Dentin Bonding Agents

Introduction

History

Basic principles of adhesion

Factors that affect adhesion

Ideal properties of adhesives

Basic chemistry of light cured resin systems

Histological differences between Enamel & Dentin

The Smear layer & its role in the generation of adhesives

Evolution of adhesives

Components in an adhesive system

What are Primers & its role?

Role of solvents

Collagen fibril collapse

Dentin- How wet is wet?

How to prevent over wet or over dry dentin?

How to achieve moist dentin?

Re-wetting agents- Are they necessary?

Classification of contemporary adhesives

Etch & Rinse approach

The Hybrid layer

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Self-etching primers

Classification of self etching systems

Adhesive Challenges:

MMP Inhibition-The Next Adhesive Paradigm

Aging of the Hybrid Layer

Degradation of the Resin

How to increase bond stability?

Conclusion

References

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ABBREVIATIONS OF MONOMERS, INITIATORS AND INHIBITORS,
FILLER PARTICLES AND COUPLING FACTORS USED IN ADHESIVES

Abbreviations - Monomers

4-AETA: 4-acryloyloxyethyl trimellitate anhydride

4-AET: 4-acryloylethyl trimellitic acid
AMPS: 2-acrylamido-2-methyl-1-propanesulfonic acid
Bis-MEP: bis[2-(methacryloyloxy)ethyl] phospate
Bis-EMA: ethoxylated bisphenol A glycol dimethacrylate
Bis-GMA: bisphenol A diglycidyl methacrylate
BPDM: biphenyl dimethacrylate or 4,40-dimethacryloyloxyethyloxycarbonylbiphenyl-3,30-
dicarboxylic acid
Di-HEMA phosphate: di-2-hydroxyethyl methacryl hydrogenphosphate
DMAEMA: dimethylaminoethyl methacrylate
EAEPA: ethyl 2-[4-(dihydroxyphosphoryl)-2-oxabutyl]acrylate
EGDMA: ethyleneglycol dimethacrylate
GDMA: glycerol dimethacrylate
GPDM: glycerol phosphate dimethacrylate
HDDMA: 1,6-hexanediol dimethacrylate
HEMA: 2-hydroxyethyl methacrylate
HEMA-phosphate: 2-hydroxyethyl methacryl dihydrogenphosphate
HFGA-GMA: hexafluoroglutaric anhydride-glycerodimethacrylate adduct
HPMA: 2-hydroxypropyl methacrylate
MA: methacrylic acid
MAEPA: 2,4,6 trimethylphenyl 2-[4-(dihydroxyphosphoryl)-2-oxabutyl]acrylate
MAC-10: 11-methacryloyloxy-1,10-undecanedicarboxylic acid
10-MDP: 10-methacryloyloxydecyl dihydrogenphosphate
MDPB: methacryloyloxydodecylpyridinium bromide
4-META: 4-methacryloyloxyethyl trimellitate anhydride
4-MET: 4-methacryloyloxyethyl trimellitic acid
MMA: methyl methacrylate
MMEP: mono-2-methacryloyloxyethyl phthalate (sometimes also called PAMA: phtalic acid
monomethacrylate)
5-NMSA (or MASA): N-methacryloyl-5-aminosalicylic acid
NPG-GMA: N-phenylglycine glycidyl methacrylate
NTG-GMA: N-tolylglycine glycidyl methacrylate or N-(2-hydroxy-3-((2-methyl-1-oxo-2-
propenyl)oxy)propyl)-N-tolyl glycine
PEGDMA: polyethylene glycol dimethacrylate
PEM-F: pentamethacryloyloxyethylcyclohexaphosphazene monofluoride
PENTA: dipentaerythritol pentaacrylate monophosphate
Phenyl-P: 2-(methacryloyloxyethyl)phenyl hydrogenphosphate
PMDM: pyromellitic diethylmethacrylate or 2,5-dimethacryloyloxyethyloxycarbonyl-1,4-
benzenedicarboxylic acid

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PMGDM: pyromellitic glycerol dimethacrylate or 2,5-bis(1,3-dimethacryloyloxyprop-2-
yloxycarbonyl)benzene-1,4-dicarboxylic acid
Pyro-EMA: tetramethacryloyloxyethyl pyrophosphate
TCB: butan-1,2,3,4-tetracarboxylic acid di-2-hydroxyethylmethacrylate ester
TEGDMA: triethylene glycol dimethacrylate
TMPTMA: trimethylolpropane trimethacrylate
UDMA: urethane dimethacrylate or 1,6-di(methacryloyloxyethylcarbamoyl)-3,30,5-
trimethylhexaan

