Permeability of adhesive resin films

The purpose of this study was to quantify the permeability of adhesive resin films to water by measuring convective flow across thin films. Cured resin films were prepared with the use of five commercially available adhesive resins and an experimental resin. Two types of resin films were prepared from solvated comonomer blends within each product; resin films made before or after evaporation of solvent (10 s of drying with air-syringe). The permeability of the resin films was measured 30 min or 24 h after polymerization by placing the films in a split-chamber device. Fluid filtration rate through the resin films was measured with the use of 20 cm of water pressure. Osmotically induced water movement was measured by applying hypertonic aqueous solutions of CaCl2 or HEMA to the resin films. The results showed that evaporation of solvent before polymerization reduced the permeability of adhesive resin films, compared to permeabilities obtained without solvent evaporation. The cured adhesive resin films were all permeable to water, but to varying degrees.     

Infiltration/evaporation-induced shrinkage of demineralized dentin by solvated model adhesives

During dentin bonding, solvated adhesive comonomers are applied to water-saturated decalcified dentin matrices. When alcohol-solvated hydrophilic or hydrophobic methacrylate monomers are applied, they chemically remove water and cause matrix shrinkage during comonomer infiltration. Evaporation of solvent induces further shrinkage. The purpose of this work was to compare the shrinkage of water-saturated dentin matrices infiltrated with ethanol- or methanol-solvated 2-hydroxyethyl methacrylate (HEMA), 2,2-bis[4(2-hydroxy-3-methacryloyloxy-propyloxy)-phenyl] propane (BisGMA), or triethyleneglycol dimethacrylate (TEGDMA) at 90/10, 70/30, 50/50, and 30/70 mass fraction % alcohol/monomer before and after evaporation of alcohol. Thin (ca 0.2 mm) disks of human mid-coronal dentin were demineralized and placed in a well beneath the contact probe of a linear variable differential transformer (LVDT). The height of the matrix was measured before and after random application of one of the twelve alcohol/monomer mixtures. Matrix height was measured during infiltration and during solvent evaporation. Between trials, residual monomer was extracted using ethanol. These studies were repeated on specimens in which 100% alcohol was used to substitute for water in the matrix. Both studies revealed that matrices shrink 30-50% but that pretreatment of matrices with alcohol prevents BisGMA phase separations from occurring. Wet bonding with ethanol instead of water permits infiltration of relatively hydrophobic alcohol/monomers.     

Effect of resin hydrophilicity and water storage on resin strength

This study evaluated the change in the ultimate tensile strength (UTS) of five polymerised resin blends of increasing hydrophilicity, after ageing in distilled water or silicon oil. Resin blocks were prepared from each resin blend by dispensing the uncured resin into a flexible, embedding mould, containing multiple cavities. The resins were polymerised in the moulds under nitrogen at 551.6 kPa and light-activated at 125 degrees C for 10 min. After dry ageing for 24 h at 37 degrees C, the middle third of each resin specimen was trimmed into an 'I' shape. Fifteen control specimens were randomly selected from each resin blend for baseline UTS evaluation. The UTS of the experimental specimens were determined after 1, 3, 6 and 12 months of ageing in water or oil. The UTS of each group of resins at different storage periods in water or oil were analysed using the Friedman multiple ANOVA on ranks and Dunn's multiple comparison tests at 95% confidence level. Significant reduction (p < 0.01) in UTS was observed in Groups II-V resins after 12-month storage in water, while the most hydrophobic Group I resin showed no significant change (p > 0.05) in the same period. The percentage reduction in UTS increased with the hydrophilicity of the resin blends. Long-term water storage of hydrophilic resin blends such as those employed in dentine adhesives, resulted in a marked reduction in their mechanical strength that may compromise the durability of resin-dentine bonds.     

