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Laser-induced damage to transparent polymers: chemical effect of short-pulsed (Q-switched) Nd:YAG laser radiation on ophthalmic acrylic biomaterials. I. A review.

The use of short-pulsed lasers in ophthalmic surgery inspired and called for research on the damage inflicted by the laser radiation upon the acrylic polymers from which artificial intraocular lenses are made. The possible release of toxic monomers by laser-induced depolymerization is of great concern but past investigations of this phenomenon have been very limited. The present knowledge of various types of laser-induced damage to transparent polymers is reviewed with particular emphasis on the acrylic materials and intraocular lenses.

Lasers↗

Photopolymerized multifunctional (meth)acrylates as model polymers for dental applications.

Polymer networks that can serve as model systems for dental applications were prepared by photopolymerizations of 1,1,1-trimethylolpropane triacrylate, 1,1,1-trimethylolpropane trimethacrylate, 1,1,1-trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, Photomer 2028 and Photomer 3015. The UV polymerizations were initiated by 2,2-dimethoxy-2-phenyl-acetophenone. Volume shrinkage was followed over the course of polymerization using a dilatometric technique. Incident light intensities ranged from 1 mW cm-2 to 20 mW cm-2. The effects of monomer structure on % volume shrinkage, including pendant group size, molecular weight between reactive double bonds, and acrylate versus methacrylate monomers were investigated. In addition, the effect of incident light intensity on % volume shrinkage was studied. Typical volume shrinkage varied from 3.5% to 13.5%. The volume shrinkage decreased with increasing monomer rank and increased pendant group size; the shrinkage for methacrylates was less than that for acrylates. Increased incident light intensity resulted in increased shrinkage rate, but not in statistically significant increases of the volume shrinkage. Conversion was calculated from shrinkage data and compared to data from monomer extraction experiments. Results indicate that although double bond conversion is low, conversion of monomer units is significantly higher.

Biocompatible Materials↗

Acrylic denture distortion following double processing with microwaves or heat.

The present study compared the fit of acrylic resin bases subjected to two curing cycles in a water-bath or in a microwave oven. Resin bases were processed on duplicate stone casts prepared from a cobalt chromium master die. Ten bases, composed of conventional polymethylmethacrylate, were cured in a water-bath for 7 h at 70 degrees C and 3 h at 100 degrees C, and a further 10 cured in a domestic microwave oven at 65 W for 25 min. Ten bases composed of polymethylmethacrylate modified by means of a chemical activator were cured at 100 degrees C in a water-bath for 20 min. All bases were then subjected to a second curing cycle following addition of new acrylic resin to the alveolar ridge areas. Following each curing cycle the fit of the posterior border of each base was evaluated. A silicone impression material was used to form indices between the bases and the master die, these were then invested in stone and sectioned to allow cross-sectional measurement by means of an eyepiece micrometer. A one-way analysis of variance and unpaired Student's t tests were employed to compare the differences in distortion of the three groups. The differences in distortion between the first and second curing cycles were significant for all curing methods (P less than 0.001). However, microwave curing caused significantly less distortion of the denture base than short water-bath curing, especially in the centre of the palate (P less than 0.001).

Analysis of Variance↗

Injectable self-curing bioactive acrylic-glass composites charged with specific anti-inflammatory/analgesic agent.

