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A new method for promoting adhesion between precious metal alloys and dental adhesives.

A new, simple method of modifying the adherend metal surface by a liquid Ga-Sn alloy (Adlloy) was applied to dental precious and base-metal alloys for adhesion with 4-META adhesive resin. Adhesions of 4-META resin to three other surface states--as-polished, oxidized at high temperature, and electroplated tin--were also performed for comparison with the adhesion on Adlloy-modified surfaces. Bond strength measurements were made, and the durability against water at the adhering interface was evaluated. The Adlloy-modified gold alloys (Type IV and 14 K) and silver-based alloys (Ag-Pd and Ag-Cu) showed not only high bond strengths but also excellent water durability at the adhesion interface. Surface modification by Adlloy, however, did not affect adhesion to Ag-In-Zn and base-metal (SUS, Co-Cr, and Ni-Cr) alloys. Adhesion to the tin-electroplated specimens was comparable with that to the Adlloy-modified specimens.

Acrylic Resins↗

Radical polymerization in biosensing.

This review briefly summarizes recently published work on radical polymerization in biosensor-related applications. Advancements in surface modification aimed at improving sensor biocompatibility and reducing nonspecific background noises are discussed. Direct applications of polymers as one of the key sensing elements in which they are used either as detection probes for the biomolecular binding events or as signal transducers to amplify sensing signals are detailed. Initial applications of radical polymerization reactions in biosensing are evident and appear promising.

Artifacts↗

Laser interference lithography as a new and efficient technique for micropatterning of biopolymer surface.

Laser interference lithography (LIL) is a straightforward technique to prepare linear micropatterns for regulating cellular adhesion behaviors on polymer substratum. This process is based on selective laser ablation directly duplicating the interference patterns of two or more coherent laser beams onto the polymer surface. Micropatterns prepared by LIL on poly(ethylene terephthalate) and Thermanox were characterized using atomic force microscopy (AFM) and white light interferometer while the chemical surface modification induced by laser was analyzed by X-ray photoelectron spectroscopy (XPS). The AFM photographs show that the micropatterns are well-defined and of great consistency. Polymer properties and laser parameters related to LIL as well as laser ablation mechanisms are discussed in this technical note.

Biocompatible Materials↗

Surface-immobilized polyethylene oxide for bacterial repellence.

Polyethylene terephthalate films were surface-modified with polyethylene oxide (18,500 g/mol) using a solution technique described previously. These films were investigated for their resistance to bacterial adhesion. Three bacterial strains most commonly associated with implant infections, Staphylococcus epidermidis, Staphylococcus aureus and Pseudomonas aeruginosa, were cultured in tryptic soya broth, human plasma and human serum on the polymeric substrates. Significant reductions (between 70 and 95%) in adherent bacteria were observed on the polyethylene oxide-modified substrates compared to the untreated control polyethylene terephthalate. Surface modification with polyethylene oxide may reduce the risk of implant-associated infections. Plasma fibrinogen was observed to play an important role in the adhesion of all three of these species on both the polyethylene oxide-modified and control polyethylene terephthalate materials.

Bacterial Adhesion↗

Photochemical modification and patterning of polymer surfaces by surface adsorption of photoactive block copolymers.

We report a simple photolithographic approach for the creation and micropatterning of chemical functionality on polymer surfaces by use of surface-active block copolymers that contain protected photoactive functional groups. The block copolymers self-assemble at the substrate-air interface to generate a surface that is initially hydrophobic with low surface tension but that can be rendered hydrophilic and functional by photodeprotection with UV radiation. The block copolymer employed, poly(styrene-b-tert butyl acrylate), segregates preferentially to the surface of a polystyrene substrate because of the low surface tension of the polyacrylate blocks. The strong adsorption of block copolymers causes a bilayer structure to form presenting a photoactive polyacrylate layer at the surface. In the example described, the tert-butyl ester groups on the polyacrylate blocks are deprotected by exposure to UV radiation in the presence of added photoacid generators to form surface carboxylic acid groups. Surface micropatterns of carboxylic acid groups are generated by UV exposure through a contact mask. The success of surface chemical modification and pattern formation is demonstrated by X-ray photoelectron spectroscopy and contact angle measurements along with imaging by optical and fluorescence microscopy methods. The resultant chemically patterned surfaces are then used to template patterns of various biomolecules by means of selective adsorption, covalent bonding and molecular recognition mechanisms. The surface modification/patterning concept can be applied to virtually any polymeric substrate because protected functional groups have intrinsically low surface tensions, rendering properly designed block copolymers surface active in almost all polymeric substrates.

