Review Article

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Biominerals in restorative dentistry

Neeta Shetty, M. Kundabala
Departments of Conservative Dentistry and Endodontics, Manipal College of Dental Science, Manipal University,
Mangalore, Karnataka, India

Address for correspondence: Dr.Neeta Shetty, Email:neetaraj70@gmail.com

ABSTRACT
Restorative treatment strategies are being developed to repair and replace lost tooth structures and surrounding bone. The teeth
under goes a constant cycle of demineralization and remineralization, but this natural remineralization process is inadequate
to prevent progression of dental caries. Hence there is a need to supplement the tooth with a biomaterial which is bio inert or
bioactive to remineralize, repair or regenerate the tissues of tooth. Calcium hydroxide is considered the gold standard material
for repair of dentin, which is presently being replaced by materials with superior properties such as mineral trioxide aggregate.
Biomaterials such as calcium phosphate cements are been advocated as bone substitute material because of properties such
as biocompatibility, osteoconductivity and moldability. This review deals with the physiochemical properties of some of the
biomineral based biomaterials which are currently used for repair, replacement or regeneration of hard tissues of teeth and bone.

CLINICAL RELEVANCE TO INTERDISCIPLINARY DENTISTRY

 ynthetic biomaterials containing biominerals are used in dentistry to repair and regenerate hard tissues of the
S
teeth and bone.
Biomaterials containing biominerals are routinely used by specialist from various fields of dentistry such as
restorative dentistry, periodontics and oral surgery.
Biomineral based biomaterials are used for direct and indirect pulp capping procedures, as an intracanal medicament
in root canals, root perforation repair, periapical surgeries, repair of bony defects.

Key words: Biomaterials, biominerals, calcium hydroxide, mineral trioxide aggregate, remineralization

INTRODUCTION

ones and teeth are biocomposites that

require controlled mineral deposition during
their selfassembly to form tissues with unique
mechanical properties.[1] Biomineral refers not only
to the minerals produced by organisms, but also to
the fact that almost all of these mineralized products
are composite materials comprised of both mineral
and organic components. [2] Biomineralization is
the process by which living forms influence the
precipitation of minerals which is a natural evolution
process that creates heterogeneous accumulations,
composed of organic and inorganic compound
products that are created and maintained during the
life by dynamic metabolism. It is a physical process
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DOI:
10.4103/2229-5194.126858

64

or a guided biological process and there are proteins

that accelerate or inhibit biomineral formation such
as Osteopontin, that can turn on mineral formation
or inhibit it.[3,4]
Biominerals such as calcium and phosphate synthetically
produced or obtained from natural sources thus has an
important function in the preventing demineralization
and encouraging remineralization of hard tissues of the
tooth along with the preservation and maintenance of
the health of the pulp. Remineralization is defined as
the process whereby calcium and phosphate ions are
supplied from a source external to the tooth to promote
ion deposition into crystal voids in demineralized
enamel, to produce net mineral gain.[5] The present
concept of remineralization is that the fluoride ions
promote the formation of fluorapatite in enamel in the
presence of calcium and phosphate ions produced
during enamel demineralization by plaque bacterial
organic acids, but the ready availability of calcium
and phosphate from saliva and plaque could be a
hindering factor in this process.[6] Hence the need for
supplementation of these minerals may be a necessity
for remineralization of enamel.

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Shetty and Kundabala: Biominerals in restorative dentistry

Application of calcium and phosphate ions for

remineralization has not been successful due to the
low solubility of calcium phosphates; insoluble calcium
phosphates do not localize effectively at the tooth surface
and require acid for solubility to produce ions capable
of diffusing into enamel subsurface lesions. Salivary
remineralization of enamel promoted by topical fluoride
has been shown to give rise to predominantly surface
remineralization which does not improve the esthetics
and structural properties of the deeper lesion.[5,7] Hence
the focus is on those biomaterials, which will promote
subsurface mineral gain rather than deposition only in the
surface layer. At present, there are technologies developed
to stabilize the amorphous calcium phosphate(ACP).
The therapeutic effect of materials such as calcium
hydroxideCa(OH)2 and mineral trioxide aggregate(MTA)
may be due to their extraction of growth factors from
the dentin matrix.[8] The release of growth factors due
to dentin injury acts as a signal to stimulate the dental
pulp for cell differentiation, proliferation, chemotaxis,
extracellular remodeling and the secretion of tertiary
dentin matrix. Growth factors, mainly transforming growth
factor beta1, are important for the stimulation of dentin
matrix secretion.[8,9] Biominerals play an important role
in remineralization of enamel, regeneration of dentin.
Biomineral substrates are also implicated to play major
roles in bone development and regeneration [Table 1].[10]
Calcium phosphate, hydroxyapatite(HA), calcium silicate,
calcium carbonate and calcium sulfate, etc., are important
materials and have been widely used in biomedical
fields such as bone cements. At present, calciumbased
inorganic biodegradable nanomaterials which have
excellent osteoconductivity, biocompatibility, bioactivity,
biodegradability, chemical stability and mechanical
strength are been experimentally used as bone graft
materials.[11]

CLASSIFICATION OF BIOMINERAL
BASED BIOMATERIALS
Biomaterials for remineralization and regeneration tooth
can be classified into[Figure1].

