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Synthesis and characterization of acrylic terpolymers with RGD peptides for biomedical applications.

The goal of this research was to design a biomaterial, using acrylic terpolymers, which could support endothelial cells and function in small diameter vascular graft applications. Hexyl methacrylate (HMA) and octyl methacrylate (OMA) were used as comonomers to produce a material with a low glass transition temperature (T(g)). Methacrylic acid (MAA) was used to provide ionic character, and methyl methacrylate (MMA) was selected because of its wide usage in biomedical applications. Cation neutralization was employed to modify the mechanical properties. RGD-based peptide sequences were attached to promote endothelial cell adhesion, because vascular grafts seeded with endothelial cells have fewer problems with thrombosis. The two methods used to incorporate peptide sequences were a chain transfer reaction during polymerization, and a coupling reaction attaching the peptides to carboxyl groups on the polymer after polymerization. The compositions that produced T(g)s of approximately 0 degrees C were 75 mol% OMA and 92 mol% HMA. The Young's modulus of the HMA copolymer was approximately 0.37 MPa, well below the desired value of 0.9 MPa. Likewise, the Young's modulus of approximately 0.50 MPa for the OMA copolymer was also below the desired value. After partial neutralization with sodium cations, the Young's moduli increased to approximately 0.93 and 0.99 MPa, respectively. The chain transfer reaction lowered the molecular weights and mechanical properties of the copolymers, while the coupling reaction method had little effect on these properties. The chain transfer method appears to be a promising one-step method to produce polymers with a wide range of peptide concentrations.

Biocompatible Materials↗

Influence of the method of blending an antibiotic powder with an acrylic bone cement powder on physical, mechanical, and thermal properties of the cured cement.

Two variants of antibiotic powder-loaded acrylic bone cements (APLBCs) are widely used in primary total joint replacements. In the United States, the antibiotic is manually blended with the powder of the cement at the start of the procedure, while, in Europe, pre-packaged commercially-available APLBCs (in which the blending is carried out using an industrial mixer) are used. Our objective was to investigate the influence of the method of blending gentamicin sulphate with the powder of the Cemex XL formulation on a wide collection of properties of the cured cement. The blending methods used were manual mixing (the MANUAL Set), use of a small-scale, easy-to-use, commercially-available mechanical powder mixer, OmoMix 1 (the MECHANICAL Set), and use of a large-scale industrial mixer (Cemex Genta) [the INDUSTRIAL Set]. In the MECHANICAL and MANUAL Sets, the blending time was 3 min. In preparing the test specimens for each set, the blended powder used contained 4.22 wt% of the gentamicin powder. The properties determined were the strength, modulus, and work-to-fracture (all obtained under four-point bending), plane-strain fracture toughness, Weibull mean fatigue life (fatigue conditions: +/-15 MPa; 2 Hz), activation energy and frequency factor for the cement polymerization process (both determined using differential scanning calorimetry, at heating rates of 5, 10, 15, and 20 Kmin(-1)), the diffusion coefficient for the absorption of phosphate buffered saline, PBS, at 37 degrees C, and the rate of elution of the gentamicin into PBS, at 37 degrees C (E). Also determined were the particle size, particle size distribution, and morphology of the blended powders and of the gentamicin. For each of the cured cement properties (except for E), there is no statistically significant difference between the means for the 3 cements, a finding that parallels the observation that there are no significant differences in either the mean particle size or the morphology of the blended cement powders. Notwithstanding these results, it is suggested that when the powder mixture is blended in the operating room, using the OmoMix 1 is more likely to produce a more consistent and reproducible mixture than when manual mixing is used.

Absorption↗

Degradable thiol-acrylate photopolymers: polymerization and degradation behavior of an in situ forming biomaterial.

Degradable thiol-acrylate photopolymers are a new class of biomaterials capable of rapidly polymerizing under physiological conditions upon exposure to UV light, with or without added photoinitiators, and to depths exceeding 10 cm. These materials are formed in situ, and the versatility of their chemistry affords a high degree of control over the final material properties. For example, variations in monomer mole fractions directly affect the final network molecular structure, varying the time required to achieve complete mass loss from 25 to 100 days, the molecular weight distributions of the degradation products, and the swelling ratios and compressive moduli throughout degradation. Additionally, varying the mole fraction of multifunctional thiol monomer in the initial reaction mixture controls the concentration of reactive sites in the network available for post-polymerization modification of the polymer.

