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Frontal polymerization synthesis of starch-grafted hydrogels: Effect of temperature and tube size on propagating front and properties of hydrogels.

The frontal polymerization process was used to produce superabsorbent hydrogels based on acrylic acid monomers grafted onto starch. Using a simple test tube which was nonadiabatic and permitted contact with air, the effects of initial temperature and tube size on the propagating front of grafting copolymerization and the properties of hydrogels were explored. The unrestricted access of the reaction mixture to oxygen delayed the formation of self-propagating polymerization front. The ignition time was markedly lengthened with the increasing of tube size attributed to the formation of large amounts of peroxy radicals. The front velocity dependence on initial temperature could be fit to an Arrhenius function with the average apparent activation energy of 24 kJ mol(-1), and on tube size to a function of higher order. The increase of the initial temperature increased the front temperature, which lead to more soluble oligomers and higher degree of crosslinking. The interplay of two opposite effects of oligomer and crosslinking determined the sol and gel content. An increase in tube size had two effects on the propagating front. One was to reduce heat loss. The other effect was to increase the number of escaping gas bubbles. The combined action of the two effects resulted in a maximum value of front temperature, an increase in sol content and a reduction in gel content with tube size. The highest swelling capacity of hydrogels was obtained when the initial temperature or tube size favored a formation of porous microstructure of hydrogels.

Journal Article↗

Effects of thermosensitivity of poly (N-isopropylacrylamide) hydrogel upon the duration of a lag phase at the beginning of drug release from the hydrogel.

The release rates of three kinds of drugs, with different charges, from poly (N-isopropylacrylamide) hydrogels were studied. The release rate was observed to be temperature dependent for the types of drug. When the temperature was lower than the phase transition temperature, the release rate was higher at lower temperatures and increased as the temperature rose. The amount of drugs released from a poly (N-isopropylacrylamide) hydrogel disk was plotted against the square root of time. It was found that the amount of drugs released was proportional to the square root of time over a certain time interval. A lag phase was observed before the amount of drug released became proportional to the square root of time. The longest time lag was observed at the phase transition temperature of poly (N-isopropylacrylamide); LCST (33 degrees C). This suggests that the penetration rate of water into the hydrogels is lowest at the phase transition temperature and drastically changes around it. The release rates of drugs was also affected by the charges of the drug molecules. This may be caused by the interaction of drug molecules with polymer chains. When anionic drugs are released, the electrostatic repulsion seems to act between polymer chains and drug molecules. Therefore, the lag phase observed at the beginning of the release of anionic drugs was shorter, as compared with other kinds of drugs at any temperatures between 25 and 40 degrees C. On the other hand, when cationic drugs are released, the time lag was longer at temperatures higher than 33 degrees C as compared with the time lag at lower temperatures. At temperatures higher than 33 degrees C, drugs are released from the surface skin layer of the hydrogel where water molecules are less mobile than those in bulk distilled water. The drug release thus shows a long lag phase.

Journal Article↗

Surface fixation of hydrogels. Heparin and glucose oxidase hydrogelated surfaces.

The authors report a new photochemical technique for the fixation of hydrogels onto the surface of fabricated devices and sensors. The preparative method is based on two different types of photochemistry: photocross-linking due to intermolecular photodimerization of cinnamoyl groups, and photoinduced covalent bonding due to the photoreactivity of azido groups. The immobilization of heparin, useful as a thromboresistant coating, onto poly(ethylene terephthalate), and the immobilization of glucose oxidase onto the surface of a carbon fiber electrode, were demonstrated. In the former, immobilized heparin was found to be continuously released from the hydrogel, and the release rate was effectively controlled by the thickness of the hydrogel. In the latter, upon the addition of glucose, a spontaneous electrical response was observed to function as a glucose sensor. No delamination was found for either system after vigorous washing with water. Thus, durable surface hydrogelation, simultaneous immobilization of bioactive substances, and functioning of the systems were demonstrated.

Biocompatible Materials↗

Macroporous hydrogels based on 2-hydroxyethyl methacrylate. Part III. Hydrogels as carriers for immobilization of proteins.

Four series of macroporous hydrogels based on crosslinked copolymers of 2-hydroxyethyl methacrylate (HEMA)-sodium methacrylate (MANa), copolymer HEMA-[2-(methacryloyloxy)ethyl]trimethylammonium chloride (MOETACl), terpolymer HEMA-MANa-MOETACl and on a polyelectrolyte complex were used as carriers for immobilization of proteins, chicken egg white albumin and avidin. The adsorption capacity of the hydrogels for the two proteins, kinetics and pH dependence of albumin adsorption and desorption were studied. The morphology of the hydrogels with and without immobilized albumin was studied by low-vacuum scanning electron microscopy.