Acrylates↗

Adsorption of phenanthrene on organoclays from distilled and saline water.

Isotherms of phenanthrene adsorption on different organoclay complexes were obtained using the HPLC technique to understand the adsorption behavior and to characterize the effect of sodium chloride (NaCl) on the adsorption. The adsorbed amounts of phenanthrene on montmorillonite exchanged by organic cations such as tetraheptylammonium, benzyltrimethylammonium, hexadecyltrimethylammonium, or tetraphenylphosphonium were several times higher than those obtained using montmorillonite clay without surface modification. At the same equilibrium concentration, the adsorbed amount of phenanthrene is higher on clay modified with benzyltrimethylammonium than on clay modified with hexadecyltrimethylammonium or other cations. Adsorption of phenanthrene on clay modified with benzyltrimethylammonium increased dramatically as the concentration of NaCl increased up to 150 g/l in the aqueous solution. The shape of the curves obtained can be classified as S-type. The adsorption data obtained from salinity experiments support a mathematical model that links the Langmuir constant with the salinity constant. This model may be useful to predict the equilibrium concentration of a contaminant in saline solution. FTIR studies showed strong interactions between the aromatic rings of phenanthrene and the preadsorbed benzyltrimethylammonium on clay surfaces.

Adsorption↗

Liposome clearance.

The clearance rate of liposomal drugs from the circulation is determined by the rate and extent of both drug release and uptake of liposomes by cells of the mononuclear phagocyte system (MPS). Intravenously injected liposomes initially come into contact with serum proteins. The interaction of liposomes with serum proteins is thought to play a critical role in the liposome clearance. Therefore, in this review, we focus on the role of serum proteins, so-called opsonins, that enhance the clearance of liposomes, when bound to liposomes. In addition to opsonin-dependent liposome clearance, opsonin-independent liposome clearance is also reviewed. As opposed to the conventional (non-surface modification) liposomes, we briefly address the issue of the accelerated clearance of PEGylated-liposomes (sterically stabilized liposomes, long-circulating liposomes) on repeated injection, a process that has recently been observed.

Animals↗

Coupling of therapeutic molecules onto surface modified coralline hydroxyapatite.

Surface modification and coupling of therapeutic molecules, tetracycline, onto coralline hydroxyapatite (CHA) and their in vitro evaluations were described in this study. Initially, CHA was graft polymerized with glycidylmethacrylate (GMA) using redox initiators and subsequently coupled to tetracycline through epoxy groups. The CHA grafted with polyGMA (CHA-g-PGMA) was characterized by Fourier transform infrared spectroscopy and powder X-ray diffraction (XRD) for proof of grafting. The absorption peaks pertaining to epoxy and ester carbonyl groups were observed for the graft polymer due to PGMA grafting. The XRD results signified that there was no secondary phase in the apatite lattice and crystallinity was also not affected by grafting, which suggested that the PGMA chains were grafted only on the surface of CHA. Drug loading and releasing was evaluated and found that CHA-g-PGMA exhibited higher loading efficiency than CHA. The in vitro release of tetracycline was performed in phosphate buffered saline under physiological condition and the release profiles showed that the tetracycline-containing graft polymer releases the drug for prolonged period as compared to CHA. Based on the experimental results, CHA-g-PGMA appears to be a promising biomaterial for drug delivery.

Adsorption↗

Effects of Nd:YAG laser on the permeability of root canal wall dentin.

