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Comparative Study on Adhesive Performance of Functional Monomers

¹ Department of Biomaterials, Okayama University Graduate School of Medicine and Dentistry, 2-5-1 Shikata-cho, Okayama 700-8525, Japan;
² Research Center for Biomedical Engineering, Okayama University, 2-5-1 Shikata-cho, Okayama 700-8525, Japan;
³ Department of Biomaterials Science, Hiroshima University Graduate School of Biomaterials Science, 1-2-3 Kasumi, Minami-Ku, Hiroshima 734-8553, Japan;
⁴ Department of Operative Dentistry and Dental Materials, Hiroshima University Graduate School of Biomaterials Science, 1-2-3 Kasumi, Minami-Ku, Hiroshima 734-8553, Japan;
⁵ Research Planning Department, Toray Research Center, Inc., Sonoyama 3-3-7, Otsu, Shiga 520-8567, Japan;
⁶ Division for General Dentistry, Hokkaido University Dental Hospital, Kita 13 Nishi 7, Kita-ku, Sapporo 060-8586, Japan;
⁷ Institute of Experimental Animals, Shinshu University School of Medicine, 3-1-1 Asahi, Matsumoto, Nagano 390-8621, Japan; and
⁸ Leuven BIOMAT Research Cluster, Department of Conservative Dentistry, School of Dentistry, Oral Pathology and Maxillo-Facial Surgery, Catholic University of Leuven, Kapucijnenvoer 7, B-3000 Leuven, Belgium;

^* corresponding author, bart.vanmeerbeek{at}med.kuleuven.ac.be

	ABSTRACT

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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.

KEY WORDS: adhesion • functional monomer • XPS • TEM • dissolution rate

	INTRODUCTION

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Self-etch adhesives are user-friendly because they do not require a rinse phase. This substantially reduces application time as well as technique sensitivity. In addition to their application after a two- vs. a single-step approach, a further distinction can be made between "mild" and "strong" current self-etch adhesives (Inoue et al., 2000; Tay and Pashley, 2001; Van Meerbeek et al., 2003). Like etch-and-rinse adhesives, strong self-etch adhesives completely remove hydroxyapatite from dentin, resulting in relatively deep dentin hybridization several micrometers thick. However, mild self-etch adhesives form only submicron-thick hybrid layers, in which hydroxyapatite partially remains around exposed collagen (Nakabayashi and Saimi, 1996; Inoue et al., 2000).

Commonly, acidic monomers in self-etch primers/adhesives are esters originating from the reaction of a bivalent alcohol with methacrylic acid and phosphoric/carboxylic acid derivatives. Each self-etch adhesive contains its specific functional monomer that, to a large extent, determines its actual adhesive performance. Thus far, however, the interaction of functional monomers with dental tissues has seldom been characterized by chemical analytical techniques. We therefore comparatively characterized the adhesive interaction of 3 functional monomers with synthetic hydroxyapatite to test the hypothesis that the bonding mechanism of mild self-etch adhesives involves chemical interaction of functional monomers with residual hydroxyapatite in addition to micro-mechanical hybridization. The functional monomers investigated originated from 3 representative two-step self-etch adhesives, and their interaction with dentin was also ultra-morphologically characterized.

	MATERIALS & METHODS

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The functional monomer 4-MET (4-methacryloxyethyl trimellitic acid) and its calcium salt 4-METCa were provided by GC (Tokyo, Japan), whereas phenyl-P (2-methacryloxyethyl phenyl hydrogen phosphate) and 10-MDP (10-methacryloxydecyl dihydrogen phosphate), and their respective calcium salts (phenyl-PCa, 10-MDPCa), were provided by Kuraray (Osaka, Japan).

X-ray Photoelectron Spectroscopy (XPS)
From each functional monomer, we prepared 15% (w/w) solutions including 45% (w/w) ethanol and 40% (w/w) water. Hydroxyapatite plates (APP-101, Asahi Optical, Tokyo, Japan) were treated with each solution at 37°C for 30 sec and 30 min, followed by ultrasonic rinsing twice in 52.9% (w/w) ethanol for 20 min prior to XPS analysis (AXIS-HS, Kratos, Manchester, UK) in vacuo of less than 10^–7 Pa. We used Al-K monochromatic x-ray with a source power of 150 W. Wide and narrow scans were measured at a pass energy of, respectively, 80 and 40 eV. Quantitative data were obtained from peak areas, and identification of chemical states was made from detailed measurement of peak positions and separations. Significant differences in adhesive performance among the functional monomers were analyzed by Student’s t test ( = 0.01).

