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Acrylic polymeric nanospheres for the release and recognition of molecules of clinical interest.

Cross-linked poly(methylmethacrylate-co-methacrylic acid) nanospheres were imprinted with theophylline through template radical polymerisation in diluted acetonitrile solution. This study will focus on the effect of functional monomer nature used (methylmethacrylate and/or methacrylic acid) in the recognition and in the release of template in order to develop a material with combined properties of drug delivery and rebinding for clinical applications. After template extraction the nanospheres showed satisfactory recognition properties (up to 1mg template/g of polymer). Moreover polymers prepared selectively removed theophylline with a theophylline rebinding of 5.1 times higher than that of caffeine, a compound of similar structure. Drug release properties were also satisfactory (up to 95% of loaded theophylline in 7 days).

Acrylic Resins↗

Core-corona polymer composite particles by self-assembled heterocoagulation based on a hydrogen-bonding interaction.

Poly(ethylene glycol dimethacrylate-co-acrylic acid) (poly(EGDMA-co-AA)) small microspheres were effectively self-assembled on poly(ethylene glycol dimethacrylate-co-4-vinylpyridine) (poly(EGDMA-co-VPy)) surfaces to form a core-corona structure with a raspberry-like polymer composite by a hydrogen interaction mechanism through an affinity complex between the carboxylic acid group and pyridine group. The control of coverage of the poly(EGDMA-co-AA) corona on the surface of poly(EGDMA-co-VPy) was studied in detail via adjustment of the nature of the mass ratio between the core and corona. The effects of the pH and solvent used on the morphology of the self-assembled core-corona polymer composites were investigated. The nature of the interaction between the core and corona polymer particles was identified as hydrogen bonding with FT-IR spectroscopy.

Acrylates↗

[Sorption immobilization of alpha-amylase from Bacillus subtilis using meshed carboxyl polyelectrolytes].

Immobilization of alpha-amylase from Bacillus subtilis by adsorption on carboxyl polyelectrolytes, copolymers of methacrylic acid and ethylene glycol dimethacrylate, was being investigated depending on the structure of the polymeric matrix. It is demonstrated that cation exchange resins can be successfully used for reversible sorption and immobilization of alpha-amylase. It was found that the more heterogeneous the structure of the polymeric carrier, the higher is reversibility of the enzyme adsorption. The isothermic process of Bac. subtilis alpha-amylase adsorption on copolymers of different structures was studied as well. The equilibrium of the sorption system was proved to be true.

Adsorption↗

Microleakage of glass ionomer/composite resin restorations: a laboratory study. Part 2. The influence of bonding systems.

Acid-etching and bonding of composite resin to bevelled enamel margins has been reported to produce a reliable seal. However, achieving a seal with dentine and cementum margins is more difficult. Four different dentine bonding systems were used in combination with Silux composite resin to restore cervical cavities in vitro. None of the bonding systems used completely sealed either the occlusal or gingival margins. Of the four systems, GLUMA provided the best seal at both the occlusal and gingival margins.

Bisphenol A-Glycidyl Methacrylate↗

Purification of the specific immunoglobulin G1 by immobilized metal ion affinity chromatography using nickel complexes of chelating porous and nonporous polymeric sorbents based on poly(methacrylic esters). Effect of polymer structure.

Ni2+ complexes of the chelating nonporous and porous bead sorbents based on methacrylic esters crosslinked with ethylene dimethacrylate were used in isolation of the horseradish peroxidase-specific immunoglobulin IgG1 from the crude mouse ascitic fluid by immobilized metal ion affinity chromatography (IMAC). Iminodiacetic and aspartic acids were attached to porous poly(glycidyl methacrylate) beads differing in size, morphology and chemical composition. Ethylenediaminetriacetic acid and quinolin-8-ol chelating groups were attached mainly to the surface hydroxyl groups in nonporous poly(diethylene glycol methacrylate) beads through spacers. The latter sorbents exhibited better kinetic characteristics than the former but a very low IgG1 sorption capacity. In a single-step IMAC procedure, the best efficiency in the specific IgG1 purification was obtained with porous sorbents (recovery 92%, purity 73%). Differences in IMAC separations are discussed from the point of view of morphology of polymer beads as well as of the type and concentration of chelating ligands.

Chelating Agents↗

Hydrolytic stability of experimental hydroxyapatite-filled dental composite materials.

