Arrest and Control of Carious Lesions: A Study Based on
Preliminary Experiments with Resorcinol-Formaldehyde Resin
C. ROBINSON, A. S. HALLSWORTH, J. A. WEATHERELL, and W. KUNZEL
Department of Oral Biology, Dental School, Leeds University, Leeds LS2 9NZ, England,
and Department of Preventive Dentistry, Medical Academy, Erfurt, G. D. R.
An experimental investigation has been
made into the possibilities of retarding the
progress of carious attack by infiltrating car-
iostatic material into enamel lesions. The
problems associated with this kind of proce-
dure are discussed against the background of
experimental observations made using a for-
mulation based on a resorcinol-formaldehyde
resin.
Many attempts have been made to reduce
the incidence of dental caries by treating
tooth surfaces after eruption. One approach,
using varnishes1 or polymerizing methacry.
late and other sealants,2,3 aims to place a
physical barrier between the sound enamel
and potentially cariogenic bacteria in the
most susceptible region of the dentition, the
enamel fissure. Other treatments, involving
solutions,4 pastes,5,6 or gels containing flu-
orides,7 long-chain amines,8 and other agents,
aim to enhance the natural resistance of
sound enamel by reacting with the tooth
surface.
However, the impervious nature of sound
enamel compared to the greater accessibility
and perhaps reactivity of the porous carious
tissue suggests that the principal means by
which many topical applications exert their
effect may be by their penetrating into and
accumulating in the porous enamel of the le-
sion itself where they retard, arrest, or even
reverse the process of lesion formation. Flu-
oride, for example, although perhaps not
retained by sound enamel seems to accumu-
late in the enamel of carious lesions.9-11
From this point of view, we believe that
more deliberate attempts should be made to
treat the porous enamel directly. In the pres-
ent study, an attempt has therefore been
Received for publication June 2, 1975.
Accepted for publication March 11, 1976.
812
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made to introduce material with certain se-
lected properties into enamel lesions both in
vitro and in vivo.
The different approaches to caries inhibi-
tion just mentioned are not, of course, mu-
tually exclusive. Any substance that will
penetrate the porous enamel of a lesion, for
instance, would enter fissures and by adher-
ing to the enamel surface might also protect
the sound enamel.
CRITERIA AND CHOICE OF AN IDEAL TOPICAL
AGENT.-In an attempt to define the func-
tions and properties of an ideal topical pro-
phylactic material, we considered the follow-
ing points were important.
1. Carious lesions tend to develop in fis-
sures, proximal surfaces and other relatively
inaccessible parts of the dentition. These
regions and the porous enamel of the lesion
itself are usually wet. Therefore, the cario-
static material should be hydrophilic when
applied, which would also permit the inclu-
sion of other cariostatic ions such as flu-
oride.2 Since an incipient lesion is often
undetected by normal clinical procedures,
the material should also be strongly surface-
active and have a low viscosity, so that it
will spread rapidly over the tooth surface,
penetrate inaccessible areas, and enter the
pores of lesions.
2. Bacteria can never be completely ex-
cluded and so the material should have bac-
teriocidal or at least bacteriostatic properties.
3. The material must, however, be toler-
ated by the pulp and other oral tissues.
4. Because the lesion consists of porous,
physically weakened enamel, in its final
state, the material should offer some me-
chanical support.
5. The material should be cosmetically ac-
ceptable.
Material that when introduced into the
lesion in an aqueous phase would subse-
Vol 55 No. S
quently polymerize to a solid would be suit-
able. Such a polymer might with advantage
