacrylate) (PMMA) was conducted over a targeted range of compositions with PLLAs of 118 and 316 kDa in molecular mass to identify morphologies and the phase relationships in these blends. These blends are of interest for use in biomaterials and the morphologies are critical for tissue-engineering studies where biodegradability, pore connectivity and surface texture control tissue viability and adhesion. Simple extrusion of the two polymers produced multiphase blends with an average domain size near 25 μm. Scanning electron microscopy and dynamic mechanical analysis demonstrated that these blends are immiscible, at least in a metastable sense, and regions of co-continuous structures were identified. Such co-continuous, which occurred generally in accordance with rheology prediction models, exhibit a fine interconnected structure that appears effective for fabricating certain biomaterials. A broad and unexpected transition appears in these blends, as measured by modulated differential scanning calorimetry between 70 and 100°C, which may be the glass transition temperature of an alloy phase. The magnitude of this transition is greatest in the fine-structured co-continuous composition region of blends, suggesting the presence of a complex or other derivative of the two primary phases.     

Hydroxyapatite deposition by alternating soaking technique on poly(vinyl alcohol)-coated polyethylene films

A poly(vinyl alcohol) (PVA)-coating on polyethylene films, prepared by repetitive adsorption/drying in an aqueous PVAsolution, accelerated hydroxyapatite (HAp) deposition by an alternate soaking in aqueous solutions containing Ca²⁺ and PO^¾- ions. X-ray photoelectron spectra of the 4 surface of the HAp-deposited film showed the presence of calcium and phosphorus of a suitable peak ratio for HAp formation. X-ray diffraction analyses also revealed peaks corresponding to HAp. Scanning electron microscopic observation showed the surface of the HAp layer to be smooth, with nano-ordered dotted threads in networks. A simple PVA coating on a surface will serve as a novel system for accelerated HAp formation via alternating soaking.     

Fabrication and characterization of hydrophilic poly(lactic-co-glycolic acid)/poly(vinyl alcohol) blend cell scaffolds by melt-molding particulate-leaching method

Porous PLGA/PVA scaffolds were fabricated by blending poly(lactic-co-glycolic acid) (PLGA) with polyvinyl alcohol (PVA) to improve the hydrophilicity and cell compatibility of the scaffolds for tissue engineering applications. PLGA/PVA blend scaffolds with different PVA compositions up to 20wt% were fabricated by a melt-molding particulate-leaching method (non-solvent method). The prepared scaffolds were investigated by scanning electron microscopy (SEM), mercury intrusion porosimetry, the measurements of water contact angles and bi-axial tensile strengths, etc. for their surface and bulk characterizations. The scaffolds exhibited highly porous and open-cellular pore structures with almost same surface and interior porosities (pore size, 200-300 microm; porosity, about 90%). The PLGA/PVA blend scaffolds with PVA compositions more than 5% were easily wetted in cell culture medium without any prewetting treatments, which is highly desirable for tissue engineering applications. In vitro cell compatibility of the control hydrophobic PLGA and hydrophilized PLGA/PVA (5wt%) blend scaffolds was compared by the culture of human chondrocytes in the scaffolds and the following analyses by MTT assay and SEM observation. It was observed that the PLGA/PVA blend scaffold had better cell adhesion and growth than the control PLGA scaffold. For in vivo evaluation of tissue compatibility, the scaffolds were implanted into the skull defects of rabbits. The results were evaluated by histology examinations. The PLGA/PVA (5wt%) blend scaffold showed better bone ingrowth into the scaffold and new bone formation inside the scaffold than the PLGA scaffold. It seems that 5% addition of PVA to PLGA to fabricate PLGA/PVA blend scaffolds is enough for improving the hydrophilicity and cell compatibility of the scaffolds.     