OBJECTIVES: The purpose of this study was to analyze the behavior in water, related to mechanical properties, of experimental composites for dental restoration. METHODS: The studied materials were composed of a visible-light-curing monomer mixture (Bis-GMA and TEGDMA or HEMA) and micrometric, nanometric or a mixture of both sizes hydroxyapatite particles as a reinforcing filler. Filler particles were modified with a coupling agent (citric, hydrosuccinic, acrylic or methacrylic acid or silane). The hydrolytic stability of the evaluated materials was studied through total elution and water-uptake tests. Percent net-mass variation was daily monitored and analyzed as a function of time. Mechanical performance was examined through flexural properties and Vickers hardness. Morphological surface changes were observed with scanning electron microscopy. ANOVA statistical analysis was performed (P<0.05). RESULTS: In general, the use of HEMA instead of TEGDMA did not substantially worsen the composite quality. Dental composites containing only nanometric particles of hydroxyapatite as a filler are unsuitable for clinical performance. Midway-filled composite resins loaded with micro-HAP particles, coated with citric, acrylic or methacrylic acid displayed low percent elution and water-uptake values. Mechanical properties were similar or even superior to those measured for silane treated particles. SIGNIFICANCE: More research is needed to further improve the interaction of nano-HAP particles with the polymeric matrix, either as a single filler or, preferentially, mixed with micro-HAP, that will allow to increase the total loading of reinforcing filler and, hence, to improve the mechanical properties.

Analysis of Variance↗

Capturing of acidic macromolecules from biological samples using a temperature-responsive polymer modified with poly-l-lysine.

We synthesized a temperature-responsive polymer, N-(isopropylacrylamide)-methacrylic acid copolymer, to which poly-l-lysine was introduced. The synthesized polymer as well as the parent polymer showed reversible soluble-insoluble changes in response to temperature changes across the lower critical solution temperature at 32 degree C in an aqueous solution. We found that the polymer efficiently captured acidic bio-macromolecules such as RNA, glycosaminoglycans and mucin-type glycoproteins in biological samples, and the captured molecules were recovered using aqueous NaCl solutions at high concentration. The target acidic molecules thus obtained will be employed for further studies such as structural analysis after brief desalting procedure. The proposed method does not require any chromatographic separations, but only needs a small volume of an aqueous salt solution for releasing captured molecules. Overall procedures are quite easy and simple, and are completed at least within 1 h. We show a few examples for capturing RNA and glycosaminoglycans from cultured cells using the polymer.

Acrylamides↗

[Application of pH-responsive polymers to oral dosage forms for insulin].

The potential of graft copolymer networks with poly(methacrylic acid-g-ethylene glycol; P(MAA-g-EG)) for oral dosage forms to enhance insulin absorption is reviewed. The polymer exhibited unique pH-responsive characteristics in which interpolymer complexes were formed and dissociated, respectively, in acidic and neutral/basic environments. Correspondingly, the polymer was capable of highly incorporating and rapidly releasing insulin in vitro. This insulin loaded polymer successfully enhanced oral insulin absorption in rats with significant hypoglycemic effects. The polymer was also shown to possess mucoadhesive properties. Furthermore, the polymer demonstrated high calcium binding which may affect the proteolytic activity of calcium-dependent enzymes and/or reduce transepithelial resistances. Thus, the polymer has the potential to be used as a carrier for oral dosage forms of insulin to enhance its mucosal absorption.

Administration, Oral↗

Hydroxyapatite/polymer composite flame-sprayed coatings for orthopedic applications.

The complex biological and mechanical requirements for implant materials in the human body generally cannot be furnished by one single material. In the present study, hydroxyapatite/polymer composite coatings with different contents of hydroxyapatite were produced using a flame spray system. This processing route is intended to obtain a coating with an optimal combination of biological and mechanical properties of these two materials for skeletal implants. The composite coatings were produced from a mechanical blend of hydroxyapatite and ethylene methacrylic acid copolymer powders, which were delivered from a fluidized bed powder feeder. Characterization of the coating surface morphology, polished coating cross-sections, and fracture surface morphology was conducted by scanning electron microscopy. The dissolution behavior of the coatings was evaluated with a calcium-specific ion meter. The stress-strain behavior was investigated by tensile testing. The biological and mechanical properties were found to be related to the volume and distribution of the hydroxyapatite in the polymer matrix. This technique provides a means of preparing hydroxyapatite/polymer coatings for application as implants.

Bone Substitutes↗

Rational design of cytophilic and cytophobic polyelectrolyte multilayer thin films.