Dissolution Rate of Ca Salts
To determine the stability of potential chemical bonding, we immersed the calcium salts of the acid monomers (0.5 g 4-METCa, 1.0 g phenyl-PCa, and 0.5 g 10-MDPCa) in 10 mL ultrapure water; samples were then shaken for 1 wk (1 Hz, 37°C). The supernatant liquid was used as a sample for experiments after insoluble substances had been removed by centrifugation (3000 rpm, 10 min) and subsequently filtered through a polytetrafluoroethylene membrane (pore size = 0.20 µm; Samprep-LCR25-LG, Millipore Corporation, Bedford, MA, USA). The solution was then analyzed for calcium by means of Atomic Absorption Spectrophotometry (AAS; AA-670, Shimadzu, Kyoto, Japan). The dissolution rate was quantified as the amount of calcium extracted from the calcium salts in ultrapure water (n = 5). The data obtained were analyzed by one-way ANOVA and Scheffé’s multiple comparison test ( = 0.05).

Transmission Electron Microscopy (TEM)
Extracted non-carious human third molars (gathered after we obtained informed consent according to a protocol approved by the Commission for Medical Ethics of the Catholic University of Leuven) were used within 1 mo of extraction (stored in 0.5% chloramine/water, 4°C). After we removed the occlusal crown third using an Isomet diamond saw (Isomet 1000, Buehler, Lake Bluff, IL, USA), we wet-sanded the exposed dentin (60 sec, 600-grit silicon-carbide paper) to produce a standard smear layer. All specimens were randomly divided into 3 groups of 2 teeth each, and were subjected to a bonding treatment according to the manufacturer’s instructions, with either UniFil Bond (UF-B, GC), Clearfil Liner Bond 2 (C-LB2, Kuraray), or Clearfil SE Bond (C-SE, Kuraray). UF-B, C-LB2, and C-SE contain 4-MET, phenyl-P, and 10-MDP, respectively.

Following adhesive treatment, the resin-bonded dentin specimens were processed for TEM according to a protocol previously described (Van Meerbeek et al., 1998). Demineralized samples were also prepared by immersion in a 10% formaldehyde-formic acid solution (36 hrs). Sections (70–90 nm thick) were cut by means of a diamond knife (Diatome, Bienne, Switzerland) in an ultramicrotome (Ultracut UCT, Leica, Vienna, Austria), and were observed unstained and positively stained (5% uranyl acetate [UA] for 20 min/saturated lead citrate [LC] for 3 min) by TEM (Philips CM10, Eindhoven, The Netherlands).

	RESULTS

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XPS wide-scan spectra of untreated hydroxyapatite and spectra of hydroxyapatite treated with 4-MET, phenyl-P, and 10-MDP, respectively, are alike, except for the C 1s peak at a binding energy of approximately 285 eV that appeared when hydroxyapatite was exposed to functional monomers (Fig. 1). The intensity of the C 1s peak of untreated hydroxyapatite (Fig. 1a) increased slightly when hydroxyapatite was treated for 30 sec with 4-MET (Fig. 1b), while it increased considerably when hydroxyapatite was exposed to 10-MDP for 30 sec (Fig. 1c). Application of 4-MET to hydroxyapatite for 30 min further increased the intensity of the C 1s peak in comparison with intensity from the 30-second application (Fig. 1d). A slightly increased C 1s peak appeared when hydroxyapatite was exposed to phenyl-P for 30 min (Fig. 1e). No increase in intensity of the C 1s peak was recorded when hydroxyapatite was exposed to 10-MDP for 30 min (Fig. 1f), as compared with the short 30-second application (Fig. 1c).

View larger version (15K): [in this window] [in a new window]   Figure 1. XPS wide-scan spectra of untreated hydroxyapatite (a), of hydroxyapatite treated with 15% (w/w) 4-MET for 30 sec (b), of hydroxyapatite treated with 15% (w/w) 10-MDP for 30 sec (c), of hydroxyapatite treated with 15% (w/w) 4-MET for 30 min (d), of hydroxyapatite treated with phenyl-P for 30 min (e), and of hydroxyapatite treated with 10-MDP for 30 min (f).

