Elemental distributions and microtensile bond strength of the adhesive interface to normal and caries-affected dentin

The aim of this study was to evaluate the microtensile bond strength (microTBS) and the elemental contents of the adhesive interface created to normal versus caries-affected dentin. Extracted human molars with coronal carious lesions were used in this study. A self-etching primer/adhesive system (Clearfil Protect Bond) was applied to flat dentin surfaces with normal and caries-affected dentin according to the manufacturer's instructions. After 24 h water storage, the bonded specimens were cross-sectioned and subjected to a microTBS test and electron probe microanalysis for the elemental distributions [calcium (Ca), phosphorus (P), magnesium (Mg), and nitrogen (N)] of the resin-dentin interface after gold sputter-coating. The microTBS to caries-affected dentin was lower than that of normal dentin. The demineralized zone of the caries-affected dentin-resin interface was thicker than that of normal dentin (approximately 3 microm thick in normal dentin; 8 microm thick in caries-affected dentin), and Ca and P in both types of dentin gradually increased from the interface to the underlying dentin. The caries-affected dentin had lost most of its Mg content. The distributions of the minerals, Ca, P, and Mg, at the adhesive interface to caries-affected dentin were different from normal dentin. Moreover, a N peak, which was considered to be the collagen-rich zone resulting from incomplete resin infiltration of exposed collagen, was observed to be thicker within the demineralized zone of caries-affected dentin compared with normal dentin.     

Biomimetic remineralization as a progressive dehydration mechanism of collagen matrices – Implications in the aging of resin–dentin bonds

Biomineralization is a dehydration process in which water from the intrafibrillar compartments of collagen fibrils are progressively replaced by apatites. As water is an important element that induces a lack of durability of resin–dentin bonds, this study has examined the use of a biomimetic remineralization strategy as a progressive dehydration mechanism to preserve joint integrity and maintain adhesive strength after ageing. Human dentin surfaces were bonded with dentin adhesives, restored with resin composites and sectioned into sticks containing the adhesive joint. Experimental specimens were aged in a biomimetic analog-containing remineralizing medium and control specimens in simulated body fluid for up to 12 months. Specimens retrieved after the designated periods were examined by transmission electron microscopy for the presence of water-rich regions using a silver tracer and for collagen degradation within the adhesive joints. Tensile testing was performed to determine the potential loss of bond integrity after ageing. Control specimens exhibited severe collagen degradation within the adhesive joint after ageing. Remineralized specimens exhibited progressive dehydration, as manifested by silver tracer reduction and partial remineralization of water-filled microchannels within the adhesive joint, as well as intrafibrillar remineralization of collagen fibrils that were demineralized initially as part of the bonding procedure. Biomimetic remineralization as a progressive dehydration mechanism of water-rich, resin-sparse collagen matrices enables these adhesive joints to resist degradation over a 12-month ageing period, as verified by the conservation of their tensile bond strength. The ability of the proof of concept biomimetic remineralization strategy to prevent bond degradation warrants further development of clinically relevant delivery systems.     

Nanoleakage within the hybrid layer: a correlative FEISEM/TEM investigation

The aim of this study was to compare the nanoleakage patterns of the resin-dentin interfaces of three dentin bonding systems at both TEM and field emission in lens SEM (FEI-SEM) levels. A standardized smear layer was created with 180-grit silicon carbide paper (SiC) on dentin disks obtained from 18 noncarious human third molars. Specimens were randomly divided into three groups and bonded with a two-step total etching adhesive (Single Bond, SB), a two-step, self-etching adhesive (Clearfil SE BOND, SEB), and a one-step, self-etching adhesive (XENO III, XEIII). Nanoleakage was evaluated by using an ammoniacal silver-nitrate solution. Specimens were processed for TEM and FEI-SEM observation. The TEM of SB revealed silver deposits in adhesive and hybrid layers (HL). High-magnification FEI-SEM micrographs clearly identified these deposits as spherical clusters mainly associated with nonembedded collagen fibrils. TEM and FEI-SEM examination of SEB revealed some clusters of silver deposits within porosities and small channels of the HL. Additional silver deposits were observed between the peritubular dentin walls and the resin tags. XEIII revealed very fine and diffuse silver grains throughout the entire HL. SEM visualization of nanoleakage at a high level of resolution has not been previously described. FEI-SEM technology supported the TEM visualization with three-dimensional morphological data of the relations between the HL constituents and nanoleakage. The results of the present study confirm the hypothesis that both total- and self-etch adhesives are not able to fully infiltrate the dentin substrate.     