ABBREVIATIONS - INITIATORS AND INHIBITORS

BHT: butylhydroxytoluene or butylated hydroxytoluene or ,2,6-di-(tert-butyl)-4-methylphenol

(inhibitor)
BPO: benzoylperoxide (redox initiator)
BS acid: benzenesulfinic acid sodium salt (redox initiator)
CQ: camphorquinone or camphoroquinone or 1.7.7-trimethylbicyclo-[2,2,1]-hepta-2,3-dione
(photo-initiator)
DHEPT: N,N-di-(2-hydroxyethyl)-4-toluidine (co-initiator)
MEHQ: 4-methoxyphenol or monoethyl ether hydroquinone (inhibitor)
ODMAB: 2-(ethylhexyl)-4-(dimethylamino)benzoate (co-initiator)
TPO: Lucirin TPO, BASF (photo-initiator)
UV-9: 2-hydroxy-4-methoxybenzophenone (photo-initiator)

ABBREVIATIONS - FILLERS AND SILANE COUPLING FACTORS

Coupling factor A174: g-methacryloxypropyltrimethoxysilane

F-PRG: full reaction type pre-reacted glass-ionomer fillers
NaF: sodium fluoride
Na2SiF6: disodium hexafluorosilicate
POSS nano-particulates: polyhedral oligomer silsesquioxanes

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Key Words:

Adhesive system, Smear layer, Bifunctional molecule, Hybridization, Wet bonding, Conditioner,
Primer, Self etching primer, Self etching adhesive

INTRODUCTION

Adhesives are substances used to retain or bond composites to dental enamel or dentin. They are
very important for any restoration that does not have macro mechanical retention. Adhesives and
the relevant adhesive techniques should, therefore, guarantee reliable bonding, withstand
separation of the individual layers and adequately distribute the forces that occur in clinical
situations.

The primary aim of dental adhesives is to provide retention to composite fillings or composite
cements. In addition to withstanding mechanical forces, and in particular shrinkage stress from
the lining composite, a good adhesive also should be able to prevent leakage along the
restoration’s margins. Clinically, failure of restorations occurs more often due to inadequate
sealing, with subsequent discoloration of the cavity margins, than due to loss of retention.
The adhesive capacity of dental adhesives is based on a twofold adhesion. First, the adhesive
adheres to enamel and dentin, and second, the adhesive binds the lining composite.

The latter has been shown to be a process of co-polymerization of residual double bonds (–
CQC–) in the oxygen inhibition layer. As for the bond to enamel and dentin, micromechanical
adhesion is assumed to be the prime bonding mechanism. This is achieved by an exchange
process, by which inorganic tooth material is replaced by resin monomers that become
interlocked in the retentions upon curing. Diffusion and capillarity are the primary mechanisms
to obtain micro-mechanical retention. Microscopically, this process is called ‘hybridization’.

History

1967: Dr Michael Buonocore describes a process for enhancing the adhesion of plastics to teeth,
thus ushering in the modern era of restorative dentistry.

1978: Dr Takao Fusayama introduced Phenyl-P

1979: 4-MET was invented & patented in Japan by S.M.Inc

1981:K.M Inc developed Phenyl-P to “10-MDP” in order to improve monomer properties.

(The promotion of adhesion by infiltration of monomers into tooth substrates. J
Biomed Mater Res.1982; 16:265-273)

1982: Hybrid Layer was first described by Prof. Nakabayashi N.

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1992: Vitrebond copolymer, a modified polyacrylic acid with polymerizable methacrylate groups
was introduced. It had a blend of hydrophilic & hydrophobic monomers, which offered
consistent bonding in the presence of high humidity.

1993: Self etching primer was introduced.

2006: Kishiro K et al. proposed the concept of Nano-interaction zone.

(New concept of resin-dentin interfacial adhesion: the nanointeraction zone.
J. Biomater 2006;77: 401-8.)

2009: Nikiado T. discovers the interface that created underneath the hybrid layer of self-etch
adhesive and named “Acid-base resistant zone (ABRZ)”.
(Assessment of the nanostructure of acid-base resistant zone by the application of all-in-one
adhesives: Super dentin formation. Biomed Mater Eng.2009; 19(2-3):163-71)

2011: Van Meerbeek et al revisited the “AD-concept (adhesion decalcification concept, Yoshida
et al. 2001) as a basis of durable bonding.
(State of art self-etch adhesives. Dent Mater.2011; 27:17-28

Basic Principles of Adhesion

Adhesion, as a phenomenon, is defined as the state in which two surfaces are held together by
interfacial forces, which may consist of chemical forces (primary or secondary valance) or
interlocking forces (mechanical), or both.
American Society of Testing and Materials, 1964

Adhesive: A substance capable of holding materials (substrate) together by surface attachment.

