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Dimensional accuracy and surface detail reproduction of two hydrophilic vinyl polysiloxane impression materials tested under dry, moist, and wet conditions.

STATEMENT OF PROBLEM: A major limitation of vinyl polysiloxane (VPS) impression materials is their hydrophobicity. There are 2 aspects to this problem, the wettability of the polymerized impression by dental gypsum materials and the ability of the unpolymerized material to wet intraoral tissues. To address this problem, manufacturers have added surfactants and labeled the new products as hydrophilic vinyl polysiloxane. PURPOSE: The purpose of this investigation was to compare dimensional accuracy and surface detail reproduction of 2 hydrophilic VPS impression materials, when used under dry, moist, and wet conditions. MATERIALS AND METHODS: A total of 102 impressions were made of stainless steel metal dies similar to those described in American Dental Association (ADA) specification 19. The dies had 2 vertical and 3 horizontal lines inscribed on their superior surfaces. Impressions were made under dry, moist, and wet conditions. Dimensional accuracy was measured by comparing the average length of the middle horizontal line in each impression to the same line on the metal die, by use of a measuring microscope with an accuracy of 0.001 mm. A 2-way analysis of variance and least significant difference post hoc test were used to compare mean dimensional changes (alpha=.05). Surface detail reproduction was evaluated in 2 ways: (1) by use of criteria similar to ADA specification 19 for detail reproduction, continuous replication of at least 2 of the 3 horizontal lines, and (2) by use of a method developed for this study that categorized the impressions as satisfactory or unsatisfactory based on their surface characteristics: presence of pits, voids, or roughness. Pearson chi(2) (alpha=.05) was used to compare detail reproduction results. RESULTS: Conditions (dry, moist, and wet) did not cause significant adverse effects on the dimensional accuracy of either material. The mean dimensional change and SD were 0.005% +/- 0.002% or less. With both surface detail analyses, dry, moist, and wet conditions had a significant effect on the detail reproduction of both materials (P<.05). Only under dry conditions did both impression materials continuously replicate at least 2 of the 3 horizontal lines 100% of the time. Under moist conditions, 82% of the Aquasil impressions and 100% of the Reprosil impressions were judged satisfactory, while under wet conditions, only 47% Aquasil and 11% Reprosil impressions were satisfactory. With the additional surface detail characterization, only under dry conditions were impressions produced with clinically acceptable surface quality (Aquasil 77% and Reprosil 100% satisfactory). CONCLUSIONS: Dimensional accuracy of both materials tested was well within ADA standards. Best surface detail results were obtained only under dry conditions for both materials.

Analysis of Variance↗

Influence of abciximab on the adhesion of platelets on a shielded plasma gradient prepared on polyethylene.

INTRODUCTION: Thrombotic effects of biomaterial implants are mediated merely through activation of the platelet glycoprotein IIb-IIIa (GpIIb-IIIa) receptor. Consequently, platelet GpIIb-IIIa receptor inhibitors are successfully used during stent implantation procedures to prevent thrombosis. However, currently a new generation of stents contains surface coating, which changes the surface to more hydrophobic or hydrophilic. This change markedly affects the interaction of platelets and may influence the efficiency of GpIIb-IIIa inhibitors. MATERIALS AND METHODS: To study the influence of the wettability of biomaterials on the effectiveness of abciximab, 5-cm polyethylene gradients with contact angles of 100 degrees to 40 degrees were made by means of glow discharge. Fresh whole blood with or without abciximab was recirculated over this gradient. RESULTS: Inhibition of platelet adhesion by abciximab was maximal, but not complete, on the hydrophobic and moderate hydrophobic part of the gradient, with contact angles of 55 degrees to 90 degrees. Percentage inhibition by abciximab was maximal around 60 degrees. CONCLUSIONS: Intermediate hydrophobicity of currently applied stent materials, such as stainless steel, seems optimal in combination with abciximab. However, on hydrophobic and particularly on hydrophilic materials, abciximab is less effective.

Abciximab↗

Surface characterization of poly(methyl methacrylate) microgrooved for contact guidance of mammalian cells.

