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Time-resolved EPR studies of main chain radicals from acrylic polymers. Effects of tacticity, solvent, and side group structure on chain stiffness.

Main chain polymeric radicals from several acrylic polymers, produced by laser flash photolysis at 248 nm in liquid solution, have been studied using direct detection time-resolved electron paramagnetic resonance (TREPR) spectroscopy at 9.5 GHz. Highly isotactic poly(methyl methacrylate) (i-PMMA) shows a sharp, well-resolved spectrum at about 95 degrees C. Using synthetic methodology to disrupt the tacticity of i-PMMA, we observed different fast-motion hyperfine coupling constants for the main chain radicals. By raising the temperature of observation, we returned the coupling constants to the same value as those in the highly isotactic sample. This result is related qualitatively to the degree of stiffness of the polymer chains as a function of tacticity. The concept is tested further by comparison to two other acrylic polymers with bulky side chains: poly(fluorooctyl methacrylate) (PFOMA) and poly(adamantyl methacrylate) (PAMA), whose main chain radicals show significant line broadening even at 110 degrees C. Solvent effects on both spectral appearance (the alternating line-width effect) and kinetic decays (attributed to T1 relaxation) are also presented and discussed in terms of main chain conformational motion.

Journal Article↗

Conformational dynamics of poly(acrylic acid). A study using surface plasmon resonance spectroscopy.

The conformational dynamics of poly(acrylic acid) induced by pH change is reported here. Poly(acrylic acid) immobilized on gold surface was exposed to pH changes, and the conformational changes thus induced were followed in real time using surface plasmon resonance spectroscopy. The temporal profile of the stretching-coiling phenomenon showed a minimum point, which was proposed to be arising due to the contradictory behavior of two different property changes in the polymeric system. Normally surface plasmon resonance (SPR) response would be a convoluted effect of the thickness and refractive index changes, but the behavior observed here, where the SPR response is predominantly governed by either one of the two, is unique and to the author's knowledge is a feature that is observed for the first time. Analysis of the kinetics of the angle change revealed that it takes longer for the polymer to stretch than it takes for it to collapse, with the kinetic rate constants varying by at least an order of magnitude. The SPR angle change as well as the kinetic constants increased linearly with molecular weight. Effect of Ca2+ was studied, and it was found that the polymer was locked in its conformation due to the binding of the multivalent cations.

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Interfacial reactions in confinement: kinetics and temperature dependence of the surface hydrolysis of polystyrene-block-poly(tert-butyl acrylate) thin films.

The effect of confinement on the kinetics of the surface hydrolysis of polystyrene-block-poly(tert-butyl acrylate) (PS(n)-b-PtBA(m)) thin films on oxidized silicon substrates in 3 M aqueous hydrochloric acid was systematically investigated. As shown by X-ray photoelectron spectroscopy (XPS) and contact angle measurements, a skin layer of acid-sensitive PtBA is present on the surface of PS(n)-b-PtBA(m) films, consistent with the lower surface tension of PtBA compared to that of PS. The thickness of the skin layer was determined by angle-dependent XPS as approximately 8 nm for PS(690)-b-PtBA(1210). Tapping mode atomic force microscopy showed an increasing surface coverage of swollen poly(acrylic acid)-rich globules with increasing hydrolysis time. Using ex situ Fourier transform infrared spectroscopy, the reaction kinetics was determined quantitatively as a function of temperature, polymer film thickness, thermal pretreatment of the films, and block copolymer composition. The initial stages of the hydrolysis can be described as a pseudo-first-order reaction under all conditions investigated. The corresponding rate constants were found to be 2 orders of magnitude lower than those reported for the hydrolysis of tert-butyl acetate in solution and depended linearly on the fraction of PtBA exposed at the surface. However, the polymer film thickness, thermal pretreatment of the films, block copolymer composition, and local composition did not affect the rate constants. The negative value of the activation entropy (DeltaS(298)++ = -103 J/mol K), determined according to the Arrhenius equation and transition state theory, indicates that the tightness of the transition state is more pronounced in the PS(n)-b-PtBA(m) film compared to reactions in solution. Thus, the spatial constraints due to the incorporation of the reactive ester groups in thin polymer films are responsible for the observed reduced reactivity.