1. Adhesion to teeth involves removing Calcium Phosphate (CaPO4) or the mineral portion of
hydroxyapatite through acidic dissolution, and the replacement of the lost mineral with acrylic
monomers.

FACTORS THAT AFFECT ADHESION:

• Surface energy of surfaces

• Surface roughness

• Surface tension of adhesives

• Thickness of adhesives

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Ideal properties of Adhesives

 Biocompatible

 Bond indifferently to enamel and dentin

 Sufficient strength to resist masticatory force

 Mechanical property close to tooth structure

 Resist to degradation in oral environment

 Easy to use

 Thin film thickness

 Fluoride-releasing

 Suitable for moist and dry environments

 Stability

Basic chemistry of light cured resin systems:

a. All adhesives and composites begin initially as fluid or plastic materials and “set” to a solid
upon curing.

i. This “set” occurs as a result of free radical attack (light activation of photo initiators such as
camphorquinone or PPD) of carbon double bonds within acrylic monomers, converting them to
carbon single bonds. These single bonds have shorter atomic distances, therefore the acrylic
chain “shortens” or shrinks, yielding a reduction of volume in the composite or adhesive mass.

ii. Additional chain shortening occurs as a result of cross linking between linear chains.

iii. This volumetric “shrinkage” upon curing is what makes the acrylic “hard” or “cured.”

iv. Fillers are placed in resins (both adhesives and composites) to reduce the physical amount of
monomer that can “shrink,” and to increase the physical properties of the resin.

v. All current adhesives and composites undergo 1.5-3% volumetric shrinkage upon setting.

vi. This volumetric shrinkage creates what is called “polymerization stress” on the bond to the
tooth.

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vii. This stress can be measured, and averages approximately 17 Mpa.

viii. Therefore, bond strengths greater than 17 Mpa are considered necessary to withstand the
polymerization stress associated with the curing of the resin.

ix. Bond strengths to acid etched enamel range from 20- 25 Mpa.

This bond strength has proven to be sufficient enough to provide long term, stable bonds in
the mouth for over 60 years.

Histological differences between Enamel and Dentin

a. Enamel:

i. Composed of 90% inorganic mineral (hydroxyapatite) keyhole shaped prisms

1. Outermost layer of uncut enamel typically lacks prisms, hence is “aprismatic.” poses
difficulty with most modern “Self Etch”systems.

2. Abrading or cutting enamel exposes prisms, making the enamel more susceptible to
etching.

ii. 6% proteins, and other inter prismatic substances

iii. 4% water – Loosely bound between the keyholes shaped prisms. Since there is no circulation
to replenish this water, enamel can be desiccated to yield an anhydrous surface (hydrophobic).

b. Dentin:

i. Composed of 60% inorganic mineral (hydroxyapatite)

ii. 30% organic collagen

1. Collagen is the basic component of skin, hair, cartilage, blood vessels, organs, and
DENTIN!

2. Not found in enamel

3. Is a helical strand often described in dentin as “noodles” or “hair”

iii. 10% water

1. A small amount of this water is bound up in the inorganic hydroxyapatite crystals.

2. But most of it comes from the dentinal tubules, which are connected, to the pulp.

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 a. Has a constant pressure from the pulp

b. As the surface moisture evaporates from the tubules, it is replenished by more

fluid from the pulp pressure.

3. The role of this moisture in the tubules in creating a hydrophilic substrate depends on
proximity to the pulp.

a. Shallow dentin preps – tubules are narrow, far apart, and a long way from the pulp

b. Deep dentin preps – tubules are wide, close together, and pulp pressure can be
significant

c. Vasoconstrictors in anesthetics reduce pulp pressure significantly

iv. Therefore, dentin is considered to be a hydrophilic substrate.

All adhesives and composites used in dentistry are HYDROPHOBIC.

a. These are moisture-HATING materials and will not stick to hydrophilic substrates
without the use of PRIMERS.

The Smear Layer and its Role in the “Generations” of Adhesives

What is a Smear Layer?

a. The layer of freshly cut dentin lining the floor of a preparation.

b. Composed of ground up hydroxyapatite, collagen, and trash.
c. Loosely attached to the dentin floor (2-3 Mpa)
d. Very thin- 1-5 microns thick
e. Packs into tubules to form “plugs”- Has been called the “Biologic Band-Aid”
because these plugs prevent fluid movement in the tubules and serve as a slight
barrier to bacterial infiltration.

All adhesives can be classified according to how they deal with this “Smear Layer.”

a. Earliest generations (3rd – 1970’-80’s) tried to modify and stick to it

b. Total Etch (4th and 5th) Generations recommend removing it.
c. Self-Etching Generations (6th and 7th) incorporate it into the bond.