Recent advances in the theory and mechanism of adhesive resin bonding to dentin: a critical review

Dentin bonding issues involving adhesive resins have attracted considerable research interest in recent years. An important advance due to the ongoing research is the concept of hybridization of the tissue with primer/adhesive systems. Hybridization involves permeation of primer monomer into the tissue substrate. Although the mechanism of adhesive permeation and interaction with tissue may be complex, significant advances have been made. In systems where etching precedes priming and bonding steps, the Hoy's solubility parameter compatibility of the primer formulation with that of demineralized dentin matrix may determine adhesive permeability. Monomer permeation brings the primer atoms in closer contact with the substrate atoms, leading to adhesive interactions through van der Waals, hydrogen bonding, and electrostatic interactions. In self-etch primer systems, stronger electrostatic interaction between primer monomers and hydroxyapatite has been used to explain the adhesion process. These interactions have been computer-modeled and analyzed. Such interactions and subsequent polymerization of the monomer promote improved bond strength and efficient margin sealing. Incomplete permeation of monomer into the full depth of demineralized region may, however, leave exposed collagen fibrils and cause nanoleakage of water into these regions through a 20-100 nm sized marginal gap, leading to subsequent hydrolytic degradation of these collagen fibrils and the hybrid layer. Microleakage is also a problem in some single step formulations. In this review, we analyze these current theoretical and mechanism-related issues of interest in adhesive resin bonding to dentin, and outline the continuing problems that need to be overcome in the future.     

The importance of size-exclusion characteristics of type I collagen in bonding to dentin matrices

The mineral phase of dentin is located primarily within collagen fibrils. During development, bone or dentin collagen fibrils are formed first and then water within the fibril is replaced with apatite crystallites. Mineralized collagen contains very little water. During dentin bonding, acid-etching of mineralized dentin solubilizes the mineral crystallites and replaces them with water. During the infiltration phase of dentin bonding, adhesive comonomers are supposed to replace all of the collagen water with adhesive monomers that are then polymerized into copolymers. The authors of a recently published review suggested that dental monomers were too large to enter and displace water from collagen fibrils. If that were true, the endogenous proteases bound to dentin collagen could be responsible for unimpeded collagen degradation that is responsible for the poor durability of resin–dentin bonds. The current work studied the size–exclusion characteristics of dentin collagen, using a gel-filtration-like column chromatography technique, using dentin powder instead of Sephadex. The elution volumes of test molecules, including adhesive monomers, revealed that adhesive monomers smaller than ～1000 Da can freely diffuse into collagen water, while molecules of 10,000 Da begin to be excluded, and bovine serum albumin (66,000 Da) was fully excluded. These results validate the concept that dental monomers can permeate between collagen molecules during infiltration by etch-and-rinse adhesives in water-saturated matrices.     