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Improving water sensitivity in acrylic films using surfmers.

The water sensitivity of films obtained from high solids content acrylic latexes was investigated, with special focus on the role of the surfactant used in the synthesis step. The performance of films obtained from latexes stabilized by nonionic surfmers was compared to that of the acrylic latexes stabilized with conventional nonionic and anionic surfactants. It was seen that the latexes stabilized with reactive surfactants exhibited a remarkably better resistance to both water permeability and water vapor permeability and therefore enlarged the durability of the films. Atomic force microscopy images suggested that the defects created by surfactant migration in the latexes stabilized with conventional surfactants promoted the permeation of water by capillarity.

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Electrokinetic characterization of poly(acrylic acid) and poly(ethylene oxide) brushes in aqueous electrolyte solutions.

Surfaces carrying hydrophilic polymer brushes were prepared from poly(styrene)-poly(acrylic acid) and poly(styrene)-poly(ethylene oxide) diblock copolymers, respectively, using a Langmuir-Blodgett technique and employing poly(styrene)-coated planar glass as substrates. The electrical properties of these surfaces in aqueous electrolyte were analyzed as a function of pH and KCl concentration using streaming potential/streaming current measurements. From these data, both the zeta potential and the surface conductivity could be obtained. The poly(acrylic acid) brushes are charged due to the dissociation of carboxylic acid groups and give theoretical surface potentials of -160 mV at full dissociation in 10(-)(3) M solutions. The surface conductivity of these brushes is enormous under these conditions, accounting for more than 93% of the total measured surface conductivity. However, the mobility of the ions within the brush was estimated from the density of the carboxylic acid groups and the surface conductivity data to be only about 14% of that of free ions. The poly(ethylene oxide) (PEO) brushes effectively screen the charge of the underlying substrate, giving a very low zeta potential except when the ionic strength is very low. From the data, a hydrodynamic layer thickness of the PEO brushes could be estimated which is in good agreement with independent experiments (neutron reflectivity) and theoretical estimates. The surface conductivity in this system was slightly lower than that of the polystyren substrate. This also indicates that no significant amount of preferentially, i.e., nonelectrostatically attracted, ions taken up in the brush.

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Precipitation-redispersion of cerium oxide nanoparticles with poly(acrylic acid): toward stable dispersions.

We exploit a precipitation-redispersion mechanism for complexation of short chain polyelectrolytes with cerium oxide nanoparticles to extend their stability ranges. As synthesized, cerium oxide sols at pH 1.4 consist of monodisperse cationic nanocrystalline particles having a hydrodynamic diameter of 10 nm and a molecular weight of 400 000 g mol(-1). We show that short chain uncharged poly(acrylic acid) at low pH when added to a cerium oxide sols leads to macroscopic precipitation. As the pH is increased, the solution spontaneously redisperses into a clear solution of single particles with an anionic poly(acrylic acid) corona. The structure and dynamics of cerium oxide nanosols and their hybrid polymer-inorganic complexes in solution are investigated by static and dynamic light scattering, X-ray scattering, and chemical analysis. Quantitative analysis of the redispersed sol gives rise to an estimate of 40-50 polymer chains per particle for stable suspension. This amount represents 20% of the mass of the polymer-nanoparticle complexes. This complexation adds utility to the otherwise unstable cerium oxide dispersions by extending the range of stability of the sols in terms of pH, ionic strength, and concentration.

Journal Article↗

Photolithographically patterned surface modification of poly(dimethylsiloxane) via UV-initiated graft polymerization of acrylates.