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Evolution of Adhesives:

 ENAMEL Adhesion:
- Buonocore (1955) 80% phosphoric acid on enamel for 60 seconds
- BIS-GMA (Bowen)
- Simple micromechanical retention with hydrophobic diluted resins

 DENTIN Adhesion:

1. “First Generation”:
 BIS-GMA, NTG-GMA = unfilled resins
 Hydrophobic, contraction gap, smear layer left intact
 Hydrolyzed quickly
 Clinically unsatisfactory
 Products:
- Adaptic Bonding Agent
- Enamel Bond Resin
- Durafill Bond

2. “Second Generation”:
 Phosphonated esters
 Ionic bonds to calcium in retained smear layer
 Hydrophobic
 Hydrolysis - rapid bond degeneration
 Limited by smear layer bond strength to underlying dentin (2-4 Mpa)
 Products:
Bondlite, Creation 3 in 1, Clearfil, Dentin Enamel Bonding Agent, Prisma Universal
Bond, Dentin Bond LC, Scotchbond

3. “Third Generation”:
 Removed/modified smear layer
 Hydrophilic
 Bifunctional molecule (Primer) - HEMA, 4-META, PMDM, PMGDM, BPDM,
PENTA, GPDM
 Then placed BIS-GMA adhesive, then composite
 Products:
- GLUMA, XR Bond, Prisma Universal Bond 3, Tenure, Scotchbond 2, Mirage Bond
Plus, Clearfil New Bond
 VLC cured for initial resistance to contraction gap formation
 Bond strengths varied widely due to differences in dentin. Great improvement.

4. “Fourth Generation”:
 Extremely hydrophilic primers.

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  Aqueous solutions, acetone, ethanol as water chasers to enhance permeation of
hydrophilic portion of primer into demineralized dentin after etching
 Smear layer removed/modified
 Intentional etching of dentin (Fusayama)
 Hybridization (Nakabayashi)
- Demineralized zone
- Collagen fibrils - Collagen Smear Layer if unsupported collagen dried
- Resin Impregnated layer (Hybrid layer)
- Wetbonding (Kanca)
- Microleakage vs. Nanoleakage

 Strength of bond:
- Not dependent on thickness of hybrid layer
- Dependent on
a) Ability of an adhesive to wet demineralized zone
b) Permeability of dentin
 Concept of universal adhesive systems initiated.
- Enamel, dentin (wet, dry, sclerotic), porcelain, composite, metals, fresh and
set amalgam

5. “Fifth Generation”:
 Consolidated systems. Etch separate. Primer and adhesive combined.
 Advertised as time savers
 No mixing
 VLC only - not universal or dual cure

6. “Sixth Generation”:
 Self –Etch products- Etchant and primer combined. Adhesive separate step. In some
cases, etchant, primer and adhesive combined in one all-encompassing step.

 Advantages – Etch and prime certain to be same depth. Time saver. Minimal
postoperative sensitivity. Don’t open tubules. Good under amalgam as well.

 Disadvantages – extremely technique sensitive. May not work well on uninstrumented

enamel. Some researchers say this is the wave of the future, but these are too
inconsistent at present. Light cured only. CRA states they are universally compatible
with different cure modes of composite, but unconfirmed in other studies.

Fifth and Sixth generations are the most technique sensitive

7. “Seventh Generation”:
Advertised to be “seventh generation” simply because they have etchant, primer and adhesive
in one bottle and require no mixing at all.

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Eg– i Bond, G-Bond, Clearfil S3 , Xeno IV, OptiBond All-In-One, AdheSE One F, Adper Easy
Bond, Go!, Excel Bond LC, I Bond SE, Bond Force, ImageBond SE, Bond 1 SF, BeautiBond,
Ace One and Done All Bond SE, Xeno IV DC, Futurabond DC, Clearfil DC Bond, BeautiBond,
Surpass (advertised to be Eighth Generation), G-aenialBond, OptiBond XTR, Bond 1 SF, Oxford
Bond SE (dual cure), Bond Force Pen

Components in an Adhesive System

Etchant
- Usually describes enamel treatment
- Commonly uses 32-40% H3PO4
- Weaker acids may not etch adequately (self-etch products)
- Enamel - must see frosted surface
- Gels, Liquids - remove inorganic components of tooth structure

Conditioner
- Not needed in “total etch” technique
- Actually a low pH weak acid etchant
- Dissolves smear layer so primer can contact intact demineralized dentin, yet
leave tubules occluded
- Created demineralized zone containing collagen fibrils
- Weak acids: Phosphoric, maleic, citric, acetic, nitric, PENTA, EDTA
- Simultaneous dentin-enamel etch may be inadequate
- Don’t over-etch and denature collagen