High-resolution patterns of grooves have been made in poly(methyl methacrylate) films, PMMA, by an electron-beam microlithographic process. The surface of films processed over a large width was characterized in terms of chemical composition (X-ray photoelectron spectroscopy (XPS). time of flight secondary ion mass spectroscopy), wettability (sessile drop) and topography (atomic force microscopy). Collagen adsorption was also studied (radiocounting, XPS) as such or in competition with Pluronic F68. The chemical alteration of the surface induced by the electron-beam irradiation disappeared after the dissolution involved in the development process. W138 human fibroblasts cultivated on microgrooved substrata (grooves 1 microm deep and 0.5-10 microm wide) showed a strong orientation parallel to the grooves. The contact guidance is induced by the topography of the surface and not by the alternation of zones with different physico-chemical properties. It may be explained in terms of probability of successful substratum contact by cell protrusions.

Adsorption↗

Effect of chemical composition on hydrophobicity and zeta potential of plasma sprayed HA/CaO-P2O5 glass coatings.

Multilayered plasma sprayed coatings on the surface of Ti-6Al-4V alloys have been prepared, which were composed of an underlayer of HA and a surface layer of a CaO-P2O5 glass-HA composite, with 2 or 4wt% of glass. Contact angle and surface tension variation with time, for both water and a protein solution, were determined by the sessile and pendent drop methods respectively using the ADSA-P software. Wettability studies showed that hydrophobicity of the coatings increase with the glass addition. The work of adhesion of albumin was also altered in a controlled manner by the addition of the CaO-P2O5 glass, being lower on the composite coatings than on HA. Zeta potential (ZP) results showed that composite coatings presented a higher net negative charge than HA coatings and that ZP values were also influenced by the content of the glass. This study demonstrated that the surface properties of those coatings may be modified by the addition of CaO-P2O5 glass.

Calcium Compounds↗

A novel phosphorylcholine-coated contact lens for extended wear use.

The preparation and characterisation of a new phosphorylcholine (PC)-coated silicone hydrogel contact lens for use in extended wear is described. The Michael-type addition of amines to acrylates forms the basis of the synthesis of a novel silicone-based macromer with hydrophilic functionality. It is demonstrated that this macromer can be combined with other silicone-based monomers, hydrophilic monomers and crosslinker to produce a contact lenses formulation. Examples of lenses with water contents of 33% and 46% are illustrated and their properties compared to other commercially available lenses. Materials with comparatively low modulus (<0.3 MPa) and adequate tear strength (>2-4MPa) with excellent elongation to break (>200%) can be obtained using this technology. In addition to the mechanical aspects. both the oxygen and solute permeabilities of the material can be controlled by the hydrophilic: hydrophobic monomer balance in the formulation. to obtain materials with attributes suitable for extended wear use. The PC coating is achieved by means of an in-mould coating (IMC) technique that produces a uniform and stable surface as determined by staining and XPS. The coating imparts both improved lens wettability (advancing contact angle of approximately 50 with virtually no hysteresis) and lower protein adsorption relative to the uncoated lens.

Adsorption↗

Immobilization of a nonsteroidal antiinflammatory drug onto commercial segmented polyurethane surface to improve haemocompatibility properties.

A method has been developed in which a layer of p-aminosalicylic acid (4-amino-2-hydroxybenzoic acid) (PAS), a water soluble pharmaceutical compound of the nonsteroidal anti-inflammatory drug (NSAID) class with antiaggregant platelet activity, is covalently immobilized onto a segmented polyurethane, Biospan (SPU) surface. Thus, SPU surfaces were modified by grafting of hexamethylenediisocyanate. and the free isocyanate remaining on the SPU surface were then coupled through a condensation reaction to amine groups of p-aminosalicylic acid. The bonding of PAS from aqueous solution onto SPU surface was studied by ATR-FTIR. UV and fluorescence spectroscopy. Plateau levels of coupled PAS were reached within 1.2 microg/cm2 using PAS solution concentrations of 1mg/ ml. The surface wettability of the polymeric films measured by contact angle indicate that the introduction of the PAS turns the surface more hydrophilic (theta(water) = 43.1 +/- 2.1) relatively to the original SPU films (theta(water) = 70.3 +/- 1.9). The in vitro albumin (BSA) adsorption shows that the PAS-SPU films adsorb more BSA (250/microgmm2) than the original SPU (112 microg mm2). Thrombogenicity was assessed by measuring the thrombus formation and platelet adhesion of the SPU containing PAS relatively to nonmodified SPU surfaces. The polymeric surfaces with immobilized PAS had better nonthrombogenic characteristics as indicated by the low platelet adhesion, high adsorption of albumin relatively to fibrinogen and low thrombus formation, making them potentially good candidates for biomedical applications.