also cross-link with the enamel mineral or
the organic material in the lesion or both.
From a survey of currently available poly-
merizing materials, none completely fulfilled
the aforementioned criteria. The methacry-
lates, cyanoacrylates, and polyurethanes al-
ready used as fissure sealants had too high a
viscosity even to penetrate deep or narrow
fissures, would not polymerize in very moist
conditions, and had limited bacteriostatic
properties.
Resorcinol-formaldehyde resins seemed to
match the criteria most closely. They poly-
merized from aqueous solutions at temper-
atures low enough to be tolerated in the
mouth (about 50 C). They could be intro-
duced at a pH (about 8) that would not
damage enamel and that would neutralize
any residual acid. Surface-active agents,
charged molecules, and water-soluble ions
could be included. The resins also possessed
considerable antibacterial activity.
The application of resorcinol-formalde-
hyde resins in clinical dentistry is not new.
Since they were introduced to endodontic
therapy.'2, their use has been investigated
by several workers.13,14 Their tendency to
shrink during polymerization, their irritant
effect around the root apex,15.168 and their
cosmetically objectionable red color result-
ing from oxidation'7 finally discouraged their
use. Resorcinol-formaldehyde formulations
nevertheless corresponded most closely to the
criteria already described and they were
therefore used in the present experimental
study.
Materials and Methods
PREPARATION OF RESIN.-The resin
pared by dissolving 1.3 gm of resorcinol in
2 ml 40% formaldehyde solution, 0.1 ml con-
centrated detergent (Teepol) a being in-
cluded as a surface-active agent and the pH
adjusted to 8.2 with saturated aqueous KOH
immediately before use. Care was necessary
at this stage to prevent overheating and pre-
mature polymerization. Polymerization oc-
curred at room temperature in about one
h-our. At 50 C, the resin polymerized in
about one minute. At a pH of more than 8,
the rate of polymerization increased, but a
a Shell Chemicals U.K. Ltd., Manchester, Eng.
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ARREST & CONTROL OF CARIOUS LESIONS 813
more brittle and highly colored material
tended to form. This property was, however,
potentially useful; when treated teeth were
brushed lightly with alkali, the resin surface
polymerized almost instantly to form a seal
over the polymerizing resin.
RESIN INFILTRATION OF NATURAL CARIOUS
LESIONS OF ENAMEL, IN vITRo.-Extracted hu-
man permanent teeth with small white- or
brown-spot lesions were painted with the
resin solution which polymerized when the
tooth was warmed to 50 C for about one
minute with a warm-air blower. In later ex.
periments, penetration was greatly improved
by first etching the teeth for five to ten
seconds using a fine spray of 1 N HCI. The
sprayer delivered less than 2 ml acid/min so
that, in the human mouth, the amount of
acid used would be tolerably low. The teeth
were subsequently sectioned using a diamond
disk and the sections examined in trans-
mitted and reflected light.
RESIN INFILTRATION OF NATURAL CARIOUS
LESIONS OF ENAMEL, IN vITRO.-Extracted hu-
man permanent teeth with small white- oT
brown-spot lesions were painted with the
resin solution which polymerized when the
tooth was warmed to 50 C for about one min-
ute with a warm-air blower. In later experi.
ments, penetration was greatly improved by
first etching the teeth for five to ten seconds
using a fine spray of 1 N HCI. The sprayer
delivered less than 2 ml acid/min so that, in
the human mouth, the amount of acid used
would be tolerably low. The teeth were sub-
sequently sectioned using a diamond disk
and the sections examined in transmitted
and reflected light.
PENETRATION INTO CARIOUS LESIONS IN
vIVO.-A monkey (Macaca irus) was main-
was pre- tained on a cariogenic diet'8 until identifiable