Synthesis of poly(vinyl alcohol)/poly(dimethylsiloxane) graft copolymer

Poly(vinyl acetate)/poly(dimethylsiloxane) graft copolymer ( 4a ), with a controlled poly(dimethylsiloxane) graft chain length, was synthesized by radical copolymerization of vinyl acetate with poly(dimethylsiloxane) ( 3 ) having a dimethylvinylsilyl end group. 3 was prepared by living anionic polymerization of hexamethylcyclotrisiloxane ( 1 ) with butyllithium and subsequent termination with chlorodimethylvinylsilane ( 2 ). Poly(vinyl alcohol)/poly(dimethylsiloxane) graft copolymer ( 4b ) was then synthesized by selective saponification of the poly(vinyl acetate) segments in the graft copolymer 4a with K₂CO₃ in methanol.     

Investigation of poly(vinyl alcohol)/poly(N-vinyl-2-pyrrolidone) blends, 3. Permeation properties of polymer blend membranes

Dense membranes made of poly(vinyl alcohol) (PVA) and poly(N-vinyl-2-pyrrolidone) (PVP) blends of different compositions were studied in gas-sweeping permeation of a water-ethanol mixture containing 10 wt.-% of water. When the PVP content increases, the steady-state permeation flux and the water content in the permeate show sudden changes at ca. 30–40 wt.-% of PVP in the membrane: the flux increases drastically, while the water selectivity of the membrane falls to a much lower level. The diffusion coefficients of both water and ethanol, as determined from the permeation flux changes in the transient regime, exhibit a large increase when the PVP content exceeds 30 wt.-%, and this accounts for the flux increase. The fall in the permeation selectivity is shown to be due to a strong decrease in the sorption selectivity. The threshold of the change corresponds approximately to the PVP content at which PVA crystallites no longer exist in the blend. A further study on the states of water in the blend membranes by differential scanning calorimetry made it possible to relate these changes with a change in the interactions of water with hydrophilic sites in the polymer blend when the PVP content changes.     

Properties of the poly(vinyl alcohol)/chitosan blend and its effect on the culture of fibroblast in vitro.

In this work, the properties of poly(vinyl alcohol) (PVA) and PVA/chitosan blended membranes were investigated by scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and electron spectroscopy for chemical analysis (ESCA). The SEM photographs show the PVA/chitosan blended membrane undergoes dramatic changes on the surface and bulk structure during the membrane formation. The DSC analysis shows that PVA and chitosan are not very compatible in the PVA/chitosan blended membrane, whereas the combination of two polymer chains of constitutionally different features is revealed. In addition, the surface of the PVA/chitosan blended membrane is enriched with nitrogen atoms at the ESCA analysis. These reflect the PVA membrane can be modified by blending with chitosan that in turn may affect the biocompatibility of the blended membrane. Therefore, adhesion and growth of fibroblasts on the PVA as well as PVA/chitosan blended membranes were investigated. Cell morphologies on the membranes were examined by SEM and cell viability was studied using MTT assay. It was observed that the PVA/chitosan blended membrane was more favorable for the cell culture than the pure PVA membrane. Cells cultured on the PVA/chitosan blended membrane had good spreading, cytoplasm webbing and flattening and were more compacting than on the pure PVA membrane. Consequently, the PVA/chitosan blended membrane may spatially mediate cellular response that can promote cell attachment and growth, indicating the PVA/chitosan blended membrane should be useful as a biomaterial for cell culture.     

Friction and wear behavior of poly(vinyl alcohol)/poly(vinyl pyrrolidone) hydrogels for articular cartilage replacement