Albumins↗

Adsorption and dissolution behavior of human plasma fibronectin on thermally and chemically modified titanium dioxide particles.

Titanium is known for its biocompatibility and is widely used in dental and orthopedic reconstructive surgery. There are reports that osteointegration of these implants is not optimal. The objective of this study was to modify titanium dioxide particles and examine the resultant effects on protein adsorption to these altered surfaces using a model cell binding protein, human plasma fibronectin (HPF). HPF is an important matrix glycoprotein that plays a major role in cell and protein attachment, Titanium dioxide surfaces were modified by heating the titanium dioxide powder at 800 degrees C for 1 h or treating with an oxidizing agent: peroxide in ammonium hydroxide followed by peroxide in hydrochloric acid. Oxidized and control samples were further treated with 9:1 butanol:water for 30 min. Brunauer-Emmett-Teller showed no change in particle surface area as a result of thermal or chemical treatment. Hydrophobicity increased with butanol treatment of titanium dioxide. Diffuse reflectance Fourier transform infrared spectroscopy showed the presence of -CH2 and -CH3 vibrations in the region of 2850-3000 cm(-1) for both the heated, butanol and peroxide/butanol-treated samples. The absence of increased C-O and O-C=O features as determined by electron spectroscopy for chemical analysis indicates that butanol adsorption is not occurring via an esterification mechanism. The interaction between butanol and pre-heated or peroxide-treated titanium dioxide may be one of association (weak electrostatic and/or Van der Waals forces) rather than direct ionic bonding. Maximum HPF adsorption on modified or unmodified titanium dioxide occurred within 30 min, with greater protein adsorption occurring on butanol-treated samples. Desorption was minimal with all modifications. Zeta potential measurements showed that HPF adsorption caused an increase in the negative zeta potential with the greatest change noted for the butanol-treated samples. These findings suggest that wettability and surface charge both play an important role in protein adsorption to titanium dioxide. Thus, by modifying the physico-chemical properties of titanium dioxide surfaces, it may be possible to alter protein adsorption and hence optimize cell attachment.

1-Butanol↗

Mineralisation of two phosphate ceramics in HBSS: role of albumin.

The role of albumin in the mineralisation process of commercial hydroxyapatite (HAp) and synthesised biphasic (HAp-tricalcium phosphate) ceramics in a bufferless simulated inorganic plasma (HBSS) was investigated by conventional in vitro tests and static and dynamic wettability measurements. Albumin was either pre-adsorbed or solubilised in HBSS. It was found that calcium complexation by albumin plays a key role in early mineralisation kinetics, so that mineralisation is favoured when albumin is pre-adsorbed and hindered when it is dissolved in HBSS. In the biphasic ceramic this picture is complicated by the fact that albumin, in solution, seems to promote the dissolution of tricalcium phosphate, and simultaneously compete for calcium with the ceramic. It also appears that albumin has a stabilising effect of octacalcium phosphate present in deposits on commercial HAp. The same effect may be present in the case of the biphasic ceramic, at earlier mineralisation times, when octacalcium phosphate appears as a precursor of HAp. Octacalcium phosphate formation on commercial apatite is accompanied by carbonate substitution in phosphate positions.

Albumins↗

Quasi-living surface graft polymerization with phosphorylcholine group(s) at the terminal end.

A surface graft polymer with one or two phosphorylcholine (PC) polarheads at the terminus of the growing chain end was prepared by sequential reactions on a glass substrate. The dithiocarbamate group covalently bound to glass surfaces was derivatized with one or two PC groups and then irradiated with ultraviolet light in the presence of N,N-dimethylacrylamide (DMAAm). X-ray photoelectron spectroscopy, wettability measurements and dye staining experiment for the PC group showed that the resultant graft copolymers were produced via iniferter-based quasi-living radical polymerization, in which the polyDMAAm graft chain contains one or two PC groups at the terminal end of the graft chain. These polymer surface grafts may help provide biocompatibility.