Functional biomimetic analogs help remineralize apatite-depleted demineralized resin-infiltrated dentin via a bottom–up approach

Natural biominerals are formed through metastable amorphous precursor phases via a bottom–up, nanoparticle-mediated mineralization mechanism. Using an acid-etched human dentin model to create a layer of completely demineralized collagen matrix, a bio-inspired mineralization scheme has been developed based on the use of dual biomimetic analogs. These analogs help to sequester fluidic amorphous calcium phosphate nanoprecursors and function as templates for guiding homogeneous apatite nucleation within the collagen fibrils. By adopting this scheme for remineralizing adhesive resin-bonded, completely demineralized dentin, we have been able to redeposit intrafibrillar and extrafibrillar apatites in completely demineralized collagen matrices that are imperfectly infiltrated by resins. This study utilizes a spectrum of completely and partially demineralized dentin collagen matrices to further validate the necessity for using a biomimetic analog-containing medium for remineralizing resin-infiltrated partially demineralized collagen matrices in which remnant seed crystallites are present. In control specimens in which biomimetic analogs are absent from the remineralization medium, remineralization could only be seen in partially demineralized collagen matrices, probably by epitaxial growth via a top–down crystallization approach. Conversely, in the presence of biomimetic analogs in the remineralization medium, intrafibrillar remineralization of completely demineralized collagen matrices via a bottom–up crystallization mechanism can additionally be identified. The latter is characterized by the transition of intrafibrillar minerals from an inchoate state of continuously braided microfibrillar electron-dense amorphous strands to discrete nanocrystals, and ultimately into larger crystalline platelets within the collagen fibrils. Biomimetic remineralization via dual biomimetic analogs has the potential to be translated into a functional delivery system for salvaging failing resin–dentin bonds.     

Application of hydrophobic resin adhesives to acid-etched dentin with an alternative wet bonding technique

Hydrophilic dentin adhesives are prone to water sorption that adversely affects the durability of resin-dentin bonds. This study examined the feasibility of bonding to dentin with hydrophobic resins via the adaptation of electron microscopy tissue processing techniques. Hydrophobic primers were prepared by diluting 2,2-bis[4(2-hydroxy-3-methacryloyloxy-propyloxy)-phenyl] pro- pane/triethyleneglycol dimethacrylate resins with known ethanol concentrations. They were applied to acid-etched moist dentin using an ethanol wet bonding technique that involved: (1) stepwise replacement of water with a series of increasing ethanol concentrations to prevent the demineralized collagen matrix from collapsing; (2) stepwise replacement of the ethanol with different concentrations of hydrophobic primers and subsequently with neat hydrophobic resin. Using the ethanol wet bonding technique, the experimental primer versions with 40, 50, and 75% resin exhibited tensile strengths which were not significantly different from commercially available hydrophilic three-step adhesives that were bonded with water wet bonding technique. The concept of ethanol wet bonding may be explained in terms of solubility parameter theory. This technique is sensitive to water contamination, as depicted by the lower tensile strength results from partial dehydration protocols. The technique has to be further improved by incorporating elements of dentin permeability reduction to avoid water from dentinal tubules contaminating water-free resin blends during bonding.     

Analysis of acid-treated dentin smear debris and smear layers using confocal Raman microspectroscopy

Smear layers are generally present on any dentin surface prepared with cutting instruments and are often the only available substrate for bonding. It is commonly reported that acid removes these layers, but to date there has been no chemical evidence to support this observation. Confocal Raman microspectroscopy was used to investigate changes in the composition and molecular structure of acid-treated smear debris and in situ dentin smear layers. The exposed dentin in human molars was abraded with 600-grit silicon carbide sandpaper. Raman spectra were acquired on the smear debris and collected from the sandpaper before and after treatment with 10% citric acid, 35% H3PO4, or 0.5M ethylenediaminetetraacetic acid (EDTA). The resultant smeared dentin samples were treated with one of the aforementioned reagents, and spectra were acquired at 1.0-microm intervals across the interfaces of the smear layers/demineralized dentin/mineralized dentin. Corresponding specimens were morphologically analyzed with scanning electron microscopy (SEM). The results showed that the composition of the smear debris and the in situ smear layers was a mixture of disorganized collagen and mineral. Spectral changes in the smear debris suggested that the disorganized collagen was denatured by acid treatment. The denatured collagen formed a gelatinous matrix around the mineral in the smear layer, thereby shielding it from the acid. The smear layers were not apparent in the SEM micrographs of acid-etched dentin prepared and processed with conventional techniques. The micro-Raman spectroscopic results presented in this study provide the first direct evidence that partially denatured collagen within smear layers is not removed and that the mineral is only partially removed with acids that represent conventional dentin adhesive etchants.     

