Japanese Dental Science Review (2011) 47, 31—42

a v a i l a b l e a t w w w. s c i e n c e d i r e c t . c o m

journal homepage: www.elsevier.com/locate/jdsr

Review article

New strategy to create ‘‘Super Dentin’’ using adhesive

technology: Reinforcement of adhesive—dentin
interface and protection of tooth structures
Toru Nikaido a,*, Go Inoue a, Tomohiro Takagaki a, Kanchana Waidyasekera a,
Yasuhiro Iida a, Mirela S. Shinohara b,c, Alireza Sadr d, Junji Tagami a,d

a
Cariology and Operative Dentistry, Department of Restorative Sciences, Graduate School of Medical and Dental Sciences,
Tokyo Medical and Dental University, 5-45, Yushima 1-chome, Bunkyo-ku, Tokyo 113-8549, Japan
b
Dental Materials Division, State University of Amazonas, Manaus, AM, Brazil
c
Uninorte - Laureate International Universities, Manaus, AM, Brazil
d
Global Center of Excellence Program, International Research Center for Molecular Science in Tooth and Bone Diseases,
Tokyo Medical and Dental University, 5-45, Yushima 1-chome, Bunkyo-ku, Tokyo 113-8549, Japan

Received 11 September 2009; received in revised form 7 March 2010; accepted 12 April 2010

KEYWORDS Summary Dentin bonding systems have been dramatically simplified and improved during the
Acid—base resistant zone; recent decades. Monomer penetration into dentin and its polymerization in situ creates a hybrid
Dentin bonding; layer, which is essential to obtain good bonding to dentin. Moreover, the presence of an acid—base
Hybrid layer; resistant zone below the hybrid layer has been documented with self-etching adhesive systems in
Secondary caries; an artificial secondary caries attack. When ultrastructure of the acid—base resistant zone is
Super Dentin; assessed by SEM and TEM observations, formation of the acid—base resistant zone is considered to
Adhesion be due to the monomer penetration potential and fluoride release in the adhesive systems.
Natural dentin has a limited potential to resist an acid attack of secondary caries; however, the
acid—base resistant zone does not purely consist of dentin in morphology, it is rather a
combination of dentin and the adjacent hybrid layer. Therefore, the reinforced dentin has been
called ‘‘Super Dentin’’ bearing the ability to prevent primary and secondary caries. Prospectively,
the great potential of adhesive technology in creation of the ‘‘Super Dentin’’ would lead to the
development of new materials for mechanical, chemical and biological protection of the dental
structures.
# 2011 Japanese Association for Dental Science. Published by Elsevier Ltd. All rights reserved.

* Corresponding author. Tel.: +81 3 5803 5483; fax: +81 3 5803 0195.
E-mail address: nikaido.ope@tmd.ac.jp (T. Nikaido).

1882-7616/$ — see front matter # 2011 Japanese Association for Dental Science. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.jdsr.2010.04.002
32 T. Nikaido et al.

Contents

1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
2. Classification of dentin bonding systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
3. Visualization of the hybrid layer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
4. SEM observation of the adhesive—dentin interface after acid—base challenge . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
5. Intact dentin vs caries-affected dentin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
6. Fluoride-releasing adhesive system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
7. All-in-one adhesive system. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
8. Acid etching adhesive system. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
9. TEM observation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
10. Concept of ‘‘Super Dentin’’ and clinical perspectives. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41

