The currently used commercial self‐etching enamel‐dentin adhesives and restoratives composites are mainly based on a mixture of various monofunctional and cross‐linking dimethacrylates. New ...developments of enamel‐dentin adhesives concern the improvement of technique insensitivity and storage stability. Improvements of restorative composites are focused on the reduction of the polymerisation shrinkage, as well as the improvement of wear resistance, biocompatibility, and processing properties. In the past five years, many research efforts have been carried out to develop new monomers and tailor‐made components for filling materials, such as fillers or initiators. New phosphonic acid ether acrylates and cross‐linking bis(acrylamide)s enable the preparation of self‐etching enamel‐dentin adhesives with improved storage stability. With free‐radically polymerisable cyclic monomers, such as bicyclic cyclopropyl acrylates or cyclic allyl sulfides, low‐shrinkage storage‐stable restorative composites could be prepared. In case of the cationic polymerisable cyclic monomers, like siloxane‐based cycloaliphatic epoxides, the lower curing rate, stronger exothermic effect and lower curing depth compared to dimethacrylate‐based composites presently prevent their dental application. Designed methacrylates with tailor‐made properties and sol‐gel polycondensates can also contribute to the improvement of the currently used restorative composites. Radical polymerisable dental materials are initiated by light curing and by redox initiator systems. Under acidic conditions amine containing initiator systems are deactivated by acid‐base reaction. Non amine‐based initiators have to be developed for acidic monomer containing dental materials. The use of discrete nano‐filler particles mainly concerns the reinforcement and, in some cases, the increase of X‐ray opacity of composite filling materials.
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.
Hydrogen-bonded, side-chain-functionalized supramolecular poly(alkyl methacrylate)s were investigated as light- and temperature-responsive reversible adhesives that are useful for bonding and ...debonding on demand applications. Here, 2-hydroxyethyl methacrylate (HEMA) was functionalized with 2-ureido-41Hpyrimidinone (UPy) via a hexamethylenediisocyanate (HMDI) linker, to create a monomer (UPy-HMDI-HEMA) that serves to form supramolecular cross-links by way of forming quadruple hydrogen bonded dimers. UPy-HMDI-HEMA was copolymerized with either hexyl methacrylate or butyl methacrylate to create copolymers comprising 2.5, 5, or 10 mol % of the cross-linker. The mechanical properties of all (co)polymers were investigated with stress–strain experiments and dynamic mechanical analysis. Furthermore, the adhesive properties were studied at temperatures between 20 and 60 °C by testing single lap joints formed with stainless steel substrates. It was found that increasing the concentration of the UPy-HMDI-HEMA cross-linker leads to improved mechanical and adhesive properties at elevated temperatures. Concurrently, the reversibility of the bond formation remained unaffected, where rebonded samples displayed the same adhesive strength as regularly bonded samples. Debonding on demand abilities were also tested exemplarily for one copolymer, which for light-induced debonding experiments was blended with a UV-absorber that served as light–heat converter. Single lap joints were subjected to a constant force and heated or irradiated with UV light until debonding occurred. The necessary debonding temperature was comparable for direct heating and UV irradiation and varied between 28 and 82 °C, depending on the applied force. The latter also influenced the debonding time, which under the chosen conditions ranged from 30 s to 12 min.
The paper gives an overview on the components and the polymer chemical aspects of currently used self-etching enamel–dentin primers/adhesives. In addition, the contribution of new adhesives monomers ...and cross-linkers exhibiting enhanced hydrolytic stability than methacrylates to improve the performance of single-bottle adhesives is discussed.
Information from original scientific papers or reviews about enamel–dentin adhesives, the patent literature concerning dental adhesives and manufacturer information of commercial self-etching adhesives were included in this review.
The most efficient self-etching enamel–dentin adhesives are based on strongly acidic adhesive monomers, containing dihydrogenphosphate, phosphonic acids or carboxylic acid groups. Serious problems of single-bottle water-based, strongly acidic self-etching enamel–dentin adhesives arise both from the hydrolytic instability of the methacrylate monomers used and the side reaction of the applied initiator components.
The stability of the self-etching enamel–dentin adhesives can be improved by using new acrylic ether phosphonic acids or mono- or difunctional acrylamides, while more stable and compatible components have to be developed in the future.
The currently used commercial restorative composites contain a mixture of various cross-linking dimethacrylates, glass- and/or silicon dioxide fillers, and a photoinitiator system. They are cured by ...irradiation with visible light. New developments of polymeric composites for restorative filling materials are mainly focused on the reduction of polymerization shrinkage, and improvement of biocompatibility, wear resistance and processing properties. This can be partially achieved by using new tailor-made monomers and optimized filler particles.
This review describes the polymeric chemical aspects of the application of new monomers, e.g. cyclic monomers, liquid-crystalline monomers, ormocers, branched monomers, compomers or Bis-GMA analogues or substitutes for restorative composites. In addition, the contribution of new filler-technologies for the improvement of restorative composites is discussed.
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.
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).
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.
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.
A self organizing antimicrobial finish on acrylate‐based materials was achieved by adding only 0.4 wt% of a biocidal macromer to the monomer mixture prior polymerization. The materials surface kills ...the infectious bacterium Staphylococcus aureus without releasing the biocide (Figure, lower section) and stays active even after 45 d of constant washing. Confocal Raman spectroscopy and fluorescence microscopy (Figure, upper section) reveal that the biocide has migrated to the surface of the materials during polymerization.
The aim of this investigation was to determine the hydrolytic stability of conventional methacrylates in comparison with a new acrylic ether phosphonic acid and a bis(acrylamide) cross-linking ...monomer under acidic aqueous conditions and to confirm the potential of these new monomers as components in a self-etching enamel-dentin primer, based on shear bond strength measurements.
Two new monomers were synthesized, an acrylic ether phosphonic acid and a bis(acrylamide). Characterization of the two monomers was carried out by 1H-NMR, and 13C-NMR spectroscopy and of the phosphonic acid by 31P-NMR spectroscopy. The hydrolytic stability of these monomers was evaluated by 1H-NMR spectroscopy or high performance liquid chromatography (HPLC), and was compared with the hydrolytic stability of conventional adhesive methacrylates, ie, MDP, 4-META, TEGDMA and GDMA. Shear bond strength to enamel and dentin was determined using the acrylic ether phosphonic acid and bis(acrylamide) formulated into what is now being marketed as a self-etching primer (AdheSE, Ivoclar Vivadent), and compared with the total-etch adhesives Prime & Bond NT (Dentsply) and Excite (Ivoclar Vivadent) and the self-etching systems One-Up Bond F (Tokuyama), Touch & Bond (Parkell), i-Bond (Heraeus Kulzer), Prompt-L-Pop (3M ESPE), and Clearfil SE Bond (Kuraray). Initial and 24-h bond strength values of AdheSE were compared with those after 16 weeks of storage at 42 degrees C.
Stability studies have shown that conventional methacrylate monomers undergo rapid hydrolysis under acidic aqueous conditions (up to 90% degradation after 16 weeks at 42 degrees C). However, the newly formulated strongly acidic acrylic phosphonic acid and cross-linking bis(acrylamide) are stable under these conditions. Moreover, a self-etching enamel-dentin primer based on these new monomers showed high bond strength values.
The shelf life of dental adhesives can be increased by using ether- or amide-linked polymerizable analogues instead of conventional, less stable ester derivatives. This should improve the performance of adhesive bonds made with these more hydrolytically stable comonomers.
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.
