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Endodontic Topics 2012, 21, 62–88 2012 © John Wiley & Sons A/S
All rights reserved ENDODONTIC TOPICS 2012
1601-1538

Dentin as a bonding substrate

RICARDO M. CAR VALHO, LEO TJÄDERHANE, ADRIANA P. MANSO,
MARCELA R. CARRILHO & CARLOS AUGUSTO R. CAR VALHO

Dentin comprises the largest dental structure available for bonding. Because of its inherent morphological and
physiological characteristics, reliable and durable resin–dentin bonding remains a challenging accomplishment
that is subjected to multi-factorial interferences. Adhesive technology has evolved significantly over the past
decade, resulting in improved predictability of resin–dentin bonds. This article reviews the present knowledge
regarding resin–dentin bonding from the perspective of the dentin substrate. Since another article in the previous
issue of Endodontic Topics already covers dentin structure and composition, the intention is not to fully review
these aspects. Instead, basic principles of current bonding strategies used by adhesive agents are presented. Specific
attention is given to describing how the morphology and physiology of dentin affect existing bonding
mechanisms, how some chemical treatments of dentin can affect its properties and bonding, and finally how
bonding to root canal dentin is currently viewed and understood.

Received 27 October 2011; accepted 2 February 2012.

Introduction Dentin composition and

Dentin comprises most of the tooth tissue. It has a
tubular structure that is intimately connected to the
pulp, and the harder enamel externally protects both.
With few exceptions, most of the adhesive procedures
in dentistry involve bonding to dentin. Dentin is a
dynamic substrate (1) and its morphology and physi-
ology directly affect the ability of adhesive systems
to produce durable bonds to its prepared surfaces.
This article reviews the present knowledge of dentin
as a bonding substrate, mostly focusing on how
dentin reacts to existing bonding strategies, how
physiologically and pathologically induced structural
and morphological changes affect bonding, and how
surface pre-treatments modify the receptiveness of
dentin to adhesives. Lastly, some current aspects of
bonding to root dentin are also reviewed and dis-
cussed. There was no intention to fully review all
aspects of bonding to dentin. There are several reviews
available on the topic that we highly recommend for
those who are interested in more detailed information
about adhesives and bonding strategies (2–8). Also,
this double issue of Endodontic Topics presents a
unique selection of review articles that, together, rep-
resent what is currently known about dentin.
morphology
Dentin has an intimate relationship with pulpal tissue
in terms of embryological development and function:
they form the dentinal–pulp complex and are not
dissociable with respect to dental therapy. Human
dentin is composed of approximately 70 w% of inor-
ganic material, 18 w% of organic material, and 12 w%
of water. When volumes are considered, organic
material and water occupy the majority of the tissue
(Table 1). These percentage ratios vary widely with the
location and condition of the dentin. For instance,
when dentin is demineralized, the water concentration
increases significantly from 20% to about 50–70% by
volume (9), which is a significant change in composi-
tion that has profound implications in the mechanical
properties of dentin and in the entire adhesive process.
Morphology and permeability
Dentin has a tubular structure and each tubule has an
inverted-cone shape, with the larger diameter facing
the pulp. As the inner dentinal surface area facing the
pulp is smaller than the external surface area facing the
dentin–enamel junction (DEJ), tubules are arranged

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 Dentin bonding

in a radial disposition, which determines the significant
regional variations in tubule concentration by surface
area. Near the pulp, the area occupied by dentinal
tubules reaches 22% while near the DEJ it represents
only 1% of the dentin surface (10,11). Each tubule is
internally surrounded by peritubular dentin, a cuff
rich in mineral content and having a variable width
according to its location along the tubule. Conversely,
intertubular dentin is rich in organic material (mostly
collagen fibrils) and plays a fundamental role in adhe-
sive procedures. Considering that dentin permea-
bility occurs primarily via dentinal tubules, regional
variations in the caliber and density of tubules cause
significant and proportional changes in dentin perme-
ability (12). Additionally, when dentin is acid-etched,
compositional characteristics are modified and a sig-
nificant increase in permeability occurs. Variations in
the morphology and permeability of dentin directly
Table 1: Basic composition of mineralized dentin
Inorganic Organic
% by weight 70 18
% by volume 30–50 30–50
Carvalho et al., 1996 (9); Marshall et al., 1997 (16).
affect bonding (2,13). As will be further discussed in
this article, such variations are important factors to be
considered during adhesive procedures with dentin.
Table 2 illustrates superficial changes that occur as a
function of location and acid treatment in dentin. The
relationship between morphology and permeability
and how that affects adhesion have been thoroughly
discussed elsewhere (12).
Mechanical properties
Although several research groups have investigated the
mechanical properties of dentin in the past, the topic has
recently gained more importance as a method of analyz-
ing and better understanding the adhesive mechanisms
of this substrate (14–16). Dentinal microstructure and
mechanical properties are determinants for most proce-
dures in restorative dentistry (15,16). Regional differ-
ences in the relative composition of dentin result in
significant differences in mechanical properties between,
for example, superficial and deep dentin, coronal and
Water radicular dentin, and also according to the orienta-
12
tion and distribution of dentinal tubules (16–26).
Physiological and pathological processes such as aging,
20 sclerosis, and dental caries can also induce significant
alterations in the mechanical properties of dentin (27–
31) (Table 3). Chemicals usually employed in dental

Table 2: Changes in the area occupied by tubules, peritubular dentin, and intertubular dentin before (B) and after
(A) acid-etch, as a function of location
Percentage of surface area
Radius of
tubules (mm) Tubules Peritubular Intertubular
Distance from Number of
pulp (mm) tubules / cm2 B A B A B A* B A

Pulp 4.5 ¥ 10 6
1.25 1.5 22.1 33.8 66.3 – 11.6 66.2

0.1–0.5 4.3 ¥ 106 0.95 1.5 12.2 30.4 36.6 – 51.2 69.6

0.6–1.0 3.8 ¥ 10 6
0.80 1.5 7.6 26.9 22.9 – 69.4 73.1

1.1–1.5 3.5 ¥ 106 0.60 1.5 4.0 24.7 11.9 – 84.2 75.3

1.6–2.0 3.0 ¥ 10 6
0.55 1.5 2.9 21.2 8.5 – 88.6 78.7

2.1–2.5 2.3 ¥ 106 0.45 1.5 1.5 16.2 4.4 – 94.2 83.9

2.6–3.0 2.0 ¥ 10 6
0.40 1.5 1.0 14.1 3.0 – 96.0 85.9

3.1–3.5 1.9 ¥ 106 0.40 1.5 1.0 13.4 2.9 – 96.2 86.6

Adapted from Nakabayashi & Pashley, 1998 (11).

* Assumes the more mineralized peritubular dentin is completely dissolved by the etchant.