Nanostructured polyelectrolyte multilayer thin films electrostatically assembled alternately from such polymers as poly(allylamine hydrochloride) (PAH) and poly(acrylic acid) (PAA) were investigated for their in vitro cell interactions. Not surprisingly, NR6WT cells, a highly adhesive murine fibroblast cell line, attached to many different multilayer combinations tested. However, PAH/PAA multilayers constructed at pH deposition conditions of 2.0/2.0 were completely bioinert. Analogous cell interactions were observed with PAH/poly(methacrylic acid) (PAH/PMA), PAH/sulfonated poly(styrene) (PAH/SPS), and poly(diallyldimethylammonium chloride)/SPS (PDAC/SPS) systems, thereby suggesting a general trend in the fibroblasts' response to multilayers. Specifically, highly ionically stitched films attracted cells, whereas weakly ionically cross-linked multilayers, which swell substantially in physiological conditions to present richly hydrated surfaces, resisted fibroblast attachment. Thus, by manipulating the multilayer pH or ionic strength assembly conditions or both, which in turn dictate the molecular architecture of the thin films, one may powerfully direct a single multilayer combination to be either cell adhesive or cell resistant.

Acrylic Resins↗

Photoregulation of the binding of an azobenzene-modified poly(methacrylic acid) to phosphatidylcholine bilayer membranes.

Radical copolymerization of a 4:1 mixture of methacrylic acid and N-[4-(phenylazo)-phenyl]methacrylamide afforded a copolymer of methacrylic acid bearing 10.4 mol% pendent azobenzene units. The copolymer was sensitive to irradiation by virtue of the photochemical trans-to-cis isomerization of the pendent chromophore. The pH-dependent conformational transition characteristic of poly(methacrylic acid) was shifted to a higher pH by the hydrophobic nature of the azobenzene units, but viscosity measurements revealed no further shift in the transition upon photoisomerization. The potentiometric titration curves of the two photoisomeric states of the chain were displaced in a manner consistent with the enhanced polarity of the cis form of the chromophore. The adsorption of the chain on phosphatidylcholine bilayer membranes was strikingly sensitive to light; at pH 7, the cis form adsorbed weakly if at all, whereas the trans form bound strongly to the membrane surface with concomitant reorganization of the lipid bilayer structure.

Azo Compounds↗

Soluble sustained release gene delivery system.

Delivery of genetic substance to target cells remains an obstacle for efficient utilization of gene therapy approaches. In this study, we describe a formulation of methacrylate acid copolymer carrier of DNA, in which the release rate of the gene can be controlled by pH. Plasmid release was coupled with the polymer's dissolution, which was accelerated in alkali conditions. The released plasmid was intact and bioactive, although alteration from closed circular supercoil to relaxed conformation was observed. Confocal laser scanning microscopy detected the plasmid DNA along the central layers of the polymeric film. Gene delivery systems controlled by the dissolution of the polymeric films offer flexibility in quantity and size of the incorporated DNA, and therefore could have a potential for in vivo use.

Biocompatible Materials↗

Preparation of an effective light-cured bonding agent for orthodontic application.

OBJECTIVE: The purpose of this study was to prepare a light-cured adhesive applicable for orthodontics by mixing monomers and a polymerized reactive organic composite filler (prepolymerized trimethylolpropane trimethacrylate-filler, TMPT-filler). METHODS: The monomer component was a mixture of 3.0 wt% 2-hydroxy-3-(2-naphthoxy)propyl methacrylate (HNPM) in triethylene glycol dimethacrylate. This was applied to extracted bovine tooth enamel after acid etching with 65 wt% phosphoric acid for 30 s. After 24 h in 37 degrees C water, the tensile bond strength was measured, and the data were analyzed with Duncan's new multiple range test (p < 0.01 or 0.05). RESULTS: The tensile bonding strength to enamel etched with 65 wt% phosphoric acid was 13.1 +/- 0.5 MPa, and the thermal stability of the bond was excellent. SEM examination of the cross-sectioned specimens modified with HCl demineralization showed that when the diffusion time prior to light irradiation was only 1 min, a well-developed resin honeycomb-like structure was created in the enamel surface in the formulation containing HNPM. SIGNIFICANCE: Monomer impregnation beyond the etched enamel surface was important for resin-enamel bonding, increasing bonding strength and thermal stability. HNPM was effective in enhancing monomer diffusion and impregnation of the etched enamel surface.

Acrylates↗

A bio-inspired approach to the synthesis of CaCO3 spherical assemblies in a soluble ternary-additive system.

Two different soluble polymers, poly(ethylene glycol) (PEG) and poly(methacrylic acid) (PMAA), with individual functions were successfully employed in combination with a third additive, sodium dodecyl sulfate (SDS), in one system, and spherical assemblies (e.g., hollow spheres) with multiscale constructs of CaCO3 were obtained. The variation of polymer concentration drastically changed both the morphology and polymorph of the produced CaCO3 crystals due to the corresponding transformation of the micelle structure. This study suggests that noncovalent interaction and cooperation between soluble macromolecules play key roles in controlling the growth of biominerals. The results also suggest a novel and facile route toward biomimetic inorganic synthesis.