1. Introduction 2. Classification of dentin bonding systems

Dentin bonding systems have been dramatically simplified Several classifications of dentin bonding systems have been
and improved during the past decades. suggested in the past and in scientific literature. However, no
Monomer penetration into dentin and its polymerization in consensus concerning terminology has been reached yet [12].
situ creates a hybrid layer, which is essential to obtain good According to the concept and mechanism of the adhesive
bonding to dentin [1]. Theoretically, the hybrid layer can systems, recent dentin bonding systems can be classified into
provide marginal sealing of the cavity and resist against acid two main categories: self-etching primer systems and acid-
challenge to prevent secondary caries [2]. However, it was etching systems. The category of self-etching primer systems
reported that none of the adhesives currently available could is further divided into two sub-categories: two-step self-
completely eliminate nanoleakage along the dentin-restora- etching primer systems and one-step self-etching primer
tive interface [3]. systems, including the so-called ‘‘all-in-one adhesive sys-
The concept of minimal cavity preparation has become tems’’. A two-step self-etching primer system is composed
widely accepted for the placement of direct composite of a self-etching primer and an adhesive. The self-etching
restorations by using an adhesive system [4]. On the other primer contains one or several acidic monomers in their
hand, recurrent caries is still considered to be one of the components that can condition and prime dentin surface
major reasons for failure of resin composite restorations [5]. simultaneously. In the one-step adhesive systems, the roles
Several methods have been developed for laboratory evalua- of the self-etching primer and the adhesive are combined
tion of secondary caries, assessing demineralized lesions and into one application step. On the other hand, the category of
inhibition zones of dentin after acid challenge. These include acid-etching systems contains conventional acid-etching sys-
polarized light microscopy [6], microhardness [7], microra- tems, three-step etching/priming/bonding systems and two-
diography [8], confocal laser-scanning microscopy and the X- step etch and rinse systems, which can be recognized by an
ray analytical microscope [9]. However, each of these meth- initial etching step. Current acid-etching systems usually use
ods has its own limitations, making it difficult to obtain 30—40% phosphoric acid, which removes the smear layer,
detailed information at the interface between cavity and while concurrently demineralizing dentin over a depth of 3—
adhesive restoration. 5 mm [12]. Therefore, phosphoric acid etching is much more
Scanning electron microscopy (SEM) has been shown to be aggressive in demineralization of the dentin surface, com-
a powerful device for analyzing the ultrastructure at the pared to the self-etching primers.
dentin/adhesive interface. Using an SEM, Tsuchiya et al.
foremost observed artificial secondary caries inhibition
around restorations bonded to bovine root dentin [10]. A 3. Visualization of the hybrid layer
new zone, the so-called ‘‘acid—base resistant zone’’ (ABRZ),
was found beneath the hybrid layer in SEM observation, which As mentioned earlier, it is essential to create a hybrid layer at
was completely different from the inhibition zone formed the resin—dentin interface in order to obtain proper adhe-
due to release of fluoride from materials such as a glass- sion. The hybrid layer is created by penetration and poly-
ionomer cement; in fact, the acid—base resistant zone was merization of adhesive monomers, after removal and/or
formed in spite of the adhesive being fluoride-free [10,11]. modification of the smear layer and superficial demineraliza-
Ultrastructural assessment of the ABRZ has considerably tion of the dentin [1]. Previously, the hybrid layer between
advanced as the specimen preparation procedures for SEM dentin and an adhesive was attempted to be visualized under
and TEM observations of ABRZ are established. the SEM, using chemical and/or mechanical modifications of
This paper has reviewed the previous studies on assess- the interface.
ment of ultrastructure of the ABRZ at the adhesive—dentin In the chemical approach, the hybrid layer was subjected
interface by SEM and TEM observations. Also, the mechanism to the combination of an acidic solution, such as hydrochloric
of the ABRZ formation and a new concept of ‘‘Super Dentin’’ acid [13] and phosphoric acid [14], and sodium hypochlorite.
have been discussed. An acidic solution demineralizes the inorganic component of
New strategy to create ‘‘Super Dentin’’ 33

dentin structure and removes hydroxyapatite, leaving a new approach for ultrastructural assessment of the inter-
organic dentin components. Sodium hypochlorite was used face was required.
to remove the demineralized collagen to enable a clear
visualization of the hybrid layer. Therefore, by definition,
the hybrid layer is characterized as a layer resisting against 4. SEM observation of the adhesive—dentin
acid challenge [1]. interface after acid—base challenge
As for the mechanical approach, argon-ion beam etching
has been used to clearly reveal the hybrid layer at the resin— Tsuchiya et al. reported the presence of an ABRZ below the
dentin interface [15]. Roughening of the hybrid layer through hybrid layer with self-etching adhesive systems subjected to
argon-ion beam etching seems to be caused by selective an artificial secondary caries attack [10]. However, morpho-
removal of the impregnated resin component in deminera- logical characteristics of this zone were highly material-
lized dentin. As a result of the edge effect of the etched dependent. The caries-like challenges at the adhesive—den-
surface, this layer was clearly distinct in the secondary tin interface can elucidate certain basic physico-chemical
electron image of the interface [15]. principles governing dissolution of the interfacial structures,
In acid-etching systems, it was possible to clearly identify which may be different from the in situ situation, due to lack
the hybrid layer by such chemical or mechanical modification of saliva and pH cycling.
techniques. However, as for mild self-etching primer adhe- Inoue et al. established the procedures for specimen pre-
sive systems, SEM observation of the hybrid layer using such paration of the adhesive—dentin interface after acid—base
methods encountered limitations, since the hybrid layer challenge to visualize the secondary caries inhibition around
classically observed as a distinguished layer in former gen- the adhesive—dentin interface [11]. The sample preparation
erations of dentin adhesives was very thin for these systems. for SEM examination of the ABRZ, as they suggested, was
With the development of mild and simplified dentin bonding illustrated in Fig. 1; human molars, obtained with the patients’
procedures, the observation method for interfaces between informed consent, were sectioned at the mid coronal portion,
tooth substrates and adhesive resins has shifted from SEM to vertical to the tooth axis, with a low-speed diamond saw
transmission electron microscopy (TEM), which provides an (Isomet, Buehler, Lake Bluff, IL, USA) to obtain 1-mm thick
images with more details interfacial characteristics. dentin disks. The dentin surfaces were ground with #600-grit
Koshiro et al. reported that the interface formed by the silicon carbide paper under running water. One surface of each
all-in-one adhesives were extremely thin (300 nm or less). disk was treated with an adhesive system according to the
They proposed that these adhesive systems should be cate- manufacturer’s instructions. A flowable resin composite was
gorized as ‘‘Nanointeraction Zone’’ type [16]. In this regard, then placed between pairs of the prepared dentin disks and

Figure 1 Specimen preparation for SEM observation (Inoue et al. [11]).