View larger version (17K): [in this window] [in a new window]   Figure 2. (a) XPS narrow-scan spectra of the C 1s region of 4-META (4-methacryloxyethyl trimellitate anhydride) powder (top spectrum) and of hydroxyapatite treated with 15% (w/w) 4-MET for 30 min (bottom spectrum). Peak deconvolution revealed that almost all carbon originated from 4-MET, with a peak at 284.6 eV representing C-C, C-H, and C=C bindings, a peak at 286.1 eV representing C-O bindings, and a peak representing ester and carboxyl groups. As compared with 4-META powder (288.6 eV), the carboxyl peak had shifted to a lower binding energy (288.3 eV). Deconvolution of the shifted peak disclosed a peak at 288.6 eV, representing the ester function and unreacted carboxyl groups, and a peak at 288.2 eV that represents carboxyl groups that reacted with the Ca of hydroxyapatite. It should be mentioned that the peak position and intensity of the C-O component (top spectrum) for 4-META powder are slightly different from what theoretically would be expected, and from the C-O subpeak in the bottom spectrum. This must be attributed to impurities within the 4-META powder sample that were readily removed during the adhesive treatment. (b) XPS narrow-scan spectra of the C 1s region of untreated phenyl-P (top spectrum) and of hydroxyapatite treated with 15% (w/w) phenyl-P (bottom spectrum). (c) XPS narrow-scan spectra of the C1s region of untreated 10-MDP (top spectrum) and of hydroxyapatite treated with 15% (w/w) 10-MDP (bottom spectrum). Peak deconvolution revealed that almost all carbon originated from 10-MDP on hydroxyapatite, with a peak at 284.6 eV representing C-C, C-H, and C=C bindings, a peak at 286.1 eV representing C-O bindings, and a peak representing ester at 288.6eV. In high-resolution XPS C 1s spectra, aliphatic carbon shows a large asymmetry due to vibrational effect, while aromatic carbon is symmetrical (Beamson and Briggs, 1992). Therefore, the peak at 284.6 eV representing C-C, C-H, and C=C bindings of 10-MDP is expressed with an asymmetrical shape.

With regard to chemical bonding efficacy, quantitative analysis revealed that the carbon concentration detected on hydroxyapatite exposed to 15% (w/w) 4-MET for 30 min (17.2 ± 0.6%) was not significantly different (p > 0.05) from that of hydroxyapatite exposed to 15% (w/w) 10-MDP for 30 min (17.3 ± 0.6%). However, 4-MET and 10-MDP have 15 and 14 carbon atoms, respectively, in a single molecule. Thus, for comparison of bonding potentials, the atom% should be adjusted by the number of carbon atoms in a single molecule. The atom%/14 value for hydroxyapatite exposed to 10-MDP (1.23 ± 0.04%) was significantly (p < 0.05) higher than the atom%/15 value of hydroxyapatite exposed to 4-MET (1.15 ± 0.04%).

AAS (n = 5) revealed that phenyl-PCa was significantly more soluble ([Ca²⁺] in water = 1.91 ± 0.14 g/L) than 4-METCa ([Ca²⁺] in water = 1.36 ± 0.27 g/L). The calcium salt of 10-MDP (10-MDPCa) was the least soluble in water ([Ca²⁺] in water = 6.79 ± 0.43 mg/L).

TEM revealed that all 3 self-etch adhesives formed a shallow (0.5–1 µm) hybrid layer (Fig. 3). Unstained, non-demineralized sections revealed that all systems demineralized dentin only partially, leaving hydroxyapatite around collagen within the submicron hybrid layer. Staining disclosed a typical hybrid-layer ultrastructure with cross-banded collagen separated by electronlucent interfibrillar spaces. A typical ‘shag carpet’ pattern often appeared at the top of the hybrid-layer. Stained, demineralized sections confirmed the acid-resistance of the hybrid layer.

View larger version (90K): [in this window] [in a new window]   Figure 3. TEM photomicrographs illustrating the resin-dentin interfaces produced by Unifil Bond (GC) (a,b), Clearfil Liner Bond 2 (Kuraray) (c), and Clearfil SE (Kuraray) (d,e). The photomicrographs in (a) and (d) represent unstained, non-demineralized sections, those in (b) and (e) stained, demineralized sections, and that in (c) a stained, non-demineralized section. A = adhesive resin; H = hybrid layer; L = lab-demineralized unaffected dentin; R = resin-impregnated smear plug; U = unaffected dentin.

	DISCUSSION

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As can be derived theoretically from the chemical formula of 4-MET, the ratio of C-C/C-H/C=C bindings to C-O bindings and to -COO- bindings is 9 to 2 to 4. Peak area analysis (n = 13) of the peak that appeared when 4-MET interacted with hydroxyapatite revealed areas of, respectively, 9.1 ± 0.2 for the C-C/C-H/C=C peak and 2.0 ± 0.0 for the C-O peak, when the area of the -COO- bindings was taken as 4. The theoretical and measured peak ratios are alike, thus indicating that the recorded C 1s peak represented 4-MET that remained attached to hydroxyapatite. This C 1s peak cannot represent any carbon contamination, since it would have resulted in totally different peak area ratios. Previously, we demonstrated—for polyalkenoic acids (Yoshida et al., 2000) as well as for some mono-, di-, and tri-carboxylic acids (Yoshida et al., 2001)—that the shift of the carboxyl peak to a lower binding energy could be explained by the formation of an ionic bond between the carboxyl groups and the Ca of hydroxyapatite. Likewise, the peak shift resulting from the interaction of 4-MET with hydroxyapatite indicates that the carboxyl groups formed an ionic bond with Ca of hydroxyapatite. While a short 30-second exposure resulted in rather weak interaction intensity, 4-MET interacted more intensely with hydroxyapatite after a 30-minute exposure.