carious lesions developed. After fasting for
17 hours, the monkey was sedated with an
intramuscular injection of metahexitoneb (20
mg/kg body weight). The vocal chords were
sprayed with 2% lignocaine HCI. A 2.5-mm
endotracheal tube was placed intranasally
and anesthesia was maintained with 1%
halothane + N20 at 2 to 3 liters/min and
oxygen, I liter/min. The airway was pro-
tected with cotton-wool rolls. After removing
plaque and soft debris, the teeth were
sprayed with I N HCI as previously de-
b Brietal, Lilly & Co., Basingstoke, Hants, U.K.
814 ROBINSON ET AL
FIG 1.-Buccolingual section of premolar ex-
posed to acid-gelatin gel at pH of 4.5 for two
to four weeks. Demineralized porous enamel can
be seen as white opaque band. E, enamel; D,
dentin; N, nail varnish; and P, porous enamel.
scribed and dried thoroughly with a warm
stream of air. Freshly prepared resin solu-
tion was applied to selected teeth with the
use of a small brush, keeping the material
as far away possible from the soft tissues.
as
The resin was polymerized in about one min-
ute using a warm-air blower. Finally, the
monkey's mouth was thoroughly rinsed with
water and 5%; sodium bicarbonate solution.
DETERMINATION OF PORE SPACE WITHIN
ENAMEL LESIONS.-During polymerization, the
resorcinol-formaldehyde resin preparation
contracted by 30 to 40% and an attempt was
made to determine what volume of the le-
sion had been occluded by the resin. To do
this, efforts were made to produce a "stan-
dard" lesion in vitro. Porous enamel was
prepared by placing sound premolars in a
10% w/v gelatin gel acidified to a pH of
4.5 with 1 M lactic acid. Most of the tooth
was protected with nail varnish, leaving a
panel of enamel exposed. After two to four
weeks at 16 C, the exposed panel of enamel
was white, chalky, and partially demineral-
ized to a uniform depth of about 100 micro-
meters (Fig 1) with an apparently intact
surface (judging from the presence of per-
ikymata)
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J Dent Res September-October 1976
A B D
100 FE
060f
4 F L
cr I
o.20
VO VI VO VI VO VI VO0VI,V,V3
BEFORE RESIN AFTER RESIN
APPt ICAtIO0N 11 A lCATfON
FIG 2.-Histograms, illustrating effect of resin
treatment on accessibility of lesion pores to
chloronaphthalene. V,, initial untreated pore
volume; V, pore volume after one treatment;
V,, pore volume after two treatments; and Vs,
pore volume after three treatments.
Results
A methlod was devised for determining the
volume of space within these artificial le-
sions before and after resin treatment. On
removal from the gel, the teeth were thor-
oughly washed with hot water and allowed
to dry in air. A drop of 3-clhloronaphthalene
(Refractive Index 1.63) was applied to the
surface of the lesion where it gradually pen-
etrated and "cleared" the porous enamel.
When imbibition was complete, the enamel
surface was wiped with paper tissue and im-
mediately immersed in 10 ml of spectro-
ph-otometric grade hexane. After one hour,
the chloronaplhthalene had diffused from the
lesion into the hexane and was determined
spectroplhotometrically at its absorption max-
imum (285 nm), and the volume of space
imbibed by the chloronaphthalene calcu-
lated.
The mass of clhloronaphthalene leached
from the pores of the lesion was calculated
from the extinction value of the hexane so-
lution at 285 nm and the molar extinction
coefficient at 285 nm, that is, 7,490 absorp-
tion units. The volume of chloronaphthalene
washed from the lesion was calculated from
its mass and density at room temperature.
Repeated determinations on natural as well
as artificial lesions indicate that the tech-
nique gives a coefficient of vari ation of
8%.
The demineralized panels were then
treated with resin and the volume deter-
mined. The difference between the two de-
terminations was presumed to represent the
Vol 55 No. 5 ARREST & CONTROL OF CARIOUS LESIONS 815