Blending polysaccharides with biodegradable polymers. I. Properties of chitosan/polycaprolactone blends

Blends of polycaprolactone (PCL) and chitosan (CHT) were prepared by casting from a solution. CHT and PCL were dissolved by using acetic acid/water mixtures. Both solutions were slowly mixed to cast blend films containing 10%, 20%, 30%, and 40% by weight of CHT. PCL and CHT form phase separated blends. The phase morphology is in large extent controlled by the casting procedure. Even if casting of the film starts from a clear solution, the solvent composition determines the form in which phase separation takes place and consequently the morphology of the resulting blend after solvent evaporation. The blend containing 20% CHT presents cocontinuous phases. The sample presents a high elastic modulus even at temperatures above melting of PCL. Blends with higher CHT contents consist of disperse PCL domains in a CHT matrix and the contrary occurs in the blend containing 10% CHT in which disperse CHT domains with a network morphology appear inside the spherulites of PCL. In all the blends, the nucleation effect of CHT accelerates the crystallization of PCL from the melt, although in the blends with high CHT contents a part of the PCL mass included in large domains might not be affected by the presence of CHT. The sample containing 20% CHT has a peculiar behavior with respect to the crystallization of PCL, only a small part of PCL crystallizes in isothermal treatments although this fraction crystallizes faster than in the rest of the blends.     

Sorption kinetics of ethanol/water solution by dimethacrylate-based dental resins and resin composites

In the present investigation the sorption-desorption kinetics of 75 vol % ethanol/water solution by dimethacrylate-based dental resins and resin composites was studied in detail. The resins examined were made by light-curing of bisphenol A glycol dimethacrylate (Bis-GMA), triethylene glycol dimethacrylate (TEGDMA), urethane dimethacrylate (UDMA), bisphenol A ethoxylated dimethacrylate (Bis-EMA), and mixtures of these monomers. The resin composites were prepared from two commercial light-cured restorative materials (Z100 MP and Filtek Z250), the resin matrix of which is based on copolymers of the above-mentioned monomers. Ethanol/water sorption/desorption was examined in both equilibrium and dynamic conditions in two adjacent sorption-desorption cycles. For all the materials studied, it was found that the amount of ethanol/water sorbed or desorbed was always larger than the corresponding one reported in literature in case of water immersion. It was also observed that the chemical structure of the monomers used for the preparation of the resins directly affects the amount of solvent sorbed or desorbed, as well as sorption kinetics, while desorption rate was nearly unaffected. In the case of composites studied, it seems that the sorption/desorption process is not influenced much by the presence of filler. Furthermore, diffusion coefficients calculated for the resins were larger than those of the composites and were always higher during desorption than during sorption. Finally, an interesting finding concerning the rate of ethanol/water sorption was that all resins and composites followed Fickian diffusion kinetics during almost the whole sorption curve; however, during desorption the experimental data were overestimated by the theoretical model. Instead, it was found that a dual diffusion-relaxation model was able to accurately predict experimental data during the whole desorption curve. Kinetic relaxation parameters, together with diffusion coefficients, are reported for all resins and composites.     

Effect of solvent on the characteristics of pentamidine loaded microcapsule

Biodegradable microcapsules of pentamidine/poly(L-lactide-co-D,L-lactide) were prepared by solvent evaporation technique using a mixture of organic solvents. The control batch of microcapsules was prepared using dichloromethane. The effect of solvent on the characteristics of pentamidine loaded microcapsules was examined by substituting up to 30% of dichloromethane with acetone, methanol, DMSO, ethyl acetate, and ethanol, respectively. No significant change in the surface morphology was observed when dichloromethane was substituted with 20% or less amount of other solvents. These microcapsules were all porous and spherical. However, the use of 30% DMSO or ethanol, along with dichloromethane, resulted in a mixture of elongated and spherical microcapsules. The efficiency of encapsulation of these two batches was also significantly higher than the other batches of microcapsules. The average particle size of the microcapsules prepared with 30% DMSO (165 microm) was significantly higher than the other batches (< 80 microm). A substitution of 10-30% dichloromethane with other listed organic solvents also showed a significant difference in the initial drug release. The drug release within the first twenty-four hours varied from 4 to 16%. The use of a second organic solvent, except ethanol, resulted in a significantly higher drug release during the second half of the dissolution study. The drug release continued more than 60 days.     