Adsorption↗

Novel biomineralization for hydrogels: electrophoresis approach accelerates hydroxyapatite formation in hydrogels.

As a first step toward hydroxyapatite (HAp) formation in agarose hydrogels, we have tailored the internal chemistry using an electrophoresis approach. HAp was formed using aqueous solutions of calcium chloride and disodium hydrophosphate, which were set in a conventional agarose electrophoresis apparatus. Calcium and phosphate ions provided cations and anions, respectively, and were shown to migrate into the agarose hydrogel toward the corresponding electrode side. HAp was formed after colliding with each ion. The time needed to reach complete HAp formation was 30 min, and 130 ng of HAp was formed in 1 mg of agarose hydrogel when the equilibrium swelling state was reached. The electrophoresis approach accelerated the HAp formation, and the linear velocity of 1 mm/min was shown to be roughly 15 times larger than that of simple diffusion (0.06 mm/min).

Crystallography, X-Ray↗

Apatite formation on/in hydrogel matrices using an alternate soaking process: II. Effect of swelling ratios of poly(vinyl alcohol) hydrogel matrices on apatite formation.

In our previous study, we reported a novel method of apatite formation on/in a three-dimensional hydrogel matrix. Using this method, bone-like apatite could be formed on/in the hydrogel matrix under normal conditions in vitro. A poly(vinyl alcohol) (PVA) gel was used as a model matrix. The method consists of two steps: first, water is transformed in a PVA gel with a CaCl2/Tris-HCl aqueous solution (pH 7.4) and second, the gel is soaked in a Na2HPO4 aqueous solution. In the present study, we report a detailed study of the effects of the swelling ratios of PVA gels on apatite formation. Cross-sectional observations and gravimetric measurements of PVA gels with various swelling ratios were done. The amount of apatite formed on/in PVA gels increased almost linearly with an increase in the reaction cycles. The rates of apatite formation on/in PVA gels largely depended on the swelling ratios, which were approximately 0.48, 0.61, 1.28, and 1.55 mg per cycle for swelling ratios of 4.1, 10.4, 16.8, and 30.1, respectively. The apatite content in PVA-apatite composites that was obtained by this method also increased with an increase of the reaction cycles. After six reaction cycles, a PVA gel with a high swelling ratio contains approximately 70 wt% of formed apatite in the composite. On the other hand, a gel with a low swelling ratio contains about 15 wt% of formed apatite in the composite. Cross-sectional views of the PVA gels after each cycle showed that apatite crystals were formed, not only on the surface of the gel but also within it after fifteen reaction cycles. The hydrogel-apatite composites that were obtained using an alternative soaking process will be useful as not only bone substitute materials but also as soft tissue adhesive materials.

Apatites↗

Hydrogel-immobilized antibodies for microfluidic immunoassays: hydrogel immunoassay.

The integration of immunoassays in microfluidic devices is a rapidly developing research area combining the power of immunoassays with the inherent benefits of microfluidics. Here, a general overview of microfluidic-based immunoassays is presented along with a method for immobilizing antibodies in polyacrylamide gel plugs set in microfluidic channels. These antigen-specific hydrogels can be rapidly formed by photopolymerizing monomer solutions mixed with antibodies or other large proteins. The resulting antigen-specific hydrogels contain pore sizes appropriate for physical entrapment of large antibodies while remaining permeable to smaller proteins. The open structure of these hydrogels enables the capture and concentration of target antigens present at low concentrations. Such physical entrapment provides a conceptually simple method of immobilization compared with immobilization of proteins on surfaces and offers advantages such as resistance to chemical and thermal denaturation.

Acrylic Resins↗

[Hydrogels: properties and application in the technology of drug form. I. The characteristic hydrogels].

The following presentation is a review of literature related to application of hydrogels in the technology of modern drug form. The review contains the description of physical-chemical properties of hydrogels, such as swelling, water structure, sol-gel temperature transitions, tacticity. Each characteristic is followed by the description of its application as a therapeutical substance carrier. In this review described also examples of polymers used to produce stimuli-sensitive hydrogels in response to physiological temperature, pH, present of ions in organism fluid, or blood glucose level and external response such as electric current, light.

Chemistry, Pharmaceutical↗

Inulin hydrogels as carriers for colonic drug targeting: I. Synthesis and characterization of methacrylated inulin and hydrogel formation.