63
Carvalho et al.
Table 3: Mechanical properties of dentin
Mechanical property Mineralized dentin
Microtensile strength (MPa)* 60–100
50–55 (caries affected)
Modulus of elasticity* 13–18 Gpa
Microhardness (Knoop) 60–70
Density (g/cm3) 2.01
* Data obtained by microtensile bond strength method.
† Superficially acid-etched with phosphoric acid.
therapy such as whitening products, cleansing agents,
etc. also affect the properties of dentin. The implica-
tions of these alterations on the ability of adhesives to
bond to dentin will be discussed later on in this review.
Principles of adhesion to dentin
Bonding to dentin can currently be regarded as a form
of tissue engineering (8). It is essentially accomplished
by an exchange mechanism that replaces mineral with
resin monomers to form a new biocomposite made
out of collagen fibrils and cured resin (32,33). Unlike
classical tissue engineering, this new biocomposite is not
intended to be resorbed and replaced by normal dentin.
Instead, it is expected to form a tight and permanent
connection between dentin and composite resins.
The first step in conventional etch-and-rinse
bonding to dentin is the creation of pathways for resin
infiltration. This is traditionally accomplished by treat-
ing dentin with acidic solutions. This dissolves the
mineral content of the top 5–8 mm of dentin and
leaves behind a porous network of highly cross-linked
type I collagen suspended in water (34). The next step
is the infiltration of resin monomers. Ideally, resin
monomers should be able to displace water within and
around the collagen fibrils without reducing the size of
the already small porosities created by acid etching
and completely replace that water with the infiltrating
resin. When infiltration is complete, light activation
is applied to cure the resin and result in a polymer–
collagen biocomposite also known as the hybrid layer
or resin-interdiffusion zone (32,33) (Fig. 1). Self-etch
adhesive systems share the same ultimate objective
64
Demineralized dentin Authors
10–25 Sano et al., 1994 (18)
14–16 (caries affected) Carvalho et al., 1996 (9)
Carvalho et al., 2001 (20)
50–70 MPa Sano et al., 1994 (18)
Carvalho et al., 1996 (9)
Maciel et al., 1996 (39)
40–50† Fuentes et al., 2003 (115)
1.05 Carvalho et al., 1996 (9)
when bonding to dentin, but they combine the crea-
tion of pathways and resin infiltration into a single
step. Regardless of the bonding strategy, the above
bonding mechanism is rarely accomplished to perfec-
tion (3,4,8). The morphological and physiological
heterogeneity of dentin have been described as the
major obstacles to achieving uniform, reproducible
and reliable bonding (2,6). Although dentin has
always been described and referred to as a whole, some
regard that as an oversimplification because different
types of dentin, reflecting different functions and
bearing their own specificities, have been identified
(28,35). Biological, structural, and clinical factors such
as dentin depth, location, age, wetness, sclerosis,
caries, pre-treatments, etc. have all been shown to
significantly interfere with the resultant quality of
resin–dentin bonds (2,16) (Fig. 2). Some of these will
be explored further in this review.
Etch-and-rinse adhesives
Etch-and-rinse adhesives are characterized by utilizing
a separate, initial etching step to create the pathways
for resin infiltration. Etching is followed by rinsing the
surface with water, which aims to completely remove
the dissolved smear layer and minerals from the dentin
surface, leaving a scaffold of collagen fibrils exposed,
the porosity of which is maintained because the
interfibrillar spaces are filled with the rinse water
(9,33,34,36). The next step consists of replacing the
water occupying the intra- and interfibrillar collagen
spaces with resin co-monomers. Traditional 3-step
etch-and-rinse adhesives utilize primers that contain
 Dentin bonding

Fig. 1. Transmission electron microscope (TEM) image of the dentin–composite interface created with a simplified
2-step etch-and-rinse adhesive. The mineralized dentin supports the collagen network exposed with acid etching and
subsequently infiltrated with the adhesive, forming the hybrid layer (HL). The more hydrophobic layer of adhesive
(AL) is located between the hybrid layer and composite. Image courtesy of Dr. Pekka Mehtälä.

hydrophilic monomers solvated in acetone, ethanol,
or water. These primers displace water and prepare the
collagen scaffold for the subsequent infiltration of
the solvent-free, hydrophobic bonding resin (6,8,12).
Simplified, user-friendly 2-step versions combine the
hydrophilic primer and the hydrophobic resin into a
single solution. This combination, however, results
in several drawbacks for the simplified versions of this
category of adhesives. These drawbacks ultimately
result in lower bonding reliability when compared
to the 3-step versions. We refer the reader to more
detailed reviews on this topic (3,6–8). Although adhe-
sive infiltration into the collagen scaffold appears to
be a straightforward mechanism, it is rather negatively
affected by several factors that always result in the
inability of resin–solvent mixtures to completely
remove water and fully infiltrate the demineralized
zone (3,6,8). In contrast to most bioengineered scaf-
folds that present porosities in the range of 5–20 mm,
natural dentin collagen scaffolds offer nanometer-sized
porosity (c. 10–30 nm) for resin infiltration (8,37).
This collagen mesh has a very low modulus of elasticity
(c. 6–10 MPa) (38–40). Rinsing water creates strong
hydrogen bonding with collagen peptides and pre-
vents interpeptide hydrogen bonding that would cause
the mesh to collapse and eliminate the already-reduced
porosity for resin infiltration (41,42) (Fig. 3). Exten-
sively air-drying demineralized dentin to remove water
should, therefore, be avoided as the porosity will
disappear due to shrinkage of the fibril network (9).
The expansion of the collagen mesh as a result of the
presence of rinsing water forms the basis of the success
of the wet-bonding technique currently recommended
for all etch-and-rinse adhesives (43). Even though the
porosity can be maintained with the presence of water
in the wet-bonding technique, its replacement by
solvents and/or monomers with a lower capacity
for hydrogen bonding with collagen will cause slight
shrinkage of the mesh during resin infiltration and
result in reduced interfibrillar spaces (41,44).

65
Carvalho et al.
Fig. 2. The common phenomena in dentin, all of which will affect the dentin as the substrate for bonding. NCCL:
non-carious cervical lesion.
Etch-and-rinse adhesives are known for being
technique-sensitive (6,8), and this is mostly due to
the difficulties in determining the adequate surface
moisture for each adhesive being applied. It has been
demonstrated that acetone-based adhesives require a
wetter surface than ethanol-based adhesives (45,46).
Water-based and ethanol-based primers have shown
a self-rewetting ability when applied to a rather dry
surface (47). This is also a result of the higher solubil-
ity parameter of ethanol when compared to acetone
(41,42). Water is considered to play an antagonistic
role in the hybrid layer formation with etch-and-rinse
adhesives (12,34). While some moisture is necessary
to maintain collagen fibril expansion, thus preserving
the pathways for resin infiltration, excess moisture may
cause a phase separation between hydrophobic and
hydrophilic monomers, resulting in the formation of
blisters and voids at the interface with the consequent
negative effects on the uniformity of the resin infiltra-
tion (12,48,49). Additionally, the inability to remove
residual solvents and water from the adhesive (50)
results in reduced conversion of resin monomers with
negative consequences to the mechanical properties
of the interface (51–53). The ultimate consequence of
poor resin infiltration into the demineralized zone is
66
a reduced durability of the bonded interface. This is
mainly caused by the uneven stress distribution along
the components of the hybridized zone (3,54,55), the
possibility of enzymatic degradation of collagen fibrils
that were left exposed (8,56), and the hydrolysis of the
poorly formed adhesive polymer (3,8,57).
To avoid problems related to the presence of water
in the traditional wet-bonding technique, the ethanol
wet-bonding concept has been proposed (58). In the
ethanol wet-bonding technique, demineralized dentin
is saturated with ethanol to replace the rinsing water
before adhesive application. The apparent success
of the method relies on the fact that ethanol has a
relatively higher solubility parameter, maintains the
interfibrillar spaces for resin infiltration, and elimi-
nates water that causes a phase separation between
hydrophilic and hydrophobic monomers. Under the
ethanol wet-bonding approach, hydrophobic resins
can be used to infiltrate the collagen mesh instead
of less stable hydrophilic monomers. The use of the
ethanol wet-bonding technique has been shown to
improve resin infiltration, increase bond strength, and
reduce nanoleakage and micropermeability within
the hybrid layer [Carrilho et al. (2011 unpublished
data); Manso et al. (2011 unpublished data)] (59,60),
 Dentin bonding