The effects of a thermally cooled pulsed Nd:YAG laser on the permeability and structural appearance of the root canal wall were investigated in vitro. Twenty specimens of freshly extracted human teeth were prepared by conventional methods. The teeth were randomly divided into two groups. Group 1 teeth were prepared conventionally but not lased. Group 2 specimens received three 15-s laser exposures totaling 45 s duration within the root canal via optical fiber delivery. Laser parameters were set at 5 W, 50 Hz, using a simultaneous air/water coolant spray of 10 psi air and 2 psi water. The external surfaces of the teeth were sealed with acrylic and placed in 2% methylene blue dye for 24 h. The teeth were then sectioned, photographed, and compared under light microscope for the extent of dye penetration. The specimens were subsequently prepared for scanning electron microscopy for correlation of permeability measurements with surface modifications. The combined use of scanning electron microscopy and dye permeability measurements revealed a sealing of the dentinal wall by deposition of glass-like material and, in one specimen, the bridging of a lateral canal that partially occluded the canal. Based on statistical comparisons, permeability of laser-treated teeth was significantly less than untreated specimens (alpha = 0.005).

Dental Pulp Cavity↗

Interfacial shear strengths of dental resin-glass fibers by the microbond test.

OBJECTIVES: The aim of this study was to investigate the feasibility of using the microbond test (MBT) to probe the durability of the bond between a polymerized dental resin with differently silanized E-glass fibers. METHODS: The E-glass fibers were silanized with equivalent amounts of two types of acrylic-silane coupling agents: 3-methacryloxypropyltrimethoxysilane (MPTMS) and 10-methacryloxydecyltrimethoxysilane (MDTMS), a more hydrophobic silane coupling agent than MPTMS. Unsilanized E-glass fibers were used as the control. Microdroplets of a photo-activated dental resin were applied on the fiber and photocured with visible light irradiation (470 nm). Subsequently, the specimens were tested in shear after 24h storage in air at 23 degrees C or water at 60 degrees C. RESULTS: The mean interfacial shear strength (tau) and the standard deviation in MPa for the three systems in 23 degrees C in air (n>7) were: 33.8(10.1), 33.7(8.9) and 15.3(4.2) for the MPTMS silanized, MDTMS silanized, and unsilanized fibers, respectively. When the three types of fibers were first exposed to 60 degrees C water for 24h prior to having the microdroplets of the resin bonded to them, the strength values of the MDTMS silanized fibers and the control fibers remained essentially unchanged at (n> or =7) 31.8(7.7) and 17.5(4.9)MPa respectively; the MPTMS specimens showed a significant decrease to 15.8(4.8)MPa. Similar trends were observed when the fibers had microdroplets of the resin bonded to them prior to aqueous exposure. SIGNIFICANCE: These results indicate that the microbond test has the sensitivity to measure changes at the interface between polymerized dental resins and variously silanized E-glass fibers. It appears that surface modification of the fibers with the more hydrophobic silane coupling agent MDTMS promotes enhanced resistance to degradation from exposure to water. The microbond test has the potential for studying dental adhesion involving small bonded areas under a variety of conditions with different adhesive systems and substrates.

Composite Resins↗

Peptide functionalized poly(L-lysine)-g-poly(ethylene glycol) on titanium: resistance to protein adsorption in full heparinized human blood plasma.

The graft copolymer poly(L-lysine)-graft-poly(ethylene glycol) (PLL-g-PEG) and its RGD- and RDG-functionalized derivatives (PLL-g-PEG/PEG-peptide) were assembled from aqueous solutions on titanium (oxide) surfaces. The polymers were characterized by NMR in order to determine quantitatively the grafting ratio, g (Lys monomer units/PEG side chains), and the fraction of the PEG side chains carrying the terminal peptide group. The titanium surfaces modified with the polymeric monomolecular adlayers were exposed to full heparinized blood plasma. The adsorbed masses were measured by in situ ellipsometry. The different PLL-g-PEG-coated surfaces showed, within the detection limit of the ellipsometric technique, no statistically significant protein adsorption during exposure to plasma for 30 min at 22 degrees C or 37 degrees C, whereas clean, uncoated titanium surfaces adsorbed approximately 350 ng/cm2 of plasma proteins. The high degree of resistance of the PEGylated surface to non-specific adsorption makes peptide-modified PLL-g-PEG a useful candidate for the surface modification of biomedical devices such as implants that are capable of eliciting specific interactions with integrin-type cell receptors even in the presence of full blood plasma. The results refer to short-term blood plasma exposure that cannot be extrapolated a priori to long-term clinical performance.

Blood Proteins↗

Reduction in tumour formation on porous polyethylene by collagen immobilization.