Calcium Carbonate↗

A multimechanistic drug release approach in a bead dosage form and in vitro predictions.

The objective of this study was to prepare a combination of immediate release, enteric coated, and controlled release (CR) beads and to mathematically model in vitro drug release characteristics of the combination based on the release profiles of individual beads. Uncoated beads were manufactured by using extrusion/spheronization technology. Fluid-bed bottom spraying was used for coating: Eudragit-L-30D for enteric coating and Eudragit-NE-30D for CR coating. In vitro drug release profiles for uncoated and coated beads were each fitted to appropriate mathematical equations. The drug release from the bead combination dosage form was predicted from the individual mathematical models and verified experimentally in vitro. The in vitro dissolution was conducted in 0.1 N HCl for 2 hr and then in buffer (pH 6.5 phosphate, 0.05 M) to mimic in vivo conditions using USP dissolution apparatus I. The results showed that uncoated beads gave similar release profiles in water, acid, and buffer with complete release within 2 hr. The release from CR beads was about 50% at 10 hr and was independent of the dissolution medium. As expected, enteric coated beads showed drug release < 5% at 2 hr in water and acid, whereas the release in buffer was comparable to that of uncoated beads. Exposure of enteric coated beads to acid for 2 hr produced a slower release rate in buffer compared with the release from beads added directly in the buffer. The release characteristics of the three beads can be described by square root and zero-order kinetics. The release characteristics from the combination dosage form were 39%, 69%, and 81% at 1, 4, and 8 hr, respectively. The experimental and predicted profiles agreed to within +/- 6% (residuals at individual data points). Our results suggest that release from the combined multimechanism oral dosage form can be predicted from the performance of individual beads.

Algorithms↗

[2 types of soluble complexes of bovine serum albumin with polyelectrolytes].

It has been shown by high-velocity sedimentation that BSA forms soluble complexes with polyacrylic acid (PAA) and sodium polystyrene sulfonate (PSSNa) with neutral water solutions. Factors responsible for polyanion binding of similarly charged BSA molecules are analysed. It has been found that occupation of PAA and PSSNa chains with BSA globules proceeds steadily. BSA-PAA and BSA-PSSNa complexes are compared with the earlier described products of BSA sorption on poly-4-vinyl-N-ethylpyridine bromide, where the occupation of polycations with protein globules proceeds unevenly. Reasons for the existence of two types of soluble BSA-polyelectrolyte complexes are described; probable structural model of BSA complex with polyacids and polyanions is suggested.

Acrylic Resins↗

[Studies on the diffusion of the remaining monomers from implantation plastics of polymethacylic acid methylester].

Positive clinical results were obtained using implanted cold polymerizates, and these were compared with the negative results of experiments made on animals. The observed local pathophysiological processes are considered to be due to the effects produced by the methacrylic methyl ester. The absolute content of residual monomers in the implants does not allow to make any definite conclusions as to the rate of diffusion into the organism. Therefore, the diffusion of residual monomers into an aqueous medium was titrimetrically measured for three weeks by the pyridine sulfate dibromide method. After a description of the method of titration and the results obtained, a discussion is given of the causes of the different rates of diffusion of residual monomers from Kallokryl K and Palacos samples, which are dependent upon the duration of polymerization in air.

Acrylic Resins↗

Engineering porous polyurethane scaffolds by photografting polymerization of methacrylic acid for improved endothelial cell compatibility.

Using a preadsorbing-monomer method, polyurethane (PU) porous scaffolds were modified by grafting polymerization of methacrylic acid (MAA) initiated under UV light. Fourier transform infrared-attenuated total reflection spectroscopy and X-ray photoelectron spectroscopy characterizations confirmed the occurrence of the grafting polymerization of poly(methacrylic acid) (PMAA) on PU scaffolds and the measurement of water adsorption also demonstrated enhanced hydrophilicity. The PMAA grafting degree correlated to the amount of MAA adsorbed, the pore average diameter, and the porosity. It was verified that the higher porosity the scaffold has, the larger porous area (or the larger contact area with MAA) it has, and therefore the higher amount of MAA adsorbed and higher grafting degree obtained. The results of human endothelial cells cultured in vitro showed that the PU scaffolds modified with the hydrophilic PMAA had more improved cell compatibility than the control matrix.

Cell Adhesion↗