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PubMed2006

Radiation processed hydrogel of poly (vinyl alcohol) with biodegradable polysaccharides.

Poly(vinyl alcohol) (PVA) can be modified to polymer hydrogels by radiation crosslinking and can be used in different biomedical applications. A study was done on the optimization of ingredients concentration for preparing good quality PVA hydrogels with natural polysaccharides. The synthesized hydrogels were also characterized by measuring the different physical properties e.g. gel fraction, swelling and absorption rate. Besides these, sterility test were also performed. Good quality hydrogels were obtained from PVA and natural polysaccharides solutions with 27 kGy radiation dose. There is an influence of natural polysaccharides on the gel fraction of hydrogel. The increase in the amount of polysaccharide causes a decrease in gel fraction that is decrease in the crosslinking density of PVA hydrogel network. The prepared hydrogels were found to be sterile.

Absorbable Implants↗
PubMed2006

In vitro skin penetration and pharmacodynamic evaluation of prostaglandin E1 ethyl ester, a vasoactive prodrug of prostaglandin E1, formulated into alcoholic hydrogels.

Alcoholic hydrogels containing prostaglandin E1 ethyl ester (PGE1-EE), a prodrug of PGE1 as a therapeutic agent for erectile dysfunction, were formulated. The prodrug was stable against chemical hydrolysis in aqueous solution (pH 7.4), devoid of esterase activities, but was hydrolyzed to the parent drug in rat skin homogenates within 240 min. In the rat skin penetration study for 24 h, the steady-state flux values (microg/cm2/h) of PGE1-EE and PGE, from alcoholic hydrogels having 20% ethanol content were 7.6 and 1.8, respectively. PGE1-EE was superior to PGE, from a skin penetration point of view due to its increased lipophilicity. The fastest skin penetration rate was obtained for PGE1-EE in 20% alcoholic hydrogel together with limonene or cineole. These formulations increased the flux of PGE1-EE up to about 4-fold compared to control hydrogel in the absence of penetration enhancers. In the pharmacodynamic study using a cat, alcoholic hydrogel with limonene or cineole showed a significant effect in terms of increasing intracavernosal pressure compared to control hydrogel. Therefore, the transdermal alcoholic hydrogel formulation of PGE1-EE with limonene or cineole can be a promising transdermal delivery system to overcome inconvenience associated with frequent intracavernosal injections for the treatment of erectile dysfunction.

Alcohols↗
PubMed1994

Oxygen performance of a prototype nonconventional hydrogel.

UNLABELLED: INTRODUCTION. Oxygen permeability (Dk) of available hydrogel materials used for soft contact lenses is currently restricted by the oxygen permeability of water at 80 Dk units. A predicted upper limit for conventional hydrogels amenable for use as a contact lens, has been 37 Dk units obtained with a water content of 80%. Methods for increasing oxygen permeability beyond that determined by water content must be explored, in order to further advance the physiological compatibility of hydrogel contact lenses. METHODS: Oxygen transport characteristics of a prototype nonconventional hydrogel contact lens material were derived in terms of human equivalent oxygen percentage (EOP) and thickness (L). The oxygen permeability of the material and oxygen transmissibilities (Dk/L) of various thicknesses were computed on the bases of a recently published nonlinear EOP vs. Dk/L relationship. RESULT: The material's oxygen permeability (Dk) was determined to be approximately 35 Dk units compared to 12.7 Dk units calculated for a conventional gel material having the same water content (52% H2O). Oxygen permeability equivalent to that obtained with high-water conventional gels was achieved using this mid-water nonconventional hydrogel. The prototype material was apparently also capable of low critical thicknesses typical of low-water conventional gels. DISCUSSION: Should new gel materials be durable with critical thicknesses in the "ultra-thin" range, nonconventional gel lenses could be capable of super and perhaps even hyper transmissibility with central minus lens EOP between 15-18.5% and Dk/L between 50-90 Dk/L units. The conventional relationships between water content and oxygen transmissibility of hydrogel contact lenses appear to have been surpassed. However, significant additional hurdles have yet to be overcome before nonconventional hydrogel materials can be ready for the ophthalmic marketplace.