Immunostaining of cell preparations: A comparative evaluation of common fixatives and protocols

Immunostaining of cytologic preparations has been beset by problems of inconsistency, high background staining, and the requirement of different fixatives for different antigens. This study sought to identify a universal fixative and a simple fixation protocol suitable for a wide range of tissue antigens commonly employed for cytologic diagnosis. In an analysis of 23 fixation protocols involving acetone, acetone/methanol, acetone/formalin, glutaraldehyde, ethanol, methanol, and formal saline, fixation in 0.1% formal saline overnight at 27°C followed by 10 min fixation in 100% ethanol produced the most consistent and optimal preservation of immunoreactivity which could be further enhanced by pre-treatment with microwaves for epitope retrieval. Blocking of endogenous peroxidase was not necessary with this fixation protocol. Provided the smears were well air-dried (for at least 14 hr) prior to immersion in formal saline, there was no need to employ adhesive-coated glass slides. The smears could be kept at 27°C (room temperature) for at least 7 days and at −70°C for 5 wk without loss of immunoreactivity as air-dried smears or after fixation in formal saline. One hundred percent acetone and 100% ethanol produced good morphology and immunoreactivity but a high level of background staining, whereas acetone-based mixtures resulted in inconsistent immunostaining. Diagn Cytopathol 1996;15:167–174. © 1996 Wiley-Liss, Inc.     

Properties of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) films modified with polyvinylpyrrolidone and behavior of MC3T3-E1 osteoblasts cultured on the blended films

A series of composite films of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx) modified with polyvinylpyrrolidone (PVP) was prepared by varying the ratio of constituents, and their properties and cytocompatibility were evaluated. The hydrophilicity of the blended materials surfaces increased and the amounts of fibronectin and laminin adsorbed on the materials surface increased remarkably compared with PHBHHx. FT-IR spectra of the blended films showed a new band, implying that a surface physical interpenetrating network structure had formed. Scanning electron microscopy showed that there were dense pits and holes on the blended films surface. For the films of PHBHHx with 20 wt% and 40 wt% PVP, MTT assay indicated that PVP enhanced cell adhesion and proliferation, but that the effects were impaired by excessive PVP. The results suggested that proper addition of PVP increased the cytocompatibility of PHBHHx because the material surface had increased hydrophilicity and presented an appropriate morphology.     

Properties of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) films modified with polyvinylpyrrolidone and behavior of MC3T3-E1 osteoblasts cultured on the blended films

A series of composite films of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx) modified with polyvinylpyrrolidone (PVP) was prepared by varying the ratio of constituents, and their properties and cytocompatibility were evaluated. The hydrophilicity of the blended materials surfaces increased and the amounts of fibronectin and laminin adsorbed on the materials surface increased remarkably compared with PHBHHx. FT-IR spectra of the blended films showed a new band, implying that a surface physical interpenetrating network structure had formed. Scanning electron microscopy showed that there were dense pits and holes on the blended films surface. For the films of PHBHHx with 20 wt% and 40 wt% PVP, MTT assay indicated that PVP enhanced cell adhesion and proliferation, but that the effects were impaired by excessive PVP. The results suggested that proper addition of PVP increased the cytocompatibility of PHBHHx because the material surface had increased hydrophilicity and presented an appropriate morphology.     

Physicochemical properties and in vitro biocompatibility of PEO/PTMO multiblock copolymer/segmented polyurethane blends

A multiblock copolymer composed of poly(ethylene oxide) (PEO) and poly(tetramethylene oxide) (PTMO) and which forms a physical hydrogel was blended with Pellethane, a commercial segmented polyurethane (SPU) developed for various biomedical devices, to provide a PEO-rich surface with improved stability. The effect of the copolymer blending was evaluated with respect to surface hydrophilicity, long-term stability, mechanical properties, in vitro protein adsorption, and platelet adhesion. A small amount of the copolymer additive (5 wt%) significantly improved surface hydrophilicity, which was then gradually enhanced by increasing the amount of the copolymer in the blends. The blend films exhibited minimal extraction of the copolymer additive when exposed to a buffer solution for 2 months at 37 degrees C, resulting in less than 1 wt% weight loss of the films even with 30 wt% content of the copolymer in the blends. Although a certain degree of alteration in the mechanical properties was observed by increasing the copolymer content, the mechanical properties were well maintained for up to 10 wt% addition of the copolymer, when compared with the bare SPU. Protein adsorption was significantly reduced with a small amount of copolymer additive as low as 5 wt%. Fibrinogen, an adhesive protein for further cellular adhesion and activation, was effectively repelled by increasing the amount of copolymer additive. The platelet adhesion test revealed that the blend film surface reduced platelet adhesion and the degree of inhibition was proportional to the content of the additive, up to 30 wt%. The high molecular weight (Mw = 66,000) and compatible chemical structure of the copolymer with SPU made the surfaces PEO-rich and stable in an aqueous environment, resulting in an enhancement of the resistance to protein adsorption and platelet adhesion without a significant deterioration in physical properties.     