Many hydrogels have been proposed as articular cartilage replacements as an alternative to partial or total joint replacements. In the current study, poly(vinyl alcohol)/poly(vinyl pyrrolidone) (PVA/PVP) hydrogels were investigated as potential cartilage replacements by investigating their in vitro wear and friction characteristics in a pin-on-disk setup. A three-factor variable-level experiment was designed to study the wear and friction characteristics of PVA/PVP hydrogels. The three different factors studied were (a) polymer content of PVA/PVP hydrogels, (b) load, and (c) effect of lubricant. Twelve tests were conducted, with each lasting 100,000 cycles against Co-Cr pins. The average coefficient of friction for synovial fluid lubrication was a low 0.035 compared with 0.1 for bovine serum lubrication. Frictional behavior of PVA/PVP hydrogels did not follow Amonton's law of friction. Wear of the hydrogels was quantified by measuring their dry masses before and after the tests. Higher polymer content significantly reduced the wear of hydrogel samples with 15% PVA/PVP samples, showing an average dry polymer loss of 4.74% compared with 6.05% for 10% PVA/PVP samples. A trend change was observed in both the friction and wear characteristics of PVA/PVP hydrogels at 125 N load, suggesting a transition in the lubricating mechanism at the pin-hydrogel interface at the critical 125 N load.     

Physical properties and biocompatibility of cellulose/soy protein isolate membranes coagulated from acetic aqueous solution

A series of cellulose/soy protein isolate (SPI) membranes was prepared from cellulose and SPI solution by casting and coagulation from 5 wt% acetic acid and 5 wt% sulphuric acid aqueous solution, respectively. The structure and properties of the membranes were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy and tensile testing. The effects of SPI content (W _SPI) and the coagulants on the structure and properties of the membranes were investigated. The membranes exhibited porous structure. The pore size in the surfaces and cross-sections of the membranes increased with an increase of W _SPI regardless of the coagulants. The membranes containing 10 wt% W _SPI showed higher tensile strength and elongation at break than other membranes. The membranes with the same W _SPI coagulated from acetic acid solution exhibited higher values of tensile strength, elongation at break and pore size in the surfaces and cross-sections than those corresponding membranes coagulated from sulphuric acid. The biocompatibility of the acetic acid-coagulated membranes was preliminarily evaluated by cell culture and in vivo implantation experiments. The results revealed that human umbilical vein endothelial cells (ECV304) grew well on this biomaterial. In comparison with the pure cellulose membrane, because of the incorporation of SPI and the resultant alteration of microstructure, the SPI-modified membranes showed an improved in vivo biocompatibility and biodegradability in the implantation experiments. These cellulose/SPI membranes warrant further explorations in biomedical fields.     

Investigations of poly(vinyl alcohol)/poly(N-vinyl-2-pyrrolidone) blends, 1. Compatibility

Blends of crystallizable poly(vinyl alcohol) (PVA) with poly(N-vinyl-2-pyrrolidone) (PVP) made from aqueous solutions appear to be miscible in the whole composition range according to DSC results. A large negative value of the interaction parameter between the two polymers was found from melting point depressions. IR spectroscopy evidenced compatibility of the two polymers on a molecular level. DSC, density and IR results all show a proportion of pure PVA crystallites in blends, which decreases with increasing PVP content and becomes nil at about 50 wt.-% of PVP. However, close examination of the hydroxyl stretching region of the blends indicates the presence of organized regions of PVA beyond this limit. According to IR results, the sequence of decreasing hydrogen-bonding power should be the following: multiple hydroxyl-hydroxyl bonding in organized PVA regions, hydroxyl-carbonyl bonding between the two polymers, and simple hydrogen-hydrogen bonding in amorphous PVA regions. It appears that the PVA component can be held in the amorphous state by hydrogen bonding with the PVP component when there is a sufficient amount of the latter in the blend. The amorphous part of PVA is compatible with PVP, but the crystallizable part is not in its most stable form.     

Egg white/poly (vinyl alcohol)/MMT nanocomposite hydrogels for wound dressing

Nanocomposite hydrogels on the basis of egg white and poly (vinyl alcohol) (PVA) containing 0, 5, and 10 wt.% of montmorillonite (MMT) nanoclay were prepared by a facile cyclic freezing–thawing technique and their properties investigated for wound dressing application. The morphological, structural, thermal, physical, and in vitro cytotoxic properties of the prepared nanocomposite hydrogel wound dressings (NHWDs) were experimentally studied. The NHWDs had an exfoliated morphology with a porous structure having pores sizes in the nanometric scale. It was shown that MMT acted as cross-linker in the network of NHWDs and improved their thermal stabilities. The prepared wound dressings were transparent and their equilibrium water contents and water vapor transmission rates, as two important factors of wound dressings, were very close to the properties of human skin which means that the prepared wound dressings could interact appropriately with the damaged tissues of wounds and protect them like an artificial skin during the wound healing process. The in vitro cytotoxicity assay also confirmed the non-cytotoxic nature of the prepared NHWDs. It was finally concluded that the prepared egg white/PVA/MMT nanocomposite hydrogels are promising materials to be used as novel wound dressings in wound and burn care.     