Biocompatible Materials↗
PubMed1997

Hydrogel contact lens-corneal interactions: a new mechanism for deposit formation and corneal injury.

PURPOSE: In this study, we examined the interactions between hydrogel contact lenses and the cornea, and the role of these interactions in the pathogenesis of interfacial debris formation and the complications of contact lens use. METHODS: We used a corneal abrasion device to simulate the motion of contact lenses on the cornea and the ensuing abrasive interactions. We examined lens and corneal surfaces by Atomic Force Microscopy (AFM), Low Voltage Scanning Electron Microscopy (LVSEM), and optical microscopy (with vital staining of corneas) for unused hydrogel contact lenses, lenses tested in the corneal abrasion device, and worn contact lenses. Young's modulus of hydrogel contact lenses was also measured and compared with the modulus of the human cornea, as reported in the literature. RESULTS: We observed patterns of abrasive damage to the rabbit cornea in vitro caused by corneal interaction with hydrogel contact lenses. Comparison of AFM and SEM of unused lens surfaces with the surfaces of lenses tested in the abrasion device showed dramatic alterations of the contact lens surfaces. Damage to the lenses was also evident by AFM for lenses worn by volunteers. The modulus of hydrogel contact lenses was lower than the modulus of the human cornea. CONCLUSIONS: The surface morphology of hydrogel contact lenses is significantly altered during use. The Young's modulus of the cornea is higher than the modulus of hydrogel contact lenses. These observations suggest a new mechanism for contact lens complications; namely, damage to the contact lens by the cornea as an initial event that produces lens particles and deposits at the lens-cornea interface, followed by corneal abrasion and the onset of other complications.

Animals↗
PubMed2005

pH-Responsive shrinkage/swelling of a supramolecular hydrogel composed of two small amphiphilic molecules.

A pH-responsive volume-change function was successfully introduced into a supramolecular hydrogel that contained GalNAc-appended (GalNAc=N-acetylgalactosamine) glutamate ester 1 by the simple mixing of it with an appropriate amount of 2 a or 2 b amphiphilic carboxylic acid. In the 1:1 mixture (1:2), the hydrogel swelled under neutral pH conditions, but shrank to almost half of its original volume under acidic pH conditions. The structure and pH response of the mixed hydrogel were characterized by using X-ray diffraction (XRD), confocal laser scanning microscopy (CLSM), transmission or scanning electron microscopy (TEM, SEM), and Fourier transform IR (FTIR) spectroscopy. Well-developed fibers formed a stable hydrogel by self-assembly, and under acidic conditions the charge of the carboxylic acid terminal (from the carboxylate anion) was neutralized and then these fibers became densely packed. This macroscopic pH response was also applied to the pH-triggered release of bioactive substances. In this mixed supramolecular hydrogel, the hydrogelator 1 provides a stable hydrogel structure and the additive 2 acts as a commander that is sensitive to an environmental pH signal. The present supramolecular copolymerization strategy should be useful for the construction of novel, stimuli-responsive, soft materials.

Journal Article↗
PubMed1977

The reactivity of alpha-chymotrypsin immobilized on radiation-grafted hydrogel surfaces.

The enzymatic activity of alpha-chymotrypsin (CT), immobilized on hydrogel-coated polymer film supports, has been investigated. The support was prepared by radiation-graft copolymerization of 2-hydroxyethyl methacrylate (HEMA) and methacrylic acid (MAAc) on silicone rubber films. The enzyme was covalently coupled to the carboxylic group of MAAc via the N-hydroxysuccinimide (NHS) ester active intermediate. Increasing MAAc contents of the hydrogel resulted in increased attachment of CT. The integrity of the CT active site after attachment was assessed by an active site titration with diisopropyl fluorophosphate (DFP). As the MAAc content of the hydrogel was increased, an increasing fraction of the attached CT retained its activity to DFP. A greater fraction of CT was active towards DFP when adsorbed than when coupled. The rates of hydrolysis of some synthetic model substrates by the immobilized CT were also measured. The negative charge on the hydrogel had a large effect on the rates of these hydrolyses. The pH optimum for the hydrolysis of N-acetyl-L-tyrosine ethyl ester (ATEE) by immobilized CT was higher than that of free CT. Increasing MAAc content of the hydrogel resulted in larger shifts in the pH optimum. The maximum rates of ATEE hydroylsis per mg CT declined sharply with increasing MAAc content of the hydrogel. This is probably related to the increasing repulsive force between the ATEE (negatively charged above congruent to pH 9.5) and the hydrogel with increasing MAAc content. The activity of immobilized CT to ATEE is small compared to that of free CT, partly due to this charge effect. Conversely, the rate of hydrolysis of BAEE, a positively charged substrate, by immobilized CT at pH 11, is almost fourfold greater than that by free CT at its pH optimum.