Application of hydrophobic resin adhesives to acid-etched dentin with an alternative wet bonding technique

Hydrophilic dentin adhesives are prone to water sorption that adversely affects the durability of resin-dentin bonds. This study examined the feasibility of bonding to dentin with hydrophobic resins via the adaptation of electron microscopy tissue processing techniques. Hydrophobic primers were prepared by diluting 2,2-bis[4(2-hydroxy-3-methacryloyloxy-propyloxy)-phenyl] pro- pane/triethyleneglycol dimethacrylate resins with known ethanol concentrations. They were applied to acid-etched moist dentin using an ethanol wet bonding technique that involved: (1) stepwise replacement of water with a series of increasing ethanol concentrations to prevent the demineralized collagen matrix from collapsing; (2) stepwise replacement of the ethanol with different concentrations of hydrophobic primers and subsequently with neat hydrophobic resin. Using the ethanol wet bonding technique, the experimental primer versions with 40, 50, and 75% resin exhibited tensile strengths which were not significantly different from commercially available hydrophilic three-step adhesives that were bonded with water wet bonding technique. The concept of ethanol wet bonding may be explained in terms of solubility parameter theory. This technique is sensitive to water contamination, as depicted by the lower tensile strength results from partial dehydration protocols. The technique has to be further improved by incorporating elements of dentin permeability reduction to avoid water from dentinal tubules contaminating water-free resin blends during bonding.     

Influence of cosolvents and in situ forming hydroxyapatite on the mechanical characteristics of collagen films

Collagen was processed into films in mixtures containing various ratios of water, propylene glycol, and ethanol. An experimental mixture design was applied to characterize the effects of individual solvents and their interactions on the mechanical properties of collagen films. Scanning electron microscopy (SEM) was used to examine the surface properties of collagen films. The ultimate tensile strength (UTS) and related characteristics of collagen films were also evaluated with dynamic mechanical analysis. The effect of in situ forming hydroxyapatite (HAP) within collagen films at a concentration of 10 mM on the physical characteristics of these films was evaluated by the same methods. With X-ray and SEM examinations, it was confirmed that HAP was formed inside the collagen film. However, the UTS of collagen films without HAP was 4-5 times higher than that with HAP. This was probably due to the discontinuity of the film structure caused by HAP in the collagen films. The results of a statistical analysis of the experimental design revealed the influence of the solvent mixtures on the mechanical properties of the collagen films with and without HAP, showing similar responses for the UTS and modulus of elasticity. Both parameters showed a maximal response in the solvent range containing a lower percentage of ethanol with the desired percentage of propylene glycol to plasticize the collagen films.     

表面图案化生物可降解聚膦腈制备及对成骨细胞的黏附

背景：纳/微米尺度的拓扑结构可影响细胞在基体上的黏附和增殖。 目的：改变制备条件,考察表面图案化聚(甘氨酸乙酯-丙氨酸乙酯)膦腈(PGAP)膜的表面性质对成骨细胞黏附和增殖的影响。 方法：将PGAP溶于氯仿配成不同浓度溶液,在25 ℃、20%或80%湿度下浇铸成膜。采用SEM、AFM、XRD和水接触角进行表征,通过体外培养,采用黏附、增殖和细胞形态等评价膜表面特性对成骨细胞生物学行为的影响。 结果与结论：高相对湿度环境有利于形成图案化表面,溶液浓度升高使图案化结构变得更加规整。溶液质量浓度120 g/L时,可得到一种蜂巢结构表面,但当其升至160 g/L后,反而不利于图案化表面的形成。高湿度环境下得到的膜表现出极性磷和氮原子在表面富集的现象。这些特性使表面图案化的PGAP膜更易于吸附蛋白质,从而使成骨细胞更易在其上黏附,增殖速度更快,细胞铺展状态也更好。说明溶液浓度和环境湿度是一种简便、可用于控制PGAP膜表面性质的方法,可用于对成骨细胞生物学行为的调控。     