After surface modification with collagen immobilization through covalent bonding, porous polyethylene pieces with an average pore size of 400 microns were implanted subcutaneously into the back of rats for 1 yr. It was found that connective tissues with abundant blood vessels were formed clearly, filling more than 90% of the pore volume and bound firmly to the pore walls. A tumour was found in only one of 24 implanted pieces (4.2%). On the other hand, the virgin porous polyethylene pieces without collagen immobilization exhibited inflammatory reactions within the pores and the connective tissues produced filled only 15% of the pore volume. Formation of a malignant histiocytoma was observed in 11 of the 24 pieces which had been implanted (45.8%). Thus, immobilization of collagen on the surface of an artificial material through covalent bonding proved to be very effective not only for firm bonding with soft connective tissues but also for a reduction of tumour formation.

Animals↗

Vascugraft microporous polyesterurethane arterial prosthesis as a thoraco-abdominal bypass in dogs.

In their progression towards clinical acceptance, any new synthetic vascular grafts under development must undisputedly prove that the chemistry and structure used in the construction of the prostheses is safe and that their biocompatibility and performance as arterial substitutes are satisfactory without degradation or weakening of the device. This study was conducted to evaluate the safety of the microporous polyesterurethane Vascugraft by investigating its biocompatibility in terms of cellular proliferation, morphology and adhesion of human fibroblasts on virgin and blood-soaked Vascugraft prostheses, and its performance in vivo as a large calibre graft in a canine thoraco-abdominal bypass model for periods of implantation ranging from 4 h to 6 months. After 3 d incubation, better cell proliferation and adhesion were observed on blood-soaked Vascugraft than on a non-porous polyurethane graft, Mitrathane, and two other polytetrafluorethylene prostheses, Impra and Goretex. Furthermore, no leachable cytotoxic contaminants were released from the prostheses. In vivo, the Vascugraft has demonstrated a good performance with the development of an endothelialised internal capsule at both anastomoses 2 weeks after implantation, reaching the medial portion of the graft at 4 months. During this period, the prostacyclin I2/thromboxane A2 ratio increased and was higher than 1.0 at 2 months. In addition, the Vascugraft exhibited low surface thrombogenicity in terms of radiolabelled platelets and fibrin deposited. Chemically, as revealed by ESCA and FTIR analyses, a slight decrease in carbonate content was observed on the external surface of the Vascugraft during the early post-implantation periods. Breaks in the microfibrous structure were also observed at 4 and 6 months, occurring mainly in the anastomotic regions and believed to be stress-related. This study shows that the polymer used in the Vascugraft is biocompatible in terms of fibroblast proliferation and promotes fair healing characteristics. However, the chemical and structural surface modifications noted in this study are disturbing and question the total inocuity of the Vascugraft. Consequently, the decision by B. Braun Melsungen AG to end this project is both highly conscientious and professional.

Anastomosis, Surgical↗

Corrosion and permanent fracture resistance of coated and conventional orthodontic wires.

The corrosion processes are presumed to have negative consequences on biocompatibility, aesthetic appearance and the frictional behavior between the bracket and the guiding arch during orthodontic treatment. A group of new guiding arches are the coated orthodontic wires. The present in-vitro study investigated the corrosion behavior and permanent fracture resistance of eight coated wires of different dimensions. Five superelastic nickel titanium (NiTi) wires (Titanol Low Force River Finish Gold and Gold 2: Forestadent Corp.; Titanol Superelastic tooth colored: Forestadent Corp.; Bioforce Sentalloy longuard: GAC Corp.; NiTi Imagination: GAC Corp.), two beta-titanium-wires (TMA Low Friction longuard: Ormco Corp.; TMA Low Friction longuard Purple: Ormco Corp.) and one steel wire (Stainless Steel Imagination: GAC Corp.) were selected. For comparison reasons three uncoated arch wires (Rematitan Lite Dimple: Dentaurum Corp.; Titanol Low Force River Finish: Forestadent Corp.; Bioforce Sentalloy: GAC Corp.) were included in the investigation. Surface modifications were made of teflon, polyethylene and by ion implantation. The corrosion processes have been carried out by the use of a specialized electrochemical cell. In a second experimental series the wires were exposed to mechanical stresses. Finally, all wires were examined in a scanning electron microscope. The results indicated that teflon coating prevented the corrosion of the wires. As expected, the beta-titanium wires did not corrode either. The other wires showed rupture potentials between 187 mV and 602 mV (NHE). After mechanical stress testing the wires could be subdivided into three groups. In the first group no differences could be recognized, the second group showed changes in their crystallographic structure and in the last group the teflon coating was peeled off from the surface of the wires.