Biodegradable poly(vinyl alcohol)/polyoxalate electrospun nanofibers for hydrogen peroxide-triggered drug release

Release of drugs in a controlled and sustainable manner is of great interest for treating some inflammatory diseases, drug delivery, and cosmetics. In this work, we demonstrated the control release of a drug from composite nanofibers mediated by hydrogen peroxide. Composite nanofibers of polyvinyl alcohol (PVA)/polyoxalate (PVA/POX NFs) blended at various weight ratios were successfully prepared by electrospinning. Rhodamine B (RB) was used as a model of drug and was initially loaded into the POX portion. The morphology of NFs was characterized using scanning electron microscopy (SEM). The functional groups presented in the NFs were characterized using IR spectroscopy. In vitro release behavior and cell toxicity of nanofibers were also investigated using the MTT assay. The results indicated that POX content had a significant effect on the size and release profiles of nanofibers. Microstructure analysis revealed that sizes of PVA/POX NFs increased with increasing POX content, ranging from 214 to 422 nm. Release profiles of RB at 37 °C were non-linear and showed different release mechanisms. The mechanism of drug release depended on the chemical composition of the NFs. RB release from the NFs with highest POX content was caused by the degradation of the nanofiber matrix, whereas the RB release in lower POX content NFs was caused by diffusion. The NFs with POX showed a loss of structural integrity in the presence of hydrogen peroxide as seen using SEM. The MTT assay showed that composite nanofibers had minimal cytotoxicity. We anticipate that nanofibrous PVA/POX can potentially be used to target numerous inflammatory diseases that overproduce hydrogen peroxide and may become a potential candidate for use as a local drug delivery vehicle.     

Preparation,characterization and properties of gradient polymer blends: discussion of poly(vinyl chloride)/poly(methyl methacrylate) blend films containing a wide compositional gradient phase

We prepared several types of thick ≈200 μm films of a poly(vinyl chloride)/poly-(methyl methacrylate) (PVC/PMMA) gradient polymer blend, which contained a widely waried compositional gradient phase, using a dissolution and diffusion method. We discussed the preparation conditions by classifying those gradient blend films into 5 types based on the results of differential scanning calorimetry (DSC) measurements and found the optimum conditions for preparing the ideal gradient blend consisting of only one extremely wide compositional gradient phase. Further, the gradient structures, which were evaluated by the results of DSC measurements, were confirmed by means of Fourier transform infrared/attenuated total reflection (FTIR-ATR). Finally, the ideal blend was found to have significantly new or improved properties (e.g. a large half-width of temperature of the dissipation factor tan δ) which cannot be observed in any PVC, PMMA homogeneously (that is ordinarily) miscible blend or a laminate system.     

Structural Characteristics and Properties of Silk Fibroin/Poly(lactic acid) Blend Films

This paper describes the preparation and characterization of blend films composed of regenerated silk fibroin (SF) and poly(lactic acid) (PLA). FT-IR and XRD of the SF/PLA blend films with different ratios indicated that the secondary structural transition of SF from Silk I to Silk II was induced upon blending with PLA. The effects of SF/PLA blend ratios on the mechanical and physical properties of the blend films were investigated. Compared to pure SF film, the mechanical and thermal properties of the blend films were improved, and surface hydrophilicity and swelling capacity decreased due to the secondary structural transition of SF to Silk II. Among the blend films with different ratios, the SF/PLA blend film with 7 wt% PLA content showed excellent mechanical properties. Meanwhile, the BSA adsorption amount on the blend film increased with the increase of PLA content. In vitro cell adhesion test showed that the blend film was a good matrix for the growth of L929 mouse fibroblast cells. Consequently, controlling the PLA content in the SF film can improve the mechanical and physical properties of the SF film and provide a promising opportunity to widen potential application of SF in the biomaterials field.     