Effect of solvent content on resin hybridization in wet dentin bonding

With wet bonding techniques, the channels between the demineralized dentin collagen fibrils are filled with debris, solvent, and water. Commercial adhesives include solvents such as ethanol or acetone to facilitate resin-infiltration into this wet substrate. Under in vivo conditions, the solvent may be diluted because of repeated exposure of the material to the atmosphere, or concentrated because of separation of the bonding liquids into layers within the bottle. The purpose of this study was to investigate the effect of different concentrations of ethanol (10-50%) on infiltration of the adhesive resin and collagen fibril encapsulation in the adhesive/dentin interface using light microscopy, micro-Raman spectroscopy, and scanning electron microscopy. The results indicated that under wet bonding conditions the hybridization process was highly sensitive to the initial solvent concentration in the adhesive system. The staining and scanning electron microscopy results showed that the quality of the interfacial hybrid layer was poor at the lower (10%) or higher (50%) ethanol content. Micro-Raman analysis indicated that there was a distinct difference in the degree of adhesive penetration among adhesives containing different concentrations of ethanol. Adhesives containing 10 or 50% ethanol did not realize effective penetration; the penetration of the adhesive monomers increased dramatically when the initial ethanol content was 30%. The amount of solvents are essential for achieving effective bonding to dentin.     

Cross-linked demineralized dentin maintains its mechanical stability when challenged by bacterial collagenase

The molecular structure, weight loss, and mechanical properties of demineralized dentin of noncrosslinked/crosslinked by glutaraldehyde (GA) were investigated when being challenged by bacterial collagenase solution over time in this study. Raman spectra proved that crosslinking occurred in demineralized dentin matrices after being treated with GA. Meanwhile, the weight of the cross-linked demineralized dentin matrices did not change after being challenged by bacterial collagenase solution up to 1 week. However, the weight of noncross-linked dentin collagen fell by almost 45% after degradation for 5 h, and up to 100% after 19 h. The tensile strength of demineralized dentin matrices did not show a significant change after being crosslinked, while the stiffness of demineralized dentin matrices showed more improvement than that of noncross-linked collagen. The toughness of demineralized dentin matrices decreased slightly after being crosslinked. Importantly, neither the tensile strength of GA-cross-linked demineralized dentin nor its stiffness changed over time in either control buffer or collagenase solution compared with that of noncross-linked controls. These results suggested that improving the degree of crosslinking in dentin collagen could be one method to inhibit its biodegradation and further to increase the durability of dental restorations.     

Deproteinizing effects on resin-tooth bond structures

This study investigated the effects of NaOCl on resin-tooth bonds to simulate the situations of long-term durability and caries invasion. Resin-tooth bonded specimens were produced with the use of two resin adhesives (Excite and One-Bond). Resin-tooth bonded beams (adhesive area; 0.9 mm2) were serially sectioned and the specimens were immersed in 10% NaOCl medium for 0 (control), 2, 4, and 6 h after being stored in water for 24 h. After immersion, microtensile bond tests were performed. SEM fractography was conducted to calculate each failure mode by image analysis. In addition, the adhesive interface was examined with the use of TEM. In the control specimens, enamel bond strengths had no difference between Excite (45.6 +/- 15.0) and One-Bond (56.9 +/- 12.9). On the other hand, dentin bond strengths had significant difference between Excite (80.6 +/- 21.2) and One-Bond (50.7 +/- 11.2). The bond strengths decreased with increased storage time for both systems with enamel and dentin bonds. The deteriorated mineralized dentin of beams resulted in bond-strength reduction for resin-enamel bonds. For dentin bonding, the adhesive interface was gradually dissolved from the outer to the center portion of the beam. The depletion of collagen fibrils within the demineralized dentin or hybrid layer deformation was found under SEM and TEM examinations. These morphological changes are responsible for bond strength reduction of resin-dentin bonds.     