Biocompatible Materials↗

Microtomography assessment of failure in acrylic bone cement.

Micromechanical studies of fatigue and fracture processes in acrylic bone cement have been limited to surface examination techniques and indirect signal analysis. Observations may then be mechanically unrepresentative and/or affected by the presence of the free surface. To overcome such limiting factors the present study has utilised synchrotron X-ray microtomography for the observation of internal defects and failure processes that occurred within a commercial bone cement during loading. The high resolution and the edge detection capability (via phase contrast imaging) have enabled clear microstructural imaging of both strongly and weakly absorbing features, with an effective isotropic voxel size of 0.7 microm. Detailed assessment of fatigue damage processes in in vitro fatigue test specimens is also achieved. Present observations confirm a link with macroscopic failure and the presence of larger voids, at which crack initiation may be linked to the mechanical stress concentration set up by adjacent beads at pore surfaces. This study does not particularly support the suggested propensity for failure to occur via the inter-bead matrix; however crack deflections at matrix/bead interfaces and the incidence of crack arrest within beads do imply locally increased resistance to failure and potential improvements in global crack growth resistance via crack tip shielding.

Biocompatible Materials↗

Preparation of acrylic bone cements for vertebroplasty with bismuth salicylate as radiopaque agent.

One of the problems of percutaneous vertebroplasty attributed to the use of acrylic cements is related to the radiopacity of the formulation. The use of bismuth salicylate as the radiopaque agent is proposed in this work, taking into account the high radiopacity of organobismuth compounds used in dental applications and the possible analgesic effect of salicylic acid. Various cements formulated with this compound (some of them modified with polyethylene oxide) were examined. Setting parameters, mechanical properties, rheological behaviour, injectability, radiopacity and biocompatibility were studied for a variety of formulations, showing that the cement formulations containing bismuth salicylate have a higher radiopacity and better injection properties than commercial bone cement preparations and present good mechanical properties.

Biocompatible Materials↗

Response of human chondrocytes to a non-uniform distribution of hydrophilic domains on poly (ethyl acrylate-co-hydroxyethyl methacrylate) copolymers.

A series of polymer and copolymer networks with varying hydrophilicity and distribution of the hydrophilic groups was synthesized and biologically tested with monolayer culture of human chondrocytes in vitro. Cell viability (MTT), proliferation (BrdU incorporation) and aggrecan expression (PG ELISA) were quantified at 7 and 14 days from seeding. Both assays (MTT and BrdU) showed complementary results that are consistent with positive cellular adhesion on the material. When human chondrocytes were cultured on polymer substrates in which the hydrophilic groups were homogeneously distributed, hydrophobic substrates showed higher values in all the biological parameters analysed. Adhesion, proliferation and viability decreased monotonously with the content of hydrophilic groups in the polymer chain. However poly(ethyl acrylate-co-hydroxyethyl methacrylate) copolymers, in which hydrophilic and hydrophobic nano-domains alternate as phase-separated domains, showed better results than the corresponding homopolymers.

Biocompatible Materials↗

Superporous hydrogels containing poly(acrylic acid-co-acrylamide)/O-carboxymethyl chitosan interpenetrating polymer networks.

Superporous hydrogels containing poly(acrylic acid-co-acrylamide)/O-carboxymethyl chitosan interpenetrating polymer networks (SPH-IPNs) were prepared by cross-linking O-carboxymethyl chitosan (O-CMC) with glutaraldehyde (GA) after superporous hydrogel (SPH) was synthesized. The structures of the SPH-IPNs were characterized with FT-IR, 13C-NMR and DSC. SEM, CLSM and light images revealed that the SPH-IPNs possessed both the IPN network and large numbers of pores and the cross-linked O-CMC molecules were located on the peripheries of these pores. The swelling behavior of SPH-IPNs was dependent on the O-CMC content, GA amount and cross-linking time. Due to the cross-linked O-CMC network, in vitro muco-adhesive force and mechanical properties, including compression and tensile modulus, of the SPH-IPN were greatly improved when compared with the CSPH. An enhanced loading capacity for insulin could be obtained by the SPH-IPNs as compared to non-porous hydrogel and CSPH, and more than 90% of the insulin was released within 1 h. With the improved mechanical properties, in vitro muco-adhesive force and loading capacities, the SPH-IPN may be used as a potential muco-adhesive system for peroral delivery of peptide and protein drugs.