The interaction of phenyl-P with hydroxyapatite cannot be explained by simple bonding to hydroxyapatite. As can theoretically be derived from the chemical formula of phenyl-P, the ratio of C-C/C-H/C=C bindings to C-O bindings and to -COO- bindings is 8 to 3 to 1. Unreacted phenyl-P (Fig. 2b) showed a peak shape that reflects the theoretical peak ratio, which differs completely from the measured peak area ratio of the C 1s peak of phenyl-P on hydroxyapatite (n = 32). Therefore, the recorded spectrum should most likely be ascribed to phenyl-P that was hydrolytically broken into several sub-components following ultrasonic rinsing. In addition, among the three monomer solutions investigated, the 15% (w/w) phenyl-P solution was the most highly concentrated in molarity, because the molecular weights of 4-MET, phenyl-P, and 10-MDP are 322.3, 286.2, and 322.3, respectively. Nevertheless, even a 30-minute application resulted in only a rather weak C 1s peak that would be indicative of chemical interaction with hydroxyapatite.

As can theoretically be derived from the chemical formula of 10-MDP, the ratio of C-C/C-H/C=C bindings to C-O bindings and to -COO- bindings is 11 to 2 to 1. Peak area analysis (n = 11) of the peak that appeared upon interaction of 10-MDP with hydroxyapatite (Fig. 2c) revealed areas of, respectively, 10.7 ± 0.6 for the C-C/C-H/C=C peak and 2.0 ± 0.1 for the C-O peak when the area of the -COO- bindings was taken as 1. The C 1s peak of 10-MDP on hydroxyapatite is very similar to that of unreacted 10-MDP (Fig. 2c). Like 4-MET, but unlike phenyl-P, the theoretical and measured peak ratios are alike, indicating that the recorded C 1s peak represented 10-MDP that remained strongly attached to hydroxyapatite.

When we compared the chemical bonding efficacy of the 3 functional monomers investigated, quantitative determination of carbon concentration on hydroxyapatite revealed that the bonding potential of 10-MDP to hydroxyapatite is significantly stronger than that of 4-MET, even after a 30-minute exposure. Moreover, the fact that even a short 30-second exposure of hydroxyapatite to 10-MDP produced a significant C 1s peak, and that the peak intensity did not increase further when the exposure time was extended, strongly suggests that 10-MDP has a high chemical bonding potential to hydroxyapatite within a clinically reasonable application time. The chemical bonding capacity of 4-MET is weaker, and it is doubtful that 4-MET, even within a short application time, is capable of chemically bonding to hydroxyapatite. This confirms the rather weak adsorption of 4-META from ethanol and dichloromethane onto synthetic hydroxyapatite reported in a study by Misra (1989). The chemical bonding efficacy of phenyl-P is clearly the lowest among the 3 functional monomers investigated.

However, chemical bonding potential on its own is insufficient to contribute to bonding performance. The ionic bindings formed should be stable in an aqueous environment. XPS showed that chemical bonding induced, in particular, by 10-MDP, even after a short 30-second application, resisted ultrasonic cleaning. In addition, AAS revealed that the calcium salt of 10-MDP was hardly soluble. The calcium salt of 4-MET could be dissolved more easily, whereas phenyl-P was very soluble in water. These data conform to the adhesion-decalcification (AD) concept previously presented (Yoshida et al., 2001; Yoshioka et al., 2001). According to the AD-concept, the less soluble the calcium salt of the acidic molecule, the more intense and stable the molecular adhesion to a hydroxyapatite-based substrate. The higher and more stable bonding performance of 10-MDP vs. that of 4-MET is also reflected in the higher micro-tensile strength to dentin of the 10-MDP-based Clearfil SE (Kuraray) compared with that of the 4-MET-based Unifil Bond (GC) (Inoue et al., 2001). In addition to increased bond strength, improved monomer-dentinal tissue interaction may also enhance sealing potential for the prevention of nano-leakage (Sano et al., 1995), and thus extend bonding longevity (Sano et al., 1999).