Acrylamides↗

Surface modification of a segmented polyetherurethane using a low-powered gas plasma and its influence on the activation of the coagulation system.

A medical grade segmented polyetherurethane (PEU) was treated with a low-powered gas plasma using O(2), Ar, N(2) and NH(3) as the treatment gases. Changes in the surface functional group chemistry were studied using X-ray photoelectron spectroscopy. The wettability of the surfaces was examined using dynamic contact angle measurements and the surface morphology was evaluated using atomic force microscopy. The influence of the surface modification to the polyurethane on the blood response to the polyetherurethane was investigated by measuring changes in the activation of the contact phase activation of the intrinsic coagulation cascade. The data demonstrate that the plasma treatment process caused surface modifications to the PEU that in all cases increased the polar nature of the surfaces. O(2) and Ar plasmas resulted in the incorporation of oxygen-containing groups that remained present following storage in an aqueous environment. N(2) and NH(3) plasmas resulted in the incorporation of nitrogen-containing groups but these were replaced with oxygen-containing groups following storage in the aqueous environment. In all plasma treatments there was a lowering of contact phase activation compared to the untreated surface, the N(2) and NH(3) treatments dramatically so.

Biocompatible Materials↗

Polyethylene/phospholipid polymer alloy as an alternative to poly(vinylchloride)-based materials.

To develop new biomaterials for making medical devices, polymer alloys composed of a phospholipid polymer, poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC), and polyethylene (PE) were prepared. The PE/PMPC alloy membrane could be obtained by a combination of solution mixing and solvent evaporation methods using xylene and n-butanol mixture as a solvent. Moreover, thermal treatment was applied to improve the mechanical properties of the PE/PMPC alloy membrane. In the PE/PMPC alloy membrane, the PMPC domains were located not only inside the membrane but also at the surface. Surface analysis of the PE/PMPC alloy membrane with X-ray photoelectron spectroscopy, wettability evaluation, and dynamic contact angle measurements revealed that the phospholipid polar groups in the PMPC covered the surface even after thermal treatment. Blood compatibility tests with attention to platelet adhesion and change in morphology of adhered platelets showed that the PE/PMPC alloy membrane had excellent platelet adhesion resistance. We finally concluded that the PE/PMPC alloy could be used as biomaterials instead of poly(vinyl chloride)-based materials.

Alloys↗

Interaction of cells on chargeable functional group gradient surfaces.

Functional group gradient surfaces where the surface density of grafted functional groups changes gradually along the sample length were prepared on low density polyethylene (PE) sheets by corona discharge treatment with gradually increasing power and graft copalymerization of acrylic acid (AA), sodium p-styrene sulphonate (NaSS), and N,N-dimethyl aminopropyl acrylamide (DMAPAA). AA and NaSS are negatively chargeable and DMAPAA is positively chargeable in phosphate buffered saline or cell culture medium at pH 7.3-7.4. The functional group gradient surfaces were characterized by the measurement of water contact angle, Fourier transform infrared spectroscopy in the attenuated total reflectance mode, and electron spectroscopy for chemical analysis. All these measurements indicated that the functional groups were grafted on the PE surfaces with gradual increase of their density. The interaction of Chinese hamster ovary cells with the functional group gradient surfaces along the sample length was investigated. The cells that had adhered and grown on the surfaces were counted and observed by scanning electron microscopy. It was observed that a greater quantity of the cells had adhered and grown onto the positions with moderate density of the functional groups. This may be related to the hydrophilicity of the surface. The DMAPAA-grafted surface showed a large amount of cell attachment probably owing to the positive charge character, while the AA-grafted surface, which is negatively charged, showed poor cell attachment, as expected. The NaSS-grafted surface which is also negatively charged showed a large amount of cell attachment. This may be closely associated with the existence of an aromatic ring close to the ionizable group in NaSS. It seems that surface functional groups and their charge character as well as wettability play important roles for cell adhesion, spreading, and growth.