Fig. 3. The effect of moisture on demineralized dentin matrix collagen. (a) Schematic description of dry dentin matrix
collagen peptides that are stiff because of interpeptide hydrogen (H) bonds. Due to the H-bond, the interpeptide
distance (<10 nm) is too small to allow monomer penetration between the collagen fibrils. (b) The collagen matrix
is collapsed and penetration of the adhesive does not occur. Arrow: the direction and width of the matrix shrinkage.
(c) In water-saturated dentin matrices, water (H2O) molecules cluster around the functional groups in collagen
peptides that can form the H-bond. Due to the water’s high Hoy’s solubility parameter, the interpeptide H-bonds
cannot form, and the interpeptide distance is wider. (d) The water-saturated matrix is expanded and soft, and allows
for the penetration of adhesive molecules between the collagen fibrils.

resulting in improved bond durability (8,60). This
improved bond durability when using the ethanol
wet-bonding approach can be explained via the
improved collagen encapsulation by resins (59) and
some inhibitory effect of dentin proteases (i.e. matrix
metalloproteinases, MMPs) known to cause collagen
degradation in resin–dentin bonds (61). While demin-
eralized dentin treated with the ethanol wet-bonding
technique seems to be a promising substrate for resin
infiltration, there are concerns regarding the effects
of ethanol-saturated dentin on the polymerization
of the adhesives (62). At the moment, no commercial
adhesive is available that has been developed to be used
according to the ethanol wet-bonding technique.
The three-step version of etch-and-rinse adhesives is
regarded as the most reliable system currently available
(5,6,8). One advantage of a three-step bonding pro-
cedure is the opportunity to use each step to introduce
therapeutic benefits (8). Examples of these are the
possibility of incorporating MMP inhibitors in the
etching and/or priming steps (63–65) and small
molecules such as fluoride in the hydrophobic resin
(8,66,67). Despite all of the advantages and scientific
evidence of the superior performance of three-step
etch-and-rinse adhesives, the multi-step clinical proce-
dure is not appealing to clinicians and results in no
innovation from the manufacturers.
Self-etch adhesives
Self-etch adhesives are characterized by the absence
of a separate acid-etching step. Instead, the creation of
resin diffusion pathways is achieved by the presence of
acidic monomers in the composition that simultane-
ously etch and prime the dental substrate (4,6). Self-
etch adhesives are also subdivided into 2-step and
1-step categories (68). Clinical and laboratory per-
formances of these adhesives seem to be material

67
Carvalho et al.
dependent, but the 2-step systems are systematically
reported as being more favorable (69,70).
The acidic characteristics of the active monomers in
self-etch adhesives are responsible for dissolving the
smear layer and demineralizing the underlying dentin
(71). This demineralization is self-limiting because the
acidity of the monomers is gradually buffered by the
mineral content of the dentin (72). This implies that
the resultant morphological aspect of the bonded
interface is largely dependent on the characteristics of
the dentin to which the adhesive is being applied and
on the aggressiveness of the acidic monomers (73–
75). Accordingly, self-etch adhesives have been classi-
fied as strong (pH < 1.0), intermediate (pH = 1.5),
and mild (pH > 2) (68). More recently, two other
adhesives became available that present lower acidity
(pH > 2.5) and were classified as ultra-mild self-etch
adhesives (Clearfil S3 Bond, Kuraray Inc., Japan and
Adper Easy Bond, 3M ESPE, USA). As expected,
the demineralization depth is directly related to the
aggressiveness (73,74). Strong self-etch systems
produce interfaces that resemble those of etch-and-
rinse systems while ultra-mild versions barely dissolve
the top dentin surface and leave tubules occluded with
smear plugs. The partial demineralization resulting
from mild and ultra-mild self-etch systems has been
reported to be an advantage because of the possibility
of chemical interaction between some functional
monomers (such as MDP and 4-META) and the
remaining hydroxyapatite crystals along the collagen
fibrils (76). It has been claimed that this chemical
bonding results in the improved bond durability
reported for these systems (6,77,78), but the experi-
mental data is conflicting (79–81).
The success of self-etch adhesives is largely related
to their simplicity of use and to the theoretical ability
to etch and infiltrate simultaneously, thus preventing
discrepancies between demineralization and infiltra-
tion (4,6,77,78). This concept, however, has been
recently challenged (82) as zones of partially deminer-
alized but not infiltrated dentin have been observed
beneath the hybrid layer. This was more evident for
the simplified versions of self-etch adhesives (1-step
and all-in-one systems), but also occurred with the
more traditional 2-step materials. Simplified, 1-step
versions of self-etch adhesives have been regarded as
the least reliable adhesives available. They have con-
sistently resulted in inferior performance in both labo-
ratory and clinical testing (6,69,70). These versions
68
are highly hydrophilic and this makes them susceptible
to water sorption and hydrolysis, thus seriously com-
promising the stability of the bonded interface over
time (3,6,83,84).
Currently, one 2-step system (Clearfil SE Bond,
Kuraray Inc., Japan) is regarded as the gold standard
of self-etch systems (4). The success of this material
has been attributed to its functional monomer (MDP),
which is capable of chemically bonding to hydroxy-
apatite, and to the stability of its filled, solvent-free
bonding resin (4,6).
Glass ionomers and glass
ionomer adhesives
Glass ionomers are currently regarded as the only
materials that self-adhere to mineralized dental tissues
(76). Bonding to dentin is generally accomplished
by a two-fold mechanism. A short polyalkenoic acid
treatment removes the smear layer and exposes colla-
gen fibrils up to about 0.5–1.0 micron (85), and glass
ionomer components can diffuse in to establish a
micromechanical interaction following the principles
of hybridization (69,86,87). Additionally, a chemical
bond is attained by the ionic interaction between the
carboxyl groups of the acid and the calcium ions of
the hydroxyapatite that remained attached to the
collagen fibrils (76). To what extent each of the
bonding mechanisms contributes to the actual inter-
facial strength is unclear. It appears that the use of the
polyalkenoic acid pre-treatment is crucial for optimiz-
ing bond strength because it removes the smear layer,
thus promoting a more intimate contact of the glass
ionomer with the underlying dentin (88). Also, the
removal of the smear layer increases dentin permeabil-
ity and provides an additional water source to benefit
the acid–base setting reaction of the glass ionomer
(89). When the smear layer is not present, i.e. in the
case of fractured dentin, it seems that the use of an
acidic pre-treatment is not necessary (88).
The adhesion of glass ionomers to dentin has been
proven to be highly successful clinically in Class V
non-carious cervical lesions (70,90). The chemical
bond to the remaining apatite and the maturation
of the glass ionomer at the interface caused by the
moisture from the dentin surface both seem to be
important mechanisms by which the bonding of glass
ionomers to dentin becomes more resistant to degra-
dation over time (69,88).