Micro-Raman imaging analysis of monomer/mineral distribution in intertubular region of adhesive/dentin interfaces

It is generally proposed that bonding of resins to dentin results from infiltration of the adhesive monomers into the superficially demineralized dentin. However, it is still not clear how well the mineral phase of dentin is removed and how far each monomer penetrates into the thin zone of "wet" demineralized dentin. The quality and molecular structure of adhesive/dentin interfaces formed under "wet" bonding conditions are studied using 2-D Raman microspectroscopic mapping/imaging techniques. Micro-Raman imaging analysis of the adhesive/dentin interface provides a reliable and powerful means of identifying the degree and depth of dentin demineralization, adhesive monomer distribution, and flaws or defects in the pattern of adhesive penetration. The image of mineral reveals a partially demineralized layer on the top of dentin substrate. Adhesive monomers readily penetrate into dentin tubules and spread into intertubular region through open tubules. The extent of adhesive monomer penetration is higher in the intertubular regions close to tubules as compared to the middle regions between the tubules. The diffusion of resin monomers differs substantially. In a comparison with a hydrophilic monomer, the hydrophobic monomer resists diffusion into the demineralized intertubular dentin area.     

The fibrillar structure of cementum and dentin at the cemento-dentinal junction in rat molars

The cemento-dentinal junction was examined in demineralized rat molars with complete roots by scanning electron microscopy combined with NaOH maceration. It is established that the NaOH maceration removes interfibrillar substances and cells from connective tissues selectively without structural damage to collagen fibrils. The cementum was detached from the dentin by the maceration. The inner cementum surface facing the dentin and the outer dentin surface facing the cementum were observed. In acellular cementum, both the outer dentin surface and the inner cementum surface had a smooth appearance. There was little indication of fibrils intermingling between dentin and cementum. In contrast, both the inner cementum surface and outer dentin surface in cellular cementum had an uneven appearance due to the irregular arrangement of collagen fibrils. Point-like protrusions of fibril bundles were observed on both surfaces. Some (not all) of these point-like protrusions appeared to correspond to places of fibrillar intermingling between dentin and cementum.     

Effect of carboxymethylcellulose on fibril formation of collagen in vitro

The effect of carboxymethylcellulose (CMC) on the fibril formation of collagen in vitro was studied by turbidity measurements and atomic force microscopy (AFM). The kinetics curves of fibril formation indicated that the rate of collagen fibrillogenesis was decreased with the addition of CMC, meanwhile the final turbidity was obviously increased as the CMC/collagen ratio reached 30%. The AFM images of collagen-CMC solutions showed that the number of nucleation sites of collagen fibrillogenesis was significantly increased with the presence of CMC, while the diameter of immature collagen fibrils was obviously decreased. Moreover, the thermal stability of collagen fibril hydrogels was obviously improved with the presence of CMC. In addition, the morphologies of collagen fibrils observed by AFM revealed that the adjacent fibril segments or fibrils were intertwisted and even tightly merged, probably due to the hydrogen bonding and molecular entanglement interactions between CMC and collagen molecules.     