Injectable bioactive acrylic formulations based on poly(methyl methacrylate) (PMMA) and different amounts of bioactive glasses in the system SiO2-CaO-Na2O-P2O5 have been prepared in the presence of the anti-inflammatory analgesic drug fosfosal, the sodium salt of 2-phosphonoxibenzoic acid, to be used in minimally invasive surgery. The injectability of the formulations evaluated according to the established protocol was around 80%. The experimental formulations provided maximum temperatures in the range 50-60 degrees C, which were lower than those of commercial acrylic bone cements currently used in percutaneous vertebroplasty (PVP). Residual monomer content of any formulation was inferior to 5%. Compressive yield strength of dry specimens was in the range 80-95 MPa, but it decreased after immersion in SBF to values in the range 30-50 MPa, due to the dissolution of the bioactive glasses and the drug in the medium. The release of fosfosal was evaluated in vitro (pH = 7.0). The release profile against time obtained from a PMMA cement was quasi-linear and the 80% of the initial amount of drug was released in 175 h. However, for bioactive cements, the 80-100% of the fosfosal charged was released in approximately 48 h, due to the dissolution of the glasses in the medium. Values of weight loss of the cements determined gravimetrically ranged between 16% and 26% depending on the initial amount of fosfosal, i.e. 20 or 30 wt%, respectively. The weight loss and the water uptake were simultaneous processes, and values of hydration degree were around 10-14%. The formation of an apatite-like layer was detected on the surface of the cements at different periods of time depending on the composition of the bioactive glasses. The cements containing the glasses with P2O5 produced the growth of the apatite layer in shorter periods of time. The presence of fosfosal accelerated the precipitation of this layer independently on the glasses. The in vivo biocompatibility studied by intramuscular implantation in rats showed the absence of an anti-inflammatory response and a fibrous layer around the implant for the cement prepared with PMMA/fosfosal which is attributed to the therapeutic action of fosfosal acting in situ. The response to cements prepared with bioactive glasses and fosfosal showed a mild inflammatory reaction with the formation of the typical fibrous capsule around the implanted material.

Analgesics↗

Estimation of the minimum number of test specimens for fatigue testing of acrylic bone cement.

In the literature on fatigue testing of acrylic bone cements, data sets of various sizes have been used in different test series for the same cement formulation. There are two important consequences of this situation. First, it means that some test series last much longer than others, with all the implications for the cost of testing. Second, it makes drawing conclusions about the fatigue performance of a cement, based on the results of different literature series, a problematic issue. Clearly then, a recommendation as to what should be the minimum number of test specimens to use that would allow for confidence in the results of the statistical treatment of the test results (Gmin) would be desirable. In the present work, a method that could be used to culminate in such a recommendation is described. This method involves (i) obtaining experimental fatigue test results and (ii) analyzing those results using the Weibull probability distribution function and other statistical methods. This methodology is illustrated using fatigue life results obtained from uniaxial tension-compression fatigue tests on specimens fabricated from the polymerizing dough of one commercially available acrylic bone cement. For a tolerable error of 5%, we estimated Gmin to be either 7 (if the fatigue life results are treated using the two-parameter Weibull distribution function) or 11 (if the fatigue life results are treated using the three-parameter Weibull distribution function). To be on the conservative side, we therefore recommend that Gmin be 11. Three key limitations of the methodology presented here are discussed.

Cementation↗

In vitro drug release studies from the polymeric hydrogels based on HEA and HPMA using 4-[(E)-[(3Z)-3-(4-(acryloyloxy)benzylidene)-2-hexylidene]methyl]phenyl acrylate as a crosslinker.

Novel crosslinker, 4-[(E)-[(3Z)-3-(4-(acryloyloxy)benzylidene)-2-hexylidene]methyl]phenyl acrylate (AMA) was synthesized using (2Z, 6E)-2,6-bis(4-hydroxybenzylidene)cyclohexanone (HBC) and acryloyl chloride. Two types of crosslinked polymeric hydrogels were prepared from 2-hydroxyethyl acrylate (HEA) and 2-hydroxypropyl methacrylate (HPMA) monomers using AMA as a crosslinking agent. 2',4-dichloro-5'-fluoro-1-ene-2-(4-hydroxyphenyl)phenone (EHP) (J. Bio Active Compat. Polym. 18 (2003) 219) was used as a drug molecule for monitoring the releasing behaviour of the hydrogels. Morphology of the hydrogels was characterized using optical microscopy (OM) and Scanning Electron Microscopy (SEM) techniques. Several modifications were made in the experimental sections to study the effect of crosslinking percentage (CLP), drug loading percentage (DLP), monomer type (HEA and HPMA) and the pH. Totally 18 experiments were carried out to study the desired parameters in the hydrogels. The drug-releasing rate was monitored by the absorption appeared at 330.5 nm using UV spectrometer. It was found that the releasing rate of the drug from the polymeric hydrogels was dependent on the crosslinking density, drug loading percentage, monomer type and pH of the medium.