Adsorption↗
PubMed1990

Evaluation of polyvinyl alcohol hydrogel as a soft contact lens material.

We prepared a transparent polyvinyl alcohol (PVA) hydrogel from a PVA solution in a mixed solvent consisting of water and a water-miscible organic solvent by cooling. The physical properties of the hydrogel were evaluated in various mixed solvents and compared with those of commercially available soft contact lens materials, such as polyhydroxyethyl methacrylate (PHEMA) and copolymers of methylmethycrylate (MMA) and N-vinyl pyrrolidone (N-VP). The PVA hydrogel showed higher tensile strength and elongation before breaking than did the other materials. Also, the PVA hydrogel was comparable in its high water content and its oxygen permeability with the MMA/VP copolymers. The protein adsorption of the PVA hydrogel was much lower than that of the other materials. Soft contact lenses of PVA hydrogel were applied to rabbit eyes for 12 weeks. The effects of the lenses on the cornea were studied by biomicroscopy, ultrasonic pachymetry, and histopathologic examination. No abnormal findings were noted, suggesting that the PVA hydrogel may be promising as a new material for use in soft contact lenses.

Animals↗
PubMed1993

Porogens in the preparation of microporous hydrogels based on poly(ethylene oxides).

To enable the synthesis of hydrogels containing microporosity, a family of pore generating additives (porogens) were synthesized from poly(ethylene glycols) (PEGs) with different molecular weights using naphthyl acetic acid. The products formed were characterized by UV-vis, differential scanning calorimetry and solution nuclear magnetic resonance techniques. Subsequently, poly(ethylene oxide)-urethane hydrogels were synthesized incorporating the above mentioned PEG porogens to modify the structure of the hydrogel. These highly water soluble PEG porogens were inert and extracted out in water. The hydrogels obtained exhibited significant increase in the equilibrium water uptake. This was attributed to the formation of a microporous structure in the hydrogel. It was also evidenced by the observed increase in the diffusion coefficients of the drugs proxyphylline and vitamin B12 through this hydrogel. The proportional increase was greater for the higher molecular weight vitamin B12 than for the proxyphylline. These results may be useful in developing porous hydrogels for controlled release technology.

Aminophylline↗
PubMed1997

In vitro degradation of pH-sensitive hydrogels containing aromatic azo bonds.

Biodegradable and pH-sensitive hydrogels containing azoaromatic moieties were synthesized from the same polymeric precursors by two synthetic methods, namely a polymer-polymer reaction and cross-linking of polymeric precursors. The effect of the synthetic route employed and the detailed network structure on in vitro degradation of hydrogels was studied. Regardless of the synthetic method used, two patterns of degradation were observed. Hydrogels with lower cross-linking density underwent a surface erosion process and degraded at a faster rate. Hydrogels with higher cross-linking densities degraded at a slower rate by a process where a colourless degradation front moved inward to the yellow core. It appears that hydrogels synthesized by a polymer-polymer reaction degraded at a slightly faster rate than their analogues synthesized by cross-linking of polymeric precursors. The degradation rate of a hydrogel was compared with those of a linear azopolymer and a low-molecular-weight azosubstrate (methyl orange) respectively. The degradation rates were in the order of hydrogel < linear azopolymer < low-molecular-weight azosubstrate.