280 r

260

240

220

200

180F
0

160

3 140
0

120
0
11'

80 _

60 F FIG 4.-Vertical section of natural approximal

40 _
20
Vo V1
BEFORE ACID-GEL
TREATMENT
AFTER ACID-GEL
TREATMENT
FiG 3.-Histograms, illustrating effect of resin
treatment on increase in porosity of prepared de-
mineralized enamel exposed to acid gel. V0,
initial pore volume; V1, pore volume after an
exposure to gel for two days without (E) and
with (F) resin treatment.
volume of space occupied by the resin.
VOLUME OF SPACE OCCLUDED BY THE RESIN.-
The pore volume of lesions (namely the
space accessible to chloronaplhthialene) was
determined for lesions as previously de-
scribed. The lesions were then infiltrated
carious lesion in human molar tooth, showing
extent of in vitro resin infiltration. Visible limit
of resin penetration is indicated by dotted line.
witli resin and the chloronaplhthalene-acces-
sible space redetermined. This indicated
that about 60% + 10% of the lesion's pore
Vo V1
volume hiad been occupied by resin. Figure
2 shows four representative lesions treated in
this way.
The hiistological demonstration that the
resin was well distributed throughout the
porous enamel suggested that it had com
pletely occluded 60% of the internal spaces
andl not meiely blocked access to them. That
the space was only 60%o occluded was prob-
ably dtLe to tthe 30 to 40(% slhrinkage in the
iesitn that occui-s during polymerization. This
is supported by the fact that second and
thiird suiccessive resin treatments reduiced the
clhloronaphtllalene-accessible space by a pre-
dictable 80 and 99%, respectively (Fig 2,D).
EFFECT OF RESIN ON SUBSEQUENT DEMINER-
ALIZATION OF TIlE LESION IN vITRo.-After de-
termining their pore volume with chloro-
naphithalene, tlhe artificial lesions were