Bonding of dual-cured resin cement to zirconia ceramic using phosphate acid ester monomer and zirconate coupler

This study evaluated the shear bond strength between dual-cured resin luting cement and pure zirconium (99.9%) and industrially manufactured yttrium-oxide-partially-stabilized zirconia ceramic, and the effect of MDP (10-methacryloyloxydecyl dihydrogen phosphate) primer (MP) and zirconate coupler (ZC) on bond strength. Two different-shaped pure zirconium and zirconia ceramic specimens were untreated or treated with various primers, including different concentrations of MP containing phosphoric acid ester monomer (MDP) in ethanol, ZC containing a zirconate coupling agent in ethanol, or a mixture of MP and ZC. The specimens were then cemented together with dual-cured resin luting cement (Clapearl DC). Half of the specimens were stored in water at 37 degrees C for 24 h and the other half were thermocycled 10,000 times before shear bond strength testing. The bond strengths of resin luting cement to both the zirconium and zirconia ceramic were enhanced by the application of most MPs, ZCs, and the mixtures of MP and ZC. For the group (MP2.0+ZC1.0) containing 2.0 wt % MP and 1.0 wt % ZC, no significant difference was observed between in shear bond strength before and after thermal cycling for both zirconium and zirconia ceramic (p > 0.05). For the other primers, statistically significant differences in shear bond strength before and after thermal cycling were observed (p < 0.05). The application of the mixture of MP and ZC (MP2.0+ZC1.0) was effective for bonding between zirconia ceramic and dual-cured resin luting cement. This primer may be clinically useful as an adhesive primer for zirconia ceramic restoration.     

Bonding performance of different adhesive systems to deproteinized dentin: microtensile bond strength and scanning electron microscopy

Deproteinization has been shown to optimize dentin bonding, but differences in adhesive composition should be considered. The objective of this study was to evaluate the effect of dentin deproteinization on microtensile bond strength (microTBS) of four total-etch adhesive systems (Single Bond/SB, Prime & Bond NT/PB, One Coat Bond/OC, and PQ1/PQ). The ultrastructure of the resin-dentin interfaces was also examined using scanning electron microscopy. Tukey's multiple-comparison tests indicated that PB and PQ produced significantly higher microTBS (p<0.05) after dentin deproteinization (PB=61.53 MPa, PQ=58.18 MPa). This treatment provided statistically lower results for SB (39.08 MPa), but the microTBS of OC to dentin was unaffected by dentin deproteinization. The bonding performance on deproteinized dentin surfaces depended on the characteristics of each adhesive system, as well as the adhesive dentin specificity to the oxidant effect of sodium hypochlorite. Incorporation of fillers in the adhesive, a possible self-etching action, and the presence of a volatile solvent (acetone) were the main factors for a better union between the adhesive system and deproteinized substrate.     

Thermal Stability of Mineralized and Demineralized Dentin: A Differential Scanning Calorimetric Study

The purpose of this study was to determine the difference, if any, in the thermal stability of collagen in mineralized and demineralized dentine compared to that in unmineralized tissues, using differential scanning calorimetry, DSC. Human tooth dentin blocks, about 1×1×2 mm in size, were used in this study. Some dentin blocks were demineralized using a Plank Rychlo solution; others, using EDTA solution. The mineralized dentin showed an exothermic peak at about 310°C and the combustion of organic materials was completed at about 450°C. For the demineralized dentin, the combustion was completed at higher temperature range and showed a strong exothermic peak at about 470°C. An exotherm at the temperature between 450°C and 470°C was also observed in DSC pattern of native type I collagen from calf skin and rat tail tendon. DSC pattern of rat tail collagen showed a close similarity to that of the demineralized dentin. Statistically, the same heat flow value was obtained both from the mineralized dentin and the demineralized dentin and from the native type I collagen.

These findings indicated that the thermal stability of collagen in dentin is lower than collagen in uncalcified connective tissue. It is suggested that in calcified collagen, the apatite crystallites may have intruded into spaces of the crosslinks of intra- and inter-fibrils, and in so doing, destroyed the crosslinks.     

