Dental Adhesives of the Future

Franklin R. Taya/David H. Pashleyb

Abstract: The current trend in the development of dentin adhesives attempts to simplify bonding steps
and make them more user-friendly. However, optimizing speed and efficiency should be accomplished
without major tradeoffs in the quality or durability of resin bonds. Although dentin adhesives have improved tremendously over the past decade, postoperative sensitivity, incomplete marginal seal, premature bond degradation, biocompatibility, and compromised bonding to abnormal substrates are still considered potential problems associated with their use. Advances in different scientific disciplines will enrich the pool from which ideas may be drawn in designing future dentin adhesives. It is probably on the
molecular level that we will see the greatest expansion of horizons. With the advances in biomimetics,
future dentin adhesive monomers may contain domains derived from protein-based, underwater bioadhesives secreted by aquatic animals such as mussels and barnacles, making them less dependent on
the surface energy of the bonding substrates as well as less susceptible to hydrolytic degradation. As
adhesive joints produced by contemporary adhesives are brittle in nature, future adhesive design may
incorporate biomimetic intermediate-strength domains that can undergo stepwise reversible unfolding
in response to varying functional stress levels before ultimate catastrophic failure of the adhesive joint
occurs. These domains may also re-establish folded configurations on stress relaxation, making the adhesive both strong and tough.
Using the concept of controlled release, future adhesives may contain fluorescent biosensors that can
detect pH changes around leaking restorations. They may even have the capacity to heal autonomously,
in response to microcracks formed by functional stresses within the adhesive joint. The ability to self-diagnose and self-repair will increase the life expectancy of adhesive restorations. Future dentin adhesives may also assume a more instrumental role in therapeutics apart from caries prevention. These
features may include the controlled release of noncollagenous proteins to promote remineralization of
collagen matrices in sound and caries affected dentin, and growth factors to induce controlled formation
of reparative dentin.
J Adhes Dent 2002; 4: 91103.

Submitted for publication: 12.09.01; accepted for publication: 02.02.02.

Honorary Assistent Professor, Pediatric Dentistry and Orthodontics, Faculty of Dentistry, The University of Hong Kong, Hong Kong
SAR, China.

Regents Professor, Department of Oral Biology and Maxillofacial

Pathology, School of Dentistry, Medical College of Georgia, Augusta, Georgia, USA.

Presented under the title of Adhesives of the future at the Annual

Meeting, Academy of Dental Materials. Scientific criteria for selecting materials and techniques in clinical dentistry. October 25-27,
2001, Policlinico Le Scotte, Siena, Italy.
Reprint requests: Dr. Franklin Tay, Faculty of Dentistry, The University
of Hong Kong, Prince Philip Dental Hospital, 34 Hospital Road, Hong
Kong SAR, China. Tel: +852-28590251, Fax: +852-25593803.
e-mail: kfctay@hknet.com

Vol 4, No 2, 2002

dhesive dentistry has been progressing at a

rapid rate over the past decade. A large part of
this success is attributed to the significant advances in dentin bonding technology. From the early
generation systems in the seventies that yielded
weak and unpredictable bonds, to contemporary hydrophilic systems that produce significant improvements in bond strength to normal dentin, the
progress in the development of dentin adhesives
has been nothing short of phenomenal.65,130 The
biophysical concept of keeping an unsupported
soft tissue matrix in a fully extended state is currently being employed in optimizing resin infiltration
in smear-layer depleted, acid-etched dentin. The re-

91

Tay et al

Fig 1
Contemporary dentin adhesives are classified
into three-step, two-step
and single-step systems,
depending on how the three
cardinal steps of etching,
priming, and bonding to
tooth substrates are accomplished or simplified.

introduction of self-etching primers and all-in-one

adhesives from earlier prototypes is further defining how clinicians can bond to smear-layer covered
dentin. Combined with optimized management of
polymerization shrinkage stress, these two adhesive strategies contribute to improved clinical predictability in the bonding of polymeric restorative
materials to dental hard tissues. Although refinement of existing technologies is still required to improve bonding reliability and reproducibility, it is
useful to speculate on possible future directions of
adhesive dentistry.

THE CURRENT TREND

There has been a trend to move away from the original 'chemistry set' type of multicomponent bonding
systems toward simplified, consolidated adhesive
systems that are more user-friendly (Fig 1). From an
evolutionary perspective, the trend toward simplifying bonding steps was a natural extension of improved paradigms in dentin bonding. A recent review
suggests that technological progress in adhesion
92

between polymeric restorative materials and dentin

has been optimized to the point that major improvements may not be anticipated within the next decade.71 In this regard, the demand for adhesives
with simpler and speedier applications appears to
be driven by the clinician-consumers selection of
single bottle or all-in-one systems that 'guarantee'
economy. Clinicians assume that traditional dentin
adhesives have already been optimized against every possible situation that is likely to be encountered, and that subsequent endeavors in optimizing
speed and efficiency can be accomplished without
major tradeoffs in the quality or durability of resin
bonds.29,120 Although high clinical proficiency is
continuously being reported, postoperative sensitivity,82 incomplete marginal seal,74 premature bond
degradation,44 bio-incompatibility,20 and compromised bonding to abnormal substrates66 are still
considered as potential problems associated with
the use of dentin adhesives. Others have resorted
to selective bonding techniques in lieu of 'total
bonding'61,63,118,131 to minimize the consequences of polymerization shrinkage stress development
in cavity preparations with low compliance.
The Journal of Adhesive Dentistry

Tay et al

Adhesion is based on a series of physicochemical principles that are as true today as when they
were first established.7,9,40,122 Physiologic and
morphologic aspects that undermine optimal adhesion to abnormal bonding substrates such as
carious38,39,75,136 and sclerotic dentin79,83,95,134
are the same as they have been for the past decades. Monocyte/macrophage foreign body responses to small resin particulates that are implanted in the human dental pulp through direct adhesive pulp capping21,42,45 are as pertinent as
those observed in other body tissues.56,78,80 Although the literature on these topics is comparatively sparse, it is unlikely that these basic principles can be violated in the design of the adhesive
of the future.

