Impact of functional satellite groups on the antimicrobial activity and hemocompatibility of telechelic poly(2-methyloxazoline)s.

Polyoxazolines with a biocidal quarternary ammonium end-group are potent biocides. Interestingly, the antimicrobial activity of the whole macromolecule is controlled by the nature of the group at the distal end. These nonreactive groups are usually introduced via the initiator. Here we present a study with a series of polymethyloxazolines with varying satellite groups introduced upon termination of the polymerization reaction. This allowed us to introduce a series of functional satellites, including hydroxy, primary amino, and double-bond-containing groups. The resulting telechelic polyoxazolines were explored regarding their antimicrobial activity and toxicity. It was found that the functional satellite groups greatly controlled the minimal inhibitory concentrations against the bacteria Staphylococcus aureus and Escherichia coli in a range of 10 to 2500 ppm. Surprisingly, the satellite groups also controlled the hemotoxicity but in a different way than the antimicrobial efficiency.

Adhesion performance of new hydrolytically stable one-component self-etching enamel/dentin adhesives.

PURPOSE: To demonstrate that hydrolytically stable methacrylamide monomers allow one-component self-etching adhesives with comparable adhesive properties and better storage stability than hitherto available methyacrylate-based adhesive formulations. MATERIALS AND METHODS: The shear bond strength and storage stability of the new one-component self-etching, methacrylamide-based adhesive AdheSE One F (Ivoclar Vivadent) to enamel and dentin was compared to the methacrylate-based Clearfil S3 Bond (Kuraray), G-Bond (GC), Hybrid Bond (Sun Medical), iBond (Heraeus Kulzer), Optibond All In One (Sybron-Kerr), and the methacrylamide-based Xeno V (Dentsply). Hydrolytic stability and adhesive performance of these adhesives was evaluated by accelerated aging at 42 degrees C over 16 weeks and monthly assessment of shear bond strength to dentin. The null hypothesis was that the bond strength of one-bottle self-etching dental adhesives is independent of storage duration and that, disregarding their higher stability against hydrolysis, methacrylamide- based materials offer performance beyond shelf-life time, comparable to methacrylate-based adhesives. Statistical analysis included 1-way-ANOVA and the Tukey-B post-hoc test (p < 0.05). RESULTS: Shear bond strengths on enamel ranged from 32.7 MPa (AdheSE One F) to 16.6 MPa (iBond) and on dentin from 36.1 MPa (Optibond All In One) to 20.5 MPa (G-Bond). During accelerated aging, methacrylate-based adhesives with a pH < 2 exhibited decreasing bond strengths over time with material-dependent losses of up to 68% (Hybrid Bond, 8 weeks, 42 degrees C). Under the same conditions, the methacrylamide-based formulations AdheSE One F and Xeno V were stable for 16 weeks regarding shear bond strength to dentin. CONCLUSIONS: The shelf life of one-component self-etching adhesives is determined by their chemical composition. In conventional methacrylate-based adhesives, the inherently acidic environment of such formulations leads to monomer degradation due to hydrolysis. In contrast, methacrylamide-based adhesives are stable to aqueous acid and exhibit much superior storage stability without monomer degradation-related losses in adhesion performance.

Testing adhesion of direct restoratives to dental hard tissue - a review.

This articles concerns itself with the testing of adhesion between direct restoratives and dental hard tissue, ie, enamel and dentin. The aim is to survey available methods for adhesion testing and influential parameters affecting experimental outcome. The testing of adhesion to indirect restorative materials, eg, ceramics and metals, is beyond the scope of this article and shall be discussed elsewhere. The longevity and success of modern dental restorations very often relies on potent dental adhesives to provide durable bonds between the dental hard substance and the restorative composite. To predict the clinical outcome of such restorative treatment, a large variety of in vitro laboratory tests and clinical in vivo experiments have been devised, analyzed, and published. The purpose of this review is to provide a current overview of bond strength testing methods and their applicability to the characterization of dental adhesives. Regardless of the method employed, subtle variations in sample preparation may already severely impact test results, usually necessitating at least co-testing of a well-known internal reference to allow conclusive interpretation. This article attempts to list and discuss the most influential parameters, such as substrate nature, age, health status, storage, clinically relevant pre-treatment, and sample preparation. Special attention is devoted to the last aspect, as numerous publications have stressed the tremendous influence of preparatory parameters on the validity and scope of obtained data. Added to the large variety of such factors, an equally large diversity of load-applying procedures exists to actually quantify adhesion between composites and dental hard substance. This article summarizes the basics of macro and micro approaches to shear and tensile bond strength testing, as well as push- and pull-out tests. The strengths and weaknesses inherent to each method and influential test parameters are reviewed and methods for accelerated sample aging and simulation of clinical conditions presented. Alternatively to shear or tensile bond strength tests, fracture toughness is introduced together with its application to dental adhesives and an overview of its physical background.

Synthesis of bis(3-{[2-(allyloxy)ethoxy]methyl}-2,4,6-trimethylbenzoyl)(phenyl)phosphine oxide - a tailor-made photoinitiator for dental adhesives.