AFM observation of collapse and expansion of phosphoric acid-demineralized dentin

The objective of this study is to provide additional data regarding morphological changes that occur to dentin matrices following demineralization with etchants. Our understanding of the mechanism of diffusion of comonomers into the demineralized substrate is very limited. It has been hypothesized that certain water-soluble polyelectrolytes (acidic proteins) and neutral proteins in dentin can influence the collapse of demineralized dentin when it is air dried. Some of these solubilized substances are thought to aggregate by the action of Ca cations, which become dissolved during H(3)PO(4) etching, ultimately resulting in some degree of collapse. In the current study, dentin surfaces were examined by atomic force microscopy (AFM) before and after treatment by 10% H(3)PO(4)containing increasing concentrations of CaHPO(4). Reversal of matrix collapse by aqueous 30% 2-hydroxyethyl methacrylate (HEMA) was evaluated by AMF for 60 min. The results demonstrate two forms of matrix collapse; we speculate that one form is induced by acidic noncollagenous polyelectrolytes and the other by neutral peptides. Our data indicate that further evaluation of the influence of endogenous noncollagenous proteins must be studied to understand the mechanism of the collapse and reexpansion dynamics of demineralized dentin networks.     

Improved wet bonding of methyl methacrylate-tri-n-butylborane resin to dentin etched with ten percent phosphoric acid in the presence of ferric ions

The objective of this study was to determine the influence of dissolved dentinal substances in demineralized dentin on the hybridization of resin for bonding to dentin. It was hypothesized that these substances, including polyelectrolytes, significantly change the substrates, which could then be assessed by the addition of Na(+), Ca(2+), or Fe(3+) in 10% phosphoric acid. Bovine dentin specimens were etched for 10 s with a solution of 10% phosphoric acid (control) or of 22.0 mM dissolved sodium chloride (10P-Na), calcium chloride (10P-Ca), or ferric chloride (10P-Fe). The specimens were then rinsed, blot-dried, and primed three times with 5% 4-methacryloyloxyethyl trimellitate anhydride in acetone for 60 s. Methyl methacrylate-tri-n-butylborane resin was then applied. The tensile bond strength of each of the dumbbell-shaped specimens was then measured. The fractured surfaces and modified cross-sections were examined by scanning electron microscopy. The cross-sections were soaked in 6N HCl for 10 s and then in 1% sodium hypochlorite for 30 min to determine the resin content in the hybridized specimens. Shrinkage of the demineralized dentins upon drying was assessed by atomic force microscopy. The tensile bond strengths were 10.8 +/- 4.5 (control), 15.0 +/- 7.0 (10P-Na), 19.3 +/- 5.5 (10P-Ca), and 27.8 +/- 8.1 (10P-Fe) MPa. The atomic force microscopy studies showed that Fe(3+) minimized the shrinkage by drying for 10 s but Ca(2+) and Na(+) did not decrease the shrinkage the same as the control. The results support the hypothesis that the monomer permeability of wet demineralized dentin is effectively improved by dissolving ferric ions in the phosphoric acid, resulting in a greater bond strength and higher resin content in the hybridized dentin. The dissolved dentinal substances, including the polyelectrolytes, had a significant influence on the characteristics of the demineralized dentin, changing the degree of hybridization and bonding.     

Degradation patterns of different adhesives and bonding procedures

Various types of resin adhesives and procedures are available in the clinical field, so comprehensive understanding of degradation is required for each material and bonding procedure. The objective of this study was to investigate the bond durability for different adhesives and bonding procedures. Resin-dentin bonded beams were prepared with the use of two adhesives (One-Up Bond F/self-etching primer system and One Bond/total-etch adhesive) and two experimental groups for the bonding procedure (wet and dry bonding of the total-etch adhesive). Those samples were soaked in water for 24 h(control), 6 and 12 months. After the water immersion, the bond strengths were measured by the microtensile bond test, and subsequently fractography was performed with the use of SEM. Statistically significant reduction of the bond strength (p < 0.05) was apparent after 12 months of water exposure in the range 22-48% of the control. The bonding resin was eluted from the hybrid layer of the self-etching and the total-etch adhesives for the wet bonding. Micromorphological alterations were found due to the hydrolysis of collagen fibrils with the total-etch adhesive for the dry bonding mode. These pathologic alterations were in accord with the bond strength.