LESSONS FROM NATURE

Adhesive dentistry has involved biomimetics long
before tissue engineering became a new discipline.12,76 One needs only to skim through the array
of international patents available on this subject to
appreciate their diverse technological and economic viability. Adhesive properties are continuously being modified by changing the type of filler or resin,
with even more dramatic effects achieved using novel catalytic systems.47 While they are certainly impressive, they do not break new ground, inasmuch
as the monomeric building block design and the initiating mechanism for polymeric conversion remain
largely unaltered. However, it is unfair to assume
that all the options available in polymer chemistry
have been exhausted. Given the time, temperature,
hydration,52,70 and biocompatibility constraints in
which a resin-based adhesive bond is allowed to
form in the oral environment, choices for dentin adhesives seem to be extremely limited. Our future selection of raw materials for dentin adhesives may be
broadened by examining bioadhesion in nature. The
creativity of evolution, in which nature timelessly explores all options and finds the best solution, is surprisingly instructive. Synthetic resin-based adhesives utilize complex, exotic starting materials that
are catalyzed by relatively simple initiators. Nature,
on the other hand, utilizes simple monomeric building units such as amino acids, and crosslinks them
with enzymes into protein-based adhesives. These
polymeric bioanalogs are so complex that molecular
biologists are only beginning to fathom their secrets
using reverse engineering techniques.17,124
Vol 4, No 2, 2002

How life-threatening is it if we fail to create durable resin-dentin bonds? There is no doubt that
post-gelation shrinkage stresses23 and functional
occlusal stresses69 tax the maturation of adhesive
bonds. However, in nature, lack of adhesion is
life-threatening. How well bivalves attach to substrates constitutes the difference between existence or extinction on an evolutionary scale for many
marine species, such as mussels and barnacles.50
These shelled mollusks are capable of forming rapid, permanent, moisture-resistant bonds under turbulent conditions along intertidal zones. They also
adhere opportunistically to a diverse array of solid
substrates, including the skin of marine mammals,
metallic propellers and hulls of ocean liners, and at
the orifices of sewage pipelines, under extreme disruption forces.30,54,84 The adaptability of adhesive
proteins secreted by these animals is astounding in
that the surface energy of the substrate does not
seem to dominate their behavior.6 These organisms
can attach to synthetic polymers with low critical
surface tensions, and even form tenacious bonds
to unmodified human enamel without having to resort to phosphoric acid etching.6 In contrast, resin-enamel bonds created by some of the latest versions of mild self-etching primers and adhesives
are modest in the absence of adjunctive phosphoric
acid etching.85 Resin-based dentin bonds produced
by the so-called wet bonding technique are also adversely affected by alterations in relative humidity,5
and thus appear to be far more technique-sensitive
when compared to the genuine underwater protein-based bonds formed by these sessile aquatic
species.
Polymerized resin matrices are also susceptible
to hydrolytic degradation after water sorption.98
This phenomenon is aggravated by the incorporation of hydrophilic resin components in contemporary dentin adhesives,111 as hydrophilicity and hydrolytic stability of resin monomers are generally
antagonistic properties.105 Recent studies showed
that deterioration of resin-dentin bonds occurs via
the leaching of resins97 instead of degradation of
collagen fibrils within the hybrid layer.19 Contemporary adhesives that contain high concentrations of
acidic resin monomers are, in essence, permeable
membranes that allow water movement between
the interface and the underlying hydrated dentin,
even after dentinal tubules are effectively sealed
with resin tags.115 One can take an impression of
the water droplets that diffuse across a polymerized, single-step adhesive layer by leaving a
93

Tay et al

Fig 2a Single-step adhesives are permeable membranes.

Scanning electron micrograph of the composite side of a
fractured, dentin beam bonded with Reactmer Bond (Shofu,
Kyoto, Japan). The composite was left on the surface of the
cured adhesive for 20 min before light activation. Water
droplets passing from the hydrated dentin through the cured
adhesive resulted in the formation of blisters along the adhesive-composite interface.

Fig 2b Single-step adhesives are permeable membranes.

Transmission electron micrograph of the resin-dentin interface of another single-step adhesive (AQ Bond; Sun Medical,
Kyoto, Japan) after delayed light activation of a resin composite (C). Blisters (arrows) along the composite-adhesive
interface corresponded with those observed in Fig 2a. This
interface separated spontaneously during laboratory specimen preparation and was infiltrated with epoxy resin (E). The
layer of cured adhesive (A) was intact over the surface of the
0.5-m-thick hybrid layer (pointer) and the underlying undemineralized intertubular dentin (U).

light-cured resin composite on top for 20 min before light activation (Figs 2a and 2b). Permeability
of hydrophilic adhesives to water probably hastens
the rate of resin leaching from these adhesive
joints. By contrast, underwater adhesives derived
from the cement glands of barnacles are hydrophobic and cross link by formation of cysteine linkages
that render them practically insoluble in water.55
The insolubility of these proteinaceous adhesives
presents major problems to those who try to remove them, and hampers their purification and
characterization.55 The idea of a biomimetic adhesive based on these marine species is not
new,31,109 but successful mimicry will require an
understanding of the mechanisms used by these
animals at the molecular level, which has not been
possible until recently. Synthetic 3,4-dihydroxyphenylalanine (DOPA)-containing polypeptide analogs
that mimic natural marine adhesive proteins have
recently been formulated. They include blocked
DOPA residues that are produced by conventional
solid phase synthesis and do not require enzymatic
oxidation for activation.137 These are alluring les-

sons for the synthetic polymer chemist. The next

step may involve grafting of these adhesive
polypeptide analogs to vinyl or oxirane monomers
to enable them to be polymerized more rapidly to
polymeric resin-based composites.

94

STIFF AND TOUGH

There is much to be learned from the structure of
nacre, the inner 'mother of pearl' layer of the abalone shell. This natural composite material consists of aragonite plates (CaCO3) that are held together by a bioadhesive protein,103 and is renowned for its combination of high strength and
toughness. Despite being highly mineralized, the
nacre has a fracture toughness that is 3,000 times
more fracture resistant than the calcium carbonate
mineral alone.53 Although contemporary resin-dentin adhesive joints achieve reasonably high tensile
strength, they have relatively low fracture toughness.1,3,110 If future dentin hybrid layers are still required to act as shock-absorbing layers,68,119,121
The Journal of Adhesive Dentistry

Tay et al

this need may be met by biomimetic adhesives that

are both stiff and tough.106
With the exception of HEMA and MMA, most
monomers in dentin adhesives are bi- or multifunctional and are capable of cross linking. This traditionally resulted in fairly stiff adhesive joints with
low fracture toughness.2,73 Demineralized dentin
collagen fibrils have a much lower modulus of elasticity compared with the apatite phase.11,100 However, they are also relatively stiff when compared
with other soft tissue or reconstituted collagen, because of their intra- and intermolecular cross
links.62,117 This limits their extensibility during
stretching,112 unlike mussel byssus collagen that
contain highly extensible, silk fibroin-like domains.22,91 Although adhesive and hybrid layers
have the capacity to act as shock-absorbing layers,
this potential is limited by the relative stiffness of
their constituents. Because these stiff joints cannot tolerate much strain, they cannot deform much
before they break, resulting in characteristic brittle
failure.112 This can be understood by considering
the area under a stress-strain curve, which is the
energy required to break the material (Fig 3). Conversely, adhesive and hybrid layers that are composed primarily of poly(HEMA) hydrogels and
poly(MMA) are more elastic than those made of bifunctional, cross-linked polymer chains.1,86 Theoretically, more energy would be required to break
such material. However, increase in fracture toughness is offset by the lower tensile strength of these
adhesive joints.18,72
Despite their different compositions, adhesive
proteins secreted by aquatic organisms share a
common motif that is highly conserved across species. cDNA sequencing revealed that these macromolecules contain repetitive globular domains, indicating that their structures are highly modular.17,30,103 One of these molecules, which has
been studied in detail, is the nacre shell adhesive
protein. Single-molecule measurements of the
force-extension of these adhesive strands using an
atomic force microscope showed that they lengthen
in a modular fashion, producing a series of 'sawtooth jumps' (Fig 3) that involve sequential unfolding of the globular domains.106 As the molecule is
stretched, the force rises gradually with extension,
producing an initial stress-strain relationship that is
characteristic of an elastic joint. When the stress
increases further, successive unraveling of these
'sacrificial' links occur, protecting the macromolecule from disrupting. This modular process is reVol 4, No 2, 2002