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816 ROBINSON ET AL
.. .< 1.
II
I
FIG 5.-Vertical section of narrow human
molar fissutres sbowinig cxtent of in vitro resin
penetration. Some peneti ation into porous
enamel oni fissLire walls is also visible. Visible
limit of penietlationi is in-idicated by dotted lines.
treated withi resin, their pore volume was
i-edetermined, antI the tectlh replaced in acidi
gel (pH, 4.5). After two to thlree days in
th-e gel, the pore volume of the lesionis was
again measuredl. It was fotind that the pore
voliuine for conti ol paniels, that is, panels
not ti-eated witlh resin, increaseti by 300 %0
moie tlian the pote volume fo- those gixNen
at single i-esirn treatment and ain example is
slhown in Fligtire 3.
IISSOuIUTION OF NTAIFRIAI, FROM FRESHLY
POLYMERIZED RESINS.-To oltain some meas-
tire of the soluhility of r-esin components,
2-gm blocks of resin were freshlly preparedl in
small plastic molds. These were suspended
in 5 ml of molar soluitionis of soditum bicar-
Iconate (buffered to a pH of 6, 8, andl 9).
Aliquots of soluition withidrawn at intervals
of 1, 5, 10, 20, 60, and 120 minutes were ex-
aiminedl for (lissolved resin components. Al-
sorption peaks at 210 and 280 nm suggestedl
that resorcinol, or some low molectular weighit
p)olymer intermetliates, were being leached
from the iesin blocks. The rate of removal
of mateiial from the resin blocks dleci-eased
logarithmically, lowever, and no increase in
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J Dent Res September-October 1976
02 .. (
1IG 6.-Longitudinal sectioni of monkey pre-
niolar, resirn treated in N-ivo. Visible limit of
lesini penetlation is iiidicatedi by dotted line.
the material removed could be dletected aftet-
otie hour.
The total aniount of material leachled from
in locks of 1C.sin1 wotdldl correspond to
2-gm
about 200 nig of i-esoi-cinol. In the ai-tificial
enamel lesions, a total of about 250o ig resin
wotuld be )1resent and, assuming a similai-
degree of leacling, oilsv alout 25 ng of re-
sorcinol wsould be t-eleasedl. 1 his estimate
miglht be low if tIre sinrface ai-ea of r-esin in
the enamel wais lhighl ant, in any instance,
the release of even siclc small amounts of
)otentially toxic miaterials into the motuth
wouldk hase 10 be tlhorouglhly investigated b)e-
fore clinical utse of this tyl)e of material could
be contemplated.
PFNF1RATION OF RESIN IN-lO NATURAL LE-
SIONS IN VITRG . Ieeti Uisith whlite-spot lesions
were sprayed witlh I N HCl for five to ten
seconds and tr-eated( wvith resin. After poly-
nieriziiig the resin witlh warm air for one
minuite, the teetlh were sectioned and left
expose(l to air ovei-niglrt. The p)resence of
tde red coloration, a resuilt of the oxidlation
of resin, indicated that the bodies of the
lesions were extensively infiltrated (Fig 4).
Vlzo 55 No. 5
Penetration into the base of deep and very
narrow fissures was also routinely observed
(Fig 5).
PENETRATION OF RESIN INTO LESIONS IN
vivo.-The teeth of a monkey (Macaca irus)
in which carious lesions were induced18 were
treated with resin as previously described.
Two years after treatment, several teeth were
extracted and sectioned. Some resin was still
in place even on the tooth surface. On ex-
posure to air for about 24 hours, the red
color, characteristic of oxidized resin, was
visible throughout most of the depth of the
treated lesions (Fig 6).
Discussion and Conclusions
One of the primary aims of this study was
to set out the requirements of a material
suitable for treating noncavitated carious
enamel lesions. An attempt was made to
find such a material, to introduce it into
porous enamel and natural carious lesions,
to assess the likely effect of such treatment
on the progress of lesion development, and
to determine whether such material would
be retained in the mouth. It was thought
that the ideal material should be (1) water-
based or, at least, hydrophilic; (2) highly
surface-active withi a low viscosity; (3) anti-
microbial; (4) nontoxic to the oral soft tis-
sues; (5) capable of polymerization into a
solid plhase under physiologically tolerable
conditions; and (6) cosmetically acceptable.
Experiments have shown that a resorcinol-
formaldehyde formulation goes some way to-
ward fulfilling these criteria, particularly the
first tlhree and the fifth. This material could
be introduced into lesions in vitro and in
vivo, and it possessed antimicrobial activity.
Treatment of porous enamel reduced the
rate of demineralization in acidified gelatin
in vitro; in addition, the resin was retained
in vivo. A more comprehensive study, prob-
ably with a large number of monkeys, would
be necessary to assess its anticarious activity
since this treatment had certain unsatisfac-
tory features. With regard to the nontoxic
to oral soft tissue criterion, local ulceration
of the oral mucosa occurred in the vicinity
of the monkey's treated teeth, which might
have been due to a rapid loss of unpolymer-
ized resin components after initial polymer-
ization. Alternatively, the ulceration, which
disappeared within 24 to 48 hours, might
merely have been due to heating and drying
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ARREST & CONTROL OF CARIOUS LESIONS 817
the mucosa with the air blower during resin
polymerization.
Perhaps the most serious objection to this
material is the possible effect of resin on
vital dentin or pulp should the lesion extend
so far. With regard to the cosmetically ac-
ceptable criterion, the dark-red color pro-
duced by oxidation could be cosmetically
objectionable although the resin would not
necessarily be visible in fissures and inter-
proximal regions.
The suitability of the resin as a caries pro-
phylactic is therefore questionable. How-
ever, the concept of such a treatment and
the techniques developed for its use seem to
point to a feasible line of approach for the
treatment of dental caries.
In view of the recent great advances in
polymer science, it seems likely that other
potentially useful materials may soon come
to light.
The authors thank Dr. W. H. Bowen and Mr. M.
Cole of the Royal College of Surgeons, England, for
their facilities and help with the monkey investigation,
and Mr. G. Moore for his technical assistance.
References
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4. MELLBERG, J.R., and NICHOLSON, C.R.: Flu-
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J Dent Res September-October 1976
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