Blending polysaccharides with biodegradable polymers. II. Structure and biological response of chitosan/polycaprolactone blends

Blends of polycaprolactone (PCL) and chitosan (CHT) were prepared by casting from the mixture of solutions of both components in suitable solvents. PCL, and CHT, form phase separated blends with improved mechanical properties and increased water sorption ability with respect to pure PCL. The morphology of the system was investigated by scanning electron microscopy (SEM), atomic force microscopy (AFM) and confocal microscopy. Dispersed domains of CHT in the semicrystalline PCL matrix were found in samples with less than 20% CHT but cocontinuous phase morphologies are found in blends with 20% or more CHT. This feature was corroborated by the temperature dependence of the elastic modulus measured by dynamic mechanical properties as a function of temperature. It was observed that for those blends above 20 wt% CHT, the mechanical stability of the system was kept even after melting of the PCL phase. Primary human chondrocytes were cultured on the different substrates. Cell morphology was studied by SEM and the viability and proliferation was investigated by the colorimetric MTT assay. Different protein conformations were found by AFM on CHT and PCL samples which were related to the biological performance of the substrates. Hydrophilicty of the material is not directly related to the biological response and the sample with 20 wt% CHT shows better results than the other blends with respect to chondrocyte viability and proliferation. However, the results obtained in the blends are worse than in pure PCL. It seems to be correlated with the surface energy of the different blends rather than hydrophilicity.     

Effects of resin hydrophilicity on water sorption and changes in modulus of elasticity

As acidic monomers of self-etching adhesives are incorporated into dental adhesives at high concentrations, the adhesive becomes more hydrophilic. Water sorption by polymers causes plasticization and lowers mechanical properties. The purpose of this study was to compare the water sorption and modulus of elasticity (E) of five experimental neat resins (EX) of increasing hydrophilicity, as ranked by their Hoy's solubility parameters and five commercial resins. METHODS: After measuring the initial modulus of all resin disks by biaxial flexure, half the specimens were stored in hexadecane and the rest were stored in water. Repeated measurements of stiffness were made for 3 days. Water sorption and solubility measurements were made in a parallel experiment. RESULTS: None of the specimens stored in oil showed any significant decrease in modulus. All resins stored in water exhibited a time-dependent decrease in modulus that was proportional to their degree of water sorption. Water sorption of EX was proportional to Hoy's solubility parameter for polar forces (delta(p)) with increasing polarity resulting in higher sorption. The least hydrophilic resin absorbed 0.55 wt% water and showed a 15% decrease in modulus after 3 days. The most hydrophilic experimental resin absorbed 12.8 wt% water and showed a 73% modulus decrease during the same period. The commercial resins absorbed between 5% and 12% water that was associated with a 19-42% reduction in modulus over 3 days.     

Membrane permeability properties of dental adhesive films

This study evaluated the permeability properties of five experimental resin membranes that ranged from relatively hydrophobic to relatively hydrophilic to seal acid-etched dentin saturated with water or ethanol. The experimental resins (R1, R2, R3, R4, and R5) were evaluated as neat bonding agents or as solutions solvated with ethanol (70% resin/30% ethanol). The quality of dentin sealing by these experimental resins was expressed in terms of reflection coefficients calculated as the ratio of the effective osmotic pressure to the theoretical osmotic pressure of test solutions. The effective osmotic pressure produced across resin-bonded dentin was induced in hypertonic solutions (CaCl(2) or albumin) at zero hydrostatic pressure. The outward fluid flow induced by these solutions was brought to zero by applying an opposing negative hydrostatic pressure. The least hydrophilic resins blends, R1 and R2, exhibited significantly (p < 0.05) higher reflection coefficients than the most hydrophilic resins (R4 and R5) in both conditions of dentin saturation (water and ethanol). The reflection coefficients of neat resins were, in general, significantly higher when compared with their corresponding solvated versions in both conditions of dentin saturation. In dentin saturated with ethanol, bonding with neat or solvated resins, resulted in reflection coefficients that were significantly higher when compared with the results obtained in dentin saturated with water. Reflection coefficients of CaCl(2) (ca. 1 x 10(-4)) were significantly lower (p < 0.05) than for albumin (ca. 3 x 10(-2)). Application of hydrophobic resins may provide better sealing of acid-etched dentin if the substrate is saturated with ethanol, instead of water.     

