Kazuomi Suzuki

Comparative Study on Adhesive Performance of Functional Monomers

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.

Monomer-Solvent Phase Separation in One-step Self-etch Adhesives:

One-step adhesives bond less effectively to enamel/dentin than do their multi-step versions. To investigate whether this might be due to phase separation between adhesive ingredients, we characterized the interaction of 5 experimental and 3 commercial self-etch adhesives with dentin using transmission electron microscopy. All adhesives were examined for homogeneity by light microscopy. Bonding effectiveness to dentin was determined with the use of a micro-tensile bond-strength protocol. The lower bond strength of the one-step adhesives was associated with light-microscopic observation of multiple droplets that disappeared slowly. Interfacial analysis confirmed the entrapment of droplets within the adhesive layer. The prompt disappearance of droplets upon application of a small amount of HEMA (2-hydroxyethyl methacrylate) or a HEMA-containing bonding agent, as well as the absence of droplets at the interface of all HEMA-containing adhesives, strongly suggests that the adhesive monomers separate from water upon evaporation of ethanol/acetone. Upon polymerization, the droplets become entrapped within the adhesive, potentially jeopardizing bond durability. This can be avoided by strong air-drying of the adhesive, thereby removing interfacial water and thus improving bonding effectiveness.

Hydrolytic Stability of Self-etch Adhesives Bonded to Dentin

Functional monomers chemically interact with hydroxyapatite that remains within submicron hybrid layers produced by mild self-etch adhesives. The functional monomer 10-MDP interacts most intensively with hydroxyapatite, and its calcium salt appeared most hydrolytically stable, as compared with 4-MET and phenyl-P. We investigated the hypothesis that additional chemical interaction of self-etch adhesives improves bond stability. The micro-tensile bond strength (μTBS) of the 10-MDP-based adhesive did not decrease significantly after 100,000 cycles, but did after 50,000 and 30,000 cycles, respectively, for the 4-MET-based and the phenyl-P-based adhesives. Likewise, the interfacial ultrastructure was unchanged after 100,000 thermocycles for the 10-MDP-based adhesive, while that of both the 4-MET- and phenyl-P-based adhesives contained voids and less-defined collagen. The findings of this study support the concept that long-term durability of adhesive-dentin bonds depends on the chemical bonding potential of the functional monomer.

Chemical Interaction of Phosphoric Acid Ester with Hydroxyapatite

Among functional monomers used in contemporary dental adhesives, 10-methacryloyloxydecyl dihydrogen phosphate (MDP) has been found to interact chemically with hydroxyapatite (HAp) most intensively and stably. This effect was thought to be the basis of the superior bonding effectiveness of MDP-based self-etch adhesives to enamel/dentin. To elucidate fully the chemical interaction and reactivity of MDP with HAp, we used 31P CP-MAS NMR spectroscopy and powder x-ray diffraction. In an aqueous ethanol solution, Ca ions were leached from HAp to form, at short term, a MDP-calcium salt (CaMHP2) layered structure on the HAp surface. When MDP was allowed to interact for longer time (< 24 hrs), CaHPO4·2H2O precipitated on top of this MDP-calcium salt layered structure. In conclusion, the intense chemical interaction of MDP with HAp must be ascribed to superficial dissolution of HAp induced by the MDP adsorption and subsequent deposition of MDP-calcium salt with a solubility lower than that of CaHPO4·2H2O.

Influence of the Chemical Structure of Functional Monomers on Their Adhesive Performance

Functional monomers in adhesive systems can improve bonding by enhancing wetting and demineralization, and by chemical bonding to calcium. This study tested the hypothesis that small changes in the chemical structure of functional monomers may improve their bonding effectiveness. Three experimental phosphonate monomers (HAEPA, EAEPA, and MAEPA), with slightly different chemical structures, and 10-MDP (control) were evaluated. Adhesive performance was determined in terms of microtensile bond strength of 4 cements that differed only for the functional monomer. Based on the Adhesion-Decalcification concept, the chemical bonding potential was assessed by atomic absorption spectrophotometry of the dissolution rate of the calcium salt of the functional monomers. High bond strength of the adhesive cement corresponded to low dissolution rate of the calcium salt of the respective functional monomer. The latter is according to the Adhesion-Decalcification concept, suggestive of a high chemical bonding capacity. We conclude that the adhesive performance of an adhesive material depends on the chemical structure of the functional monomer.

Histological and compositional evaluations of three types of calcium phosphate cements when implanted in subcutaneous tissue immediately after mixing

To evaluate the soft tissue response of calcium phosphate cement (CPC), consisting of an equimolar mixture of tetracalcium phosphate (TTCP) and dicalcium phosphate anhydrous (DCPA) under conditions close to those encountered in actual surgical procedures, we implanted three types of CPC [conventional CPC (c-CPC), fast-setting CPC (FSCPC), and antiwashout type FSCPC (aw-FSCPC; formerly called nondecay type FSCPC or nd-FSCPC)] subcutaneously in the abdomens of rats immediately (1 min) after mixing. At 1 week after surgery, histological examination and compositional analysis were performed using light microscopy and powder X-ray diffraction (XRD), respectively. The implanted c-CPC was crumbled completely, whereas FSCPC and aw-FSCPC retained their shape. Large vesicles containing copious inflammatory effusion were subcutaneously formed around the c-CPC. Histologically, many foreign-body giant cells were collected around the c-CPC, and moderate inflammatory cell infiltration was observed at 1 week after surgery. In contrast, the FSCPC and aw-FSCPC were covered with a thin layer of granulation tissue that included few giant cells and presented slight inflammatory cell infiltration, and no effusion was observed. The XRD analysis of the c-CPC revealed the presence of some unreacted DCPA even 1 week after implantation, whereas almost no DCPA was found in the FSCPC or aw-FSCPC. In conclusion, it was found that CPC does not always show excellent tissue response. When c-CPC is implanted subcutaneously in rats immediately after mixing, it fails to set and causes a severe inflammatory response. Therefore, the type of CPC should be chosen according to the clinical particulars. CPC should be used in a manner that assures its setting reaction. We recommend the use of FSCPC and aw-FSCPC for surgical applications, such as orthopedics, plastic and reconstructive surgery, and oral and maxillofacial surgery, where the cement might otherwise crumble due to the pressure before setting.