Acrylamides↗

New regioselective derivatives of sucrose with amino acid and acrylic groups.

We report here a range of new sucrose derivatives obtained from '3-ketosucrose' in aqueous medium with few reaction steps. As an intermediate, 3-amino-3-deoxy-alpha-D-allopyranosyl beta-D-fructofuranoside (1) was obtained via the classical route of reductive amination with much improved yield and high stereoselectivity. Building blocks for polymerization were synthesized by introduction of acrylic-type side chains, for example, with methacrylic anhydride. Corresponding polymers were synthesized. Aminoacyl and peptide conjugates were obtained through conventional peptide synthesis with activated and protected amino acids. Deprotection yielded new glycoderivatives having an unconventional substitution pattern, namely 3-(aminoacylamino) allosaccharides. Both mono- and di-peptide conjugates of allosucrose have been synthesized.

Amination↗

Glass-fiber reinforced poly(acrylate)-based sorptive materials for the enrichment of organic micropollutants from aqueous samples.

A novel and simple approach to sorptive materials for the extraction of organic compounds from environmental samples is presented. It entails the use of glass fiber fabric strips coated with a customized poly(acrylate) (PA) formulation as extraction medium. Analytes were enriched by means of shaking of the PA strip in the sample and then subsequently thermally desorbed and analyzed by GC-MS. The performance of the sorptive materials was evaluated by the enrichment of compounds with different polarities (phenols, hexachlorobenzene and hexachlorocyclohexanes) from water samples. Parameters that affect the extraction process such as pH, ionic strength of the solvent, mixing mechanism, extraction time and desorption conditions were investigated. The extraction abilities of the PA extraction medium were compared with that of commercially available poly(dimethylsiloxane) (PDMS) Twisters. The results revealed that the new material shows higher affinity for phenolic compounds presumably due to the presence of polar groups. The partition coefficients for the PA strips estimated in this work were up to 15 times higher than for the PDMS Twister, resulting in higher recoveries and lower detection limits. The method was applied for the quantification of the aforementioned compounds in contaminated surface water samples from Bitterfeld (Germany). Using both PA strips and PDMS Twisters, good agreement of the extraction data was achieved.

Dimethylpolysiloxanes↗

Tuning of shell and core characteristics of chitosan-decorated acrylic nanoparticles.

The aim of the work was to develop a new family of chitosan-coated acrylic nanoparticles to increase the specificity of absorption of drugs associated given by the mucosal route. To achieve this goal, techniques of radical and anionic emulsion polymerisation of isobutylcyanoacrylate (IBCA) were used. Changes in the shell composition were made by using chitosan of different molecular weight and thiolated chitosan to modify the particle surface properties in order to vary the mucosae-nanoparticle interactions. The core was also modified by the inclusion of methyl methacrylate (MMA) as second monomer potentially able to improve the control of drug release. Finally, the labelling of nanoparticles core with a fluorophore, methacryloxyethyl thiocarbamoyl rhodamine B (Polyfluor), was successfully achieved, necessary for the in vitro and in vivo evaluation of the systems created. Results showed that nanoparticle size varied from 200 to 500 nm, depending on the molecular weight of chitosan used. Positive surface charge values were obtained in all cases. In addition, evidences of the presence of thiol groups were obtained (0.03-0.16 x 10(-3)micromol/cm(2) of nanoparticle).

Bucrylate↗

Protective effects of soft acrylic yellow filter against blue light-induced retinal damage in rats.