34 T. Nikaido et al.

light-cured to make a dentin disk sandwich. After storing for affected dentin. These measurements were similar to the
24 h in distilled water, each prepared specimen was sectioned previous studies [22,23]. In addition, an ABRZ was observed
perpendicular to the adhesive—dentin interface with a dia- beneath the hybrid layer (H) in SEM micrographs of both the
mond saw and embedded with an epoxy resin (Epoxicure Resin, intact and caries-affected dentin specimens. An ABRZ,
Buehler). approximately 1 mm thick, was observed beneath the hybrid
Each specimen was first stored in 100 ml of a buffered layer (H) for the intact dentin, while a thicker ABRZ, approxi-
demineralizing solution, containing 2.2 mmol/L CaCl2, mately 1.5 mm thick, was created in the caries-affected
2.2 mmol/L NaH2PO4 and 50 mmol/L acetic acid adjusted dentin.
at pH 4.5 for 90 min to create artificial secondary caries [17]. The mechanism of action for this two-step self-etching
The specimens were then immersed in 5% NaOCl for 20 min in primer adhesive involves dissolution of the smear layer and
an attempt to remove any demineralized dentin collagen demineralization of the underlying dentin by an acidic mono-
fibrils, and rinsed with running water for 30 s. Following this, mer, namely 10-methacryloxydecyl dihydrogenphosphate
a self-curing adhesive resin, 4-META/MMA-TBB resin (Super (MDP) in the primer, resulting in mild surface etching. For-
Bond C&B, Sun Medical, Moriyama, Japan), was applied with- mation of an ABRZ by Clearfil SE Bond would be related to the
out acid etching of the treated surface in order to prevent penetration of the adhesive, but also to the quality of the
wear of the adhesive during polishing, as the edge of the hybrid layer (H).
adhesive could be torn away during specimen polishing [11]. Since the caries-affected intertubular dentin is already
After curing of the 4-META/MMA-TBB resin, the specimens partially demineralized and more porous, caries-affected
were sectioned perpendicular to the dentin—adhesive inter- dentin is softer than normal dentin [24,25]. Thus, the inter-
face, and reduced to approximately 1 mm thickness, then tubular dentin in caries-affected dentin should be more
polished with diamond pastes (Struers A/S, Copenhagen, permeable to the primer than in normal dentin. Moreover,
Denmark) down to 0.25 mm grit size. The polished surfaces the smear layer of caries-affected dentin might be more
were etched with an argon-ion beam (EIS-IE, Elionix, Tokyo, porous than that of normal dentin [21]. Therefore, it was
Japan) for 6 min to bring the hybrid layer into a sharp relief. suggested that resin monomer could penetrate deeper into
Operating conditions for the argon-ion beam etching were an caries-affected dentin than intact dentin, resulting in a
accelerating voltage of 1 kV and an ion current density of thicker hybrid layer (H) in caries-affected dentin.
0.2 mA/cm2, with the ion beam directed perpendicular to the In the mentioned study, the ABRZ and the surrounding
polished surface. The specimens were then gold-sputter lesion were also characterized by the nanoindentation tech-
coated, and morphological changes to the dentin—adhesive nique. The mean values of the nanoindentation test (Fig. 3)
interface due to acid—base challenge were observed using a demonstrated differences in the microhardness between the
SEM (JSM-5310LV, JOEL, Tokyo, Japan). The procedure intact and caries-affected dentin specimens. As expected,
became a standard for ABRZ observation studies carried microhardness of the intact dentin area was significantly
out since then. The adhesive materials used for morpholo- higher than that of the caries-affected dentin [26]. Interest-
gically analysis of an ABRZ are listed in Table 1. ingly, the area 2 mm beneath the hybrid layer (H) in caries-
affected dentin indicated a significantly higher microhard-
ness compared to other dentin areas. This zone was coincid-
5. Intact dentin vs caries-affected dentin ing with the ABRZ in the SEM observation (Fig. 2).
Dentin microhardness around the hybrid layer (H) was
Inoue et al. observed the ultrastructures of the interface approximately 35 mgf/mm2 for both the intact and caries-
between intact or caries-affected dentin and a two-step self- affected groups. In addition, microhardness values of the
etching primer adhesive system [11]. In that experiment, adhesive and the resin composite were approximately
Clearfil SE Bond (Kuraray Medical, Tokyo, Japan) was used. 27 mgf/mm2 and 36 mgf/mm2, respectively, in both intact
This system is a fluoride-free two-step self-etching primer and caries-affected dentin. Higher microhardness of the
system. A good bonding to human sound dentin with a self- caries-affected dentin 2 mm beneath the hybrid layer sup-
etching primer system has already been demonstrated in ported the theory that the ABRZ was composed of penetrated
numerous laboratory studies [18—20] However, the tensile monomer and dentin [11].
bond strength of a self-etching primer adhesive system to the Secondary caries begins at the margin between dentin and
caries-affected dentin was lower than that to the normal the restorative material. In this study resin—dentin interface
dentin [21,22]. of the tested adhesive demonstrated resistance against
Fig. 2 demonstrated SEM images at the interface between acid—base challenge much more than both intact and car-
the adhesive and intact dentin (a, left) and between the ies-affected dentin. Thereby, the paper suggested that for-
adhesive and caries-affected dentin (b, right), respectively. mation of an outer lesion away from the margins around the
In the results, the outer lesion, which is the dentin surface restoration should be primary caries rather than secondary
demineralized to simulate caries dentin lesion, was observed caries [11]. In this regard, it could be stated that formation of
in both intact and caries-affected dentin. The depth of the an ABRZ is important in the prevention of secondary caries
outer lesion ranged from 10 mm to 15 mm, in which there was around a restoration.
no difference between intact and caries-affected dentin.
The adhesive demonstrated a good resistance to the acid—
base challenge in the intact and caries-affected dentin speci- 6. Fluoride-releasing adhesive system
mens. The hybrid layer detected after argon-ion etching (H)
was approximately 1 mm thick for the intact dentin, while a To date, manufacturers have been trying to develop various
slightly thicker hybrid layer (H) was observed for the caries- fluoride-releasing adhesive systems and resin composites
New strategy to create ‘‘Super Dentin’’ 35