Structural characteristics that
affect bonding
Smear layer
Whenever dentin is operated on by cutting or abrading
instruments, the resulting surface will be covered by a
0.5–2 micron smear layer and dentinal tubules will be
filled with several microns of smear plugs. It has been
generally accepted that smear layers and plugs are
composed of hydroxyapatite particles and disrupted,
denatured collagen fibrils that change according to the
characteristics of the region from where they were
formed (91–96). The presence of the smear layer and
smear plugs drastically reduces dentin permeability
(12). While this can be seen as beneficial for biological
protection of the pulp, it is regarded as an obstacle that
directly affects how adhesives interact with dentin.
Etch-and-rinse adhesives are reported to be less
affected by the presence of the smear layer and smear
plugs because the strong phosphoric acid dissolves,
and further water rinsing removes, the residues from
the surface. This, however, results in increased perme-
ability and increased moisture on the surface that can
interfere with adhesion (2). Additionally, the ability of
phosphoric acid to remove collagen remnants from the
surface has been questioned. Raman microspectro-
scopic studies revealed that collagen within the smear
layer is denatured by acid-etching and not removed
upon rinsing (94,95). The gelatinized collagen left on
the surface may interfere with further resin infiltration
and represent another confounding factor in bonding
to dentin (3).
Self-etch adhesives incorporate the smear layer and
smear plugs into the bonded interface. Hence, the
type of smear layer produced on the dentin surface
largely influences the bonding effectiveness (97,98).
Smear layers of different thickness, density, and
composition are formed depending on the cutting
instrument used (97,99). Because smear layers can
physically block the diffusion, and chemically buffer
the acidity of the resin monomers (98,100–102),
the bonding effectiveness of self-etch adhesives
depends on their ability to deal with the smear layer
(73,99,103). In that regard, there is evidence that
thick smear layers can impair the bonding of (ultra-)
mild self-etch adhesives (73,97,98,103). It is thus
recommended that cavity walls be finished with extra-
fine diamond burs (97,104), and that mild self-etch
Dentin bonding
adhesives be applied with continuous agitation to
improve monomer infiltration and uniform hybrid
layer formation (105–107).
Aging
Dentin structure, chemistry, and properties change
over time (108–111). Physiological sclerosis (with the
reduction in tubule diameter) and the presence of
mineral deposits (with the consequent reduction in
dentin permeability) are among several events that
occur with aging which are potential deterrents of
dentin bonding effectiveness (2). However, few
studies have investigated the effects of tooth age on
dentin bond strength (112–114). While some differ-
ences in the mode of failure and material dependence
have been reported in these studies, in general there
were no significant differences in bond strengths
between young and old teeth.
Depth, location, and tubule orientation
Because of the regional variance of dentin mor-
phology relative to tubule density and lumina, the
water content of dentin also varies accordingly, as well
as its properties (115) and permeability when the
smear layer and smear plugs are removed. The intrinsic
water content of dentin is greater near the pulp and
diminishes significantly toward the dentin–enamel
junction (DEJ). This difference in surface moisture
has been considered to be a factor that affects
dentin bonding and results in lower bond strengths
in deep compared to superficial dentin (12,116,117).
However, as adhesive systems became more hydro-
philic, lower bond strengths obtained in deeper dentin
have been more associated with the reduced availabil-
ity of intertubular dentin for the hybrid layer forma-
tion than with surface wetness when the bond is closer
to the pulp (13,118,119). In general, bond strengths
in deep dentin are reported to be 30–50% lower than
in superficial dentin (118,120). By using the micro-
tensile bond strength testing method (121), research-
ers were able to demonstrate regional variances in
bond strength to root dentin (122) and to the differ-
ent walls of an MOD cavity preparation (123). In
general, bond strengths tend to be lower in the apical
third of the root and at the cervical margins of a cavity.
The orientation of the dentinal tubules has been re-
ported to have a significant effect on the morphology of
69
Carvalho et al.
the hybrid layer produced by etch-and-rinse adhesives.
Hybrid layers were thicker and resin tags were longer
when bonding to dentin with a perpendicular tubule
orientation. Conversely, thinner hybrid layers and an
absence of resin tags were reported for dentin with a
parallel tubule orientation (124). The effect of tubule
orientation on bond strength, however, remains incon-
clusive as it appears to vary according to the adhesive
used and testing method, as well as being subjected to
confounding variables such as dentin depth and location
(125,126).
Bonding to altered dentin
Caries-affected and caries-infected dentin
While most of the current knowledge about dentin
bonding has been generated from laboratory studies
(5), it is self-evident that adhesives should prove their
effectiveness when bonded to clinically relevant dentin
substrates. In that regard, fewer studies are available
that have profoundly investigated the bonding charac-
teristics to clinically altered dentin, and most impor-
tantly, devised approaches to improve the quality of
bonding to such substrates (2,7). The minimally
invasive dentistry concept (127) determines that cavity
preparation should be limited to caries removal.
Regardless of the debatable question as to the extent
to which carious dentin should be removed, most
of the caries excavation methods are known to leave
caries-infected and/or caries-affected dentin as the
bonding substrate for adhesives (128). Additionally,
resultant bond strengths may also be influenced by the
caries removal method and the type of adhesive used
(128,129).
The bond strengths to caries-affected dentin have
been systematically reported to be 20–50% lower
than to sound dentin (2,30,128,130–132). Bond
strengths tend to be even lower when bonding to
caries-infected dentin (133,134). Caries-affected and
caries-infected dentin are more porous (31,135),
contain significantly more water (136), and the hybrid
layers tend to be much thicker, but not necessarily
well-infiltrated in caries-altered dentin, irrespective of
the bonding strategy (131,137,138).
The lower bond strength to caries-affected dentin is
a consequence of the structural changes caused by the
progression of the caries lesion. Caries progression
reduces the mineral content and crystallinity of the
70
hydroxyapatite, and causes alterations in the secondary
structure of collagen (139). As well, reduced distribu-
tion of sound collagen fibrils and proteoglycans were
found in caries-affected dentin (140). All of this results
in a substrate with reduced mechanical properties
(16,136,141,142), which directly affects the result-
ant bond strength. Infiltration of adhesive resins is
also hampered by the presence of mineral casts (i.e.
whitlockites) along the tubules (52,132,143,144).
There is also evidence that adhesives are poorly polym-
erized at the bonded interfaces of caries-affected
dentin (52,144).
Reported variations in the bond strength to caries-
altered dentin are likely a result of the differences in
the aggressiveness of the methods used to remove
carious tissue in each specific study (128). In each
study, etch-and-rinse adhesives tend to produce higher
immediate bond strength to caries-affected dentin
than self-etch ones (130,145,146). However, such
differences seem to disappear after short-term water
storage (145). In that regard, long-term bond
strength studies to caries-affected dentin are still
lacking, despite the obvious higher relevance of such
studies when compared to sound dentin. Because
dentin reactions initiate readily after caries lesions
affect enamel, it is expected that therapeutic adhesive
restorations will always be bonded to different degrees
of altered dentin in a clinical setting. In that scenario,
reported bond strengths to sound dentin are not pre-
dictive of the adhesive performance when bonded
to altered dentin. Considering the long-term clinical
success of posterior composite restorations in retro-
spective studies (147–149), it is possible that the
reported lower bond quality produced by adhesives to
caries-altered dentin is not as clinically relevant as one
would think. How much bond strength is necessary to
determine clinical success remains to be determined,
perhaps by testing the interfacial strength of adhesive
joints of retrieved teeth that had been in clinical func-
tion for several years (7).
Sclerotic non-carious cervical lesions
Non-carious cervical lesions (NCCL) present a unique
structure that has no similarities with any other type of
dentin. It is characterized by a structure composed
of a top hypermineralized layer of varied thickness
with several bacterial inclusions that is sitting on a
bed of denatured collagen fibrils (Fig. 4). This top