Biominerals based biomaterials for

remineralization of enamel
Calcium phosphate
In 1920s Albee reported the use of calcium phosphate known
as triple calcium phosphate in a bony defect to promote
osteogensis or new bone formation.[12] Further research lead
to the development of a calciumandphosphatecontaining
glass ceramic, known as Bioglass, which chemically bonded
to the bone.[13] In 1987, Brown and Chow described
selfsetting calcium phosphate cement(CPC) containing
tetracalcium phosphate(TTCP) and either dicalcium
phosphate anhydrous(DCPA) or dicalcium phosphate
dihydrate which when mixed with water hardened into
cement with a chemical composition and crystal structures
similar to tooth and bone.[14] Tricalcium phosphate(TCP)
has been added to oral hygiene products to remineralize
white spot lesions. Astudy by Yoshiba etal. suggested that
TCP containing Ca(OH)2, induces consistent hard tissue
formation, without excessive destruction of underlying pulp
tissue and can be used as a pulp capping agent.[15] TCP,
is the most commonly used as synthetic bone substitutes.
Calcium phosphate fillers are recently been incorporated in
composite resins and shown to released calcium(Ca) and
phosphate(PO4) ions to supersaturated levels for apatite
precipitation and effectively remineralized tooth lesions
in vitro.[16]
ACP
It is the initial solid phase that precipitates from a highly
supersaturated calcium phosphate solution and can convert
readily to stable crystalline phases such as octacalcium
phosphate or apatite products. It is osteoconductive,
bioactive, biodegradable, noncytotoxic.[17] ACP acts as
a precursor to bioapatite, used as filler in glass ionomer
cements. [18] ACP has been added to composites as
fillers which release Ca and PO ions into saliva, which
are deposited on tooth structures as apatite minerals.
Furthermore, nanoparticles of calcium phosphates have
been synthesized and incorporated into dental resins.
The high surface area of the nanoparticles, along with

Table1: Clinical restorative application of biomineral based biomaterials

Clinical application of
biomaterials
Calcium phosphate cement

Dentinogensis
-

Apexification
-

Repair of resorption
defects
-

-tricalcium phosphate
Bioactive glass

Synthetic hydroxyapatite

Portland cement

Mineral trioxide aggregate

Calcium hydroxide

Biodentine

Enamel
remineralization

Cement-ogensis

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Perforation
repair

Repair of bony
defects

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Shetty and Kundabala: Biominerals in restorative dentistry

Figure 1: Classification of biominerals based biomaterials

strong reinforcement fillers, resulted in composites with

stressbearing and Ca and PO4 releasing capabilities.[19,20]
Various technologies developed to stabilize calcium
phosphate are:[21]
Casein phosphopeptide(CPP) stabilized ACP
Unstabilized ACP(EnamelonTM)
NovaMinTM technology.
CPPACP
CPPACP is ACP complexed with the milk protein, CPP. On
acid challenge, the attached CPPACP releases calcium and
phosphate ions, thus maintaining a supersaturated mineral
environment and thereby reducing demineralization and
enhancing remineralization of enamel.[22,23] The rationale
for the use of ACPCPP is that the remineralized enamel is
generally more resistant to decalcification than untreated
enamel.[24] Therefore CPPACP is being incorporated
into chewing gums, toothpaste, mouth rinses etc., for
preventive treatment of dental caries. The ability to
stabilize calcium phosphate and thereby enhance mineral
solubility and bioavailability, confers upon the CPP the
potential to be biological delivery vehicles for calcium and
phosphate.[25,26] The acid resistance of enamel exposed
to CPPACP is increased by the addition of fluoride.[27]
Since CPPACP are natural derivatives of milk and readily
available in dairy products, they could be added as a food
additive and aid in prevention of caries.[28]

developed and patented by NovaMin Technology, Inc., for

the treatment of hypersensitivity by physical occlusion of
dentinal tubules, when it is incorporated into a dentifrice,
these particles are deposited onto dentin surfaces and
mechanically occlude dentinal tubules.[29] Bioglass reacts
when it comes in contact with water, saliva or other
body fluids. This reaction releases calcium, phosphorus,
sodium and silicon ions, which result in the formation of
crystalline HCA layer that is structurally and chemically
similar to natural tooth mineral.[30] The material behaves
as a biomimetic mineralizer. Bioactive glass when used as
prophy powder could induce immediate remineralization
of dentin by its ability to precipitate HA.[31]
Synthetic hydroxapatite
Yamagishi et al. developed a white crystalline paste of
modified HA, which chemically and structurally resembles
natural enamel and used it to repair an early caries lesion.[32]
Dental enamellike structure of HA was achieved through
a solution mediated solidstate conversion process with
organic phosphate surfactant and gelatin as the mediating
agent. HA by itself can be prepared artificially using a variety
of methods such as precipitation reactions and solgel
synthesis. However, reproducing various parameters such as
solubility, super saturation and energetics is challenging.[33]
Biomineral based biomaterial for repair and
replacement of dentin