壳聚糖/聚己内酯共混膜的制备及性能

背景：壳聚糖/聚己内酯共混材料在生物材料领域具有广泛的应用前景,但与蛋白、细胞反应机制尚不明确。 目的：观察壳聚糖/聚己内酯共混膜表面蛋白黏附和细胞活性。 方法：将不同配比的壳聚糖/聚己内酯混合溶液旋转涂膜法成膜。分别通过原子力显微镜、滴形分析仪、石英晶体天平和MTT比色法测量膜的表面形貌、亲疏水性、蛋白吸附和细胞增殖活性。 结果与结论：膜的表面形貌、亲疏水性、蛋白吸附和细胞增殖活性在很大程度上取决于壳聚糖和聚己内酯的质量配比。细胞在壳聚糖膜上具有较好的伸展形态,在聚己内酯膜上具有较高的增殖活性。     

Properties and structural characterization of chitosan/graphene oxide biocomposites

Novel chitosan (CS)/graphene oxide (GO) biocomposites (CS/GO-n) in the form of films are prepared in a casting and solvent evaporation method. Fourier-transform infrared spectroscopy (FT-IR), X-ray diffractions (XRD), atomic force microscopy (AFM), tensile testing and moisture uptake are used to study the structure and properties of these biocomposites. The results indicated that the biocomposite containing 0.6 wt% GO exhibits high tensile strength (64.42 MPa) with a large elongation at break (38.80%). GO improved the mechanical properties and the water-resistance of chitosan-based biocomposites.     

聚乳酸/聚乙烯醇共混膜的亲水性与降解性能研究

采用流延法和溶剂蒸发技术,以聚乳酸(PLA)和聚乙烯醇(PVA)为原料,制备可降解PLA/PVA共混膜.研究PLA/PVA共混膜的吸湿、吸水性能及水降解性能,探索共混膜的水降解机制.结果表明,共混膜的吸湿率与吸水率随共混膜中PLA含量的增加而降低;共混膜在生理盐水中的降解过程是分步进行的,降解初期,PLA降解起主导作用,降解后期,PVA降解起主导作用.在PLA降解过程中,溶液的酸性具有催化降解效果,且PLA降解是从非晶区到晶区;PVA的引入,增加了共混膜的亲水性,并对PLA的结晶性能造成一定的破坏,加速PLA降解过程.因此,可通过调整PLA与PVA配比,在一定范围内对PLA/PVA共混膜的亲水性能与降解性能进行调控.     

Effect of resin hydrophilicity and temperature on water sorption of dental adhesive resins

This study examined the effects of copolymer hydrophilicity and temperature on water sorption and solubility characteristics of five copolymer blends of increasing degree of hydrophilicity using gravimetric measurements. Six resin disks (15 mm in diameter x 1 mm in thickness) were prepared from each copolymer blend and were stored in deionised water at 23, 37 and 55 degrees C. Water sorption and solubility of the resin disks were measured before and after water immersion and desiccation. Multiple regression analysis of water sorption was performed on two independent variables, copolymer hydrophilicity and temperature. Maximum water sorption increased significantly with Hoy's total cohesive energy density (delta(t)), Hoy's solubility parameter for polar forces (delta(p)) and hydrogen bonding (delta(h)), but was not influenced by temperature. However, a significant positive relationship was observed between diffusion coefficients (obtained using Fick's law of diffusion) and temperature. The water absorption activation energy was 10 kJ/mol for the most hydrophilic copolymer blend R5 and 35-51 kJ/mol for copolymer blends R1-R4. The positive relationship between maximum water uptake and copolymer hydrophilicity suggests that water molecules diffuse through the polymer matrices by binding successively to the polar sites via hydrogen bonding. Such water sorption may determine the durability of resin-dentine bonds.