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brief communications

A synthetic enamel for rapid tooth repair


Seamless fixing of an early caries lesion can be achieved without prior excavation.
he conventional treatment of
packed array after 3 min (Fig.1e),and
a
d
dental caries involves mechaniare three-dimensionally stacked after
cal removal of the affected part
15 min (Fig. 1f). The acidic condiand filling of the hole with a resin or
tions probably contribute to the
metal alloy14. But this method is
fast growth of highly crystalline
hydroxyapatite by dissociating the
not ideal for tiny early lesions5,6
calcium phosphate clusters into
because a disproportionate amount
calcium and phosphate ions10,11; the
of healthy tooth must be removed
to make the alloy or resin stick. Here
clusters would otherwise slow growth
b
e
we describe a dental paste of synrates and cause low crystallinity.
thetic enamel that rapidly and
We have shown that our synthetic
seamlessly repairs early caries
material can reconstruct enamel
lesions by nanocrystalline growth,
without prior excavation, in a
with minimal wastage of the natural
process that not only repairs early
enamel.
caries lesions but can also help
The human tooth is protected
to prevent their reoccurrence by
by enamel of 12 mm thickness
strengthening the natural enamel. In
c
f
that is composed of hydroxyapatite
the clinic, the paste should not come
(Ca10(PO4)6(OH)2) crystals. In early
into contact with the gums, where
its acidity and its high concentration
caries lesions, acid-forming bacteria
of hydrogen peroxide could cause
cause microscopic damage to the
inflammation (though materials
enamel, creating cavities that are less
with similarly adverse properties are
than 50 m deep. Such cavities canalready used on patients12).
not be repaired by simple setting of
restorative materials because these
Kazue Yamagishi*, Kazuo Onuma,
do not adhere perfectly to the enamel Figure 1 Repair of an early caries lesion using a synthetic enamel paste. ac, Transmis- Takashi Suzuki, Fumio Okada,
owing to differences in chemical sion electron micrographs, and df, atomic-force microscopy images of tooth repair. Junji Tagami, Masayuki Otsuki,
composition and crystal structure.
a, Image of the interface between the regrown layer (upper region) and the enamel (lower Pisol Senawangse
We prepared a white crystalline region); the arrow indicates the direction of the tooth surface. b, Atomic image of a grown *FAP Dental Institute, 3-2-1, Kakinokizaka,
paste of modified hydroxyapatite, crystal of synthetic enamel. c, Tooth treated with acidic phosphate fluoride; dotted line 502 Meguro-ku, Tokyo 152-0022, Japan
which chemically and structurally indicates the interface between the calcium fluoride layer (CF) and enamel (E). d, Original e-mail: FZT02705@nifty.com
resembles natural enamel, and used enamel surface; arrow, hydroxyapatite crystal. e, Surface after 3 min of repair time; National Institute of Advanced Industrial
it to repair an early caries lesion in a arrow, newly grown hydroxyapatite crystal. f, Surface after completion of repair (15 min). Science and Technology, Institute for
lower premolar tooth (for methods, Scale bars: a, c, f, 100 nm; b, 1 nm; d, e, 50 nm.
Human Science and Biomedical
see supplementary information).
Engineering, Central 6, 1-1-1 Higashi,
The affected site was sealed off within 15 high durability and acid tolerance (see sup- Tsukuba, Ibaraki 305-8566, Japan
min. Examination of the microstructure of plementary information).
Department of Applied Chemistry and
the restoration using transmission electron
For comparison, we repaired a similar Biotechnology, Faculty of Engineering,
microscopy (TEM) reveals no obvious struc- lesion with acidic phosphate fluoride solu- Yamanashi University, 43-11, Takeda, Kofu,
tural gap at the interface between the regrown tion, an alternative treatment for early caries Yamanashi 400-8511, Japan
layer and the enamel region (Fig. 1a). The lesions that does not necessitate the removal Department of Restorative Science, Graduate
regrown layer contains elongated crystals of healthy tooth enamel, and examined the School, Tokyo Medical and Dental University,
(100400 nm long and 2080 nm wide) that restoration by TEM (Fig. 1c). The image 5-45, Yushima 1-chome, Bunkyo-ku,
have grown across the interface and are regu- shows the presence of a calcium fluoride Tokyo 113-8549, Japan
larly orientated to the tooth surface. This layer of inhomogeneous thickness8,9 (and less 1. Raskin, A., Michotte-Theall, B., Vreven, J. & Wilson, N. H. F.
J. Dent. 27, 1319 (1999).
shows that the paste has properly integrated than 1 m thick) covering the enamel, and a
N. H. F. & Mjor, I. A. J. Dent. 28, 1521 (2000).
with the tooth enamel.
clear gap at the interface (Fig.1c,dotted line). 2.3. Wilson,
Carvalho, R. M., Pereira, J. C., Yoshiyama, M. & Pashley, D. H.
An atomic-resolution TEM image of a
Time-lapse atomic-force microscopy
Oper. Dent. 21, 1724 (1996).
grown crystal (Fig. 1b) reveals that it has two indicates that the hydroxyapatite crystals of 4. Hilton, T. J. Am. J. Dent. 15, 198210 (2002).
lattice periodicities that are consistent with the original tooth enamel (Fig. 1d) initially 5. Frank, R. M. & Brendel, A. Archs Oral Biol. 11, 883912
(1966).
the inter-lattice distances for the c and a direc- dissolved slightly during the repair, but 6. Johnson,
N. W. Caries Res. 1, 356369 (1967).
tions of a hydroxyapatite crystal (0.688 and quickly grew again because the paste was act- 7. Elliot, J. C. (ed) Structure and Chemistry of the Apatites and
Other Calcium Orthophosphates (Elsevier, Amsterdam, 1994).
0.817 nm, respectively). From these results, ing as a source of crystals. This dissolution
combined with those from X-ray photoelec- and regrowth occurs as a result of the strong 8. Gerould, H. J. Dent. Res. 24, 223-233 (1945).
H., Gotz, H. & Ogaard, B. Eur. J. Oral Sci. 105,
tron spectroscopy analysis (data not shown), acidity (pH2) of the mother solution and 9. Duschner,
466472 (1997).
we conclude that the hydroxyapatite crystals paste. The process creates a continuous, 10. Onuma, K. & Ito, A. Chem. Mater. 10, 33463351 (1998).
in the regrown layer are oriented with their nanometre-scale structure that extends from 11. Banfield, J. F., Welch, S. A., Zhang, H., Ebert, T. T. & Penn, R. L.
Science 289, 751754 (2000).
(0001) face parallel to the tooth surface7. The the enamel to the regrown layer by epitaxial
12. Yamagishi, K. & Suzuki, T. J. Esthetic Dent. 7, 7880 (1995).
regrown layer contains about 1% by atoms growth of crystals.
Supplementary information accompanies this communication on
The newly grown crystals of hydroxy- Natures website.
of fluoride ions and has a calcium-to-phosphorus molar ratio of 1.580.03. It also has apatite cover the whole surface in a densely Competing financial interests: declared none.

NATURE | VOL 433 | 24 FEBRUARY 2005 | www.nature.com/nature

819
2005 Nature Publishing Group

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