Bioactive glass

Ca(OH)2

Bioactive glass containing calcium sodium phosphosilicate

originally developed as boneregenerative material which
was reactive when exposed to body fluids and deposited
hydroxycarbonate apatite(HCA). NovaMin in oral care was

Ca(OH)2 was introduced to the dental profession in 1921,

Hermann demonstrated the formation of dentinal bridge
in an exposed pulpal surface and it is now considered the
gold standard for direct pulp capping agents.[34] The

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Shetty and Kundabala: Biominerals in restorative dentistry

calcium oxide(CaO) known as quicklime contacts water,

the following reaction occurs: CaO+H2 > Ca(OH)2. CH
is a white odorless powder with a molecular weight of
74.08. The material is chemically classified as a strong
base with a high pH(12.5) and is only slightly soluble
in water with a solubility of 1.2g/l, at a temperature of
25C.[35] The of dissociating of Ca(OH)2 into calcium and
hydroxyl ions results in increased pH locally. Ca(OH)2 high
pH causes irritation of the pulp tissue, which stimulates
repair of dentin by the release of bioactive molecules such
as Bone Morphogenic Protein and Transforming Growth
FactorBeta One.[34,36] The induction of mineralization
seems to be the result of the highly alkaline pH of CH
and its antimicrobial activity is due to the hydroxide ions
which promote enzymatic inhibition of microorganisms.[37]
Draw backs of CH as remineralization agent are:[38]
Inadequate strength
Longterm solubility
Lack of chemical and mechanical adhesion to the
surrounding hard tissues
Accelerated degradation after being acid etched
during bonding procedures
Tunnel formation seen in dentinal bridge formed.
Tricalcium silicate(Ca3SiO5)
Ca3SiO5 is a major component of MTA and has been
used on its own or with additives. The Ca3SiO5 exhibited
adequate physical properties and induces cell growth,
differentiation and the deposition of HA on its surface. It
can induce HA formation and dissolve slowly in simulated
body fluids. Peng et al. in their study suggested that
Ca3SiO5 can induce the proliferation and odontogenic
differentiation of human dental pulp cells in vitro.[39]
Portland cement(PC)
PC is construction cement with great similarity to MTA. It
is a fine powder composed of 65% lime, 20% silica, 10%
alumina and ferric oxide and 5% other compounds. The
setting reaction of PC is similar to that of MTA.[40] Part of
the end product of the setting reaction is Ca(OH) 2 which
is enclosed in the form of complex gels or crystalline
substances.[41] PC has been reported to have intrinsic
radiopacity values ranging from 0.86 to 2.02mm
aluminum(Al), which is a drawback. [42] The primary
differences between both(grey and white) types of MTA
and PC is lack of potassium and the presence of bismuth
oxide.[43] PC contains arsenic which is an impurity of
limestone used to manufacture PC, but studies have
shown that the arsenic level release is low and unable
to cause toxic effects.[44] According to Camilleri et al.
the commercial versions of MTA were shown to have
broadly similar constitution to ordinary PC except for the
addition of bismuth compounds and white MTA did not
contain iron.[40] The disadvantage of PC is that it has lower
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radioopacity and the main advantage is its very low cost.

If PC is intended for clinical use it should be tested for any
pollution effects by heavy metal ions, should be sieved to
unique particle size and sterilized.[41]