Table 1 Adhesive systems previously evaluated for ultrastructure of the acid—base resistant zone.

Adhesive system Manufacturer Components Reference

Absolute 2 Dentsply-Sankin, acetone, water, [42]
Tokyo, Japan pyrophosphatetetramethacrylate,
4-MET, PEM-F, UDMA, nanofillers,
CQ, stabilizers
AQ Bond Plus Sun Medical, Moriyama, Liquid: water, acetone, 4-META, [43]
Japan polyfunctional acrylate,
monomethacrylate, photo-initiators
Sponge; p-toluene sulfinate salt, amine
Clearfil Protect Bond Kuraray Medical Primer: MDPB, MDP, HEMA, hydropilic [10,33,48]
dimethacrylate, water
Tokyo, Japan Adhesive: MDP, HEMA, hydropilic
dimethacrylate, PI, microfiller, NaF
Clearfil SE Bond Kuraray Medical Primer: MDP, HEMA, hydropilic [10,11,33,34,43,48]
dimethacrylate, water, PI
Tokyo, Japan Adhesive: MDP, HEMA, hydrophilic
dimethacrylate, PI,
Bis-GMA, microfiller
Clearfil Tri-S Bond Kuraray Medical, MDP, HEMA, Bis-GMA, hydrophobic [40]
Tokyo, Japan dimethacrylate, sillanated colloidal
silica, camphorquinone, ethanol, water
FL-Bond Shofu FB Primer A: water, solvent, initiator [34]
Kyoto, Japan FB Primer B: 4-AET, 4-AETA, HEMA,
UDMA, TEGDMA, initiator
Bond: HEMA, UDMA, TEGDMA,
F-PRG filler, photo-initiator
FL-Bond II Shofu, Kyoto, Japan Primer: carboxylic acid monomer, [34]
6-MHPA, Water, solvent, photo-initiator
Bond: HEMA, UDMA, TEGDMA, S-PRG filler,
photo-initiator
G-Bond GC, Tokyo, Japan 4-MET, phosphate acid monomer, [40]
UDMA, silica, photo-initiator, acetone, water
Reactmer Bond Shofu, Kyoto, Japan A: distilled water FASG, F-PRG filler, CA [10]
B: 4-AET, 4-AETA, HEMA, UDMA, Pl
Single Bond 3M ESPE, St. Paul, MN, USA Etchant: 35% phosphoric acid gel [10,43,48]
Adhesive: Bis-GMA, HEMA, polyalkenoic
acid copolymer, ethanol, water, PI
Super Bond C&B Sun Medical, Moriyama, Conditioner: 10% citric acid with 3% [44]
Japan ferric chloride
Powder: PMMA, Liquid: MMA, 4-META
Catalyst: TBB
SI-R20603 (experimental) Shofu, Kyoto, Japan solvent, water, phosphonic acid, [42]
monomer, carboxylic acid monomer,
polymeric monomer, photo-initiator, others
Tokuyama Bond Force Tokuyama Dental, isopropyl alcohol, water, 3D SR [42]
Tokyo, Japan monomer, Bis-GMA, TEGDMA, HEMA,
glass fillers, photo-initiators
Abbreviations: 4-AET (4-AETA): 4-acryloxyethyltrimellitic acid (anhydride); Bis-GMA: bisphenol-A-glycidyl dimethacrylate; CA: catalyst;
CQ: camphorquinone; 3D-SR: 3D self-reinforcing; FASG: fluoroalminosilicate glass; HEMA: 2-hydroxyethyl methacrylate; MDP: 10-metha-
cryloxydecyl dihydrogenphosphate; MDPB: 12-methacryloyloxydodecylpyridinium bromide; 6-MHPA: 6-methacryloyloxyhexcyl phospho-
noacetate; 4-MET (4-META): 4-methacryloxyethyl trimellitate (anhydride); MMA: methylmethacrylate; PMMA: poly methylmethacrylate; PI:
photo-initiator; PRG: pre-reacted glass ionomer (F: full, S: surface); PEM-F: fluoromethacryloxy cyclophosphazen; TEGDMA: triethylene
glycol dimethacrylate; TBB: tri-n-butyl borane; UDMA: urethane dimethacrylate.
36 T. Nikaido et al.

