Mild self-etch adhesives demineralize dentin only partially, leaving hydroxyapatite around collagen within a submicron hybrid layer. We hypothesized that this residual hydroxyapatite may serve as a receptor for chemical interaction with the functional monomer and, subsequently, contribute to adhesive performance in addition to micro-mechanical hybridization. We therefore chemically characterized the adhesive interaction of 3 functional monomers with synthetic hydroxyapatite, using x-ray photoelectron spectroscopy and atomic absorption spectrophotometry. We further characterized their interaction with dentin ultra-morphologically, using transmission electron microscopy. The monomer 10-methacryloxydecyl dihydrogen phosphate (10-MDP) readily adhered to hydroxyapatite. This bond appeared very stable, as confirmed by the low dissolution rate of its calcium salt in water. The bonding potential of 4-methacryloxyethyl trimellitic acid (4-MET) was substantially lower. The monomer 2-methacryloxyethyl phenyl hydrogen phosphate (phenyl-P) and its bond to hydroxyapatite did not appear to be hydrolytically stable. Besides self-etching dentin, specific functional monomers have additional chemical bonding efficacy that is expected to contribute to their adhesive potential to tooth tissue.

For many years, glass-polyalkenoate cements have been described as possessing the unique properties of self-adherence to human hard tissues, such as bones or teeth. However, direct experimental evidence to prove the existence of chemical bonding has not been advanced. X-ray Photoelectron Spectroscopy (XPS) was used to analyze the chemical interaction of a synthesized polyalkenoic acid with enamel and synthetic hydroxyapatite. For both enamel and hydroxyapatite, the peak representing the carboxyl groups of the polyalkenoic acid was detected to have significantly shifted to a lower binding energy. De-convolution of this shifted peak disclosed two components with a peak representing unreacted carboxyl groups and a peak suggesting chemical bonding to hydroxyapatite. On average, 67.5% of the carboxyl groups of the polyalkenoic acid were measured to have bonded to hydroxyapatite. XPS of hydroxyapatite also disclosed its surface to be enriched in calcium and decreased in phosphorus, indicating that phosphorus was extracted at a relatively higher rate than calcium. Analysis of these data supports the mechanism in which carboxylic groups replace phosphate ions (PO4(3-)) of the substrate and make ionic bonds with calcium ions of hydroxyapatite. It is concluded that an ultrathin layer of a polyalkenoic acid can be prepared on a hydroxyapatite-based substrate by careful removal of non-bonded molecules. With this specimen-processing method, XPS not only provided direct evidence of chemical bonding, but also enabled us to quantify the percentages of functional groups of the polyalkenoic acids that bonded to calcium of hydroxyapatite.

Fundamental to the processes of decalcification of or adhesion to mineralized tissues is the molecular interaction of acids with hydroxyapatite. This study was undertaken to chemically analyze the interaction of 1 mono-, 2 di-, 1 tri-, and 2 polycarboxylic acids with hydroxyapatite in an attempt to elucidate the underlying mechanism. Maleic, citric, and lactic acid decalcified hydroxyapatite, in contrast to oxalic acid and the two polycarboxylic acids that were chemically bonded to hydroxyapatite. Solubility tests showed that the calcium salts of the former were very soluble, whereas those of the latter could hardly be dissolved in the respective acid solutions. Based on these data, an adhesion/decalcification concept was advanced that predicts that carboxylic acids, regardless of concentration/pH, either adhere to or decalcify hydroxyapatite, depending on the dissolution rate of the respective calcium salts in the acid solution. This contrasting behavior of organic acids most likely results from their differential structural conformations.

Ionic bonding between polyalkenoic acid and hydroxyapatite may explain the excellent bonding retention of glass-ionomers in clinical trials. We have here investigated the extent to which the self-adhesiveness of resin-modified glass-ionomers (RMGIs) can be attributed to this chemical bonding capacity. Therefore, the interaction of 3 RMGIs with tooth substrates was comprehensively characterized, with electron and atomic force microscopy correlated with x-ray photoelectron spectroscopy (XPS). Interfacial ultrastructural analysis for 2 RMGIs disclosed a shallow hybridization of hydroxyapatite-coated collagen, on which a submicron gel phase was deposited through reaction of the polyalkenoic acid with calcium extracted from the dentin surface. One RMGI, however, bonded to dentin without hybrid layer or gel phase formation. XPS indicated that polycarboxylic acids included in the RMGIs electrostatically interacted with hydroxyapatite. We conclude that the self-adhesiveness of RMGIs should be attributed to ionic bonding to hydroxyapatite around collagen, and to micro-mechanical interlocking for those RMGIs that additionally hybridize dentin.

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SynopsisGas phase chemical modification (GCM) is found to be more preferable as a pretreatment for the XPS surface analysis of polymer materials than the conventional liquid phase treatment because it can circumvent problems such as solvent contamination and swelling. We have tried the quantification of the surface compcsition successfully by estimating the yield of the reaction from model samples. GCM was then applied to correlate the surface composition of NH, plasma-treated polystyrene films with their cell-affinity. The amount of primary-amine and that of carboxylic acid were directly determined by GCM. Although the amount of primary-amine, 15-20% of total nitrogen, did not depend on the treatment intensity, the total amine content for the treated samples increased with the plasma treatment intensity. The quantity of carboxylic acid generated was found to be very small. All treated samples had better cell-affinity than the control. The sample N2 (of medium treatment) showed the best cell-affinity. The most strongly treated sample N3, with larger amine content than N2, showed worse cell-affinity because of the interference by the sputtered SiO, on the surface.Most of the chemical modification reactions have been conducted in liquid phase'-8 except for a few c~s~s ,~~' ' although problems as residual solvent on surface and swelling of the substrate are experienced in the XPS measurement. Gas phase reactions have been tried here to avoid such problems. I n the h t part of the paper, we report a preliminary study of gas phase chemical modification reactions, in which the detection limit and quantitativity are examined for primary amine, carboxylic, and hydroxyl groups on polymer surface.

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