Fig 3 Application of tensile stress to hypothetical linear

polymer chains. (A) A brittle adhesive joint bonded by a stiff
polymer that breaks under high stress but with little deformation. Such a joint is characteristic of most currently available dentin adhesives. (B) A stiff and tough joint bonded by
a hypothetical linear polymer chain with multiple folded domains that provide sequential 'sacrificial' unraveling prior to
ultimate catastrophic failure. This results in a strong adhesive joint with increased fracture toughness.

peated until all domains are unfolded, before fracture of the macromolecule finally occurs. By combining the relative stiffness of each intermediate-strength bond, with elasticity derived from sequential unraveling of the domains, a high fracture
energy is attained, rendering the adhesive strong
as well as tough.
One of the main challenges of biomimetics is
that it demands creative solutions. Natures store
of ideas is valuable to us only if it can be translated into usable technology, particularly in terms of
materials and processing methods. Thus, future innovations in dentin adhesives will probably involve
the synergistic efforts of synthetic polymer chemists and molecular biologists. It is possible that
ideal dentin adhesive monomers will incorporate
biomimetic intermediate-strength domains that
can undergo stepwise reversible unfolding in response to varying functional stress levels before
ultimate catastrophic failure of the adhesive joint
occurs.81 They may also re-establish folded configurations on stress relaxation. These crucial, naturally occurring, protein-like components are not
easily reproducible under the conditions of ex95

Tay et al

treme energies or high pressures that are commonly employed in organic chemical syntheses,
and may require new technologies. These components may be cultured in bacteria, or grown from
plants that contain spliced genes derived from
aquatic adhesive-producing species.89,90 Block copolymers containing tandem repetition of specific
amino acid sequences may then be grafted to vinyl
monomers.35 Incorporation of these bulky proteinaceous groups may sterically block oral esterase
access to the ester bonds in methacrylic polymers,8,67,99 resulting in adhesive resins that are
more durable over time.

SELF-DIAGNOSTIC CAPABILITY
If the disparity between natures creative solutions
and the synthetic art of dentin adhesive manufacturing appears formidable, then adaptive strategies borrowed from other disciplines can offer
more tangible alternatives. After all, dentin bonding is but one use of a wide variety of industrial adhesive applications.93 In adhesive dentistry, a diagnostic mechanism to detect early signs of impending bond degradation is sorely lacking. This
may be due, in part, to the general perception by
the profession that ailing restorations are disposable and hence replaceable. On the contrary, the
consequence of loss of lives incurred by catastrophic failure of an adhesive joint in the aviation
industry is insurmountable, and cannot be directly
assessed in monetary terms. In situ electrochemical sensors are routinely incorporated in aircraft to
detect coating deterioration and substrate corrosion underneath paint coatings.27 These sensors
have recently been modified to monitor moisture
ingress into adhesive bonds that causes plasticizing of the adhesive, and vapor-pressure induced
blistering that leads to premature delamination.26
However, they are currently too bulky for intraoral
use. Adhesive blistering attributed to visibly undetectable moisture penetration has recently been
reported in dentin adhesive joints produced by
some two-step, self-priming adhesives96 as well as
single-step, all-in-one adhesives.114,115 As nanotechnology continues to advance, dentin adhesive
joints may eventually be monitored for moisture
content and early stages of degradation, using
miniaturized sensors that detect the electrical or
electrochemical impedance across these permeable membranes.
96

The incorporation of controlled-release materials into dentin adhesives of the future may provide
expanded capabilities such as the potential for
self-diagnosis, autonomic healing, and therapeutic
functions. Fluorescent dyes with shifts in emission
spectra in response to pH changes are currently
being employed in self-etching primers and adhesives.57 Bonded restorations in caries-prone individuals or in hard to reach areas may ultimately be
monitored by adhesives that contain microencapsulated fluorescent dyes that can detect sustained
increases in acidity or bacterial toxins at a leaking
interface.94 pH-sensitive hydrogels that incorporate methacrylate-based comonomers can be
made into microspheres by emulsion polymerization.87,107 Swelling of ionic hydrogels13,58 could induce release of a pH-sensitive dye or dye-enzyme
conjugates that could hydrolyze bacterial toxins. In
the future, such in situ chemical or biosensors
could provide an intraoral self-referencing, early-warning system against a low pH environment or
recurrent caries that may occur underneath a leaking restoration. Combined with molecular imprinting technology,64 prepolymerized resins with specific recognition sites may be incorporated as fillers into dentin adhesives.15 They may function as
biomimetic sensors by providing synthetic antibody
templates for detecting intraoral toxic substances.127,133 Preliminary work on the incorporation of
polymeric microspheres containing encapsulated
dyes underneath composite restorations has already demonstrated the feasibility of this self-diagnostic concept.102 As phase separation of polymer
blends is a common feature observed in many dentin adhesives,33,113 it may be feasible, perhaps
with the use of suitable surfactants or living free
radical polymerization, to incorporate these prepolymerized hydrogel nanoparticles into dentin adhesives in a more predictable and controllable
manner46,107 that would allow them to serve as interfacial sensors.