Animals↗
PubMedDate not supplied

Bone regeneration by basic fibroblast growth factor complexed with biodegradable hydrogels.

The objective of this study is to enhance the bone induction activity of basic fibroblast growth factor (bFGF) for reconstruction of skull bone defects which has been clinically recognized as almost impossible. For this purpose, we prepared biodegradable hydrogels from gelatin with an isoelectric point of 4.9 which is capable of polyionic complexing with basic bFGF. When implanted in rabbit skull defects of 6 mm in diameter (6 defects per experimental group), the gelatin hydrogels incorporating 100 microg of bFGF promoted bone regeneration at the defect in marked contrast to free bFGF of the same dose, finally closing the bone defects after 12 weeks of implantation as is apparent from histological examination. In dual energy X-ray absorptometry analysis, the bone mineral density at the skull defects enhanced by the hydrogels was significantly higher than that by free bFGF at doses ranging from 2 to 200 microg/defect (P < 0.05). The extent of bone regeneration induced by gelatin hydrogels incorporating 100 microg of bFGF increased with a decrease in their water content. Histological examination indicated that more slowly degrading hydrogels of lower water content prolonged the retention period of osteoblasts in the bone defects. This led to enhanced bone regeneration compared with faster degrading hydrogels of higher water content. It was concluded that this biodegradable hydrogel system was a promising surgical tool to assist self-reconstruction of the skull bone.

Animals↗
PubMed2001

Drug diffusion mechanism through pH-sensitive hydrophobic/polyelectrolyte hydrogel membranes.

Methylmethacrylate/dimethylaminoethyl methacrylate cross-linked with divinylbenzene is a pH-sensitive hydrogel. We have studied the diffusion mechanisms of drugs with different water solubilities through this hydrogel. A water-soluble model drug (aminopyrine) was used to study the diffusion coefficient changes in different pHs. The results showed a water-content dependent diffusion for this pH-sensitive polycationic hydrogel. However, decreasing the solubility of the drug and increasing the hydrophobic character of the polymer by changing the pH caused a greater affinity (or partition coefficient) between the hydrogel and the drug. Aminopyrine diffusion was shown to follow the free-volume theory, suggesting the 'pore' type mechanism for water soluble drugs, while the 'partition' or 'solution-diffusion' mechanism better described the slow diffusion of water insoluble solutes through this pH-sensitive hydrogel. Comparing the swelling interface number for aminopyrine release through this pH-sensitive hydrogel showed a non-Fickian mechanism in the hydrated form of the hydrogel (pH 1.2), while Fickian in the dehydrated form (pH 7.4).

Aminopyrine↗
PubMedDate not supplied

Histopathologic appearance of arterial occlusions with hydrogel and polyvinyl alcohol embolic material in domestic swine.

PURPOSE: This study observes the histologic changes resulting from a hydrogel embolic agent (polyacrylonitrile [PAN]) compared with polyvinyl alcohol particles (PVA) of similar size. MATERIALS AND METHODS: Hepatic and renal embolizations were performed in 13 domestic swine by selecting small (1-mm) branches utilizing a coaxial 3-F microcatheter. The hydrogel embolic agent (tantalum-loaded and plain) and PVA were delivered through microcatheters. The longest follow-up period was 8 weeks. Postmortem examination of the embolized tissues included gross examination and histologic analysis. RESULTS: Tantalum-loaded PAN particles were radiopaque and seen in groups fluoroscopically and individually with specimen radiography. Histologic studies showed similar luminal and cellular response to PVA and the hydrogel embolic agents. The arterial lesion induced by the hydrogel embolic agents led to an absence of the arterial wall locally in the area of deployment. Hydrogel embolic particles became surrounded in fibrous connective tissue with no arterial wall. PVA and porous hydrogel capsules produced an inflammatory response, resulting in less wall reorganization, and surrounding fibrous connective tissue at 8 weeks than the solid PAN particles. CONCLUSION: These hydrogel embolic create a permanent arterial occlusion by transmural arterial damage. Mechanical effects and, to a lesser degree, inflammatory changes are responsible.