PURPOSE: Vinyl groups were introduced in inulin chains in order to form hydrogels of this sugar polymer by free radical polymerization. METHODS: Inulin was reacted with glycidyl methacrylate in N,N-dimethylformamide in the presence of 4-dimethylaminopyridine as catalyst. 1H and 13C NMR spectroscopy were used for the characterization of the obtained reaction product. Solid state 13C NMR spectroscopy revealed the conversion of the incorporated vinyl groups into covalent cross-links upon free radical polymerization of aqueous solutions of the derivatized inulin. RESULTS: During reaction of inulin with glycidyl methacrylate, transesterification occurred, leading to the direct attachment of the methacryloyl group to inulin. Consequently, the obtained reaction product is methacrylated inulin. The extent of chemical modification of inulin could be tuned by varying the molar ratio of glycidyl methacrylate to inulin in the reaction mixture. Aqueous solutions of methacrylated inulin were converted into cross-linked hydrogels by free radical polymerization using ammonium persulphate and N,N,N',N'-tetramethylethylenediamine as initiating system. CONCLUSIONS: Inulin hydrogels can be formed by free radical polymerization of aqueous solutions of methacrylated inulin.

4-Aminopyridine↗

Hydrogel properties influence ECM production by chondrocytes photoencapsulated in poly(ethylene glycol) hydrogels.

When using hydrogel scaffolds for cartilage tissue engineering, two gel properties are particularly important: the equilibrium water content (q, equilibrium swelling ratio) and the compressive modulus, K. In this work, chondrocytes were photoencapsulated in degrading and nondegrading poly(ethylene glycol)-based hydrogels to assess extracellular matrix (ECM) formation as a function of these gel properties. In nondegrading gels, the glycosaminoglycan (GAG) content was not significantly different in gels when q was varied from 4.2 to 9.3 after 2 and 4 weeks in vitro. However, gels with a q of 9.3 allowed GAGs to diffuse throughout the gels homogenously, but a q < or = 5.2 resulted in localization of GAGs pericellularly. Interestingly, in the moderately crosslinked gels with a K of 360 kPa, an increase in type II collagen synthesis was observed compared with gels with a higher (960 kPa) and lower (30 kPa) K after 4 weeks. With the incorporation of degradable linkages into the network, gel properties with an initially high K (350 kPa) and final high q (7.9) were obtained, which allowed for increased type II collagen synthesis coupled with a homogenous distribution of GAGs. Thus, a critical balance exists between gel swelling, mechanics, and degradation in forming a functional ECM.

Animals↗

Protein migration through hydrogels: a tool for measuring porosity--application to hydrogels used as contact lenses.

A rapid two-dimensional electrophoretic system for evaluating the penetration of proteins into hydrogels (used as contact lenses) is presented. The proteins are sieved through the hydrogel under conditions which produce minimum deformity of pores. In another step, the proteins migrating through the pores are identified. An effective pore size measurement is deduced.

Contact Lenses, Hydrophilic↗

Molecular recognition remolds the self-assembly of hydrogelators and increases the elasticity of the hydrogel by 10(6)-fold.

Addition of vancomycin (1, the receptor) to the supramolecular hydrogel of self-assembled pyrene-d-Ala-d-Ala (2, the ligand) increases the storage modulus of the hydrogel of 2 by about 106-fold. Rheology, microscopy, and spectroscopy investigations suggest that the two-dimensional polymers, formed by the ligand-receptor interaction between 1 and 2, and the self-dimerization of 1, are mainly responsible for the observed dramatic increase in elasticity.

Biomimetic Materials↗

Comparing goblet cell densities in patients wearing disposable hydrogel contact lenses versus silicone hydrogel contact lenses in an extended-wear modality.

PURPOSE: The current study evaluates the response of the ocular surface to extended contact lens wear by comparing a new silicone hydrogel lens to an ACUVUE 2 lens. METHODS: Twenty subjects with an average age of 28 years were randomly assigned to a fitting with ACUVUE 2 or PureVision lenses. Ocular surface assessment by impression cytology was performed at baseline and for the 6 months after initiation of lens wear. RESULTS: Although goblet cell density significantly increased with wear time, no statistically significant difference was observed between the contact lens groups. The average baseline goblet cell percentages were as follows: ACUVUE 2 group, 1.44; PureVision group, 1.11. The 6-month averages were as follows: ACUVUE 2 group, 3.16; PureVision group, 2.22. CONCLUSIONS: It appears that silicone hydrogel lenses may be slightly less irritating to the ocular surface than lenses not containing silicone. This could be a promising indicator for successful 30-day continuous wear.