Patterned surface modification of poly(dimethylsiloxane) (PDMS) is achieved by combining ultraviolet-initiated graft polymerization (UV-GP) and photolithography. Poly(acrylic acid) (PAA) and poly(methacrylic acid) (PMAA) patterns were grafted onto PDMS with micrometer-scale feature edge resolution. The morphology and chemical composition of the grafted layers were assessed by optical and atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and XPS imaging. AFM section analyses demonstrated the deposition of 33 +/- 1 and 62 +/- 8 nm thick patterned films of PAA and PMAA, respectively. Spatially resolved C 1s XPS provided images of carboxylic acid functionalities, verifying the patterned deposition of acrylate films on PDMS. These observations demonstrate the general usefulness of UV-GP and photolithography for micropatterning.

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Soluble-insoluble-soluble transitions of aqueous poly(N-vinylacetamide-co-acrylic acid) solutions.

Several poly(N-vinylacetamide-co-acrylic acid)s with various copolymer compositions have been synthesized, and their unique phase-transition behavior in aqueous salt (Na2SO4 or NaCl) solutions was investigated. Copolymers containing more than 51 mol % N-vinylacetamide (NVA) show reentrant soluble-insoluble-soluble transitions with increasing temperature. The soluble-insoluble transition temperature (T(p1)) increased linearly with increasing NVA content, whereas the insoluble-soluble transition temperature (T(p2)) was almost constant irrespective of the NVA content. Potentiometric titration of the copolymer solutions suggested that the acrylic acid (AA) carboxyl groups form hydrogen bonds with the NVA amide groups even under soluble conditions. Dehydration of the NVA amides and their consequent hydrogen bonding with the AA carboxyl groups during the soluble-insoluble transition process was indicated by FTIR measurements. Addition of salt (Na2SO4 or NaCl) to the aqueous media reduces the solvent quality and enhances the intra- and interchain interactions of the copolymers. Thus, T(p1) was observed to decrease and T(p2) was observed to increase with increasing salt concentration. However, the addition of urea to the media reverses the concentration dependence of T(p1) and T(p2) by disturbing the intra- and interchain interactions of the copolymers.

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Oxidative cross-coupling of acrylates with vinyl carboxylates catalyzed by a Pd(OAc)2/HPMoV/O2 system.

Oxidative cross-coupling of acrylates with vinyl carboxylates was first successfully achieved by the use of a Pd(OAc)(2)/HPMoV/O(2) system in fair to good yields. For instance, the reaction of n-butyl acrylate with vinyl acetate in the presence of catalytic amounts of Pd(OAc)(2) and H(4)PMo(11)VO(40).nH(2)O under O(2) in acetic acid at 70 degrees C for 12 h afforded the corresponding cross-coupling product, n-butyl 5-(acetoxy)-2,4-pentadienoate, in 70% yield.

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Synthesis of acrylate functional telechelic poly(lactic acid) oligomer by transesterification.

The controlled synthesis of low molecular weight (Mn from 700 to 10 000 g/mol) poly(lactic acid) (PLA) telechelic oligomers end-capped with acrylate groups by a one-step reaction was investigated. A transesterification reaction was carried out in solution with a Lewis acid titanium catalyst using a high molecular weight PLA and a low molar mass diacrylate. End-functionalization was demonstrated by proton NMR spectroscopy which was also used for quantitative analysis and number average molecular weight determination using the ratio between the acrylic chain ends to the main groups of poly(D,L-lactic acid). The formation of low molar mass oligomers from high molecular weight poly(lactic acid) was verified by gel permeation chromatography. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry showed that the above oligomerization was accompanied by the formation of cyclic compounds. By these means the feasability of a simple transesterification for a controlled synthesis of telechelic oligomers with molecular mass being a function of the added amount of diacrylate has been demonstrated. The glass transition temperatures of the elaborated oligomers varied from -35 to -5 degrees C. Subsequent thermal crosslinking was performed using benzoyl peroxide which enabled the formation of amorphous networks with Tg's close to the body temperature of 40 degrees C. Upon storage in a humid atmosphere the initially fairly hard and brittle networks became, due to hydrolysis, progressively more flexible thus demonstrating the potential biodegradability of these materials.

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The influence of poly(acrylic acid) molar mass on the properties of polyalkenoate cements formed from zinc oxide/apatite mixtures.

