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Bio Emulation
Bio Emulation
HYBRID
h 1963 Masuhara et al reported that when M-n-
butyl bosane EBB)was used as an initiator, methyl
methanylate (&lMf% ch a w grafted to the collagen
in wet ivory and produced an egcellent bond.' The
133
.idhwoii w,i\ srronc .ind rxtrrrriely durable. As 01 THL3 to enamel. A number of new organic molecules
,J.iniIan' l!W 1 . \miples ol this system have k*enaging were studicd.7'Though virtually all of them significantly
in water for 15 yrars at 37 C and the h i d is still improved the bond (Table 1). by far the most stable
I I inct lon,d bonds whcre achieved when small amounts of 4-
Linfortunately. the system did not adhere togroiind met hacryloxyet hyl trimellitate anhydride (4-META)were
dentin. added to the monomer.H
In 1969 this MMA-THB system was introduced as Microscopic examination of enamel that had been
a n orthodontic- adiiesivc called "Direct E3onding-Sys- bonded with this new copolymer yielded a surprising
tern' for enumel bonding.' " It was one of the first dental finding.According to the generally-accepted, tag-theory
adhesives commercially introduced alter Huonocore of enamel bonding, pretreatment using phosphoric acid
proposed thc concept of 'wid-etching enamel. creates mechanical undercuts by selectively attacking
While exploring ways to improve the MMA-TBB the interprismatic material. The resin adhesive then
system at the Institute for Medical and Dental Engineer- locks into these undercuts to create mechanical reten-
ing. we discovered that the addition of monomers that tion. In other words. even the best monomers could not
contained both hydrophobic groups (like the phenyl penetrate beyond the depth of the etch. A n yet, that is
group) and hydrophilic groups (like the carboxyl group) precisely what examination of the 4-META-resin-to-
dramatically enhanced the bonding stability of MMA- tooth interface suggested was happening. The resin
appeared to penetrate beyond the etch and encapsulate
the prisms (Figs. 1 and 2). Chemical analysis of the
interface showed that the tags themselves were pure
resin, but at the end of the tags there was a thin zone,
where the resin had impregnated the interprismatic
Additwe Etchant' Bond MPo Strengih Reference material and formed a new material that was part tooth
-- - .~- - . - .
and part resin. We called this zone a resin-reinforced
None 10-3 133 2 49 10 tissue the "hybrid layer." Because no such layer was
5% HPPM' 10-3 104 2 38 18
3%HNPM' 10-3 105 t 40 19
found when we examined the MMA-TE3B-to-enamel
EDTA 3 - 2 209 ?: 28 20 interface, we hypothesized that this hybrid was the
5% 4-META' 10 - 3 173 .t 49 19 reason for the dramatic difference in bond stability.
1-1 163 i: 02 10 The hybrid layer is highly acid resistant. It remains
EDTA 3 2- 157 .t 24 21 intact even after both enamel and dentin have been
596Phenylc1 10-3 105 5 1.8 22 dissolved in HCl. This suggested the intriguing possi-
-10 - 3 fOr 3Qs: EDTA fW bos. bility of simultaneously bonding to the tooth and ren-
tSeeFie1. dering it caries-resistantwithout the use of fluoride.
A B
Flgam I. SEM ofencapsulated dprisms. A. ?he 4-META-basedadhcslvc penetrates beyond the etch and diffuses into the
tnkrpdemtk Ussue. 7he hybrid It forrns when It combtnes Wlth this tlssue Is hlghly acid mistant.The honeycomblike pattern Is
t h c v matahl that mnatncd aReh theenamel rods- dimolvedin HCl. B.When 4-METAwasomitted hmn the formula. the
xxstn -not penetrate the intqi-bmatictissucto forma hybrid.” R curcdrestn. E: enamel.
134
f iybrid L;\yrr as a I)entin-Bonding Mechanism
m
also denaturing the collagen, decreasing its diffusivity
and preventing monomer contalning 4-META and 4-
Resln Resin MET from penetrating the tissue to form a hybrid.
Building on the suggestion of Dr. Raphael Bowen. a
technique was developed involvinga short pretreatment
using an aqueous solution of 10 percent citric acid and
u
Generally accepted concept
C Hybrd
Hybrld concept
3 percent ferric chloride. l o In contrast to the phosphoric
acid, a short 10-second treatment with the 10-3 solu-
tion permitted the operator to dissolve a thin layer of
calcium without damaging the collagen. The strength of
the 4-META/MMA-TBB system to bovine dentin pre-
pared with the 10-3solution increased by a factor of 200
percent to 18 MPa.