In conclusion, besides self-etching dentin, some functional monomers may, within a clinically reasonable time, interact chemically with hydroxyapatite. Hydroxyapatite, however, needs to remain available at the partially demineralized dentin surface. The specific molecular formula of the functional monomer and the subsequent dissolution rate of its calcium salt determine actual bonding efficacy and stability.

	ACKNOWLEDGMENTS

 
This study was supported in part by a Grant-in-Aid for Scientific Research from the Ministry of Education, Science, Sports and Culture of Japan and by funds from the Uehara Memorial Foundation, The Nakatomi Foundation, and the Toshio Nakao Chair for Adhesive Dentistry, inaugurated at the Catholic University of Leuven (B. Van Meerbeek and P. Lambrechts, Chairholders). We thank GC and Kuraray for providing the monomers and calcium salts. We also thank J. Yearn (GC Europe) for critically reviewing the manuscript.

Received January 21, 2003; Last revision April 7, 2004; Accepted April 14, 2004

	REFERENCES

TOP ABSTRACT INTRODUCTION MATERIALS & METHODS RESULTS DISCUSSION REFERENCES

 
Beamson G, Briggs D (1992). Lineshapes. In: High resolution XPS of organic polymers. The Scienta ESCA 300 Database. Chichester: John Wiley & Sons Ltd., pp. 33–36.

Inoue S, Van Meerbeek B, Vargas M, Yoshida Y, Lambrechts P, Vanherle G (2000). Adhesion mechanism of self-etching adhesives. In: Advanced adhesive dentistry. Proceedings of the 3rd International Kuraray Symposium, Dec. 3–4, 1999, Granada, Spain. Tagami J, Toledano M, Prati CA, editors. Cirimido, Italy: Grafiche Erredue, pp. 131–148.

Inoue S, Vargas MA, Van Meerbeek B, Abe Y, Yoshida Y, Lambrechts P, et al. (2001). Micro-tensile bond strength of eleven modern adhesives to dentin. J Adhes Dent 3:237–246.[Medline]

Misra DN (1989). Adsorption of 4-methacryloxyethyl trimellitate anhydride (4-META) on hydroxyapatite and its role in composite bonding. J Dent Res 68:42–47.[Abstract/Free Full Text]

Nakabayashi N, Saimi Y (1996). Bonding to intact dentin. J Dent Res 75:1706–1715.[Abstract/Free Full Text]

Nakabayashi N, Kojima K, Masuhara E (1982). The promotion of adhesion by the infiltration of monomers into tooth substrates. J Biomed Mater Res 16:265–273.[ISI][Medline]

Sano H, Takatsu T, Ciucchi B, Horner JA, Matthews WG, Pashley DH (1995). Nanoleakage: leakage within the hybrid layer. Oper Dent 20:18–25.[ISI][Medline]

Sano H, Yoshikawa T, Pereira PN, Kanemura N, Morigami M, Tagami J, et al. (1999). Long-term durability of dentin bonds made with a self-etching primer, in vivo. J Dent Res 78:906–911.[Abstract/Free Full Text]

Tay FR, Pashley DH (2001). Aggressiveness of contemporary self-etching systems. I. Depth of penetration beyond dentin smear layers. Dent Mater 17:296–308.[ISI][Medline]

Van Meerbeek B, Yoshida Y, Lambrechts P, Vanherle G, Duke ES, Eick JD, et al. (1998). A TEM study of two water-based adhesive systems bonded to dry and wet dentin. J Dent Res 77:50–59.[Abstract/Free Full Text]

Van Meerbeek B, De Munck J, Yoshida Y, Inoue S, Vargas M, Vijay P, et al. (2003). Buonocore memorial lecture. Adhesion to enamel and dentin: current status and future challenges. Oper Dent 28:215–235.[ISI][Medline]

Yoshida Y, Van Meerbeek B, Nakayama Y, Snauwaert J, Hellemans L, Lambrechts P, et al. (2000). Evidence of chemical bonding at biomaterial-hard tissue interfaces. J Dent Res 79:709–714.[Abstract/Free Full Text]

Yoshida Y, Van Meerbeek B, Nakayama Y, Yoshioka M, Snauwaert J, Abe Y, et al. (2001). Adhesion to and decalcification of hydroxyapatite by carboxylic acids. J Dent Res 80:1565–1569.[Abstract/Free Full Text]

Yoshioka M, Yoshida Y, Inoue S, Lambrechts P, Vanherle G, Nomura Y, et al. (2001). Adhesion/decalcification mechanisms of acid interactions with human hard tissues. J Biomed Mater Res 59:56–62.

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