Acrylic Resins↗
PubMedDate not supplied

Synthesis and hydration properties of pH-sensitive p(HEMA)-based hydrogels containing 3-(trimethoxysilyl)propyl methacrylate.

An amphiphilic hydrogel network was synthesized from a cross-linked poly(2-hydroxyethyl methacrylate) backbone copolymerized with the monomers 3-(trimethoxysilyl)propyl methacrylate (PMA) and dimethylaminoethyl methacrylate (DMAEMA) using tetraethylene glycol diacrylate (TEGDA) as cross-linker and using the radical initiator system comprising N,N,N',N'-tetramethylethylenediamine and ammonium peroxydisulfate. The degree of hydration of hydrogel slabs was investigated as functions of varying monomer compositions and cross-link density and as a function of pH and ionic strength of the bathing medium. As much as a 45% increase in hydration was observed for hydrogels containing 15 mol % DMAEMA upon reducing the pH of the bathing medium from 8.0 to 2.0. This confirms the pH-modulated swelling of amine-containing hydrogels. Increasing the concentration of TEGDA cross-linker from 3 to 12 mol % in a 10 mol % DMAEMA-containing hydrogel resulted in only a 10% reduction in the degree of hydration of the gel. There was, however, a 40-50% reduction in the degree of hydration of a 15 mol % DMAEMA hydrogel upon increasing the molar composition of PMA from 0 up to 20 mol %. The presence of PMA confers hydrophobic character that reduces hydration and introduces additional cross-links that reduce network mesh size. The water content of the hydrogel was consistently higher in buffers of lower ionic strength. The reversible pH-dependent swelling observed in these studies, along with the control of cross-link density afforded by the PMA component, endows these biocompatible materials with potential for use in pH-controlled drug delivery of more hydrophobic drugs and present new compositions for in vitro and in vivo biocompatibility studies.

Acrylates↗
PubMed1997

Synthesis and properties of poly(ethylene glycol) macromer/beta-chitosan hydrogels.

Semi-interpenetrating polymer network (semi-IPN) hydrogels composed of beta-chitosan and poly(ethylene glycol) diacrylate macromer (PEGM) were synthesized and characterized for the application as potential biomedical materials. The mixture of PEGM and beta-chitosan, dissolved in water including a small amount of acetic acid, was cast to prepare hydrogel films, followed by a subsequent crosslinking with 2,2-dimethoxy-2-phenylacetophenone as a non-toxic photoinitiator by ultraviolet irradiation. Photocrosslinked hydrogels exhibited relatively high equilibrium water content in the range 77-83% which is mainly attributed to the free water content rather than to the bound water, hydrogen bonded with components in semi-IPN hydrogels. The crystallinity, thermal properties and mechanical properties of semi-IPN hydrogels were studied. All the photocrosslinked hydrogels revealed a remarkable decrease in crystallinity. The glass transition temperatures, Tg, of crosslinked PEGM segment in semi-IPNs increased compared with poly(ethylene glycol) itself. However, with increasing beta-chitosan content their Tg decreased owing to the higher degree of crosslinking. The tensile strengths of semi-IPNs in dry state were rather high, but those of hydrogels in wet state decreased drastically.

Journal Article↗
PubMed2005

l-Lysine-based supramolecular hydrogels containing various inorganic ions.

The preparation of supramolecular hydrogels containing various inorganic acids and salts using L-lysine-based hydrogelators is conducted and their thermal stabilities, gel strengths, FT-IR spectra, and electron micrographs are measured. These hydrogelators can form supramolecular hydrogels over a wide pH range and contain inorganic acids and salts. The supramolecular hydrogels based on ester-type hydrogelators have good thermal stabilities (high Tgel), while the hydrogelator with a carboxyl group forms a thermally sensitive gel with high mechanical strength. Furthermore, the gelation mechanism is discussed using FT-IR spectroscopy and TEM observations.

Journal Article↗
PubMed1995

Application of polyvinyl alcohol hydrogel membrane as anti-adhesive interposition after spinal surgery.