Figure 2 SEM observations at the interface between Clearfil SE Bond and dentin after acid—base challenge (3500) (Inoue et al.
[11]). (a) Intact dentin and (b) caries-affected dentin. OL: outer lesion; B: adhesive; H: hybrid layer; ABRZ: acid—base resistant zone;
D: dentin. An acid—base resistant zone (ABRZ), approximately 1 mm thick, was observed beneath the hybrid layer (H) for the intact
dentin (left), while a thicker acid—base resistant zone, approximately 1.5 mm thick, was created in the caries-affected dentin (right).

[27]. Studies have reported that fluoride-containing dentin adhesive has a fluoride-releasing component (treated sodium
adhesive may release fluoride into marginal gap and it may fluoride). The SEM analysis showed that the adhesive layer
have a beneficial effect on the adjacent demineralized and hybrid layer were not damaged after acid—base chal-
enamel and dentin [28,29]. Nakajima et al. [30] reported lenge. A thin hybrid layer, approximately 0.5 mm thick could
that the durability of dentin bonding created by a fluoride- be observed. As pointed out, the interfaces of Clearfil Protect
releasing adhesive was improved for the six-month storage Bond group sharply demonstrated formation of a thick ABRZ
compared with a fluoride-free adhesive. They hypothesized (over 1.0 mm thick) adjacent to the hybrid layer. In addition,
that the fluoride somehow prevented the degradation of the ABRZ observed a slope increase in the thickness from the
dentin, resulting in improvement of long-term stability at top towards the bottom of the outer lesion. Thereby, it was
the adhesive interface. Toba et al. [31] stated using confocal speculated that the formation of a thick ABRZ was related
laser-scanning microscopy that a fluoride-releasing adhesive with fluoride release in the adhesive resin [33], because of
system demonstrated the potential for artificial secondary the formation of a thicker ABRZ took place only when the
caries inhibition around the restoration, although thickness fluoride-containing adhesive was used.
of the inhibition zone had been relatively thinner than those Iida et al. verified the dentin bond performance and the
created with the conventional glass-ionomer cements formation of the ABRZ at the bonded interface of two-step
[8,32]. self-etching primer adhesive systems, Clearfil SE Bond, FL-
Knowing that the ABRZ was basically different in nature Bond and FL-Bond II (both the latter by Shofu Inc., Kyoto,
from the fluoride-inhibition zone, questions were raised on Japan) [34]. FL-Bond and FL-Bond II are fluoride-releasing
the possible effect of fluoride release from an adhesive on systems, which have fluoride-releasing components of F-PRG
the formation of the ABRZ. Shinohara et al. performed an filler and S-PRG filler, respectively. These filler particles were
experiment using different self-etching primer systems and created by pre-reacted glass ionomer (PRG) technology
reported that a thicker ABRZ adjacent to the hybrid layer [35,36]. Similar to the observation of the former study by
could be observed only when a fluoride-releasing adhesive Shinohara and others, the ABRZ of FL-Bond II sloped and
was used (Fig. 4a) [33]. increased in thickness from the top to the end of outer lesion
In their study, Clearfil Protect Bond (Kuraray Medical) was (Fig. 4b), while the ABRZs of Clearfil SE Bond and FL-Bond
used as the fluoride-releasing adhesive system. The primer of were parallel to the hybrid layer and homogeneous. It was
this system has an antibacterial monomer (MDPB) and the speculated that the gradual increase in the ABRZ thickness