AUTONOMIC HEALING POTENTIAL

Durability of adhesive resins is an area of continuing concern. Many in vitro16,43,60,104,126 and several in vivo studies44,97 have shown decreases in the
strength and structural integrity of resin-dentin
bonds over time. This problem has plagued mechanical engineers since Wieghardt129 and Inglis49
queried why ships spontaneously broke in halves
The Journal of Adhesive Dentistry

Tay et al

almost a century ago. For brittle dental polymeric

resins, conceivable routes of failure include hydrolytic or enzymatic degradation, as well as cyclic fatigue. Concentration of stress fields around microvoids results in nucleation of microcracks that can
propagate to catastrophic proportions and cause
total failure of the material.41 Despite advances in
the field of fracture mechanics, a pragmatic solution has not been available, as hidden structural
flaws in existing polymeric materials or adhesive
joints are difficult to diagnose, and almost impossible or impractical to repair once these materials
are in service.
The idea of self-mending adhesive joints is helpful in improving the life expectancy of bonded restorations. However, there is a formidable array of requirements that must be met before such a concept can be realized.132 The polymerized resins
have to contain self-repair components that do not
affect the materials overall properties or performance. These 'smart' materials must also be able
to sense damage, react to the damage, and initiate
healing. Finally, crack closure and healing must restore the material properties to those of the virgin
materials (ie, high 'quantitative healing efficiency'),125 and retard further crack propagation.32 Previous attempts on crack welding in polymers utilized thermal (eg, hot-stretching of PMMA)59 or solvent processes125 that are removed from intraoral
applications. They also require manual manipulation and thus do not constitute autonomic healing
in the strictest sense.
The reaction of glass-ionomer cements12,24 and
glass-ionomer based dentin adhesives51 appears to
satisfy at least some of the stipulations for self-repair. Ion-leachable glass fillers in the set cement can
respond to pH changes by the release of ionic species that diffuse through the permeable, water-based
polyalkenoate matrix. Similar to bioactive glass reactions with body fluids or simulated body fluids, deposition of amorphous calcium phosphates (Stage 4
reaction) can occur within the hydrogel layers of the
glass fillers in glass-ionomer cements. This is followed by their subsequent conversion to hydroxycarbonate apatites (Stage 5 reaction).14,36 A recent
study on a glass-ionomer based all-in-one dentin adhesive showed that during laboratory dentin demineralization in formic acid, artifactual deposition of
dendritic mineral salt complexes occurred within the
porosities of the ion-permeable adhesive resin matrix.116 Glass ionomers may be viewed as 'white
knights' of contemporary dental materials, in that
Vol 4, No 2, 2002

they demonstrate some potential to sense and respond to damages autonomously by eliciting self-repair. However, as the mineral salt or salt complexes
are simply deposited within the potential spaces and
not chemically united with the resin matrix, the quantitative healing efficiency may not be fully optimized.
There is also good reason to separate the structural
supporting components (ie, ion-leachable glass fillers) from self-repair components in future material
design. Recent studies of bioactive glass granules,92 glass-ionomer cements135 and a glass-ionomer based adhesive116 (Fig 4a) ubiquitously demonstrated that deposition of salt or salt complexes
is achieved at the expense of ion-depletion from the
filler cores, resulting in their transformation into hollow shells (Fig 4b).
It is intriguing to see how strikingly similar design
principles are utilized across disciplines as diverse
as biopharmaceutics and mechanical engineering.
The autonomic self-healing approach devised by
White et al128 is an exemplary illustration of how
the concept of controlled release is employed in a
structural epoxy resin composite in response to
crack initiation. The material incorporates unpolymerized resin-containing microcapsules that are
ruptured upon crack intrusion during mechanical
stress. The released repair resin fills up the crack
plane through capillary action. Polymerization is initiated by contact with a catalyst that is pre-dispersed within the polymeric resin matrix, bonding
the crack faces. The catalyst and the unpolymerized repair resin must not meet until they are needed in the damaged zone, which is the function of
the microcapsule membrane. The ingenuity of the
design resides in a balance between the stiffness
of the microcapsule membrane and that of the resin matrix, so that stress fields in the proximity of
the crack tip are directed toward the microcapsules
to ensue their rupture, instead of being deflected
away from these inclusions. A high 'quantitative
healing efficiency' is attained with this experimental system, recovering as much as 75% of the
toughness of the composite.
It is possible that future dentin adhesive and resin composites may be implemented with similar autonomic healing systems (Fig 5). Microcracks are
the precursors to structural failure and the ability to
heal them will enable longer lasting restorations
that require less maintenance. Filling nanoleakage
sites within hybrid layers will also mitigate the deleterious effects of environmentally assisted degradation such as moisture-induced swelling.
97

Tay et al

Fig 4a Transmission electron micrograph of a glass-ionomer based, single-step adhesive bonded to sound dentin.
RM: resin matrix; G:fluoroaluminosilicate glass core; H: siliceous hydrogel layer; pointer: fumed silica. Arrowhead: fluoride-rich phases within glass fillers.

Fig 4b The same adhesive after the bonded dentin specimen was demineralized in formic acid. Complete leaching of
ions from glass fillers resulted in hollow shells surrounded
by a siliceous hydrogel layer (H) and peripheral electron-dense deposits (pointer). Re-deposition of artifactual
dendritic salt complexes occurred within sites that are permeable to ion movement (arrowhead) within the resin matrix
(RM). S: Space occupied by glass filler core before complete
demineralization.

Fig 5
A hypothetical dentin adhesive with the capacity of autonomous self-repair in response to functional stress. A. Propagation of crack plane causes rupture of microcapsules containing unpolymerized repair resin monomers. B. Repair resin fills
up crack by capillary action and polymerizes when it comes into contact with catalysts that are dispersed within the adhesive.

98

The Journal of Adhesive Dentistry

Tay et al

THERAPEUTIC POSSIBILITIES
As low shrinkage resins soon become available for
use in restorative dentistry,77 the need for adhesives with increasingly high initial bond strengths to
resist high c-factor stresses may be less important.25 Future dentin adhesives may assume a
more instrumental role in therapeutics apart from
caries prevention.34,48,101 It is now possible to couple alkaline phosphatase to poly(HEMA) without losing its enzymatic activity, to promote in vitro mineralization.37 It may also be reasonable to take advantage of the diffusivity and hydrogel characteristics of HEMA-containing adhesives, by incorporating
noncollagenous dentin matrix proteins, such as
phosphophoryns, to promote remineralization of incompletely infiltrated collagen matrices in sound or
caries affected dentin.10,123 Alternatively, it may be
possible to create phosphorylated methacrylates
that mimic the 3-D interactions between collagen
and phosphophoryns that are necessary for nucleation of Ca-P crystal growth. With the rapid advance
in molecular imprinting technology,15 other noncollagenous proteins such as bone sialoprotein28 may
be tethered specifically to positive temperature-sensitive polymeric hydrogel nanofillers that
have an upper critical solution temperature
(UCST).87 As the adhesive is applied close to the
pulp, these growth factors may be released in a controlled manner by purposely raising the local temperature of a restoration above body temperature
using a light source. To enable the application of
these functionalized adhesives directly to the pulp,
the 'stealth' properties of polyethylene glycol may
be utilized either as coatings or as constituents of
adhesive hydrogels, to reduce the uptake of particulate carriers by antigen-presenting or other immune cells.88,108 Although early attempts to 'infect'
pulpal cells with a modified adenovirus containing
bone morphogenetic protein-7 sequences to induce
dentinogenesis in pulpal wounds were only partially
successful (Rutherford RB, personal communication, 2001), their delivery by microencapsulated fillers or nanometer-sized hydrogel particles may lead
to successful hard-tissue wound healing.