Biocompatible Materials↗

[Surgery and percutaneous injection of acrylic cement in bone metastases].

The first step for treatment of bone metastases is to confirm the diagnosis, particularly if there is only one localisation, so as to exclude a primary bone tumour. Surgery and percutaneous injection of acrylic cement are both efficient to relieve pain. Their indications and timing have to be discussed in pluridisciplinary staff. Long bones metastases have to be nailed before pathologic fracture. If there is suspicion of hypervascularisation, the lesion has to be embolized before any procedure. Treatment of spinal metastases with neurological impairment is an emergency. Paraplegia may be a consequence within a few hours. They have to be treated in an orthopedic or neurosurgery department with the experience of posterior and anterior approach of the spine. Surveillance may be useful to diagnose these metastases before neurological impairment. Depending from the type of cancer, the chemo- and radiotherapy sensibility, the number of metastases, the condition of the posterior wall of the vertebra and the general condition of the patient, different surgical treatments may be possible going from complete resection of the lesion to percutaneous injection of acrylic cement. Conventional radiotherapy is associated to surgery. Satisfactory results of such treatments justify greater involvement of orthopaedic surgery team in multidisciplinary staff.

Administration, Cutaneous↗

Non-particulate (continuous bed or monolithic) acrylate-based capillary columns for reversed-phase liquid chromatography and electrochromatography.

Three approaches are described to synthesize acrylic non-particulate beds (also called continuous beds or monoliths) in aqueous polymerization media for reversed-phase capillary liquid chromatography/electrochromatography. In the first, hexyl acrylate comonomer was dissolved together with water soluble polar comonomers using a non-ionic detergent. In the second, a new alkyl ammonium salt comonomer, (3-allylamino-2-hydroxypropyl)dodecyldimethylammonium chloride was used, which is water soluble and has detergent properties itself. The alkyl group of this comonomer provides hydrophobicity while the ionic groups generate electroosmosis in the non-particulate bed. In the third approach, the alkyl comonomer was used as a detergent to dissolve another hydrophobic comonomer in an aqueous polymerization medium. All three approaches were evaluated with respect to hydrophobicity, efficiency and electroosmotic properties of the beds. Hydrophobicity expressed as methylene group selectivity for the three types of the beds in 50% methanol mobile phase was 1.86, 1.16 and 1.78, electroosmotic mobility -5.14 x 10(-5), 6.89 x 10(-5) and 6.37 x 10(-5) cm2 V(-1) s(-1) and efficiency for the retained compound (methylparabene) 67,000, 93,000 and 110,000 plates m(-1) correspondingly. The columns were tested using pressure driven capillary chromatography and capillary electrochromatography. The influence of polymerization temperature on hydrodynamic permeability, separation impedance and inverse size exclusion porosimetry characteristics were used to evaluate the separation columns. The increase of the polymerization temperature resulted higher permeability of the bed, separation impedance and lower polymeric skeleton porosity. Further characterisation was provided by examining the separation efficiency observed for a series of benzoic acid esters and alkyl parabens.

Chromatography, Gel↗

Control of the electrical conductivity of composites of antimony doped tin oxide (ATO) nanoparticles and acrylate by grafting of 3-methacryloxypropyltrimethoxysilane (MPS).