Recently, a yellow intraocular lens (IOL) was developed for the purpose of reducing potential blue light-induced retinal damage after cataract surgery. However, the effect of yellow filters on retinal protection remains to be clarified. To test the protective effects of yellow filters on blue light-induced retinal damage, a yellow and a clear soft acrylic filter were attached to the right and left eyes, respectively, of albino rats and exposed to 4.5 k lux blue fluorescent lights with peak wavelength at 420 nm (ranging 380-500 nm; short blue) or 446 nm (ranging 400-540 nm; long blue) for 6h. To assess retinal damage, the electroretinogram (ERG) was recorded at 7 days, outer nuclear layer (ONL) thickness and area were measured at 7 days, apoptosis was analyzed by TUNEL staining at 24 h, and the level of lipid peroxidation in retinas was assessed by Western dot blots using specific antibodies against 4-hydroxynonenal (4-HNE)- and carboxyethylpyrrole (CEP)-modified proteins immediately after light exposure. After short blue light exposure, a- and b-wave ERG amplitudes and the ONL thickness at 1-2.5 mm inferior and 0.5-2.5 mm superior to optic nerve head (ONH) were significantly reduced. TUNEL staining in the ONL at 0-2 mm inferior and 1-2 mm superior to the ONH, and retinal levels of 4-HNE- and CEP-modified proteins were significantly increased in the clear filter-covered eyes compared to yellow filter-covered eyes. After long blue light exposure, the only difference seen was a greater ONL thickness at 1.5 mm superior to the ONH in yellow filter-covered eye. Transmission of light through the yellow filter was 58% for short blue and 89% for long blue compared to the clear filter. The ONL area was not different between clear filter-covered and -uncovered eyes after exposure to short or long blue light. Given the results, yellow IOL material protects the retina against acute shorter wavelength blue light exposure more effectively than the clear IOL material.

Animals↗

Employing glass refractive index measurement (GRIM) in fiber analysis: a simple method for evaluating the crystallinity of acrylics.

The refractive index (RI) of 40 colorless acrylic fiber samples was determined by the immersion oil and Mettler hot stage method, implemented in the glass refractive index measurement (GRIM) instrument by Foster and Freeman. Low standard deviations for nearly all the samples were obtained and differentiation of fibers even with the same trade name was possible just on the basis of RI. Wide angle X-ray scattering (WAXS) and differential scanning calorimetry (DSC) were employed to establish a linear correlation between RI and the degree of crystallinity. Insights on the structural order of this group of fibers is then obtainable by a quick and easy technique, adding value to casework comparisons.

Journal Article↗

Binary immobilization of tyrosinase by using alginate gel beads and poly(acrylamide-co-acrylic acid) hydrogels.

The use of the immobilized and the stable enzymes has immense potential in the enzymatic analysis of clinical, industrial and environmental samples. However, their widespread uses are limited due to the high cost of their production. In this study, binary immobilization of tyrosinase by using Ca-alginate and poly(acrylamide-co-acrylic acid) [P(AAm-co-AA)] was investigated. Maximum reaction rate (Vmax) and Michaelis-Menten constant (Km) were determined for the free and binary immobilized enzymes. The effects of pH, temperature, storage stability, reuse number and thermal stability on the free and immobilized tyrosinase were also examined. For the free and binary immobilized enzymes on Ca-alginate and P(AAm-co-AA), optimum pH was found to be 7 and 5, respectively. Optimum temperature of the free and immobilized enzymes was observed to be 30 and 35 degrees C, respectively. Reuse number, storage and thermal stability of the free tyrosinase were increased by a result of binary immobilization.

Agaricales↗

Influence of selected surfactants on the tackiness of acrylic polymer films.