CONCLUSION
The future of adhesive dentistry is bright. Advances in different scientific disciplines will enrich the
pool of ideas for future advances. The scope for
Vol 4, No 2, 2002

deepening this pool is still tremendous. It is at the

molecular level, however, that we will see the greatest expansion of horizons. This will require far
more collaboration between molecular biologists
and polymer chemists than has previously occurred. Commercialization of such technology can
only be done by large corporations that have both
types of scientists in their research and development divisions.

REFERENCES
1. Ai H, Nagai M. Effect of the adhesive layer thickness on the
fracture toughness of dental adhesive resins. Dent Mater J
2000;19:153-163.
2. Armstrong SR, Boyer DB, Keller JC, Park JB. Effect of hybrid
layer on fracture toughness of adhesively bonded dentin-resin composite joint. Dent Mater 1998;14:91-98.
3. Armstrong SR, Keller JC, Boyer DB. Mode of failure in the dentin-adhesive resin-resin composite bonded joint as determined by strength-based (TBS) and fracture-based (CNSB)
mechanical testing. Dent Mater 2001;17:201-210.
4. Armstrong SR, Keller JC, Boyer DB. The influence of water
storage and C-factor on the dentin-resin composite microtensile bond strength and debond pathway utilizing a filled
and unfilled adhesive resin. Dent Mater 2001;17:268-276.
5. Asmussen E, Peutzfeldt A. The influence of relative humidity
on the effect of dentin bonding systems. J Adhes Dent
2001;3:123-127.
6. Baier RE, Gucinski H, Olivieri MP, Meyer AE. Rapid underwater
bond formation and adhesion of zebra mussel attachment
disc protein. Proceedings for the Symposium on: 6th International Symposium on Structural Adhesives Bonding. American Defense Preparedness Association. Morristown, New
Jersey, May 4-7, 1992:1-9.
7. Baier RE, Shafrin EG, Zisman WA. Adhesion: mechanisms
that assist or impede it. Science 1970;168;1360-1368.
8. Bean TA, Zhuang WC, Tong PY, Eick JD, Yourtee DM. Effect
of esterase on methacrylates and methacrylate polymers in
an enzyme simulator for biodurability and biocompatibility
testing. J Biomed Mater Res 1994;28:59-63.
9. Beech D. Adhesion in the oral environment: biophysical and
biochemical considerations. Int Dent J 1978;28:338-347.
10. Beniash E, Traub W, Veis A, Weiner S. A transmission electron
microscope study using vitrified ice sections of predentin:
structural changes in the dentin collagenous matrix prior to
mineralization. J Struct Biol 2000;132:212-225.
11. Borsato KS, Sasaki N. Measurement of partition of stress
between mineral and collagen phases in bone using x-ray diffraction techniques. J Biomech 1997;30:955-957.
12. Bowen RL. Adhesive bonding of various materials to hard
tooth tissues. II. Bonding to dentin promoted by a surface-active comonomer. J Dent Res 1965;44:895-902.
13. Brannon-Peppas L, Peppas NA. Dynamic and equilibrium
swelling behaviour of pH-sensitive hydrogels containing 2-hydroxyethyl methacrylate. Biomaterials 1990;11:635-644.
14. Brook IM, Hatton PV. Glass-ionomers: bioactive implant materials. Biomaterials 1998;19:565-571.

99

Tay et al
15. Bures P, Huang Y, Oral E, Peppas NA. Surface modifications
and molecular imprinting of polymers in medical and pharmaceutical applications. J Control Release 2001;72:25-33.
16. Burrow MF, Tagami J, Hosoda H. The long term durability of
bond strengths to dentin. Bull Tokyo Med Dent Univ 1993;
40:173-191.
17. Burzio LO, Burzio VA, Silva T, Burzio LA, Pardo J. Environmental
bioadhesion: themes and applications. Curr Opin Biotechnol
1997;8:309-312.
18. Carter DR, Gates EI, Harris WH. Strain-controlled fatigue of
acrylic bone cement. J Biomed Mater Res 1982;16:647657.
19. Carvalho RM, Tay F, Sano H, Yoshiyama M, Pashley DH.
Long-term mechanical properties of EDTA-demineralized dentin matrix. J Adhes Dent 2000;2:193-199.
20. Costa CA, Hebling J, Hanks CT. Current status of pulp capping
with dentin adhesive systems: a review. Dent Mater
2000;16:188-197.
21. Costa CA, Teixeira HM, Nascimento AB, Hebling J. Biocompatibility of two current adhesive resins. J Endod 2000;26:
512-516.
22. Coyne KJ, Qin XX, Waite JH. Extensible collagen in mussel
byssus: a natural block copolymer. Science 1997;277:
1785-1786.
23. Dauvillier BS, Feilzer AJ, de Gee AJ, Davidson CL. Visco-elastic parameters of dental restorative materials during setting.
J Dent Res 2000;79: 818-823.
24. Davidson CL. Glass ionomer cement, an intelligent material.
Bull Group Int Rech Sci Stomatol Odontol 1998;40:38-42.
25. Davidson CL, Feilzer AJ. Polymerization shrinkage and polymerization shrinkage stress in polymer-based restoratives.
J Dent 1997;25:435-440.
26. Davis GD, Dacres CM, Krebs LA. In-situ sensor to detect moisture intrusion and degradation of coatings, composites, and
adhesive bonds. Proc. 1999 Tri-Services Conference on Corrosion, Myrtle Beach, SC, USA, 1999.
27. Davis GD, Dacres CM, Shook M, Wenner BS. Electrochemical
in-situ sensors for detecting corrosion on aging aircraft. In:
Ferregut C, Osegueda R, Nuez A (eds). Proc Workshop on
Intelligent NDE Sciences for Aging and Futuristic Aircraft, University of Texas, El Paso, TX, USA, 1997:141-144.
28. Decup F, Six N, Palmier B, Buch D, Lasfargues JJ, Salih E,
Goldberg M. Bone sialoprotein-induced reparative dentinogenesis in the pulp of rats molar. Clin Oral Invest 2000;
4:110-119.
29. Degrange M. The cost of saving time (Editorial). J Adhes Dent
2000;2:79-80.
30. Deming TJ. Mussel byssus and biomolecular materials. Curr
Opin Chem Biol 1999;3:100-105.
31. Despain RR, De Vries KL, Luntz RD, Williams ML. Comparison
of the strength of barnacle and commercial dental cements.
J Dent Res 1973;52:674-679.
32. Dry C. Procedures developed for self-repair of polymeric matrix composite materials. Comp Struct 1996;35:263-269.
33. Eliades G, Vougiouklakis G, Palaghias G. Heterogeneous distribution of single-bottle adhesive monomers in the resin-dentin interdiffusion zone. Dent Mater 2001;17:277-283.
34. Ferracane JL, Mitchem JC, Adey JD. Fluoride penetration into
the hybrid layer from a dentin adhesive. Am J Dent 1998;
11:23-28.