Journal Article↗

Stability of plasma-treated silicone rubber and its influence on the interfacial aspects of blood compatibility.

Medical-grade polydimethylsiloxane elastomer was subjected to low-powered plasma treatment in the presence of four different gases: O(2), Ar, N(2) and NH(3). Changes to the surface chemistry immediately after processing and the stability of the treatments following ageing in phosphate buffered saline or air for up to 1 month were investigated using X-ray photoelectron spectroscopy and dynamic contact angle analysis. Changes in surface morphology were assessed using optical microscopy and atomic force microscopy. All treatments resulted in an increase in wettability, attributed to major changes in chemistry combined with modest etching. Furthermore, the primary site of attack of the plasma species appeared to be dependent upon the feed gas implemented. The two main chemical changes observed after ageing were due to reactions with the storage media and relaxation processes resulting in further changes in wettability. The influence of the surface modifications on the blood compatibility of the materials was investigated by assessing contact phase activation using a partial thromboplastin time assay. It was demonstrated that the O(2) and Ar plasma treatments reduced the performance of the silicone but the N(2) and NH(3) treatments had a significantly beneficial effect on the activation of the coagulation cascade.

Biocompatible Materials↗

Diamond-like carbon: a potential means of reducing wear in total joint replacements.

This paper begins with a review of recent studies of the progressive mechanisms of degradation in total hip and knee replacements. It is concluded that wear is a major problem due to resulting tissue reactions especially to fine polymeric debris. Methods of lessening or overcoming these problems by modern methods of surface modification are considered, among these being ion implantation and ion beam-assisted deposition. It is argued that the physical and chemical properties of diamond-like carbon (DLC) coatings make them especially promising for the reduction of friction and adhesive wear in all forms of joint replacement. An ion beam-assisted method of depositing DLC efficiently at low temperatures is described, together with the physical properties of the resulting material.

Adhesiveness↗

Decreased bacterial adherence to silver-coated stent material: an in vitro study.

Bacteria are important in causing biliary stent blockage through adherence and subsequent biofilm formation. In our in vitro system, surface modification using test polyurethane discs with silver coating led to a reduction in the number of adherent bacteria compared with untreated controls by 10- to 100-fold in an apparently dose-related manner. The effect was more marked in the presence of bile. These results suggest that silver coating may have a potential benefit in preventing stent blockage.

Bacterial Adhesion↗

Mechanical properties of visible light-cured resins reinforced with hydroxyapatite for dental restoration.

OBJECTIVES: The purpose of this study was to measure and analyze the mechanical properties of several composite materials designed for dental restoration. METHODS: The materials were composed of a visible light-curing monomer mixture (either Bis-GMA+TEGDMA or Bis-GMA+HEMA) as a matrix and hydroxyapatite (either microscopic or nanoscopic particles) as a reinforcing filler. The surface of the hydroxyapatite particles was modified by using a coupling agent (citric, malic, acrylic or methacrylic acid). Five specimens of 14 different composites were prepared for each mechanical test: flexural strength, Young's modulus and Vickers hardness. Mean values and standard deviations were calculated, and ANOVA and Student Newman Keuls multiple comparison tests were applied (P < 0.05). RESULTS: The addition of 50-60 wt% of hydroxyapatite particles to the unfilled monomer mixtures led to the increase of both Young's modulus and surface hardness of the material, while the flexural strength decreased. In general, when microscopic instead of nanoscopic hydroxyapatite was used as a reinforcing filler, mechanical properties were favored. The mechanical properties were also improved by adding citric, acrylic or methacrylic acid as a coupling agent. CONCLUSIONS: An adequate surface modification of the hydroxyapatite particles conferred enhanced mechanical properties to the final dental composite. Microscopic-hydroxyapatite particles are preferred to nanoscopic ones.

Acrylates↗