Fig. 4. The dentinal surface in a non-carious cervical
lesion (NCCL). (a) Light microscope image from the
deepest part of a NCCL. B: stained, unmineralized bac-
teria; HM: hypermineralized surface layer covering the
lesion; SD: intact sclerotic dentin. The pointers indicate
the remnants of mineralized bacteria. (b) Corresponding
TEM micrograph of the same area of the NCCL lesion.
The hypermineralization of the surface layer (HM) is
identified by its electron density compared to the under-
lying sclerotic dentin (SD). Reproduced with permission
from Tay et al., 2000 (71).
layer transitions to a dentin underneath that presents
irregular tubular occlusion by mineral casts, typical
of sclerotic dentin (150). Similarly to caries-affected
dentin, bond strengths to NCCL have been reported
to be 20–40% lower than to sound dentin, irrespective
of the bonding strategy (150–152). This has been
attributed to the presence of the microbial matrix and
entrapment of bacteria during the hybrid layer forma-
tion, the inability of acids to completely dissolve the
Dentin bonding
hypermineralized layer, the presence of denatured col-
lagen at the base of the hypermineralized layer, and the
presence of sclerotic casts that obliterate the tubules
(71,150). All of these factors compromise the ability of
adhesives to create pathways for resin infiltration and,
consequently, the ability to completely infiltrate the
adhesive resin. The irregular edges of the hybrid layer
and the presence of bacterial inclusion have also been
pointed out as stress-raising sites that cause premature
failure when the interface is stressed (150). Methods
attempting to improve bond strength to NCCL
have rendered inconclusive findings. Roughening the
surface with burs to remove the hypermineralized layer
prior to bonding has resulted in thicker hybrid layers
with different adhesives (153), but did not seem to
increase retention rates in clinical trials (90,154). Simi-
larly, extending etching times from 20 s to 30 s have
been shown to increase bond strength for some adhe-
sives, but to reduce it for others (155).
Most of the knowledge concerning the structure of
NCCL and how it responds to bonding approaches
was generated during the late 1990s and early 2000s
(74,122,150,151). Recent laboratory studies that
investigate the bonding mechanisms with current
adhesive systems are lacking. Clinical trials, however,
are widely available because NCCL are the lesions
recommended for testing the clinical effectiveness of
adhesive systems (156). Interestingly, the surprisingly
high clinical survival rates of NCCL restorations
suggest that the difficulties in producing reliable bonds
to NCCL as reported by laboratory studies may not be
as relevant as previously thought (2,5–7).
Dentin pre-treatments that
adversely affect bonding
This section reviews chemical treatments that have
been reported to affect both the physical and bonding
properties of dentin, and that are more closely related
to clinical procedures involving coronal and root
dentin.
Sodium hypochlorite
Sodium hypochlorite (NaOCl) is a well-known, non-
specific proteolytic agent that is capable of removing
organic material, magnesium, and carbonate ions from
the dentin surface (157). It remains the most widely
used chemical irrigant for endodontic therapy due to
71
Carvalho et al.
its antibacterial and organic tissue-dissolution proper-
ties (158–160). Despite the propagated benefits of
disinfection and cleaning of root canals, NaOCl has
potential negative effects on the mineral content of
dentin structures (161) that may reduce its mechanical
properties (22,158,162) and compromise the sealing
ability of endodontic fillings (163).
Although NaOCl is not a pre-treatment typically
recommended for adhesive procedures in general, it is
not uncommon that, during endodontic therapy, the
irrigant “contaminates” the coronal portion of the
tooth, which may later be restored with an adhesive
restoration. Also, clinicians may use NaOCl to irrigate
root canals prior to luting fiber-reinforced resin posts
using adhesive systems and resin cements. Several
studies have demonstrated that NaOCl compromises
the bond strength between adhesive agents and dentin
(164–171). The compromising mechanism likely
occurs because the reactive residual free-radicals gen-
erated by the oxidizing effect of NaOCl compete with
the propagating vinyl free-radicals generated during
the curing of the adhesive, thus leading to incomplete
polymerization by premature chain termination (165).
This compromising effect seems to occur similarly with
both etch-and-rinse and self-etch adhesives (165,169)
whenever the adhesives are applied to dentin that has
been previously treated with NaOCl.
Antioxidants/reducing agents have been recom-
mended to reverse the compromised bond strengths
to dentin pre-treated with NaOCl. A 10% solution of
sodium ascorbate is among the most investigated
agents used to revert the oxidizing effect of NaOCl
prior to bonding with adhesive resins (165,169,171,
172). Antioxidants such as sodium ascorbate control/
revert oxidation effects by mechanisms that involve
free radical chain-breaking, metal-chelating, and free
radical quenching (169). All of these can restore the
redox potential of the oxidized dentin surface and
improve the polymerization of the adhesive resin. The
ability of sodium ascorbate to revert the effects of
NaOCl seems to depend on the concentration and
application time of the former (172). For instance,
10% sodium ascorbate applied for 5 s was not capable
of reverting the negative effects of a 6% NaOCl treat-
ment for 30 s, but a 10 s treatment was (169). Other
antioxidants/reducing agents have been more recently
investigated as potential candidates to revert the nega-
tive effects of oxidants such as NaOCl on resin–dentin
bonds. These include sodium thiosulfate solutions
72
(i.e. p-toluenesulfinic acid sodium salt; Accel, Sun
Medical Co. Ltd., Kyoto, Japan) (169,173) and ros-
marinic acid (a-o-caffeoyl-3,4-dihydroxyphenyllactic
acid) extract from rosemary (169). These agents seem
to be more effective than sodium ascorbate as lower
concentrations are used for shorter application times
(169). While effective bonding to NaOCl-treated
dentin can be accomplished with the prior use of
antioxidant/reducing agents, posterior resin infiltra-
tion of NaOCl-treated dentin was not capable of
restoring damaged surface properties (22). The clini-
cal importance of this remains to be determined.
Hydrogen peroxide
Hydrogen peroxide or peroxide-releasing agents such
as carbamide peroxide and sodium perborate are well-
known compositions largely used for external and
internal tooth bleaching (174). Bleaching is currently
regarded as a safe and effective method of inexpen-
sively treating discolored teeth (175).
The effects of hydrogen peroxide, the active bleach-
ing species, on dentin and dentin bonding share a lot
of similarities with sodium hypochlorite. Hydrogen
peroxide is a potent oxidant and a number of studies
have reported microstructural changes in dental hard
tissues induced by bleaching (176). Histological
alterations to enamel, changes in the mechanical prop-
erties of dentin (177), and alterations in the organic
component of dentin (178) have been reported. These
were more recently reviewed and considered, in
general, to be minor and not clinically relevant (179).
Conversely, studies are almost unanimous in demon-
strating that hydrogen peroxide has negative effects on
resin–dentin bonding. Reduced bond strengths have
consistently been reported when adhesives are imme-
diately applied to bleached dentin, regardless of the
bonding strategy (165,180–184). The mechanisms
involved are similar to those resulting from the use
of NaOCl on dentin prior to bonding (see above).
Hydrogen peroxide diffuses and remains entrapped in
dentin. The compromising effect is due to the residual
oxygen present in the dentin pores that impairs infil-
tration and inhibits polymerization of the adhesive
resin (184–186). The effects seem to be dependent on
the concentration of the bleaching agent, being worse
with higher concentrations (181). Because of this,
there is a general recommendation that bonding pro-
cedures to bleached teeth should be delayed for 24 h