The influence of poly(acrylic acid) molar mass was investigated on cements formed from zinc oxide-apatite mixtures at three aging times; one, seven and 28 days. Cements based on both hydroxyapatite and fluorapatite were investigated. The compressive strength, un-notched fracture strength and fracture toughness increased markedly with poly(acrylic acid) molar mass. The fracture toughness and un-notched fracture strength increased with aging time for the two highest molar mass cements, but decreased with time for the two lowest molar mass cements. The greater chain entanglement density present in the higher molar mass cements is thought to contribute significantly to the cement stability in addition to the crosslinking of the polyacrylate chains by calcium and zinc ions. Substitution of hydroxyapatite by fluorapatite had no significant influence on the mechanical properties of the cements at aging times longer than one day.

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Improvement of the mechanical properties of acrylic bone cements by substitution of the radio-opaque agent.

Acrylic bone cements become radio-opaque by the addition of an inorganic compound, commonly BaSO4 or ZrO2. However, the use of these additives has some negative effects such as loss of mechanical properties, risk of release and bone resorption. The use of the monomer 2,5-diiodo-8-quinolyl methacrylate (IHQM), which shows adequate polymerization and radio-opacity properties, is proposed as a new X-ray opaque, methacrylate iodine-containing agent. The aim of this study is to determine the effect of this new radio-opaque agent on the mechanical properties of acrylic bone cements. The addition of the iodine-containing methacrylate provides a statistically significant increase in the tensile strength, fracture toughness and ductility, with respect to the barium sulphate-containing cement. This effect can be attributed to the fact that the use of a radio-opaque monomer eliminates the porosity associated with the barium sulfate particles, which show no adhesion to the matrix. However, some reinforcing effect must also be attributed to the iodine-containing monomer, since the tensile and fracture toughness values reached are even higher than those shown by the radiolucent cement.

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Factors affecting the mechanical and viscoelastic properties of acrylic bone cement.

The aim of this paper is to report a series of experiments investigating the factors that influence the viscoelastic properties of acrylic bone cement. The effects of the brand of cement, the length of time since mixing, temperature, the hydration of the cement, and the influence of fat and or blood in the environment on the creep and stress relaxation behavior of the cement have been studied in laboratory-prepared specimens in tension, compression and four point bending. Although there are significant differences in the viscoelastic behavior of some of the different brands of polymethylmethacrylate based cements, these differences are small by comparison with the major effects that can be exerted by the length of time since mixing and some environmental factors. These effects have important practical consequences, especially with regard to the ability of bench top and theoretical studies to predict reliably the mechanical and viscoelastic behavior of acrylic cement in vivo.

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A novel acrylic copolymer for a poly(alkenoate) glass-ionomer cement.

The interest in the clinical use of polyalkenoate cements stems mainly from their behavior as bioactive adhesive materials with therapeutic action. Glass-ionomer cements set by an acid-base reaction between a degradable glass and a poly(alkenoic acid) and the therapeutic action is related to the release of fluoride ions which are present in the hardened cement that show a sustained release over years, responsible for caries inhibition in teeth. Conventional glass-ionomers, however, suffer from some disadvantages such as short working time, initial moisture sensitivity and prone to desiccation after setting and are generally brittle. In the present study, a poly(alkenoic acid) copolymer was synthesized based on acrylic acid and 2-hydroxyethylmethacrylate (HEMA) using azobisisobutyronitrile as the initiator and characterized. The acid-base reaction was carried out by reacting aqueous solutions of the new copolymer (40 and 60%) with a commercial aluminofluorosilicate glasses as used in conventional glass-ionomer cements. The results showed that the copolymer of HEMA and acrylic acid was a viable poly(alkenoic) acid for formation of glass-ionomer cements.

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Custom cranioplasty using stereolithography and acrylic.