proms a. Traclimnd envnel bonding theory postulates that Interestingly, when the ferric chloride was elimi-
resin tags mecbnkaIiy lock into undercuts in the etched nated from the etching formula, and the dentin was
e n d . The hybrid conceptproposesthat bondingstability will prepared wlth a 10 percent solution of citric acid, the
incnase stgnlacantty if the rrsfn tags arc supplemented by a
thin u 3 of~resin-ninfomdtissue & y M d layer). bond strength plummetted to just 6 MPa, which was no
better than when the surface was prepared with phos-
phoric acid. The resin tag length in both the 6 MPa and
the 18 Mpa samples was identical. The only observed
dtfference was that the 18 MFb samples showed forma-
tion of a win impregnated zone -a hybrid layer. The
6 MPa sample showed no hybrid layer (Fig. 3).The ferric
A B
135
<JCN'R!SAl.OF ESTtiFTlC DEWISTHY VOLUME 3.NUMBER 4 July/Augusl 1 9 9 1
tons in the 10-3solutlon arc essential to the preserva- The unique water-compatibilityof the TBB catalyst
tion of the cwllagcn bundles 50 they can become infil- may also be a major reason why the 4-META/MMA-TBB
trated and entangled by the p l y (MMA-co-4-MET) system is the only one 90 far shown to form strong
resin. dentln bonds in the face of tubular fluid under pulpal
The long resin tags formed when a bonding agent pressure. I Z - I 4
flows into the tubules may be very impressive in SEM Finally. because water and oxygen act in concert
photographs: however. these experiments suggest that with TE3B as an initiator, the 4-META resin polymerizes
they contribute only minimally to the overall dentin first within the dentinal tissue itself. All resins shrink as
bond strength. they cure. Furthermore. they shrink toward the point
If treatment period is increased from 10 seconds to where polymerization begins. This suggests that the 4-
30 seconds, the 10-3solution can also be used to etch META/MMA-Tf3B system shrinks toward the dentin
enamel. 'I' during polymerization and thus presemes the high
degree of tissue-infiltration that was established before
Water-Triggered Polymerization polymerization began.
In contrast, a more traditional self-cure adhesive
As mentioned earlier. dentinal tissue is rich in based on the BPO-amine system begins curing at the
oxygen and water. Oxygen and water prevent emcient center of its mass. and therefore tends to pull away from
polymerization of most bonding agents, so they nor- the tissue as it shrinks. Worse yet. light-cure adhesives
mally impede the bonding mechanism. begin polymerizing at the point farthest from the tooth
The catalyst in the 4-META/MMA-TBB system is surface, so they create the maximum chance for micro-
unique in that oxygen and water actually enhance its scopicpolymerizationgaps at the tissue interface (Fig.4).
effectiveness. In fact, TBB requires the presence of
water and oxygen to lnltiate polymerization. When a
drop of CBB-Metabond (a 4-META/MMA-TBB based CONCLUSION
cement) i s gently floated in a bowl of water, it begins
polymerizing first wherever it touches the water. Based on our work at the Institute for Medical and
The benefits of a dentin bonding agent that starts Dental Engineering Wokyo Medical and Dental Univer-
curing wherever it contacts water and oxygen are sity), we believe that the traditional conceptions of
obvious.First of all, it assures effective polymerization dentin bonding should be modified to include the hy-
in deep preparations where the dentin is highly brid layer mechanism in which certain monomers can
tubularized and impossible to dry (and even if the infiltrate the dentin and combine with the collagen and
dentist manages somehow to dry it. what can he do hydroxyapatiteto form a new material that is part tooth
about the oxygen in the tissue?). and part resin.
Effective polymerkation in fluid-filled deep dentin When true hybridization occurs, bond strength
reduces the chance of fhe monomer that might act as (particularly to deep, wet, highly tubularized dentin)
a pulpal initant. (Some studies of traditional bonding increases dramatically. The hybrid layer forms an acid-
agents suggest that as much as 50 percent of the resistant envelope that seals the dentin, preventing
monomer remains unpolymerfied.l') hypersensitivity and secondary caries.
Resin
Tooth
136
Hybrid Layer as a Denth-Bonding Mechanlsm
137
7 Nakabayashi N. Uiwompatibility and promotion of adhe-
sion to tooth substances. CKC Crit Rev Bio-Compatibility
1984: I :25-52.
8. Taktyania M, Kashibuchi N. Nakabayashi N, Masuhara E.
Studicsondentalself-rurinRresins(17).AdhesionofPMMA
with bovine enamel or dental alloys. J Jpn Dent Appar
Mater 1978; 19:179-185.
9. Fuuyaiiia T. Nakamura M. Kurosaki N. lwaku N. Non-
pressure adhesion of a new adhesive restorative resin. J
Dent Hes 1979; 58:1364-1370.
10. Nakabayashi N. Kojlnia K. Masuhara E. The promotion of
adhesion by the lnflltration of monomers into tooth
substrates. J Biomcd Mater Res 1982: 16:265-273.
11. Pashley D. Dentin bonding: an ovcrview. Paper presented
at the First International Conference on Adhesive Den-
tistry. 1991 (To be published).
12. Tao L. Pashley DH. McGuMn R. In vivo bond strength: effect
Figure& &cause4-METAwillmcdlatebondsbetwwnawlde of depth and tooth type. J Dent Res 1990: 69:285 (Abstr
range of materials (metals. plastics. porcelain, etc.) a number of 141 1).
adheslve products have been built on this molecule. However, of 13. Taganii J. Tao L, Pashley DH. Correlation among dentin
these only the 4-META/MMA-TBBsystem, whlch forms the depth, permeability, and bond strength of adhesive resins.
bask of C&B-Metabondcement and t h e h l g a m b o n d bonding Dent Mater 1990; 6:45-50.
agent has been shown to form a substantial dentln/resin hybrid 14. Prati C, Pashley DH. Montanari G. Hydrostaticintra-pulpal
layer. pressureand bond strength ofbondingsystems. J Dent Res
1990; 69: 1 16(Abstr63).
15. Kiyomura M. Bonding strength to bovine dentin with 4-
META/MMA-TBB resin: long-term stability and influence
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138