Primer
- Bifunctional molecule with one end hydrophobic, one end hydrophilic
- Permeation of conditioned dentin by hydrophilic end assisted by water and
water chasers such as ethanol or acetone.
- Hydrophobic end available for bonding to adhesive
- Best examples: HEMA, 4-META derivatives, BPDM, GPDM, PAAMA,
PMDM, PMGDM, PENTA

*0 Adhesive (Bonding agent)

- Unfilled resin - BIS-GMA or UDMA, thinned with TEG-DMA diluent
- Cure - VLC, Auto, Dual
- Follow directions!
- Filled adhesives
- Increase bond strength
- Better stress absorbers
- Resist microflexure
- Intermediate modulus of elasticity between tooth and restorative
- “Contraction stress was absorbed and relieved by the application
of an increasing thickness of low-stiffness adhesive”, J Dent Res,
March 2000

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 - “This finding at three years may indicate that the filled adhesive
is more resistant to fatigue forces and could provide more durable
retention than the unfilled adhesive.” Swift, JADA, August 2001.

What are Primers & its role?

a. These are bipolar monomers that have a hydrophilic molecule on one end of the
chain and a hydrophobic acrylic group on the other end (hence bipolar)

b. The hydrophilic end permits wetting (intimate contact) with wet surfaces such as
dentin, while the hydrophobic end bonds to the acrylic adhesive or composite that
follows.

c. HEMA is a typical primer found in many adhesive systems.

d. Primers are usually suspended in hydrophilic, water-chasing volatile solvents such

as acetone, alcohol, water or a combination of these.

Role of solvents

a. Solvents serve to carry the suspended primers deep into the wet dentin substrate
and tubules.

b. They are NOT essential in the chemistry of the primer – THEY NEED TO BE

EVAPORATED OFF. The more volatile the solvent… typically the better?

In adhesives, water, ethanol and acetone are the most commonly used solvents. The
use of these organic solvents in adhesives must be explained by their inexpensiveness, their
wide availability, and their good biocompatibility. DENTSPLY added tert-butanol to a recent
2 step –Etch &Rinse, because of its similar vapor pressure as ethanol, but better stability
towards chemical reaction with monomers.

Chemists have classified solvents into three categories according to their polarity:

polar protic, dipolar aprotic and apolar solvents

Polar protic solvents consist of a hydroxyl-group that can form strong hydrogen bonds. Examples
are water and ethanol.

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Polar aprotic solvents do not have the required hydroxyl-group to form hydrogen bonds, but do
have a large dipole moment. They usually also contain a keton group. Typical example is
acetone.

Apolar solvents have both a low dielectric constant and dipole moment. The polarity of a solvent
is also important to predict the shelf life of adhesives, as apolar solvents will more easily pass
through traditional polyethylene packaging.

Collagen Fibril Collapse

1. What is collagen fibril collapse?

a. Once the collagen in dentin is exposed, these fibrils are left vulnerable to levels
of moisture present on the dentin surface.

b. Many researchers have proven that these collagen fibers must be suspended in a
reasonable amount of water so that they will remain “fluffy” or “floating” in such a
way that they don’t obstruct the infiltration of bipolar primers as they seek to wet the
demineralized intertubular dentin and pass into the tubules to wet the peritubular
dentin.

c. If dentin is inadvertently or deliberately air dried to the point that not enough water is
present to “float” or suspend the collagen fibers, these fibers may clump together
through Van Der Waals and hydrogen bonding, forming an impenetrable “mat” or
barrier to the primers.

d. Many dentists have been taught to desiccate enamel until a dry, frosty appearance is
notice to “verify” the etch. While this is not detrimental to enamel, it is catastrophic
to dentin bonding as it causes the collagen in dentin to “collapse” or fail to be “fluffy.”

e. Therefore, desiccating preparations that expose both enamel and dentin is

CONTRADINDICATED.

How wet is “wet?”

a. Shortly after researchers discovered the need to leave vulnerable collagen moist and
fluffy, they began to realize that leaving too much water on the tooth after rinsing the
etchant off weakened the dentin bond and increased the likelihood of postoperative
sensitivity.

b. Work by Franklin Tay and others demonstrated that too much water created an “oil
and water” type suspension, and water blisters formed on the overwet dentin surface.
These water blisters caused a phase separation in the primers, and dispersed them
unevenly across the demineralized dentin surface and into the dentin tubules.