Adult↗

Silicone rubber-hydrogel composites as polymeric biomaterials. IV. Silicone matrix-hydrogel filler interaction and mechanical properties.

Composite materials consisting of a silicone rubber matrix and particulate synthetic hydrogels were prepared and their mechanical properties were studied. The influence of the size, shape, aggregation of hydrogel particles, chemical reactions of polymer phases on tensile properties and tear strength of the composite materials were investigated. The relations between the properties, structure and chemical composition of polymer phases of the composite materials and their mechanical properties are discussed.

Biocompatible Materials↗

Silicone rubber-hydrogel composites as polymeric biomaterials. IX. Composites containing powdery polyacrylamide hydrogel.

A composite material has been prepared consisting of a silicone rubber matrix and particulate lightly cross-linked polyacrylamide hydrogel. The material, resembling common silicone rubber, is hydrophilic and swells in water like hydrogels. The polyacrylamide has a high specific surface area, a relatively low content of water-soluble low-molecular-weight compounds and, owing to its non-ionogenic character, a pH-independent swelling degree. For the composite material consisting of the silicone rubber and very fine powdery cross-linked polyacrylamide, we have measured the rate of swelling in water, the mechanical properties (tensile strength, break elongation, hardness, resilience), biological properties (implantation test, cytotoxicity, cell cultivation) and UV absorption of its water extracts. The polyacrylamide and polysiloxane purity, as the composite material starting components, has been determined to be satisfactory. As a result, a high swelling rate of the prepared composite material has been observed, resulting in reaching more than 70% wt of water of the equilibrium swelling. The results show that the composite material is suitable for biological and medical use.

3T3 Cells↗

Electrolyte diodes and hydrogels: determination of concentration and pK value of fixed acidic groups in a weakly charged hydrogel.

Current-voltage (CV) characteristics of polyvinyl alcohol (PVA)-glutardialdehyde hydrogel cylinders were measured in aqueous KCl solutions. To this end a new special apparatus was constructed where the gel cylinder connects two electrolyte reservoirs. The measured quantities are the electric current flowing through the gel and the potential difference between the two reservoirs. Concentration polarization near the gel-liquid interfaces is decreased considerably by applying an intense mechanical stirring in both reservoirs. Under these conditions below 1 V concentration polarization is negligible, and the CV curves are nearly straight lines. It was found that the gel applied here is a weakly charged anionic hydrogel. Concentration of fixed anions was determined from the slope of these lines measured in 0.001 and 0.01 molar KCl solutions. Fixed anion concentration of the same piece of gel was measured also with a different method, when the gel was used in an acid-base diode. In this case one reservoir contained 0.1 molar HCl, and the other 0.1 molar KOH. From the results of the two measurements, the concentration (4.45 x 10(-3) M) and the pK value (4.03) of the fixed acid groups responsible for the anionic character of the gel was calculated. The pK value is compatible with fixed carboxylic acid groups contaminating the PVA gel. Furthermore, concentration polarization phenomena in the boundary layers nearby the gel were studied in 0.001 M KCl solutions, measuring the diodelike CV characteristic of a gel cylinder, when stirring was applied only at one side of the gel. Boundary layers facing the cathode or the anode responded in a different way to stirring. The difference cannot be explained completely with the hypothesis of electroconvection suggested previously.

Journal Article↗

An investigation into the influence of hydrogel composition on swelling behavior and drug release from poly(acrylamide-co-itaconic acid) hydrogels in various media.

The hydrogels prepared by free radical copolymerization of acrylamide and itaconic acid were investigated with regard to their composition and crosslinking degree to find materials with satisfactory swelling and drug release properties. Samples were characterized by measuring the swelling behavior and in vitro release of paracetamol as a model drug in aqueous media with different pH values. The two-factor, three-level experimental design and response surface methodology were applied to statistically evaluate the influence of investigated factors.

Acrylic Resins↗

Hydrophilic polyphosphazenes as hydrogels: radiation cross-linking and hydrogel characteristics of poly[bis(methoxyethoxyethoxy)phosphazene].

The water-soluble polyphosphazene, [NP(OCH2CH2OCH2CH2OCH3)2]n, cross-links when exposed to gamma rays to form hydrophilic, water-swellable membranes and hydrogels. The degree of cross-linking increases with irradiation dose in a manner that can be utilized to change the properties. gamma irradiation studies of the small molecule model compound, [NP(OCH2CH2OCH2CH2OCH3)2]4, were also carried out to probe the relationship between irradiation dose and cross-link density.

Chemical Phenomena↗