The effect of the addition of antimony doped tin oxide (ATO) nanoparticles on the electrical conductivity of acrylate films is described. To enable dispersing of ATO in acrylate matrices, 3-methacryloxypropyltrimethoxysilane (MPS) was grafted on the surface of the filler. The amount of MPS used for this surface modification was found to strongly affect the electrical conductivity. Surface modification with a large amount of MPS resulted in colloidally stable dispersions of ATO, leading to a homogeneous distribution. Surface modification with small amounts of MPS led to instable ATO dispersions and aggregation of ATO into a fractal type network, which gives a much higher conductivity especially at low-volume fractions. For composites with a fractal type ATO network a second effect was found. Decreasing the amount of on ATO grafted MPS resulted in an increase of the electrical conduction between the ATO particles.

Journal Article↗

Acrylic cement pulmonary embolus masquerading as an embolized central venous catheter fragment.

An acrylic cement pulmonary embolus is a rare complication of percutaneous vertebroplasty. Many patients remain completely asymptomatic, but others may present with chest discomfort, dyspnea, and even cardiovascular collapse leading to death. Here we present an asymptomatic patient initially thought to have a central venous catheter pulmonary artery embolus based on the morphology of the foreign body on imaging exams. A more thorough investigation established the diagnosis of an acrylic cement pulmonary embolus resulting from percutaneous vertebroplasty procedures performed many months before the embolus discovery. The diagnostic work-up, treatment strategy, and a review of the literature are presented.

Aged↗

Acrylic bone cements: composition and properties.

Cementing endoprostheses is one of the most frequently performed orthopedic procedures in the world today. The bone cements that are currently available commercially are all based on the chemical substance methylmethacrylate. Although all of them have the same chemical basis, acrylic bone cements are not all alike. This article discusses the composition of acrylic bone cements and the influence of the composition on the properties of the material.

Anti-Bacterial Agents↗

Acrylic bone cements: mechanical and physical properties.

Mechanical and physical properties are of particular significance for the performance of acrylic bone cement. Several mechanical test methods are described in the literature to characterize the mechanical performance of bone cements. The simulation of the in vivo situation is extremely difficult, however, because of the complex mechanism of loading in the bone. The usefulness of the different mechanical and physical test methods, several results of commercial acrylic bone cements, and the influence of different parameters, such as temperature, test environment, and preparation of specimens on these results are discussed in this article.

Bone Cements↗

Management of pulmonary embolism during acrylic vertebroplasty.

A 55-year-old man diagnosed with osteogenesis imperfecta had multiple pulmonary embolism from acrylic cement during vertebroplasty. The patient immediately developed respiratory distress, renal failure, and right cardiac failure. A computed tomographic scan showed the presence of cement in the right and left pulmonary arteries, and in both lungs. Cardiac and respiratory functions did not improve with medical treatment, therefore the patient underwent pulmonary artery embolectomy. Cement was easily removed from both pulmonary arteries. The patient quickly recovered from respiratory and cardiac failure. We believe pulmonary embolectomy is a reliable and effective procedure to treat this rare and dreadful complication of acrylic vertebroplasty.

Embolectomy↗

Synthesis and antitumor evaluation of some new substituted amidino-benzimidazolyl-furyl-phenyl-acrylates and naphtho[2,1-b]furan-carboxylates.

The multistep synthesis of a series of substituted amidino-benzimidazolyl-furyl-phenyl-acrylic acid's esters and substituted amidino-benzimidazolyl-naphtho[2,1-b]furan-carboxylic acid's esters is described starting from corresponding 3-(2-furyl)-2-phenyl-acrylic acids. The new compounds were tested on the cytostatic activities against malignant cell lines: pancreatic carcinoma (MiaPaCa2), breast carcinoma (MCF7), cervical carcinoma (HeLa), laryngeal carcinoma (Hep2), colon carcinoma (HT 29), melanoma (HBL), and human fibroblasts cell line (WI38). All compounds inhibited the proliferation of tumor cell lines. Inhibitory effect of examined compounds depended on concentration, but without significant difference among the type of tumor cells. The compounds 2 and 5 exerted very low inhibitory effect on the growth of human fibroblasts. Unsubstituted derivative 8 has not inhibited any tested cell lines.