Origin of Interfacial Droplets with One-step Adhesives

Contemporary one-step self-etch adhesives are often documented with interfacial droplets. The objective of this study was to research the origin of these droplets. Two HEMA-rich and one HEMA-free adhesive were applied to enamel and dentin, with the lining composite either immediately cured or cured only after 20 min. All one-step adhesives exhibited droplets at the interface; however, the droplets had two different origins. With the HEMA-free adhesives, droplets were located throughout the adhesive layer and were stable in number over time. With the HEMA-rich adhesives, the droplets were observed exclusively at the adhesive resin/composite interface, and their number increased significantly when the composite was delay-cured. Only the latter droplets caused a significant drop in bond strength after delayed curing. While the droplets in the HEMA-free one-step adhesives should be ascribed to phase separation, those observed with HEMA-rich adhesives resulted from water absorption from dentin through osmosis.

Nano-controlled molecular interaction at adhesive interfaces for hard tissue reconstruction

Although decayed/fractured teeth can be reconstructed minimally invasively and nearly invisibly using adhesive technology, the clinical longevity of dental composite restorations is still too short. Water sorption is thought to be the principal cause of destabilization of the biomaterial-tooth bond. However, the actual mechanisms of interfacial degradation are far from understood. Here we report how nano-controlled molecular interaction at the biomaterial-hard tissue interface can improve bond durability. The use of functional monomers with a strong chemical affinity for the calcium in hydroxyapatite is essential for long-term durability. Correlative X-ray diffraction and solid-state nuclear magnetic resonance disclosed a time-dependent molecular interaction at the interface with stable ionic bond formation of the monomer to hydroxyapatite competing in time with the deposition of less stable calcium phosphate salts. The advanced tooth-biomaterial interaction model gives not only an insight into the mechanisms of bond degradation, but also provides a basis to develop functional monomers for more durable tooth reconstruction.

Basic properties of calcium phosphate cement containing atelocollagen in its liquid or powder phases

The basic properties of calcium phosphate cement (CPC) containing atelocollagen, the main component of the organic substrate in bone, were studied in an initial evaluation for the fabrication of modified CPC. The setting time of conventional CPC (c-CPC) was prolonged to over 100 min when c-CPC contained 1% or more atelocollagen. The diametral tensile strength (DTS) of c-CPC decreased linearly with the collagen content, descending to below the detection limit when the c-CPC contained 3% or more atelocollagen. Therefore, use of c-CPC as the base cement seems inappropriate for the fabrication of atelocollagen-containing CPC. In contrast, the cement set at 9-34 min when fast-setting CPC (FSCPC) was used as the base cement and contained 1-5% atelocollagen, respectively. Although addition of atelocollagen resulted in the decrease of DTS of the set mass, the DTS was approximately the same, 6-8 MPa, at contents of atelocollagen between 1% and 5%. When atelocollagen was added to FSCPC, the handling property was improved significantly. The paste also became more adhesive with increase in atelocollagen content. These properties are desirable for its use in surgical procedures since, for example, bony defects can be filled easily and without a space interposed between the bone and cement paste. Although there are some disadvantages for the addition of atelocollagen to CPC, it can be accepted as long as FSCPC was used as the base cement. We conclude that further evaluations of the effects of atelocollagen, such as biocompatibility, bone synthesis, and bone replacement behaviour should be done, using FSCPC as the base cement.

Antibacterial effect of bactericide immobilized in resin matrix

OBJECTIVE Biomaterials with anti-microbial properties are highly desirable in the oral cavity. Ideally, bactericidal molecules should be immobilized within the biomaterial to avoid unwanted side-effects against surrounding tissues. They may then however loose much of their antibacterial efficiency. The aim of this study was to investigate how much antibacterial effect an immobilized bactericidal molecule still has against oral bacteria. METHODS Experimental resins containing 0, 1 and 3% cetylpyridinium chloride (CPC) were polymerized, and the bacteriostatic and bactericidal effects against Streptococcus mutans were determined. Adherent S. mutans on HAp was quantitatively determined using FE-SEM and living cells of S. mutans were quantified using real-time RT-PCR. The amount of CPC released from the 0%-, 1%- and 3%-CPC resin sample into water was spectrometrically quantified using a UV-vis recording spectrophotometer. RESULTS UV spectrometry revealed that less than 0.11 ppm of CPC was released from the resin into water for all specimens, which is lower than the minimal concentration generally needed to inhibit biofilm formation. Growth of S. mutans was significantly inhibited on the surface of the 3%-CPC-containing resin coating, although no inhibitory effect was observed on bacteria that were not in contact with its surface. When immersed in water, the antibacterial capability of 3%-CPC resin lasted for 7 days, as compared to resin that did not contain CPC. SIGNIFICANCE These results demonstrated that the bactericidal molecule still possessed significant contact bacteriostatic activity when it was immobilized in the resin matrix.