Effect of filler on kinetics and energy of activation of phase separation in poly(methyl methacrylate)/poly(vinyl acetate) blend

The effect of a filler on the rate and energy of activation of phase separation was studied for binary poly(methyl methacrylate)/poly(vinyl acetate) blends (system with LCST) using light scattering. It was found that the rate of phase separation of the filled blends at close quench depth ΔT = T–T_s is much lower as compared with the unfilled one at close quench depth. The activation energy for the filled blends is lower than that of unfilled blends. The drop of the rate of phase separation and of the activation energy in filled systems is explained by the formation of a border layer at the interface with solid where molecular packing is less dense and molecular mobility is restricted in comparison with unfilled polymer. Equal rates of phase separation or the equilibrium state may be achieved at higher quench depth for the filled blend.     

Fabrication and characterization of poly(DL-lactic-co-glycolic acid)/zirconia-hybridized amorphous calcium phosphate composites

Several minerals, such as hydroxyapatite and β-tricalcium phosphate, have been incorporated into bioresorbable polyester bone scaffolds to increase the osteoconductivity both in vitro and in vivo. More soluble forms of calcium phosphate that release calcium and phosphate ions have been postulated as factors that increase osteoblast differentiation and mineralization. Recently, a zirconia-hybridized pyrophosphate-stabilized amorphous calcium phosphate (Zr-ACP) has been synthesized allowing controlled release of calcium and phosphate ions. When incorporated into bioresorbable scaffolds, Zr-ACP has the potential to induce osteoconductivity. In this study, 80–90% (w/v) porous poly(DL-lactic-co-glycolic acid) (PLGA) scaffolds were formed by thermal phase separation from dioxane while incorporating Zr-ACP. Scanning electron microscopy revealed a highly porous structure with a pore size ranging from a few μm to about 100 μm, smaller than we had hoped for. Zr-ACP particles were evenly dispersed in the composite structure and incorporated into the pore walls. The amorphous structure of the Zr-ACP was maintained during composite fabrication, as found by X-ray diffraction. Composite scaffolds had larger compressive yield strengths and moduli compared to pure polymer scaffolds. These initial efforts demonstrate that PLGA/Zr-ACP composites can be formed in ways that ultimately serve as promising bone scaffolds in tissue engineering.     

Cell-adhesive and blood-coagulant properties of ultrathin poly(methyl methacrylate) stereocomplex films

Isotactic (it) and syndiotactic (st) poly(methyl methacrylate)s (PMMAs) were assembled on a poly(ethylene terephthalate) cell disk (as a solid substrate), which is normally used for cell culture, to produce ultrathin stereocomplex films. Static contact angles of the films using air bubbles in aqueous phase revealed the stepwise assembly of both polymers. More L929 fibroblast cells adhered and were flattened on the ultrathin stereocomplex films, compared to homogeneous PMMA films and to spin-coated films comprised of a mixed solution of it- and st-PMMAs with a molar ratio of 1 : 2, which is the stoichiometry of a stereocomplex. The difference in the number of adherent cells was greatest after the first 3 h of incubation. Pre-adsorption of proteins, which are related to cell adhesion, onto the stereocomplex film potentially modulated the cell-adhesive properties. Fresh whole human blood did not coagulate on the complex film for 20 min, although blood coagulated after 15 min on the homogeneous films and on the 1 : 2 mixed film. Platelets did not adhere onto the complex films after 15 min of incubation, which was consistent with the results of blood coagulation. These observations indicate that the stereocomplex formation of PMMAs on the surface of films strongly affects the bioactivity of these films.