Acetates↗

Distribution of water-soluble and surface-active low-molecular-weight species in acrylic latex films.

Monodisperse core-shell latices were synthesized, differing in the acrylic acid (AA) content in the particle shell (1 or 4 wt%) and the Tg of the acrylic core (around -40 or 10 degrees C). In a first step, the drying mechanisms of the dialyzed latices were studied by confocal Raman spectroscopy. It was shown that, besides some unexpected features (briefly described in the article), drying occurred in a rather classical way, i.e., simultaneously from top to bottom and from edge to center. Then, the distributions of sulfate ion (SO4) (from sodium sulfate) and sodium dodecyl sulfate (SDS) in the dry latex films were established by confocal Raman spectroscopy and attenuated total reflectance (ATR). The two techniques were complementary. SO4 and SDS distributions were quite different, although presenting some common characteristics. In both cases, repartition of the low-molecular-weight species in the film was even less homogeneous when the AA content was lower and the particle core softer. However, SO4 showed enrichment at the film-substrate interface and depletion at the air side, whereas SDS showed concentration maxima at both interfaces. Interpretations stress the importance of desorption from the particle-water interface, transport by water, size effects, and diffusion.

Journal Article↗

Influence of surface and bulk structures of acrylic PSA films onto their tack properties.

PSA films are obtained by coalescence of latices synthesized by free-radical emulsion polymerization of methyl methacrylate (MMA) and 2-ethylhexyl acrylate (EHA). For the same overall 50/50 molar composition, the polymer particles have well-defined structures when the feed composition and the feed mode (using batch or semicontinuous processes) are adjusted. The characterizations of the film structures by surface (tapping mode AFM) and bulk (DSC, rheology) analyses argue for the conservation of the initial particle structure when coalescence occurs. The influence of the chemical heterogeneity on the tack properties of the films is investigated to extend the study of these original acrylic PSA films up to relevant structure-property correlations.

Journal Article↗

Chemo-enzymatic synthesis and characterization of graft copolymers from lignin and acrylic compounds.

Chemo-enzymatic initiation of graft copolymerization of acrylic compounds onto different technical lignosulfonates (LS) was compared to a Fenton-like system (ferrous ion, t-BHP). The enzyme tested was a phenoloxidase laccase (EC 1.10.3.2) from the white rot basidomycete Trametes versicolor. Most applied lignins were successfully grafted, resulting in a polymer yield of more than 90%. The effect of initiator concentration and the lignin/monomer ratio on the yield and M(w) of enzymatically grafted polymers were studied. The homopolymer proportion in the enzymatically produced grafts of Ca-LS and acrylic acid was 5 to 6x lower than those initiated by the Fenton-like reagent; no such differences were observed for Na-LS.

Journal Article↗

New partially degradable and bioactive acrylic bone cements based on starch blends and ceramic fillers.

This work reports the development of new partially biodegradable acrylic bone cements based on corn starch/cellulose acetate blends (SCA), prepared by the free radical polymerization of methyl methacrylate and acrylic acid at low temperature. Amounts of biocompatible, osteoconductive and osteophilic mineral component such as hydroxylapatite (sintered and non-sintered), were incorporated in different percentages to confer a bone-bonding character to the bone cements in this type of applications. All cement formulations were characterized by 1H NMR spectroscopy. Curing parameters and mechanical properties were determined finding formulations which complete the ASTM legislation. Hydration degree, degradation studies, as well as bioactivity tests were performed in all prepared formulations. The developed systems show a range of properties that might allow for their application as self-curing bone cements, exhibiting several advantages with respect to other commercially available bone cements.

Bone Cements↗