to 2 weeks after bleaching, when the negative effects
are no longer observed (183,187–191).
Alternatively, reversal of compromised bonding can
be obtained by treating hydrogen peroxide-treated
dentin prior to bonding with sodium ascorbate (165,
192), catalase, ethanol (193), or ascorbic acid (194,
195). All of these are antioxidants/reducing agents
that have been shown to be able to eliminate the
adverse effects of hydrogen peroxide and restore
bond strengths to values which are comparable to
those obtained on untreated dentin in a similar way as
observed for dentin treated with NaOCl. In general,
antioxidants/reducing agents are applied for the same
duration as the bleaching treatment (165). One recent
study showed that the amount of sodium ascorbate
required for the reduction of hydrogen peroxide is
directly related to the concentration of the latter. In
addition, the reaction kinetics between oxidant and
antioxidant showed that a longer application time of
sodium ascorbate did not influence the effectiveness of
the reaction and that 5 min is sufficiently long for this
antioxidant to exert an antioxidant effect (196).
Dentin pre-treatments with
potential advantageous effects
on bonding
In addition to the mostly unfavorable effects of chemi-
cal treatments on dentin bonding, there are several
approaches that aim to improve either the immediate
or the long-term resin–dentin bond strength (197).
Most of them aim to preserve the integrity of the
hybrid layer.
Chlorhexidine as an enzyme inhibitor
Originally, the collagen matrix exposed with acid
etching was thought to be protected by the polymer-
ized adhesive enveloping the fibrils. However, dentin
contains several enzymes that in concert can degrade
practically all extracellular matrix proteins, including
type I collagen and other dentinal matrix components.
Most of the identified enzymes belong to the family of
matrix metalloproteinases (MMPs), of which at least
MMP-8 (collagenase), MMP-2 and -9 (gelatinases),
MMP-3 (stromelysin), and MMP-20 (enamelysin) are
present in dentin (170,198–202). Recent studies have
also demonstrated another group of enzymes, cysteine
cathepsins, in human dentin (203,204). For a detailed
Dentin bonding
description of the presence and roles of these enzymes
in dentin, please see the article by Mazzoni and others
in this issue.
In mineralized dentin, enzyme activity is prevented
by the mineral component, but once liberated and
activated by acid-etching, it can slowly degrade the
collagen fibrils even in the resin-infiltrated hybrid
layers (205–208) (Fig. 5). As well, the etch-and-rinse
adhesives (63,209) and self-etch adhesives (210,211)
can activate dentinal MMPs. Even though the func-
tional mechanisms of dentin matrix enzymes are not
exactly known, it is believed that collagen is first
broken down to 3⁄4 and 1⁄4 fragments by MMP-8, a true
collagenase. The resulting product, called gelatin, is
further degraded by the gelatinases MMP-2 and -9.
However, the interplay between MMPs and cysteine
cathepsins in dentin may be much more complex, as
suggested by Nascimento and co-authors (203) in the
supplemental Appendix for the manuscript. Whatever
the mechanism, the conversion of insoluble collagen
fibrils to soluble fragments leads to the loss of attach-
ment of the hybrid layer with the collagen anchored
into the underlying mineralized dentin (Fig. 5). This
time-dependent loss of resin–dentin adhesion has been
repeatedly demonstrated (8,197,212).
Ever since the discovery that dentin-bound enzymes
degrade exposed dentinal collagen (56), research has
searched for ways to improve the bond strength dura-
bility by inhibiting the enzymes. The most interest has
been directed toward chlorhexidine, which is known
to inhibit purified MMP-8, -2, and -9 (213) and also
to effectively reduce dentin matrix enzyme activity
(200,214–216). Both in vitro and in vivo studies have
demonstrated that hybrid layer MMP inhibition with
chlorhexidine is an effective approach to improving the
durability of the resin–dentin bond, both with etch-
and-rinse adhesives (64,205,206,208,217–221) and
also with self-etch adhesives when used in high enough
concentrations (219,222). In general, treating acid-
etched dentin with chlorhexidine demonstrates 1.9%
monthly loss in bond strength compared to approxi-
mately 5% loss in no-treatment groups (223). Chlor-
hexidine also effectively eliminates the reduction of
bond strength in vivo: after 14 months in clinical
service, the bond strength of chlorhexidine-treated
composite fillings was reduced only 1.5% from the
immediate bond strength, the respective loss in the
control group being 35% (206). Currently, the use
of chlorhexidine during the bonding procedure to
73
Carvalho et al.
Fig. 5. Schematic representation of the firmness of the
hybrid layer over time. (a) Immediately after bonding,
the exposed dentinal collagen matrix, firmly attached to
mineralized dentin (MD) underneath, is mostly embed-
ded with the adhesive, forming the hybrid layer (HL).
At least with etch-and-rinse adhesives and most likely
also with self-etch adhesives, the layer of more or less
demineralized, but not adhesive-embedded, collagen
matrix between the hybrid layer and mineralized dentin
forms the so-called nanoleakage (NL) area. The adhesive
layer (AL: usually more hydrophobic layer than that in
the hybrid layer) forms the chemical bond with the
compostite resin (CR). (b) The time-dependent degra-
dation of the collagen fibrils in the nanoleakage layer
and hybrid layer itself lead to the loss of collagen in the
hybrid layer, resulting in the loss of the firm anchorage
of the hybrid layer, and thus the whole restorative com-
posite to the dentin underneath.
increase the longevity of dentin bond strength is
recommended for clinical practice (223–225).
Other approaches to improve
dentin bonding
Even though chlorhexidine has been proven to effec-
tively improve the long-term bond strength both
74
in vitro and in vivo, it still requires an additional
step during the bonding procedure. Therefore, other
approaches to improve the longevity of dentin
bonding have also been studied with the goal of
finding more practical or even more durable means
to preserve the hybrid layer integrity (197). These
include at least ethanol wet-bonding (58,60,226–
228), the use of MMP-inhibiting monomers (229) or
other MMP inhibitors (61,65,230), increasing hybrid
layer collagen cross-linking prior to adhesive applica-
tion (231–234), and the biomimetic remineralization
of the hybrid layer (235–237).
At present, ethanol wet-bonding is perhaps the most
promising approach, resulting in good preservation of
the hybrid layer and high long-term bond strength
values. The promising findings may at least partially be
due to the reduced hydrolytic degradation of the
hybrid layer collagen (223,224,226), but also to the
better encapsulation of collagen matrix and the pres-
ence of more durable hydrophobic adhesive in the
hybrid layer (224). However, the original protocol
requires several steps and is too time-consuming to
be acceptable in clinical work. More recently, Manso
and others were able to demonstrate that the ethanol
wet-bonding concept can be used in conjunction
with commercially available adhesives within a clini-
cally acceptable time (Manso et al., unpublished
results). Ultimately, further research is required to
determine a simple, reliable, and clinically practical
application protocol (227). The efficacy and the
advantages of the use of MMP-inhibiting monomers
and other MMP inhibitors compared to the use
of chlorhexidine still needs to be demonstrated.
Increased cross-linking and improving hybridization
by increasing the collagen matrix stiffness (232,233)
may improve both immediate and long-term bond
strength (232,234), and the increased durability may
at least partially be due to MMP inhibition (224,232,
234). As with ethanol wet-bonding, current applica-
tions with biocompatible and non-toxic cross-linking
agents are time-consuming and thus faster and simpler
protocols are needed before introducing their use in
clinical procedures (224). Biomimetic remineraliza-
tion, aimed at returning to the mineralized state of the
collagen matrix within the hybrid layer, is biologically
very attractive and has been shown to result in good
preservation of bond strength (238). However, the
approach is highly experimental, and clinical applica-
tions may still be far away.