STUDY DESIGN: Three inflammatory and adhesive changes inside the spinal canal were analyzed histopathologically in cats. OBJECTIVE: To investigate the usefulness of a polyvinyl alcohol hydrogel sheet as an interposition over the dura to prevent inflammatory and adhesive reaction after laminectomy. SUMMARY OF BACKGROUND DATA: A major concern after laminectomy is scar tissue formation that may result in extradural compression or make subsequent surgery to the same area difficult and hazardous. METHODS: Wide laminectomy was performed at L5 in 30 adult cats. The dura was covered with a polyvinyl alcohol hydrogel sheet, free fat graft, or without interposition as a control. Animals were killed at 3 or 12 weeks. RESULTS: In the control group, adhesion of the exposed dura was apparent. Thick, fibrous connective tissue was observed between the dura and the paravertebral muscles. In the fat graft group, the dura was separated from the scar tissue by living grafted fat. However, the dura was adherent to the grafted fat and fibroblasts migrated into the interstitial space. In the polyvinyl alcohol hydrogel group, only a thin synovium-like layer was formed around the polyvinyl alcohol hydrogel sheet. CONCLUSIONS: Polyvinyl alcohol hydrogel is made of water and alcohol, and has been shown to be nontoxic to tissues. This is permeable to low molecular weight, but impermeable to large cells such as fibroblasts. Thus, the polyvinyl alcohol hydrogel sheet prevents migration of inflammatory cells and subsequently reduces intraspinal canal scar tissue formation and adhesive reaction. Other beneficial properties are extreme elasticity and low friction, which eliminate mechanical reaction to the spinal cord. The polyvinyl alcohol hydrogel sheet is believed to be useful in eliminating scar tissue formation and does not interfere with the dynamic gliding movement of the spinal cord and nerve roots.

Adipose Tissue↗
PubMed1982

Hydrogel implants for refractive keratoplasty: corneal morphology.

Refractive keratoplasty procedures for large dioptric corrections utilize a lenticular addition to the cornea which is typically cut from a donor cornea, but can also be fabricated from hydrogel plastics (1). The success of an intrastromal hydrogel implant depends on the nonreactiveness of both the hydrogel to the stroma tissue and the tissue environment to the hydrogel. Permalens hydrogel (Cooper Labs, Inc.) was fabricated into 6 mm diameter, 0.24 mm thick, and +15.00 diopter lenticules and surgically implanted into intracorneal pockets of rabbit corneas for eleven months. Light and electron microscopy revealed scattered zones of abnormal fibroblast activity at the posterior interface of the hydrogel and stroma. The anterior pocket lining was covered with a single cell layer of keratocytes, but there were no irregular areas that might be light scattering. The remaining ultrastructure appeared normal. Preliminary work with primates did not reveal this type of abnormal fibroblast activity. The data indicates that hydrogels for intrastromal implantation in refractive keratoplasty have a promising future.

Animals↗
PubMed1997

Potential efficacy of basic fibroblast growth factor incorporated in biodegradable hydrogels for skull bone regeneration.

Biodegradable gelatin hydrogels incorporating basic fibroblast growth factor (bFGF) were evaluated for their efficacy in bone regeneration using a rabbit model. Hydrogels with water contents of 85% and 98% were prepared using chemical crosslinking of gelatin with an isoelectric point of 4.9 in aqueous solution and, after freeze drying, were impregnated with an aqueous solution of bFGF to obtain bFGF-incorporated gelatin hydrogels. When they were implanted into bone defects measuring 6 mm in diameter in rabbit skulls (six animals/group), complete closure of the defect was observed at 12 weeks after implantation, regardless of the water content of the hydrogels. In contrast, bFGF did not enhance bone regeneration when applied to the skull defect in solution with phosphate-buffered saline (PBS). Also, gelatin hydrogels lacking bFGF were not effective in inducing bone formation, with fibrous tissue growing into the defect instead, similar to the skull defect seen in control rabbits treated with PBS. This indicates that the presence of hydrogels did not interfere with bone regeneration at the skull defect, probably because of their disappearance during biodegradation. It is concluded that the gelatin hydrogel is a promising matrix for effective induction of biological activity of bFGF for bone regeneration in skull and sinus defects.

Animals↗