Numerous methods of cranioplasty have been described. Customization and prefabrication have been reported to reduce operating time and improve cosmesis. An original technique for the manufacture of customized cranioplastic implants has been developed and tested in 30 patients.Thirty patients requiring cranioplasties were selected. Data acquired from computed tomography (CT) were used to manufacture exact plastic replicas (biomodels) of craniotomy defects and master cranioplastic implants using the rapid prototyping technology of stereolithography (SL). The three-dimensional (3D) imaging techniques of mirroring and interpolation were used to extrapolate on existing anatomy to design the master implants. The master implants were hand finished to fit the defect in the corresponding cranial biomodel exactly and were then used to create a cavity mould. The mould was used to cast thermally polymerised custom acrylic implants. The surgeons reported that the customized implants reduced operating time, afforded excellent cosmesis and were cost effective. The patients reported that the opportunity to see the biomodel and implant preoperatively improved their understanding of the procedure. Two complications were noted, one infection and one implant required significant trimming. The simultaneous manufacture of the master implant (male) and biomodel (female) components from SL allowed custom accurate implants to be manufactured. Disadvantages identified were the time required for computer manipulations of the CT data (up to 2 h), difficulty in assessing the accuracy of the computer generated master as a 3D rendering, the potential for SL parts to warp, manufacturing time (minimum 2 days) and the cost of approximately $1300 US per case ($1000 for the SL biomodel and $300 for the acrylic casting).

Humans↗

Advances in the morphological diagnosis of bone tumours: cytology, cytochemistry, acrylate embedding and electron microscopy (author's transl).

An exact morphological diagnosis of bone tumours is the prerequisite for selective treatment. In a given case this may present great difficulties, partly because of the rarity of a tumour group and thus lack of experience, partly faulty removal of the specimen and unsatisfactory further technical handling. Progress can be expected only by widening the spectrum of methods by using modern morphological tests. In a programme using imprint cytology, cytochemistry, rapid section, histochemistry, paraffin, non-decalcified embedding in acrylate and electron microscopy it was demonstrated in 78 cases of bone tumour (seen over a period of two years) that with these tests, especially cytology, cytochemistry and non-decalcified acrylate histology, significant improvement can be obtained in the morphological diagnosis of bone tumours. In addition, new lights on cytogenesis and pathogenesis of these tumours and possible points of attack of cytostatic treatment are provided.

Adolescent↗

Bimodal release of theophylline from "seed-matrix" beads made of acrylic polymers.

The purpose of this research was to design a "seed-matrix" structure for an in vitro bimodal theophylline release profile and to investigate the mechanism and kinetics of drug release as well as the influence of various factors on the properties of the theophylline-containing microspheres. "Seed" microspheres with high theophylline content were prepared from Eudragit L100 and Eudragit S100, copolymers of methyl methacrylate and methacrylic acid, by the solvent removal process. The seed-matrix beads were subsequently prepared by incorporation of the seed microspheres into Eudragit RL100, a copolymer of acrylic and methacrylic acid esters with a low content of quaternary ammonium group. Increasing the size of encapsulated drug particles and the rate of agitation during the preparation, or decreasing the amount of surfactants led to an increase in the size of the microspheres produced. Scanning electron microscopy revealed porous morphology of the microspheres. The release rate of theophylline was enhanced as the content of methacrylic acid in the copolymer increased and the size of the microspheres decreased. The kinetics of drug release from the microspheres was controlled by swelling at the early stage and by diffusion in the later stage. The drug was released from the matrix of the seed-matrix beads at pH 1.2 and from both the matrix and the seeds at pH 6.8. A bimodal release profile of theophylline was obtained from the seed-matrix beads made of acrylic polymers.

Hydrogen-Ion Concentration↗

Craniofacial contouring and porous acrylic cement.

Porous acrylic cement permitting ingrowth of soft and hard tissue was developed in the mid-1970s. After several years of animal experimentation, a clinical trial started in 1978. Twenty-nine selected patients had craniofacial contouring with in situ curing porous acrylic cement. It is an easy one-stage procedure with a good fixation of the prosthesis. The result is a definite good contour reconstruction. It offers the craniofacial surgeon a useful alternative in selected cases when autogenous bone grafting or an intracranial approach is not indicated or not sought by the patient.

Carboxymethylcellulose Sodium↗