100

35. Ferrari FA, Cappello J. Functional recombinantly prepared synthetic protein polymer. United States patent number
6,184348. February 6, 2001.
36. Filgueiras MR, La Torre G, Hench LL. Solution effects on the
surface reactions of a bioactive glass. J Biomed Mater Res
1993;27:445-453.
37. Filmon R, Basle MF, Barbier A, Chappard D. Poly(2-hydroxy
ethyl methacrylate)-alkaline phosphatase: a composite biomaterial allowing in vitro studies of bisphosphonates on the
mineralization process. J Biomater Sci Polym Ed 2000;11:
849-868.
38. Frank RM. Structural events in the caries process in enamel,
cementum, and dentin. J Dent Res 1990;69(special issue):559-566;634-636.
39. Fusayama T, Okuse K, Hosoda H. Relationship between hardness, discoloration, and microbial invasion in carious dentin.
J Dent Res 1966;45:1033-1046.
40. Glantz PO, Arnebrant T, Nylander T, Baier RE. Bioadhesion--a
phenomenon with multiple dimensions. Acta Odontol Scand
1999;57:238-241.
41. Griffith AA. The phenomena of rupture and flow in solids. Phil
Trans Roy Soc London A 1920;221:163-198.
42. Gwinnett AJ, Tay F. Early and intermediate time response of
the dental pulp to an acid etch technique in vivo. Am J Dent
1998;11(special issue):35-44.
43. Gwinnett AJ, Yu S. Effect of long-term water storage on dentin
bonding. Am J Dent 1995;8:109-111.
44. Hashimoto M, Ohno H, Kaga M, Endo K, Sano H, Oguchi H.
In vivo degradation of resin-dentin bonds in humans over 1
to 3 years. J Dent Res 2000;79:1385-1391.
45. Hebling J, Giro EM, Costa CA. Biocompatibility of an adhesive
system applied to exposed human dental pulp. J Endod
1999;25:676-682.
46. Hodges JC, Harikrishnan LS, Ault-Justus S. Preparation of
designer resins via living free radical polymerization of functional monomers on solid support. J Comb Chem 2000;
2:80-88.
47. Ikemura K, Endo T. Effect on adhesion of new polymerization
initiator systems comprising 5-monosubstituted barbituric
acids, aromatic sulphonate amides, and tert-butyl peroxymaleic acid in dental adhesive resin. J Appl Polym Sci
1999;72:1655-1668.
48. Imazato S, Torii Y, Takatsuka T, Inoue K, Ebi N, Ebisu S. Bactericidal effect of dentin primer containing antibacterial
monomer methacryloyloxydodecylpyridinium bromide (MDPB) against bacteria in human carious dentin. J Oral Rehabil
2001;28:314-319.
49. Inglis C.E. Stresses in a plate due to the presence of cracks
and sharp corners. Proc Inst Naval Arch 1913;55:219-241.
50. Inoue K, Takeuchi Y, Takeyama S, Yamaha E, Yamazaki F, Odo
S, Harayama S. Adhesive protein cDNA sequence of the mussel Mytilus coruscus and its evolutionary implications. J Mol
Evol 1996;43:348-356.
51. Inoue S, Van Meerbeek B, Vargas M, Yoshida Y, Lambrechts
P, Vanherle G. Adhesion mechanism of self-etching adhesives. In: Tagami J, Toledano M, Prati C (eds). Proceedings
of Conference on: Advanced Adhesive Dentistry. Third International Kuraray Symposium. December 3-4, 1999, Granada, Spain. Cirimido, Italy: Grafiche Erredue,2000:131-148.
52. Itthagarun A, Tay FR. Self-contamination of deep dentin by
dentin fluid. Am J Dent 2000;13:195-200.

The Journal of Adhesive Dentistry

Tay et al
53. Jackson AP, Vincent JFV, Turner, RM. The mechanical design
of nacre. Proc R Soc Lond B 1988;234:415-440.
54. Kamino K. Novel barnacle underwater adhesive protein is a
charged amino acid-rich protein constituted by a Cys-rich repetitive sequence. Biochem J 2001;356(Part 2):503-507.
55. Kamino K, Inoue K, Maruyama T, Takamatsu N, Harayama S,
Shizuri Y. Barnacle cement proteins. Importance of disulfide
bonds in their insolubility. J Biol Chem 2000;275:
27360-27365.
56. Kao WJ. Evaluation of protein-modulated macrophage behavior on biomaterials: designing biomimetic materials for cellular engineering. Biomaterials 1999;20:2213-2221.
57. Kazama H, Oguri M. Visible ray polymerization initiator and
visible ray polymerizable composition. United States Patent
number 5,744,511;1998.
58. Khare AR, Peppas NA. Release behavior of bioactive agents
from pH-sensitive hydrogels. J Biomater Sci Polym Ed
1993;4:275-289.
59. Kies JA, Smith HL. Toughness testing of hot-stretched acrylics. Proc Aircraft Industries Association and Air Research &
Development Command Joint Conference. Dayton, OH,
March 1955.
60. Kitasako Y, Burrow MF, Katahira N, Nikaido T, Tagami J. Shear
bond strengths of three resin cements to dentine over 3 years
in vitro. J Dent 2001;29:139-144.
61. Knight GM. The co-cured, light-activated glass-ionomer cement-composite resin restoration. Quintessence Int 1994;
25:97-100.
62. Koide T, Daito M. Effects of various collagen crosslinking
techniques on mechanical properties of collagen film. Dent
Mater J 1997;16:1-9.
63. Krejci I, Schpbach P, Lutz F. Klinik der Dentinadhsive - Das
Konzept der differenzierten Applikation: totales und selektives Bonding und Dentinversiegelung. Der Freie Zahnarzt
1995;3:34-38.
64. Kriz D, Ranstrm O, Mosbach K. Molecular imprinting - new
possibilities for sensor technology. Anal Chem 1997;69:
345A-349A.
65. Kugel G, Ferrari M. The science of bonding: from first to
sixth generation. J Am Dent Assoc 2000;131(suppl):20S25S.
66. Kwong SM, Tay FR, Yip HK, Kei LH, Pashley DH. An ultrastructural study of the application of dentine adhesives to
acid-conditioned sclerotic dentine. J Dent 2000;28:515528.
67. Larsen IB, Munksgaard EC. Effect of human saliva on surface
degradation of composite resins. Scand J Dent Res
1991;99:254-261.
68. Le SY, Chiang HC, Huang HM, Shih YH, Chen HC, Dong DR,
Lin CT. Thermo-debonding mechanisms in dentin bonding
systems using finite element analysis. Biomaterials
2001;22:113-123.
69. Lee WC, Eakle WS. Stress-induced cervical lesions: review
of advances in the past 10 years. J Prosthet Dent 1996;
75:487-494.
70. Leikin S, Parsegian VA, Yang W, Walrafen GE. Raman spectral
evidence for hydration forces between collagen triple helices.
Proc Natl Acad Sci USA 1997;94:11312-11317.
71. Leinfelder KF. Dentin adhesives for the twenty-first century.
Dent Clin North Am 2001;45:1-6.