Amines↗

Protein absorption and ellipsometry in biomaterial research.

Ellipsometry is an optical surface-sensitive method for the investigation of various aspects of protein adsorption mainly at reflecting metal surfaces and ceramic surfaces. One interesting feature of the method is the possibility of detailed and accurate determination of real-time adsorption kinetics of proteins without labelling of the protein. It is also possible to detect protein adsorption with the use of antibodies that adsorb onto the antigen-coated surfaces and to detect antibodies by their adsorption behaviour with regard to antigen-coated surfaces. Compared to other solid phase methods such as enzyme linked immunosorbent assay (ELISA), immunofluorescence and radioimmunoassay, ellipsometry has the advantage of not involving any labelling of the reactant and it is a relatively inexpensive method to maintain. This review is a current report of 15 years of contributions in biomaterials and biochemical research. Special consideration has been given to biologically related surface phenomena such as protein conformation changes, protein displacement effects, early events in blood clotting and complement activation. Among the technical achievements given prominence are the wettability gradient method and the rational use of silicon as an experimental surface. It is clear that ellipsometry and related methods such as reflectometry and surface plasmon resonance (Biacore) are now being increasingly used in biomaterial research as well as in other areas of research.

Absorption↗

Plasma copolymer surfaces of acrylic acid/1,7 octadiene: surface characterisation and the attachment of ROS 17/2.8 osteoblast-like cells.

The purpose of this study was: (a) to examine the effect of plasma-gas composition on plasma polymer oxygen/carbon (O/C) ratio, functional group composition and stability in water, and then (b) to examine cell attachment to surfaces containing different concentrations of O/C and functional groups. Oxygen-functionalised surfaces were deposited by means of the plasma copolymerisation of acrylic acid/1,7-octadiene. The use of a diluent hydrocarbon allowed the deposition of surfaces with a range of O/C concentrations. Plasma copolymer surfaces were characterised by X-ray photoelectron spectroscopy (XPS). Changes in functional group composition with % acrylic acid monomer and the non-dispersive and dispersive parts of the surface energy of these plasma copolymers were measured. The solubility of the plasma copolymers was assessed by means of XPS. The degree of attachment of ROS 17/2.8 osteoblast-like cells to plasma copolymer surfaces deemed to be 'stable' in aqueous medium was measured. Tissue culture polystyrene (TCPS) was included as a control. Attachment was found to be greatest to the plasma copolymer surface with an O/C of 0.11. This surface had a carboxylic acid concentration of ca. 3%. Attachment did not correlate with increased surface wettability (i.e. the non-dispersive component of the surface energy).

Acrylates↗

Preparation of insulin-immobilized polyurethanes and their interaction with human fibroblasts.

Insulin-immobilized polyurethanes (PU) were prepared by the graft polymerization of acrylic acid on oxygen plasma-treated PU, followed by a coupling reaction with polyethylene oxide (PEO) and subsequently with insulin. Modified PUs were characterized by measuring the water contact angle, the electron spectroscopy for chemical analysis and the attenuated total reflection Fourier-transform infrared spectroscopy. The wettabilities of the PU surfaces were increased by the introduction of acrylic acid, PEO and insulin. The amount of insulin immobilized was controlled by changing the concentrations of grafted acrylic acid and PEO. The interactions of human fibroblasts with surface-modified PUs were investigated using [3H]-thymidine incorporation and optical microscopy. Compared to the PU control, the proliferation of cells on the insulin-immobilized PUs was accelerated irrespective of the presence of serum while it was not influenced by PEO grafting. It seemed to be certain, from the experiments with high performance liquid chromatography, that A chain of insulin mainly reacted with the amine-end group of PEO grafted during the immobilization reaction.

Acrylates↗

pH-sensitive freeze-dried chitosan-polyvinyl pyrrolidone hydrogels as controlled release system for antibiotic delivery.