Anti-tacking agents are always necessary in polymeric film coating formulations in order to prevent substrate agglomeration. The objective of this study was to investigate the abilities of certain nonionic surfactants in a group of sorbitan ester in reducing the tackiness of the films obtained from aqueous acrylic polymer dispersions (Eudragit), compared with those of talc and glyceryl monostearate (GMS). The results from the peel tests demonstrated that GMS, Span 60 and Span 40 could significantly reduce the tackiness of both Eudragit NE 30D and Eudragit RS 30D films. The mechanisms in reducing the film tackiness were investigated by analyzing the film compositions, using attenuated total internal reflectance infrared spectroscopy (ATR-IR) and optical microscopy. The storage modulus of the films was also examined. The results indicated that GMS, Span 60, and Span 40 could reduce the film tackiness by decreasing the polymer contents at the film surfaces, resulting in a notable reduction in the contact area of the polymers between the surfaces. The use of only 5% (w/w) of either GMS, Span 60 or Span 40 in the coating formulations is enough to prevent pellet agglomeration without adverse effects on film flexibility. The pellets coated with Eudragit RS 30D/RL 30D (9:1, w/w) did not exhibit any difference in the drug release profiles when either 100% (w/w) talc or 5% (w/w) GMS was used, whereas the formulations containing Span 60 or Span 40 gave a slightly faster release rate.

Polymethacrylic Acids↗

The influence of cyclic loading on gentamicin release from acrylic bone cements.

Antibiotic-loaded acrylic bone cement is widely used in total joint replacement to reduce infections. Walking results in cyclic loading, which has been suggested to stimulate antibiotic release. The goal of this study is to compare antibiotic release from cyclically loaded bone cement with the release from unloaded bone cement. Two models of the frontal aspect of a femoral stem were cemented with CMW 1 Radiopaque G, Palacos R-G and Palamed G. Both were immersed in water, and the gentamicin concentration in the water was monitored. One model was cyclically loaded at 5 Hz during immersion achieving physiological stresses in the bone cement mantle. After 10.8 x 10(6) cycles, initial release of gentamicin from Palamed G was increased significantly for loaded over unloaded, but not from CMW 1 Radiopaque G and Palacos R-G.

Arthroplasty, Replacement, Hip↗

Fatal systemic allergic reaction following acrylic cranioplasty: a case report.

South Africa has a high death rate as a result of motor vehicle collisions. The motor vehicle accident fund is struggling with compensation claims made by the next of kin of the deceased. This report presents an unusual case of death as a result of systemic allergic reaction to acrylic material used to cover the frontal bone defect in a head injury patient. In independent forensic pathologist hired by the independent complaint directorate concluded that the cause of death was not related to the motor vehicle accident, and therefore the family cannot be compensated. The history, post mortem findings, management and issue of compensation claim are discussed.

Accidents, Traffic↗

Micropatterned self-assembled film based on temperature-responsive poly(N-isopropylacrylamide-co-acrylic acid).

Micropatterned cross-linked film making up a temperature-responsive component has been fabricated through the following two steps: layer-by-layer electrostatic assembly of photosensitive nitrodiazoresin (NDR) and a thermosensitive copolymer of poly(N-isopropylacrylamide-co-acrylic acid) (P(NIPA-AA)), and subsequent selective exposure to UV light through a photomask followed with development in sodium dodecyl sulfate (SDS) aqueous solution. The irradiated regions of the film are retained due to the formed covalently linked structure, whereas the unirradiated parts of the film are removed fully from the substrate in SDS solution. The well-defined micropatterns were characterized with field-emission scanning electron spectroscopy (FE-SEM) and atomic force microscopy (AFM).

Journal Article↗

Study of influence on the surface energy heterogeneity of multiwalled carbon nanotubes after the adsorption of poly(acrylic acid).

The heterogeneity of the surface energy of multiwalled carbon nanotubes (MWNTs) before and after the adsorption of poly(acrylic acid) (PAA) at 77 K was investigated by a nitrogen probe adsorption technique in a wide range of pressures. The adsorption energy distributions (AEDs) were calculated from the low-pressure data of isotherms (i.e., the data of submonolayer adsorption) using the regularization method. Based on the AED, two types of dominant energetic surfaces are identified and assigned to the graphite-like carbon and disordered carbon or defects in the pure MWNTs, respectively. While the adsorption amount of PAA is raised, a significant decrease in the contribution of higher-energy surface in AEDs is observed for those PAA-adsorbed MWNTs. It is thus demonstrated that PAA prefers interacting with higher-energy surfaces to lower-energy surfaces in MWNTs. Nitrogen probe adsorption measurements including low-pressure data are shown to be a feasible and effective tool to characterize the heterogeneity of structure and surface properties of porous materials.

Journal Article↗