Because of the poor solubility of the commercially available bisacylphosphine oxides in dental acidic aqueous primer formulations, bis(3-{[2-(allyloxy)ethoxy]methyl}-2,4,6-trimethylbenzoyl)(phenyl)phosphine oxide (WBAPO) was synthesized starting from 3-(chloromethyl)-2,4,6-trimethylbenzoic acid by the dichlorophosphine route. The substituent was introduced by etherification with 2-(allyloxy)ethanol. In the second step, 3-{[2-(allyloxy)ethoxy]methyl}-2,4,6-trimethylbenzoic acid was chlorinated. The formed acid chloride showed an unexpected low thermal stability. Its thermal rearrangement at 180 ° C resulted in a fast formation of 3-(chloromethyl)-2,4,6-trimethylbenzoic acid 2-(allyloxy)ethyl ester. In the third step, the acid chloride was reacted with phenylphosphine dilithium with the formation of bis(3-{[2-(allyloxy)ethoxy]methyl}-2,4,6-trimethylbenzoyl)(phenyl)phosphine, which was oxidized to WBAPO. The structure of WBAPO was confirmed by ¹H NMR, ¹³C NMR, ³¹P NMR, and IR spectroscopy, as well as elemental analysis. WBAPO, a yellow liquid, possesses improved solubility in polar solvents and shows UV-vis absorption, and a high photoreactivity comparable with the commercially available bisacylphosphine oxides. A sufficient storage stability was found in dental acidic aqueous primer formulations.

Radiopaque dental adhesives: dispersion of flame-made Ta2O5/SiO2 nanoparticles in methacrylic matrices.

OBJECTIVES: Radiopaque dental adhesive (DA) of low viscosity were made by forming stable suspensions of weakly agglomerated Ta2O5/SiO2 nanoparticles with primary particle size of about 10nm. METHODS: The particles were prepared by one-step flame-spray pyrolysis. Particles were functionalized with gamma-methacryloxypropyltrimethoxysilane (MPS) and dispersed in a methacrylic monomer matrix by centrifugal mixing and ultrasonication. Particle size distributions were analyzed by X-ray disc centrifugation of suspensions and TEM analysis of cured sample composites, while average primary particle size was obtained by N2 adsorption and X-ray diffraction. RESULTS: The dispersion method affected the aggregate size distribution of both untreated and surface functionalized particles in these suspensions. The influence of particle content on suspension viscosity, aggregate size distribution and that of Ta2O5 content on radiopacity was investigated. The shear bond strength of such radiopaque particle-containing adhesives on enamel and dentin was comparable to that of the particle-free reference adhesive. CONCLUSIONS: Flame-made Ta2O5/SiO2 nanoparticles can be introduced readily into dental adhesives as they form quite stable suspensions. Viscosity stayed low even after adding radiopaque particles up to 20 wt.%. The resulting composites had radiopacity comparable to that of enamel facilitating their distinction from marginal gaps. Bond strength was not significantly influenced by the presence of particles in the adhesive.

Is chlorhexidine-methacrylate as effective as chlorhexidine digluconate in preserving resin dentin interfaces?

OBJECTIVES: The aim of the current study was to evaluate the effect of 2% CHX and 2% CHX-methacrylate compared to the resin-dentin bonds created by a two-step etch-and-rinse adhesive system after 24h, 6min and 12min. METHODS: Microtensile bond strengths and interfacial nanoleakage within resin-dentin interfaces created by Adper Single Bond 2, with or without CHX or CHX-methacrylate pre-treatment for 30s on acid-etched dentin surfaces, were evaluated after 24h, 6min and 12min of storage in distilled water at 37°C. RESULTS: Twelve months of storage resulted in a significant decrease in microtensile bond strength in the control group, and significant increases in silver nanoleakage. In contrast, Single Bond 2+CHX, and to a greater extent CHX-methacrylate, significantly reduced the rate of deterioration of resin-dentin interfaces over the 12min water storage period, in terms of bond strength. CONCLUSIONS: Similar to Single Bond 2+CHX, Single Bond+CHX-methacrylates reduced the degradation of resin-bonded interfaces over a 12 month storage period. Thus it can be concluded that Single Bond 2+CHX-methacrylate may be important to improve durability of bonded interfaces and therefore, prolong the life span of adhesive restorations. CLINICAL SIGNIFICANCE: Although CHX primers have been shown to enhance the durability of etch-and-rinse adhesives, that protection is lost after 2h. The use of CHX-methacrylate should last much longer since it may copolymerize with adhesive monomers, unlike CHX.

Telechelic poly(2-oxazoline)s with a biocidal and a polymerizable terminal as collagenase inhibiting additive for long-term active antimicrobial dental materials.

Dental repair materials face the problem that the dentin below the composite fillings is actively decomposed by secondary caries and extracellular proteases. To address this problem, poly(2-methyloxazoline) with a biocidal and a polymerizable terminal was explored as additive for a commercial dental adhesive. 2.5 wt% of the additive rendered the adhesive contact-active against Streptococcus mutans and washing with water for 101 d did not diminish this effect. The adhesive with 5 wt% additive kills S. mutans cells in the tubuli of bovine dentin. Further, the additive inhibits bacterial collagenase at 0.5 wt% and reduces activity of MMP-9. Human MMPs bound to dentin are inhibited by 96% in a medium with 5 wt% additive. Moreover, no adverse effect on the enamel/dentine shear bond strength was detected.