Figure 3 Mean value of microhardness at the adhesive—dentin interface (Inoue et al. [11]). Adhesive: Clearfil SE Bond. The area 2 mm
beneath the hybrid layer (H) in caries-affected dentin indicated a significantly higher microhardness compared to other dentin areas.
This zone was coinciding with the acid—base resistant zone (ABRZ) in the SEM observation (see Fig. 2).
New strategy to create ‘‘Super Dentin’’ 37

Figure 4 SEM observations at the interface between a fluoride-releasing adhesive and dentin after acid—base challenge. (a) Clearfil
Protect Bond (3500) (Shinohara et al. [33]) and (b) FL-Bond II (5000) (Iida et al. [34]). OL: outer lesion; B: adhesive; H: hybrid layer;
ABRZ: acid—base resistant zone; D: dentin. ABRZ adjacent to the hybrid layer could be observed only when the fluoride-releasing
adhesive was used.

was not observed in FL-Bond, which may have been due to that of the etchants in the acid-etching systems, such as
insufficient fluoride release from the FL-Bond adhesive. phosphoric and citric acids [39]. Therefore, all-in-one adhe-
Adding up the findings of the mentioned studies, it was sive systems demineralize dentin partially, leaving mineral
suggested that the ABRZ formation is due to the monomer crystals in the hybrid layer.
penetration, and fluoride release contributes to the process. Representative SEM pictures of the dentin—adhesive
interfaces in Clearfil Tri-S Bond and G-Bond after acid—base
7. All-in-one adhesive system challenge are shown in Fig. 5 [40]. For Clearfil Tri-S Bond
(Fig. 5a) and G-Bond (Fig. 5b), the thickness of both adhe-
In order to simplify the bonding procedures, all-in-one adhe- sives was less than 10 mm, respectively. A hybrid layer dis-
sive systems have been developed and commercialized. All-in- tinguished by argon-ion beam etching (H) was hardly
one adhesives contain acidic monomers, water, and solvents in observed at the interface. An ABRZ was observed beneath
order to create a bond between tooth substrate and resin the hybrid layer, which was approximately 1 mm thick (white
composite by a single step. These systems may be advanta- triangles) for both materials. However, the thickness of the
geous for clinicians in saving time. However, the adhesive resin ABRZ was adhesive material-dependent.
layer of the all-in-one adhesives is permeable and allows the In all-in-one adhesives, hydrophobic and hydrophilic resin
formation of a water channel or water tree [37,38]. components are intermixed prior to polymerization. Phase
Two well-known examples for these systems are Clearfil separation can occur as the solvent — alcohol or acetone — is
Tri-S Bond (Kuraray Medical) and G-Bond (GC Corp., Tokyo, evaporated. The larger portion of adhesive solvents is
Japan). They both are fluoride-free all-in-one adhesive sys- removed by air drying after adhesive application, but resi-
tems, which contain acidic monomers of MDP and 4-META, dual water still persists due to lowering of the vapor pressure
respectively. As mentioned in previous sections, acidic mono- of water by HEMA. It is known that monomers can infiltrate
mers play roles to condition and prime dentin simultaneously. deeper than the hybrid layer, and that water inhibits poly-
However, the acidity of these adhesive systems did not reach merization of the adhesives. So it is possible to speculate that

Figure 5 SEM observations at the interface between an all-in-one adhesive and dentin after acid—base challenge (3500) (Nikaido
et al. [40]) (3500). (a) Clearfil Tri-S Bond and (b) G Bond. A hybrid layer distinguished by argon-ion beam etching (H) was hardly
observed at the interface. An ABRZ was recognized beneath the hybrid layer, which was approximately 1 mm thick. It was very hard to
detect the hybrid layer (H). An ABRZ (white triangles) was recognized beneath the hybrid layer.
38 T. Nikaido et al.

Figure 6 SEM observations at the interface between 4-META/MMA-TBB resin and dentin after acid—base challenge (3500) (Takagaki
et al. [44]). (a) No treatment (NT), (b) 65% phosphoric acid for 10 s (PA), and (c) 10% citric acid—3% ferric chloride (10-3) for 10 s. In the
NT group, the hybrid layer was not created at the interface, however, wall lesion (WL) was observed along to the interface (a).
Formation of the hybrid layer (H) was observed in both the PA (b) and 10-3 (c) groups; however, an acid—base resistant zone was not
detected in any of the groups.