MTA
MTA was developed byTirebinejad(1995) at Loma Linda
University as a rootend filling material. In 2002, white
mineral trioxide aggregate(WMTA) was introduced to
overcome esthetic concerns.[45] The MTA patent shows that
it contains CaO and silicon(SiO). The major component is a
mixture of dicalcium silicate, Ca3SiO5, tricalcium aluminate,
tetracalcium aluminoferrite and trace amounts of SiO2,
CaO, MgO, K2SO4 and Na2SO4. Grey mineral trioxide
aggregate basically consists of dicalcium and Ca3SiO5 and
bismuth oxide, whereas WMTA is primarily composed
of Ca3SiO5 and bismuth oxide.[40] When MTA powder is
mixed with water, Ca(OH)2 and calcium silicate hydrate
are initially formed and eventually transform into a poorly
crystallized and porous solid gel.[46] MTA powder is mixed
with a vehicle such as sterile water in a 3:1 powder/liquid
ratio. Amoist cotton pellet is placed in direct contact with
the material, which facilitates its setting. Upon hydration
the material forms a colloidal gel that solidifies to a hard
structure in 34h.[47] The initial pH of the mixed material
is 10.2 which rise to 12.5 after 3h, which is considered
as the setting time for MTA. It is considered a bioactive
material, it is hard tissue conductive, hard tissue inductive
and has the potential to interact with the natural fluids
present in tissues, also it is proven to be nonmutagenic
and noncytotoxic.[48,49] Compared to Ca(OH)2 cement,
MTA has demonstrated a greater ability to maintain
the integrity of pulp tissue. Histological evaluations of
exposed pulp tissue from animals capped with MTA have
shown the formation of a thicker dentinal bridge, with low
inflammatory response, hyperemia and pulpal necrosis
compared with Ca(OH)2 cement.[50,51] Analysis of clinical
treatment by Mente etal. concluded that MTA appears to
be more effective than Ca(OH)2 for maintaining longterm
pulp vitality after direct pulp capping.[52]
Biodentin
Biodentin is projected as dentin substitute by the
manufacturers since it stimulates teriatary dentin formation.
It is a calcium silicatebased restorative cement with
dentinlike mechanical properties.[53] The powder mainly
contains tricalcium, dicalcium silicate, calcium carbonate
and zirconium dioxide as contrast medium. The liquid
consists of calcium chloride in aqueous solution with an
admixture of polycarboxylate. The powder is dispensed
in a capsule which is mixed with the liquid in a triturator
for 30 s. Biodentine sets in approximately 10min. The
material can be applied directly in the restorative cavity
with a spatula as a bulk dentin substitute without any
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Shetty and Kundabala: Biominerals in restorative dentistry

conditioning treatment Ca(OH2) is formed during the

setting of the cement.[54]
Calcium enriched mixture
In the study by Asgary etal., introduced new endodontic
cement known as CEM which is alkaline cement which
releases CH during and after setting. [55] The major
components of the powder are 51.75% wt CaO, 9.53%
wt SO3, 8.49% wt P2O5, 6.32% wt SiO2 respectively.
When mixed with the waterbased solution, a bioactive
calcium and phosphate enriched material forms. It has
the advantage of shorter setting time(<1h), increased
flow and decreased film thickness, when compared with
MTA and the clinical uses are similar to MTA.[55] CEM
cement releases calcium and phosphate ions and then
forms HA.[56] A series of case reports suggest that CEM
is a bioactive material with various favorable properties
such as good sealing ability, high alkalinity, antibacterial
ef fect, biocompatibility along with dentinogenesis,
cementogenesis, low cytotoxicity, pain relief effect,
antiinflammatory external root resorption) effect, HA
formation.[57,58]
Biomaterials for repair of bone
CPC
CPC is an injectable, moldable, fastsetting and
bioabsorbable material with high compressive strength
that can act as a stable scaffold for bone formation.[59] CPC is
comprised of a mixture of(TTCP: Ca4(PO4) 2O) and(DCPA:
CaHPO4), which forms resorbable HA. CPC was approved
in 1996 by the Food and Drug Administration for repairing
craniofacial defects.[60]

CONCLUSION
Caries has been recognized as a multifactorial disease
process, which can be controlled and managed at various
stages of its development. Remineralization is considered
a natural repair for caries lesion, which requires at
times external therapeutic aid. At present, the focus is
shifting toward halting demineralization and promoting
remineralization, understanding its dynamics and interplay.
Materials and therapies are being developed to encourage
overriding mineral uptake in the tissue, which will not only
result in repair of the damage done, but concomitantly assist
in preventing new lesions from forming. With advances in
technology there is a sincere effort toward the development
and synthesis of biominerals at nanoscale to encourage
the remineralization of destroyed mineralized tissues to
preserve the health of the soft tissues. After caries process
is halted it is necessary to select an appropriate material
which will encourage the repair of the affected hard tissue.
There is a need for further research in the field of biomimetic
in the development of the synthetic materials based on the
concepts of biology to create mineralized matrices that can
mimic the natural hard tooth structure and the surrounding
bone. Currently focus is on regenerative endodontic
procedures so as to regenerate pulplike tissue and the
challenge is to regenerate damaged coronal dentin, such
as following a carious exposure; and regenerate resorbed
root, cervical or apical dentin.

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to an increase in the biological activity of OCP, resulting
in enhancing bone regeneration. [63] OCP is easy to
handle, has biodegradable properties, enhances bone
regeneration without cell transplantation and exogenous
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How to cite this article: Shetty N, Kundabala M. Biominerals in restorative
dentistry. J Interdiscip Dentistry 2013;3:64-70.
Source of Support: Nil, Conflict of Interest: None declared.

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