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 c. Failure to get adequate primer coverage over and into the tubules produced
unacceptable bond strengths and permitted fluid movement within the unsealed
tubules.

d. Minute amounts of moisture, described as “damp” is recommended. This is sufficient

to keep collagen “fluffy,” but no abundant enough to cause a phase separation when
the primer is applied.

e. So the issue of “how wet is wet” arose.

How do prevent “overwet” or “overdry” dentin ?

a. First off, never desiccate or even blow air into a prep when both dentin and enamel
are exposed. Keep in mind that when primers are applied (either as a separate step, or
when the primer is included in the single bottle product i.e. 5th generation materials),
ENAMEL CAN BE LEFT WET, ALONG WITH THE DENTIN.

b. I believe that it is the belief left over from dental school that enamel must be dry to
bond to it that causes us to want to dry the tooth in the first place. With bipolar
primers, this is simply NOT NECESSARY!

How to achieve “moist” dentin?

i. After simultaneously etching dentin and enamel for no more than 15

seconds.

ii. Rinse thoroughly with air/water spray for 5 seconds or more to remove
etchant.

iii. Dry the working field around the prep… NOT THE PREP ITSELF. . to
assure the excess moisture can’t reach the prep once the drying stops.

iv. Using the high volume suction, seal the suction directly on top of the prep
for 2-3 seconds (Ross Perot Technique).

v. Inspect the prep. This should routinely remove excess, flowing water from
the prep. Repeat if necessary.

vi. Only rarely will you need to dip a micro brush into the prep to blot away
excess

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What about “Re-Wetting Agents?” Are they necessary?

a. The truth is, if you never desiccate dentin in the first place, you never need to rewet!
SO DON’T DO THAT!

b. Current re-wetting agents such as Gluma (Heraeus Kulzer), MicroPrime (Danville),

Aqua-Prep (Bisco) are helpful when concerns of overdrying are present. These
materials contain predominantly water, some primers, and often “bug killers” like
glutaraldehyde.

c. It is not recommended intentionally to desiccate dentin for any reason, even when
rewetting agents are used.

CLASSIFICATION OF CONTEMPORARY ADHESIVES ACCORDING THE

ADHESION STRATEGY AND THE CLINICAL APPLICATION STEPS

ETCH & RINSE APPROACH (TOTAL ETCH)

Etch-and-rinse adhesives can readily be recognized by an initial etching step, the so-called
conditioning step, followed by a compulsory rinsing phase. Another frequently used name for
this category of adhesives is “total-etch” adhesives, which is, however, less appropriate because
self-etch adhesives can also etch and demineralize tooth tissue.

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This etching step demineralizes dentin in order to remove the smear layer and smear plugs, and
to achieve a microporous surface with enhanced bonding capacity. To demineralize dentin, both
chelating acids and mineral acids can be used. Many different conditioners with varying
concentrations have been investigated, such as citric, maleic, nitric, oxalic and phosphoric acid.
As etch-and rinse systems are applied on both enamel and dentin, the etching effectiveness of
weak acids or low concentrations on enamel are doubtful. Current etch-and-rinse
systems usually use 30–40% phosphoric acid.

Originally, etch-and-rinse systems typically consisted of three separate application steps:

(a) Conditioning; (b) Priming; and (c) Adhesive resin application.

Modern “Total Etch” Systems

The placement of 34-37% Phosphoric acid on:

a. Enamel:

i. Demineralizes (dissolves) the CaPO4 of hydroxyapatite – “Eats into the tooth!”

ii. This demineralization is self-limiting – The Calcium in the tooth neutralizes the acid
and the process stops. Due to the highly calcified nature of enamel, it is virtually
impossible to over-etch enamel.
iii. The debris from this demineralization is washed off when the etchant is rinses off,
leaving a clean, disinfected favorable surface for the application of the adhesive.
iv. Exposes the prismatic ends of the enamel rods revealing their jagged edges, and
roughens the interprismatic substance between these rods.
v. Billions of microscopic irregularities are created into which adhesives flow and gain
MECHANICAL RETENTION once cured by being “locked in.”
vi. First introduced by Buonocore in 1955, we’ve been using this technique to bond to
enamel for 60 years with great clinical success.

b. Dentin:

i. Removes the smear layer and smear plugs:

1. Thought to be ideal by many researchers

2. Permits micromechanical adhesion similar to enamel
3. Opens tubules and places the onus of “sealing” these tubules on the
dentist to prevent sensitivity due to tubule fluid movement (Brannstrom’s
Theory of Sensitivity) as a result of thermal expansion or contraction, or bite
pressure creating a vacuum.

ii. Demineralizes (dissolves) the CaPO4 of the hydroxyapatite between tubules

(intertubular dentin) and around the walls of the tubules (peritubular dentin).

iii. Occurs at a greater rate and depth than enamel because this tissue is less mineralized

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 and porous due to the presence of dentin tubules.

iv. The collagen in dentin (like “hair” or “noodles”) is NOT removed by etching,
therefore is exposed as the surrounding mineral is dissolved. This leaves the superior
surface of etched dentin with a 5- 10 micron thick layer of “hair” or collagen fibrils

v. Etching times are critical on dentin.