a weak area beneath the hybrid layer and ABRZ may be on the ground dentin surface prevented monomer penetra-
created, which is partially demineralized, while the pene- tion into underlying dentin. In the SEM observation after
trated monomers are not completely polymerized [41], due acid—base challenge, no hybrid layer formation was
to the phase separation and water existence. In contrast to observed. However, wall lesions were found along the inter-
the ABRZ, it is reasonable to assume that this area is probably face (Fig. 6a). Formation of wall lesion suggested that the
more vulnerable to acid challenge, resulting in the formation interface without hybrid layer could not resist against acid—
of typical erosion areas beneath the ABRZ in some adhesive base challenge, indicating that a dentin margin without a
systems [42,43]. hybrid layer would suffer secondary caries in the oral envir-
onment.
8. Acid etching adhesive system The hybrid layer was recognized in both 10-3 and PA.
However, thickness of the hybrid layer with PA was 2 mm,
The ABRZ was discovered using a self-etching primer system. while thickness with the 10-3 was 1 mm (Fig. 6b and c), the
It was initially thought that the ABRZ may be specifically difference in thickness must be due to different acidity in two
formed below the hybrid layer of adhesives that do not solutions.
require acid etching of dentin. In order to probe this spec- Based on the results of the studies mentioned in the
ulation and further clarify the attributes of this zone, Taka- previous sections, an ABRZ was formed beneath the hybrid
gaki et al. evaluated the ultrastructural change of the layer with a self-etching primer adhesive system. However,
adhesive—dentin interface after acid—base challenge using the ABRZ was not observed in the acid-etching system
an acid etching adhesive system, 4-META/MMA-TBB resin with [10,43,44]. Schematic summary of the results of acid—base
three different conditions [44]. Super Bond C&B is methyl- challenge was shown in Fig. 7 [44]. It was suggested that the
methacrylate (MMA)-based, and contains a chemical initiator existence of the ABRZ could be related to monomer penetra-
of a tri-n-butyl borane (TBB) derivative and a functional tion into the partially demineralized dentin, only when a self-
monomer of 4-methacryloxyethyl trimellitate anhydride etching primer adhesive system was used. Further evidence
(4-META), giving an excellent adhesion to dentin, when to support their speculations will be presented in the TEM
dentin surface is pretreated with citric acid solution contain- observation section.
ing ferric chloride [45—47].
The dentin surfaces received one of the following pre- 9. TEM observation
treatments: no treatment (NT), 65% phosphoric acid for 10 s
(PA) or 10% citric acid—3% ferric chloride for 10 s (10-3). After As pointed out in Section 1, TEM has become a valuable tool in
application of PA or 10-3, the dentin surfaces were rinsed the ultrastructural observation of resin—dentin interfaces.
with water and gently air-dried. The mixture of liquid and Waidyasekera et al. used two self-etch adhesive systems, and
powder of Superbond C&B was applied on dentin surface with an acid-etch adhesive system in order to elucidate the
a brush-on technique according to the manufacturer’s laboratory artificial caries inhibition properties of the rein-
instructions to bond a PMMA rod. The bonded specimens forced dentin with the evidence of TEM ultramorphology
were left at room temperature for 30 min to secure the [48].
initial polymerization, and then stored in distilled water at Sample preparation for TEM examination of the ABRZ in
37 8C for 24 h. their experiment was basically similar to the procedure
The SEM photographs of the adhesive—dentin interface established for ABRZ observation using the SEM, as illustrated
after acid—base challenge are revealed in Fig. 6. In the NT in Fig. 8. Dentin surfaces were treated with one of three
group, the hybrid layer was not created at the interface, dentin adhesives, Clearfil SE Bond, Clearfil Protect Bond, and
however, wall lesion (WL) was observed along the interface. Single Bond (3M ESPE, St. Paul, MN, USA). For the acid—base
Formation of the hybrid layer was observed in both the 10-3 challenge, each specimen was stored in the buffered demi-
and PA groups; however, an ABRZ was not detected in any of neralizing solution for 90 min and 5% NaOCl for 20 min. After
the groups. sectioning and drying, the TEM specimen preparation was
Nevertheless, without surface conditioning (NT), 4-META/ performed in accordance with common procedures used for
MMA-TBB resin could not bond to dentin, because smear layer ultrastructural TEM examination of biological tissues. In this
New strategy to create ‘‘Super Dentin’’ 39

Figure 7 Schematic summary of the results of acid—base challenge (Takagaki et al. [44]). (a) No treatment, (b) acid-etching system,
and (c) self-etching system. Hybridization is essential to prevent secondary caries. However, an acid—base resistant zone (ABRZ) was
not observed in the acid-etching system. The ABRZ was formed only with a self-etching system.