Bonding to root dentin
The major goals of successful endodontic therapy are
disinfection and perfect obliteration of the root canal
space with an inert filling material to create an optimal
seal with the tooth structure. Although predictable
clinical results have been reported with the use of
non-bonding root canal sealer/filling materials (239,
240), there has been a natural request for alternative
materials that bond simultaneously to root canal walls
and filling materials, in order to achieve compact
monoblock sealing. Notwithstanding, adhesive proce-
dures have become popular for root canal obturation,
pulp chamber sealing, cementation of posts and cores,
and other endodontic therapies. However, successful
bonding to root dentin can be regarded as one of the
greatest challenges in adhesive dentistry. This is, in
part, due to the limited knowledge regarding how the
structural and physiological characteristics of this par-
ticular substrate affect the bonding mechanism of con-
temporary methacrylate resin-based materials that are
used for endodontic applications.
Despite the fact that the principles of adhesion to
coronal dentin can also be applied to root dentin,
specific variations on dentin structure (241–243), local
morphology (10,244,245), and physiological shifts
due to aging and/or pathological processes (16) play
important roles in the performance of dental adhesives
and the quality of the resultant bonded interfaces.
Morphological, compositional, and structural par-
ticularities regarding dentin in sclerotic non-carious
cervical lesions (NCCL), localized on the coronal
third of dental roots, were previously addressed in this
review as imposing a relative barrier to achieving a
perfect bonding procedure. This section will explore
the multiple aspects that can be involved with the
success/failure of the interaction between adhesive
materials, specifically the methacrylate-based resins
and the intraradicular dentin (i.e. root canal dentin) of
non-vital teeth.
As with any other dental hard tissue, the prevailing
mechanism to bond methacrylate-based resins to
intraradicular dentin is dependent on micromechanical
retention of these resins in the treated/primed tissue,
regardless if the bonding procedure is the filling/
obturation of root canals or the cementation of posts
and cores. Because of the limited vision and access,
predominance of sclerotic dentin along the apical part
of the root canal (245), regional differences in bond
Dentin bonding
strength (123,246), presence of a thick smear layer
(247,248), and high cavity configuration factor
(C-factor) (246,249,250), the achievement of
perfect infiltration and micromechanical retention of
methacrylate-based resins in the root canal environ-
ment remains a clinical challenge.
Similarly to coronal dentin, intraradicular dentin is a
non-homogeneous tissue characterized by the pres-
ence of tubules extending outward from the pulp
cavity to the tooth (245). Studies that have morpho-
logically analyzed human intraradicular dentin did not
report significant differences in tubule density and
tubule cross-sectional area between the cervical and
middle thirds of root dentin (244,251). In addition,
these studies demonstrated only minor morphological
differences between deep coronal and cervical in-
traradicular dentin, which suggests that cervical and
middle intradicular dentin should behave similarly to
cervical coronal dentin (i.e. deep coronal dentin) with
respect to bonding substrates. Despite such apparent
morphological and compositional similarities (244,
251), the bond strength to intraradicular dentin
bonded with methacrylate-based resins has been
mostly reported as being extremely variable along the
root canal (246,252–254) and significantly lower than
that observed for coronal dentin (245,246,250,253,
255,256).
A noticeable morphological characteristic that is
reported to be exclusively part of intraradicular dentin
is the presence of convex, dome-shaped projections,
called calcospherites, which produce globular undula-
tions along the entire root canal surface (251). The
influence of calcospherites on the bonding perfor-
mance of methacrylate-based resins to intraradicular
dentin has not been sufficiently investigated, but
as these projections create an irregular and non-
homogenous surface to dentin, they may contribute to
making intraradicular dentin a less responsive substrate
(or a more challenging one) for bonding maneuvers.
For instance, there is evidence indicating that in-
adequate dentin–resin hybridization might occur in
non-instrumented calcospherite-containing dentin
when sodium hypochlorite (NaOCl) is used as the
only active root canal irrigant (235).
Another limiting entity affecting the adhesion to
intraradicular dentin is the presence of the smear layer.
The smear layer has been defined as any debris, calcific
in nature, produced by instrumentation of dentin,
enamel, or cementum (257) or as a contaminant (258)
75
Carvalho et al.
that hampers the interaction of the underlying tissues
with restorative/filling materials. On radicular dentin,
the morphological features, composition, and thick-
ness of the smear layer are determined by the type of
endodontic instrument used, the method of irrigation,
and the tooth substrate from which it is formed
(247,248).
As previously mentioned, two bonding strategies are
currently employed to bond methacrylate-based resins
to dentin and both approaches have a paradigmatic
relationship with the smear layer. With the etch-and-
rinse approach, the acid-etching and rinsing steps
totally remove the smear layer prior to the bonding
step, while for the self-etching systems, the smear layer
is partially dissolved and incorporated in the hybridized
complex. The more acidic and aggressive the condi-
tioner, the more completely the smear layer is removed
(259). While the modification and incorporation of
smear layer into hybrid layers by using self-etching
adhesive systems can have clinical advantages when
considering the bonding to coronal dentin, such as less
technique sensitivity (260) and less post-operative sen-
sitivity (261,262), for endodontic therapy, the perma-
nence of smear layer might not only represent a barrier
to achieving effective bonding to instrumented canal
walls (263,264), but it may also work as a bacterial
deposit that puts the prognosis of root canal treatment
at risk. Thus, in Endodontics, it is prudent to remove
the smear layer from infected root canals to allow for
better infiltration of intraradicular medications into the
dentinal tubules (265) and further improve tissue
bonding capabilities (265–267).
For some years now, a line of methacrylate resin-
based sealers has been specifically designed for endo-
dontic applications. For better elucidation on the
characteristics of each system available on the market,
we advise reading the review by Kim et al. (235).
Taking into consideration that self-etching systems are
less technique-sensitive and more user-friendly (i.e.
reduced application steps), the most recently intro-
duced bondable root canal sealers (180,268,269)
belong to the category of “bonding system.” Recent
results that report the limited aggressiveness of con-
temporary self-etch and self-adhesive resin composites
(270–272) raised similar concerns on the potential of
self-etching and self-adhesive sealers to truly hybridize
intraradicular dentin. Indeed, it has been shown that
the true etching capability of self-etching and self-
adhesive endodontic sealers is a critical factor that
76
affects the bonding effectiveness to intraradicular
dentin (228,235).
Manufacturers of self-etching methacrylate resin-
based endodontic sealers recommend the removal of
the smear layer with EDTA, assuring the relevance
of this step to reduce leakage and improve the seal of
filled canals (235). Thus, the retention mechanisms
suggested by the manufacturers of methacrylate resin-
based endodontic sealers (i.e. hybridization of intratu-
bular dentin and resin tag formation) are likely to be
enhanced by the combined dentin demineralization
resultant from EDTA (228) and the sealer system
(235).
In addition to the “primary” smear layer created by
instrumentation of the root canal walls, when clinically
indicated, the subsequent preparation for post cemen-
tation using “post drills” resulted in an even thicker
smear layer composed of previous debris supple-
mented with fragments of sealer/gutta-percha rem-
nants that were shown to significantly affect the
penetration and chemical action of the agents used to
bond fiber posts to root walls (266,273). Moreover,
at this stage of the endodontic treatment, only
minimal irrigation can be performed inside the endo-
dontic canal (274). Retention of methacrylate-based
cements to intraradicular dentin may be improved
by EDTA pre-treatment (275). Other protocols have
also recommended a combination of ultrasonic instru-
mentation with EDTA pre-treatment (276) or even
the use of stronger conditioners such as phosphoric
acid (277). The resultant bond strength will, however,
be dependent on the residual effect of the dentinal
irrigant/disinfectant (278) as well as on the bonding
strategy selected (279).
Shrinkage stresses associated with polymerization
of methacrylate-based resins are higher in low-filled,
lower viscosity resin cements and root canal sealers
than in highly filled resin composites (280–282).
During polymerization of methacrylate-based resins,
the intermolecular spaces between the resin monomers
are reduced, generating sufficient shrinkage stresses to
debond the material from dentin, thereby decreasing
retention and increasing leakage (250). Undoubtedly,
amongst all concerns associated with bonding meth-
acrylate based-resins to intraradicular dentin, the chal-
lenge of achieving a balanced relief for the shrinkage
stresses of these resinous materials seems to be the
most limiting factor toward obtaining a perfect and
durable sealing of the root canal apparatus (250).