1. Etching times greater than 15 seconds potentially Demineralizes more

dentin than can be infiltrated by subsequent monomers, possibly
leaving . a void under the adhesive layer.
2. This area of etched, but not supported demineralized dentin is structurally
weak and may prove to be a weak link in the durability of the adhesive
bond.

THE 'HYBRID LAYER'

Unfilled resin, when applied, penetrates the primed dentine, copolymerizing with the primer to
form an intermingled layer of collagen and resin, termed the resin-reinforced zone, resin-
infiltrated zone, resin-infiltrated layer, or the hybrid layer. Formation of this hybrid layer, as
described by Nakabayashi et al. in 1982, is thought to be the primary bonding mechanism of
most current adhesive systems.

Self-Etching Primers (SEP’s)

1. Rationale of SEP’s

a. These systems employ the use of acidic monomers that penetrate the smear layer,
demineralize the mineral portion of dentin, and infiltrate intertubular and peritubular
dentin.

b. Since phosphoric acid is not applied and rinsed off, collagen is not left exposed and
vulnerable to desiccation and collapse during the period between etching, rinsing and
primer application.

c. The moisture in the dentin is not critical – eliminating the concern for “how wet is wet?”

d. The smear layer is never removed. This debris is literally incorporated into the bonding
layer.

e. By removing the potential for collagen fibril collapse and the concern for “wet” bonding,
the potential for sensitivity resulting from inadequate seal of exposed tubules is avoided.

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 f. Since these systems “etch” and prime to the same depth, the concern for nanoleakage, or
areas etched but not penetrated by monomers is eliminated.

2. What SEP’s Don’t Do?

a. Most do not shorten treatment time nor save any steps

b. Most do not bond well to uncut enamel

i. All manufacturers are recommending that enamel be abraded or roughened with

a diamond to assure micromechanical adhesion.

c. SEP’s are only indicated for direct procedures – No indirect applications

Classification of Self-Etching Systems

Type I Type II Type III

2 Bottles – 2 Applications 2 Bottles – One Application One Bottle – No Mixing

Apply Primer,
Apply Adhesive Mix Primer and Adhesive One Application

Clearfil SE Bond One Up Bond (Tokuyama)

(Kurrary)
I-Bond (Heraeus Kulzer)
Tyrian SP/One Step Adper Prompt L Pop (3M/Espe)

(Bisco) Xeno III (Dentsply/Caulk)

Mechanisms of Adhesion for SEP’s

1. Mechanical –
•Acidic monomers demineralize enamel and dentin and simultaneously, fill microvoids with
resin
•Acid usually “activated” through ionization fueled by water in the mixture – systems are
less sensitive to water levels present in dentin (no need for “wet bonding”)
•Acid remains on the tooth – but neutralized by the binding of calcium and phospate ions
present in hydroxyapatite – Self limiting
•pH of this acidic component varies depending on product – range from 1 – 3

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 •depths of resin tags into enamel and dentin range from non-existent to similar to total etch
Products

2. Chemical-

•Possibly bonds through chelation to Ca+?

•Forms calcium salts – but how stable are these bonds?

ADHESIVE CHALLENGES?

 MMP Inhibition: The Next Adhesive Paradigm?

Indeed, one of the most interesting and potentially important areas in adhesive research today
concerns the use of antimicrobial solutions that inhibit matrix metalloproteinases (MMPs).
MMPs are zinc-dependent proteolytic enzymes that are capable of degrading the organic matrix
of dentin after demineralization with acids. Essentially, MMPs can be thought of as “collagen
eaters” and may play a significant role in the degradation of the hybrid layer produced by both
total- and self-etch systems.