regard, twenty specimens, each 100 nm in thickness, were deep that the bottom of the demineralized dentin would be
observed under a transmission electron microscope (Hitachi inaccessible to complete impregnation by the resin [49]. In
H-600, Hitachi, Tokyo, Japan) in an accelerating potential of this case, a collagenous band at the base of the hybrid layer
75 kV and objective aperture diameter of 100 mm. will not be impregnated by the resin. Signs of this incomplete
Results of the TEM observations of the adhesive—dentin resin penetration were observed as a nanoporous zone pre-
interface after acid—base challenge are shown in Figs. 9 and sent at the base of the hybrid layer [50], which could become
10. Moreover, selected area electron diffraction (SAED) pat- a pathway for nanoleakage fluid [51]. This incompletely
terns obtained from a small crystal cluster at the ABRZ in the sealed interface may have facilitated the acid penetration
two self-etching systems are shown in Fig. 11. The peak vigorously and given rise to the demineralization of the
positions (d-spacing) 0 0 2 and 2 1 1 were identical, which dentin below the hybrid layer.
suggested the presence of hydroxyapatite in the ABRZ. On the other hand, this study evidently proved that the
The acid-etch system, Single Bond, did not show an ABRZ self-etch adhesive systems demineralize dentin mildly and
in this study (Fig. 9). This result was in accordance with the partially, leaving hydroxyapatite crystals in the base of the
previous SEM studies on acid-etch systems [10,43]. As pointed hybrid layer (Fig. 10) [52]. Such residual apatite crystals may
in the previous section of the current review, when the serve as a template for additional chemical reaction with the
surface is aggressively etched using an inorganic acid, the functional monomer, such as MDP in Clearfil SE Bond and
underlying dentin may become completely demineralized so Clearfil Protect Bond. It has been reported that MDP adhered

Figure 8 Specimen preparation for TEM observation (Waidyasekera et al. [48]).

40 T. Nikaido et al.

Figure 9 TEM observation at the interface between Single

Bond and dentin after acid—base challenge (5000) (Waidyase-
kera et al. [48]). OL: outer lesion; B: adhesive; H: hybrid layer; D: Figure 11 SAED pattern obtained for the apatite crystallites in
dentin. Single Bond did not show an acid—base resistant zone. the acid—base resistant zone of dentin treated with Clearfil SE
Bond (Waidyasekera et al. [48]). The peak positions (d-spacing)
to hydroxyapatite readily and intensively [53], forming a less 0 0 2 and 2 1 1 were identical, which suggested the presence of
soluble salt, compared to the functional monomers, such as hydroxyapatite in the ABRZ.
4-MET (hydrated 4-META) and 2-(methacryloxy) ethylphenyl
hydrogenphosphate (Phenyl-P) [52]. In these self-etch adhe- [10,11,33,34,43]. The top area of the ABRZ was exposed
sives, the ABRZ was detected in the TEM observations, which to the acid attack for a longer period than the mid and bottom
were in accordance with the previous SEM studies portions, where the electron dense region contained a few
haphazardly arranged apatite crystallites with partial dissolu-
tion. On the other hand, the bottom area of ABRZ showed
densely packed crystallites. These regions with apatite crys-
tallites were continuous with the dentin, although the dentin
below (outer lesion) is demineralized and dissolved.
As previously mentioned, Clearfil Protect Bond is a fluor-
ide-ion releasing adhesive system [33]. Fluoride ions are
reported to increase the rate of calcium phosphate crystal-
lization and decrease the rate of apatite dissolution [54].
Dentin decalcified by acids is more sensitive to react with
fluoride due to the increased porosity [55]. It was assumed in
this study that the theory for reduced tendency of the apatite
crystal dissolution in the presence of fluoride ions may be
applicable for the formation of the thickest ABRZ observed
with Clearfil Protect Bond, which has resulted to a better
reinforced dentin. Formation of acid resistant fluoroapatite
may be another possibility for this finding. But further differ-
entiation among pure hydroxyapatites, carbonated apatites
and fluoroapatites should be performed in the future.
This suggests that the ABRZ is not purely composed of
dentin, but is rather a combination of dentin and the adja-
cent hybrid layer, which is said to be acid resistant [49] and
created by penetration and polymerization of adhesive
monomers after demineralization of dentin [53].
Figure 10 TEM observation at the interface between Clearfil SE
Bond and dentin after acid—base challenge (5000) (Waidyase-
kera et al. [48]). OL: outer lesion; B: adhesive; H: hybrid layer; 10. Concept of ‘‘Super Dentin’’ and clinical
ABRZ: acid—base resistant zone; D: dentin. In the top area of ABRZ, perspectives
the electron dense region contained a few haphazardly arranged
apatite crystallites with partial dissolution, while the bottom area As the studies reviewed suggested, the detailed mechanism for
of ABRZ showed densely packed crystallites. These regions with the ABRZ formation has not been understood yet; however, it is
apatite crystallites were continuous with the dentin. considered to be associated with monomer penetration deeper
New strategy to create ‘‘Super Dentin’’ 41

than previously expected. In addition, formation of the ABRZ [8] Torii Y, Itota T, Okamoto M, Nakabo S, Nagamine M, Inoue K.
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