The aim of this study was to develop a pH-sensitive chitosan/polyvinyl pyrrolidone (PVP) based controlled drug release system for antibiotic delivery. The hydrogels were synthesised by crosslinking chitosan and PVP blend with glutaraldehyde to form a semi-interpenetrating polymer network (semi-IPN). The semi-IPN formation was confirmed by Fourier transform infrared spectroscopic (FTIR) analysis. Semi-IPNs, viz, air-dried and freeze-dried, were compared for their surface morphology, wettability, swelling properties and pH-dependent swelling. Air- and freeze-dried membranes were also incorporated with amoxicillin and antibiotic release was studied. Porous freeze-dried hydrogels (pore diameter, 39.20+/-2.66 microm) exhibited superior pH-dependent swelling properties over non-porous air-dried hydrogels. A high octane contact angle (144.20+/-0.580) of hydrogel was indicative of its hydrophilic nature. Increased swelling of hydrogels, under acidic conditions, was due to the protonation of a primary amino group on chitosan, as confirmed by FTIR analysis. Freeze-dried membranes released around 73% of the amoxicillin (33% by air-dried) in 3 h at pH 1.0 and, thus, had superior drug-release properties to air-dried hydrogels. Freeze-dried membranes could serve as potent candidates for antibiotic delivery in an acidic environment.

Anti-Infective Agents↗

Enhanced bone formation by controlled growth factor delivery from chitosan-based biomaterials.

For the purpose of obtaining high bone forming efficacy, development of chitosan was attempted as a tool useful as a scaffolding device. Porous chitosan matrices, chitosan-poly(L-lactide) (PLLA) composite matrices and chitosan coated on PLLA matrices were dealt with in this research. Porous chitosan matrix was fabricated by freeze-drying and cross-linking aqueous chitosan solution. Porous chitosan matrix combined with ceramics and constituents of extracellular matrices were prepared and examined for their bone regenerative potential. Composite porous matrix of chitosan-PLLA was prepared by mixing polylactide with chitosan and freeze-drying. All chitosan based devices demonstrated improved bone forming capacity by increasing mechanical stability and biocompatibility. Release of platelet-derived growth factor-BB (PDGF-BB) from these matrices exerted significant osteoinductive effect in addition to the high osteoconducting capacity of the porous chitosan matrices. The hydrophobic surface of PLLA matrices was modified by chitosan to enhance cell affinity and wettability. The chitosan coated PLLA matrix induced increased osteoblast attachment as compared with intact PLLA surface. Overall results in this study demonstrated the usefulness of chitosan as drug releasing scaffolds and as modification tools for currently used biomaterials to enhance tissue regeneration efficacy. These results may expand the feasibility of combinative strategy of controlled local drug delivery concept and tissue engineered bone formation in reconstructive therapy in the field of periodontics, orthopedics and plastic surgery.

Animals↗

Incorporation of polymeric nanoparticles into solid dosage forms.

Besides parenteral delivery, polymeric nanoparticles have been used for oral drug delivery. In this study, model polymeric nanoparticles (aqueous colloidal polymer dispersions: Eudragit(R) RL 30D, L 30D, NE 30D, or Aquacoat(R)) with different physicochemical properties were incorporated into various solid dosage forms (granules, tablets, pellets or films). The compatibility of the nanoparticles with commonly used tabletting excipients and the redispersibility of the nanoparticles after contact of the solid dosage forms with aqueous media were investigated. Ideally, the nanoparticles should be released from the solid dosage forms with their original properties. The addition of polymeric binders (e.g. polyvinylpyrrolidone, Na carboxymethylcellulose or hydroxypropyl methylcellulose) to the aqueous nanoparticle dispersions prior to wet granulation resulted in phase separation (depletion or bridging flocculation) for many nanoparticle/binder systems. Two critical parameters for the complete redispersibility/release of the nanoparticles with the original particle size properties from the solid dosage forms were a (1) high minimum film formation temperature (MFT) of the polymer dispersion and (2) a good wettability of the dried polymeric nanoparticles. Nanoparticle dispersions with a low MFT were not redispersible, they coalesced into larger agglomerates/films during the drying step. Contact angle measurements correlated well with the redispersibility of the nanoparticles, with ethylcellulose particles having high contact angles and poor redispersibility and Eudragit(R) RL, a polymer stabilized with quaternary ammonium groups, having low contact angles and good redispersibility.

Acrylic Resins↗