Vol 4, No 2, 2002

72. Lewis G, Mladsi S. Correlation between impact strength and

fracture toughness of PMMA-based bone cements. Biomaterials 2000;21:775-781.
73. Lin CP, Douglas WH. Failure mechanisms at the human dentin-resin interface: a fracture mechanics approach. J Biomech 1994;27:1037-1047.
74. Manhart J, Chen HY, Mehl A, Weber K, Hickel R. Marginal quality and microleakage of adhesive class V restorations. J Dent
2001;20:123-130.
75. Massler M. Pulpal reactions to dental caries. Int Dent J
1967;17:441-460.
76. Masuhara E, Kojima K, Tarumi N, Nakabayashi N. Studies on
dental self-curing resins. VII. Adhesive bonding to dentin improved by polymer-ligand. Tokyo Ika Shika Daigaku Iyo Kizai
Kenkyusho Hokoku 1966;2:782-787.
77. Millich F, Jeang L, Eick JD, Chappelow CC, Pinzino CS. Elements of light-cured epoxy-based dental polymer systems. J
Dent Res 1998;77:603-608.
78. Mullner-Eidenbock A, Amon M, Schauersberger J, Kruger A,
Abela C, Petternel V, Zidek T. Cellular reaction on the anterior
surface of 4 types of intraocular lenses. J Cataract Refract
Surg 2001;27:734-740.
79. Nalbandian J, Federico G, Sognnaes RF. Sclerotic age
changes in root dentin of human teeth as observed by optical,
electron, and x-ray microscopy. J Dent Res 1959;39:
598-607.
80. Neale SD, Athanasou NA. Cytokine receptor profile of arthroplasty macrophages, foreign body giant cells and mature osteoclasts. Acta Orthop Scand 1999;70:452-458.
81. Oberhauser AF, Hansma PK, Carrion-Vazquez M, Fernandez
JM. Stepwise unfolding of titin under force-clamp atomic
force microscopy. Proc Natl Acad Sci USA 2001;98:468-472.
82. Opdam NJ, Feilzer AJ, Roeters JJ, Smale I. Class I occlusal
composite resin restorations: in vivo post-operative sensitivity, wall adaptation, and microleakage. Am J Dent 1998;
11:229-234.
83. Palamara D, Palamara JE, Tyas MJ, Messer HH. Strain patterns in cervical enamel of teeth subjected to occlusal loading. Dent Mater 2000;16:412-419.
84. Parsons EC, Overstreet RM, Jefferson TA. Parasites from Indo-Pacific hump-backed dolphins (Sousa chinensis) and finless porpoises (Neophocaena phocaenoides) stranded in
Hong Kong. Vet Rec 2001;148:776-780.
85. Pashley DH, Tay FR. Aggressiveness of contemporary
self-etching adhesives. Part II: etching effects on unground
enamel. Dent Mater 2001;17:430-444.
86. Paul SJ, Leach M, Rueggeberg FA, Pashley DH. Effect of water
content on the physical properties of model dentine primer
and bonding resins. J Dent 1999;27:209-214.
87. Peppas NA, Bures P, Leobandung W, Ichikawa H. Hydrogels
in pharmaceutical formulations. Eur J Pharmaceut Biopharmaceut 2000;50:27-46.
88. Peracchia MT, Fattal E, Desmale D, Besnard, M Nol JP, Gomis JM, Appel M, dAngelo J, Couvreur P. Stealth PEGylated
polycyanoacrylate nanoparticles for intravenous administration and splenic targeting. J Control Release 1999;60:
121-128.
89. Poirier Y. Production of polyesters in transgenic plants. Adv
Biochem Eng Biotechnol 2001;71:209-240.

101

Tay et al
90. Poirier Y, Nawrath C, Somerville C. Production of polyhydroxyalkanoates, a family of biodegradable plastics and elastomers, in bacteria and plants. Biotechnology (NY) 1995;
13:142-150.
91. Qin XX, Coyne KJ, Waite JH. Tough tendons. Mussel byssus
has collagen with silk-like domains. J Biol Chem 1997;272:
32623-32627.
92. Radin S, Ducheyne P, Falaize S, Hammond A. In vitro transformation of bioactive glass granules into Ca-P shells. J
Biomed Mater Res 2000;49:264-272.
93. Roulet J-F. A world without adhesion? (Editorial) J Adhes Dent
2001;3:119.
94. Russell RJ, Pishko MV, Simonian AL, Wild JR. Poly(ethylene
glycol) hydrogel-encapsulated fluorophore-enzyme conjugates for direct detection of organophosphorus neurotoxins.
Anal Chem 1999;71:4909-4912.
95. Sakoolnamarka R, Burrow MF, Prawer S, Tyas MJ. Micromorphological investigation of noncarious cervical lesions treated with demineralizing agents. J Adhes Dent 2000;2:
279-287.
96. Sanares AME, Itthagarun A, King NM, Tay FR, Pashley DH.
Adverse surface interactions between one-bottle light-cured
adhesives and chemical-cured composites. Dent Mater
2001;17:542-556.
97. Sano H, Yoshikawa T, Pereira PNR, Kanemura N, Morigami
M, Tagami J, Pashley DH. Long-term durability of dentin
bonds made with a self-etching primer, in vivo. J Dent Res
1999;78:906-911.
98. Santerre JP, Shajii L, Leung BW. Relation of dental composite formulations to their degradation and the release of hydrolyzed polymeric-resin-derived products. Crit Rev Oral Biol
Med 2001;12:136-151.
99. Santerre JP, Shajii L, Tsang H. Biodegradation of commercial
dental composites by cholesterol esterase. J Dent Res
1999;78:1459-1468.
100. Sasaki S, Odajima S. Stress-strain curve and Youngs modulus of a collagen molecule as determined by the x-ray diffraction technique. J Biomechanics 1996;29:655-658.
101. Segura A, Donly KJ, Quackenbush B. In vitro dentin demineralization inhibition effects of an experimental fluoridated HEMA and water wetting agent. J Oral Rehabil 2000;27:
532-537.
102. Shen C, Sarrett D, Batich CD, Anusavice KJ. System for the
pH-dependent release of a dye in model dental restorations.
J Dent Res 1994;73:1833-1840.
103. Shen X, Belcher AM, Hansma PK, Stucky GD, Morse DE.
Molecular cloning and characterization of lustrin A, a matrix
protein from shell and pearl nacre of Haliotis rufescens. J
Biol Chem 1997;272;32472-32481.
104. Shono Y, Terashita M, Shimada J, Kozono Y, Carvalho RM,
Russell CM, Pashley DH. Durability of resin-dentin bonds.
J Adhes Dent 1999;1:211-218.
105. Simo-Alfonso E, Gelfi C, Sebastiano R, Citterio A, Righetti
PG. Novel acrylamido monomers with higher hydrophilicity
and improved hydrolytic stability: I. Synthetic route and product characterization. Electrophoresis 1996;17:723-731.
106. Smith BL, Schffer TE, Viani M, Thompson JB, Frederick NA,
Kindt J, Belcher A, Stucky GD, Morse DE, Hansma PK. Molecular mechanistic origin of the toughness of natural adhesives, fibres and composites. Nature 1999;399:
761-763.