Breakdown of the hybrid layer may be one of the primary reasons for the ultimate failure of
many bonded restorations over time, and it makes sense to attenuate this degradation if possible.
Studies show that the application of chlorhexidine or benzalkonium chloride solutions before or
in conjunction with the placement of both total- and self-etch adhesives has the potential to
inhibit MMP activity, resulting in a more durable adhesive interface. One particularly significant
in vivo study examined occlusal composite restorations placed in premolars with a 5th
generation total-etch system. Eight teeth in the experimental group were re-wet with a 2%
chlorhexidine solution for 30 seconds after etching, washing, and briefly air-drying. Eight teeth
in the control group were treated similarly, except chlorhexidine was not applied. The teeth were
extracted for orthodontic purposes after 12 months in situ. The authors found that experimental
samples in which the dentin was re-wet with the 2% chlorhexidine solution after etching had
virtually no degradation of the hybrid layer, while the control samples all demonstrated
significant hybrid layer breakdown.
In any case, based on this and other studies, the current technique when using a rewetting
protocol for total-etch systems is the placement of a 2% chlorhexidine solution after the etching
step. The solution is allowed to dwell for 30 seconds and then blot-dried, then the
primer/adhesive is placed and polymerized. Even clinicians using self-etching systems may
benefit by the use of MMP inhibitors that are directly incorporated into the chemistry of the
primers or from cleaning and disinfecting the tooth tissues with MMP inhibitors before the use of
self-etch adhesives.

. More research is needed regarding MMPs, both to ascertain their true clinical significance and
to develop specific, practical, and scientifically driven protocols for both total- and self-etch
systems.

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  AGING OF THE HYBRID LAYER

Since bonding is created by the impregnation of the dentin substrate by blends of resin
monomers, the stability of the bonded interface relies on the creation of a compact and
homogenous hybrid layer.

Clinical longevity of the hybrid layer seems to involve both physical and chemical factors.
Physical factors such as the occlusal chewing forces, and the repetitive expansion and
contraction stresses due to temperature changes within the oral cavity are supposed to affect the
interface stability. Acidic chemical agents in dentinal fluid, saliva, food and beverages and
bacterial products further challenge the tooth/biomaterials interface resulting in
various patterns of degradation of unprotected collagen fibrils elution of resin monomers
(probably due to sub-optimal polymerization) and degradation of resin components. As the
hybrid layer is created by a mixture of dentin organic matrix, residual hydroxyapatite crystallites,
resin monomers and solvents, aging may affect each of the individual components or may be due
to synergistic combinations of degradation phenomena occurring within the hybrid layer.

 DEGRADATION OF THE RESIN

Hashimoto et al. described two degradation patterns within the hybrid layer that includes
disorganization of collagen fibrils, and hydrolysis of resin from interfibrillar spaces within
the hybrid layer, thereby weakening the strength of resin–dentin bond.

Hydrolysis is a chemical process that breaks covalent bonds between the polymers by addition
of water to ester bonds, resulting in loss of the resin mass: this is considered as one of the main
reason for resin degradation within the hybrid layer contributing to the reduction in bond
strengths created by dentin adhesives over time.

This leads to the creation of hybrid layers that behave as semi-permeable membranes permitting
water movements throughout the bonded interface even after the adhesive is polymerized. This
water passage was revealed by studying the permeability of bonded interfaces and by using a
tracer detectable by electron microscopy such as ammoniacal silver nitrate. This tracer stains
pathways water-filled diffusion throughout the bonded interface that are often manifested as
creating the so-called “water trees”, i.e. characteristic water channels at the surface of the
hybrid layer that extends into the adhesive layer, supporting the hypothesis of complete
permeation of simplified adhesive bonded interfaces to water.

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  HOW TO INCREASE BOND STABILITY

1. Use of an hydrophobic coating: since the incorporation of hydrophilic monomer blends in

simplified adhesives (two-step etch-and-rinse and one-step self-etch adhesives) dramatically
reduced bond longevity, the need of an hydrophobic coating with a not-solvented bonding layer
seems to be pivotal to reduce water sorption and stabilize the hybrid layer over time, i.e. etch-
and-rinse three steps and self-etch two-step adhesives should be preferred to simplified ones.

2. Extended polymerization time: extending the curing times of simplified adhesives beyond
those recommend by the manufacturers resulted in improved polymerization and reduced
permeability, and appears to be a possible means for improving the performance of these
adhesives.

3. Use of MMPs inhibitors: the use of MMPs inhibitors as additional primer has been claimed to
reduce interfacial aging over time by inhibiting the activation of endogenous dentin enzymes
which are responsible for the degradation of collagen fibrils in the absence of bacterial
contamination.

4. Improved impregnation: various methods have been recently proposed to enhance dentin
impregnation, i.e. prolonged application time, vigorous brushing technique and electric impulse
assisted adhesive application. The latter technique recently revealed increased bond strength and
reduced nanoleakage expression if adhesives are applied under the effects of an electric signal.

CONCLUSION

Proper management of the adhesive interface is crucial for the predictable placement of many
current dental restorative materials. This requires an understanding of the materials being used,
the substrate being bonded, and a correct and precise clinical protocol. The bottom line is that it
is incumbent on every dentist to learn about his or her specific adhesive system, its
idiosyncrasies, its strengths and weaknesses, and how to maximize its performance.

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