All of the factors previously discussed can, in
concert, affect the bonding effectiveness to intra-
radicular dentin. Ultimately, there is a general consen-
sus that the use of methacrylate-based resins for
sealing intraradicular dentin has not brought a para-
digm shift in the strategy toward achieving perfect
sealing of the root canal system (283–290). One of the
major focuses of current root canal therapy has relied
on the attempt to replace the non-bonding filling
systems with resin-based materials that can supposedly
establish intimate contact with intraradicular dentin,
thereby reinforcing the tooth structure and preventing
root recontamination. However, this achievement
has not been fully supported, at least considering the
results of a number of ex vivo studies (283–293). In
addition, very few of the limited clinical outcome trials
have included a control group so that the advantages
of these new materials over conventional non-bonding
materials could be supported (235). In fact, the lack
of evidence-based clinical information on the perfor-
mance of some of these endodontic resin-based mate-
rials should foment professionals to think carefully
about whether or not and when to adopt resin mate-
rials to seal intraradicular dentin.
Cementation of posts
Removal of the sealer and gutta-percha from the root-
filled teeth is required for post-space preparation (294,
295). The resulting debris produced leads to an increase
of leakage (296) and occlusion of dentinal tubules
(297), thereafter impairing adequate bonding of the
fiber post into the root canal (298). As discussed above,
the removal of the smear layer plays a critical role in the
quality of the bonding to the root canal. Despite the use
of ultrasonic instruments, chemical agents, and lasers,
the complete removal of the smear layer in the apical
third of the root space remains unpredictable. A com-
bination of chemical agents and ultrasonic instru-
ments via acoustic streaming could significantly improve
smear layer removal after endodontic instrumentation.
However, the use of EDTA alone may result in incom-
plete debris removal; similarly, the use of ultrasonics
without the aid of chemical agents produces packing of
debris into the dentin tubules (299). There is general
agreement that the removal of smear layers generated
during root canal instrumentation is more efficient in
the coronal and middle thirds than in the apical part of
the root (300,301).
Dentin bonding
Because the efficacy of the bonding has a direct
correlation with dentinal tubule characteristics, it is
important to make a statement regarding the apical
third of the root. Mjör et al. reported that the apical
third of the root has the most disparity in morphology
and includes the following: accessory root canals;
areas of resorption and repaired resorptions; occa-
sional attached, embedded, and free pulp stones;
varied quantities of asymmetrical secondary dentin;
and cementum-like tissue lining the apical root canal
wall (302). Overall, the diverse morphology exhibited
by root dentin may make coaxing methacrylate resin
bonding into the root canal an endless challenge.
The role of friction as a mean of retention of posts
cemented into the root canal has been raised (245,303,
304). While it is not yet clear how much the resistance to
dislodgement of fiber posts from the root canal is the
result of bonding or friction, it is remarkable that posts
cemented with zinc phosphate presented a resistance
to dislodgement similar to posts cemented with a com-
bination of adhesives and resin cements (305,306).
Because adhesion does not seem to play a crucial role
in the retention of posts, clinicians may prefer the
user-friendliness of self-adhesive resin cements.
Concluding remarks
Bonding to dentin remains a major challenge in adhe-
sive dentistry. The dynamic substrate characteristics
that change regionally with age and according to
several intrinsic and extrinsic stimuli make bonding
attempts to dentin far from standard and poorly pre-
dictable. Adhesive systems have evolved to better cope
with these challenging nuances of dentin, but resin–
dentin bonds are still less predictable and less reliable
than resin–enamel bonds. Recent research has exam-
ined alternative methods to increase the durability of
resin–dentin bonds. These include the use of anti-
enzymatic agents such as chlorhexidine, benzalconium
chloride, galardin, and ethanol in the ethanol wet-
bonding technique, which also improves the durability
by allowing relatively more hydrophobic resins to be
bonded to dentin. Collagen cross-linking agents
and procedures have also been introduced as ways to
stabilize collagen fibrils, thus increasing resistance to
enzymatic degradation over time. However, these are
not yet applicable in routine clinical practice. Root
canal dentin seems to be an even harsher environment
for effective bonding to be accomplished. In addition
77
Carvalho et al.
to the obstacles encountered when bonding to coronal
dentin, bonding to root canal faces the challenges
imposed by the shrinkage stresses of resin-based
bonding and luting agents. How much the limitations
in bonding to dentin truly result in or are caused by
clinical procedural failures remains to be determined.
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