102

107. Soppimath KS, Aminabhavi TM, Kulkarni AR, Rudzinski WE.

Biodegradable polymeric nanoparticles as drug delivery devices. J Control Release 2001;70:1-20.
108. Stolnik S, Illum L, Davis SS. Long circulating microparticulate drug carriers. Adv Drug Deliv Rev 1995;16:195-214.
109. Strassler HE. If only we could use the tenacious barnacle
for cementing restorations. Dent Off 1992;11:4-5.
110. Tam LE, Khoshand S, Pilliar RM. Fracture resistance of dentine-composite interfaces using different adhesive resin layers. J Dent 2001;29:217-225.
111. Tanaka J, Ishikawa K, Yatani H, Yamashita A, Suzuki K. Correlation of dentin bond durability with water absorption of
bonding layer. Dent Mater J 1999;18:11-18.
112. Tay FR, Carvalho R, Yiu CKY, King NM, Zhang Y, Agee K, Bouillaguet S, Pashley DH. Mechanical disruption of dentin collagen fibrils during resin-dentin bond testing. J Adhes Dent
2000;2:175-192.
113. Tay FR, Gwinnett JA, Wei SH. Micromorphological spectrum
from overdrying to overwetting acid-conditioned dentin in
water-free acetone-based, single-bottle primer/adhesives.
Dent Mater 1996;12:236-244.
114. Tay FR, King NM, Suh BI, Pashley DH. Effect of delayed activation of light-cured resin composites on bonding of
all-in-one adhesives. J Adhes Dent 2001;3:207-225.
115. Tay FR, Pashley DH, Suh BI, Carvalho RM, Itthagarun A. Single-step adhesives are permeable membranes. J Dent (in
press).
116. Tay FR, Sano H, Tagami J, Hashimoto M, Moulding K, Yiu
C, Pashley DH. Ultrastructural study of a glass ionomer-based, all-in-one adhesive. J Dent 2001;29:489-498.
117. Thompson JI, Czernuszka JT. The effect of two types of
cross-linking on some mechanical properties of collagen.
Biomed Mater Eng 1995;5:37-48.
118. Thonemann B, Federlin M, Schmalz G, Grndler W. Total
bonding vs selective bonding: marginal adaptation of Class
2 composite restorations. Oper Dent 1999;24:261-271.
119. Uno S, Finger WJ. Function of the hybrid zone as a stress-absorbing layer in resin-dentin bonding. Quintessence Int
1995;26:733-738.
120. van Dijken JW. Clinical evaluation of three adhesive systems
in class V non-carious lesions. Dent Mater 2000;16:
285-291.
121. Van Meerbeek B, Willems G, Celis JP, Roos JR, Braem M,
Lambrechts P, Vanherle G. Assessment by nano-indentation
of the hardness and elasticity of the resin-dentin bonding
area. J Dent Res 1993;72:1434-1442.
122. Vogler EA. Structure and reactivity of water at biomaterial
surfaces. Adv Colloid Interface Sci 1998;74:69-117.
123. Wada Y, Fujisawa R, Nodasaka Y, Kuboki Y. Electrophoretic
gels of dentin matrix proteins as diffusion media for in vitro
mineralization. J Dent Res 1996;75:1381-1387.
124. Waite JH. Reverse engineering of bioadhesion in marine
mussels. Ann N Y Acad Sci 1999;875:301-309.
125. Wang EP, Lee S, Harmon J. Ethanol-induced crack healing
in poly(methyl methacrylate). J Polym Sci B 1994;32:
1217-1227.
126. Watanabe I, Nakabayashi N. Bonding durability of photocured phenyl-P in TEGDMA to smear layer-retained bovine
dentin. Quintessence Int 1993;24:335-342.

The Journal of Adhesive Dentistry

Tay et al
127. Whitcombe MJ, Rodriguez, ME, Villar P, Vulfson E. A new
method for the introduction of recognition site functionality
into polymers prepared by molecular imprinting - Synthesis
and characterization of polymer receptors for cholesterol.
J Am Chem Soc 1995;117:7105-7111.
128. White SR, Sottos NR, Geubelle PH, Moore JS, Kessler MR,
Sriram SR, Brown EN, Viswanathan S. Autonomic healing
of polymer composites. Nature 2001;409:794-797.
129. Wieghardt K. ber das Spalten und Zerreissen elastischer
Krper. Z. Mathematik und Physik 1907;55:60-103. (English translation by HP Rossmanith: Wieghardt K. On splitting and cracking of elastic bodies. Fatigue and Fract Eng
Mater Struct 1995;12:1371-1405).
130. Wilson NH. Conference report. Direct adhesive materials:
current perceptions and evidence - future solutions. J Dent
2001;29:307-316.
131. Wilson NH, Cowan AJ, Unterbrink G, Wilson MA, Crisp RJ.
A clinical evaluation of Class II composites placed using a
decoupling technique. J Adhes Dent 2000;2:319-329.
132. Wool RP, OConner KM. A theory of crack healing in polymers. J Appl Phys 1982;52:5953-5963.
133. Wulff, G. Molecular imprinting in cross-linked materials with
the aid of molecular templates - a way towards artificial antibodies. Angew Chem In Edn Eng 1995;34:1812-1832.
134. Xhonga FA . Bruxism and its effect on the teeth. J Oral Rehabil 1977;4:65-76.
135. Yip HK, Tay FR, Ngo HC, Smales RJ, Pashley DH. Bonding
of contemporary glass ionomer cements to dentin. Dent
Mater 2001;17:456-470.
136. Yoshiyama M, Tay FR, Torii Y, Nishitani, Y, Doi J, Ciucchi B,
Pashley DH. Resin adhesion to caries-infected dentin. Am
J Dent 2002 (in press).
137. Yu M, Deming TJ. Synthetic polypeptide mimics of marine
adhesives. Macromolecules 1998;31:4739-4745.

Vol 4, No 2, 2002

103