REVIEW ARTICLE

Review of the Mechanism of Tooth Whitening

SO RAN KWON, DDS, MS, PHD*, PHILIP W. WERTZ, PHD

ABSTRACT
Purpose: This review integrated the current literature on diffusion of whitening agents, their interactions with stain
molecules, and changes to the surface, with the aim of establishing a better understanding of the mechanism underlying
tooth whitening.
Materials and Methods: An electronic PubMed database search, with combinations of the following terms was
performed: Tooth Bleaching, Tooth Bleaching Agent, Hydrogen Peroxide, Pharmacokinetics, Tooth Permeability,
Oxidation-Reduction, Tooth Demineralization, and Color.
Results: Tooth whitening is a dynamic process that involves diffusion of the whitening material to interact with stain
molecules and also involves micromorphologic alterations on the surface and changes within the tooth that affect its
optical properties. The interaction seems not to be limited to stain molecules, but rather an affinity-based interaction
process that also accompanies effects on sound enamel and dentin structures.
Conclusions: This review underlines that supervision by dental health professionals as recommended by the American
Dental Association (ADA) Council on Scientific Affairs is critical to achieving a successful and safe whitening outcome.

CLINICAL SIGNIFICANCE
The mechanism that underlies tooth whitening with the use of peroxide-based materials is a complex phenomenon
encompassing diffusion, interaction, and surfaces changes within the tooth. Therefore, supervision by dental health
professionals as recommended by the ADA Council on Scientific Affairs is imperative to achieve a successful and safe
whitening outcome.
(J Esthet Restor Dent 27:240257, 2015)

INTRODUCTION whitening materials by dental professionals, as well as

The demand for tooth whitening has been building for
more than a decade as a growing number of people
envision and desire a Hollywood smile. Tooth whitening
now represents the most common elective dental
procedure1 and has been proven safe and eective when
supervised by the dentist.2 More than 1 million
Americans whiten their teeth annually, driving nearly
$600 million in revenues for dental oces.1
Additionally, many dentists are using tooth whitening
as a tool to market additional esthetic procedures
available in their clinic. The high demand is also
reected in the distribution and use of a vast variety of
in over-the-counter sales of materials directly to
consumers.
In spite of the tremendous growth in the tooth
whitening market, the basic mechanism underlying the
whitening process remains unexplained.
Color-producing stains within tooth structures are
often organic compounds that contain conjugated
double bonds. It is known from dye chemistry that
decoloration can occur due to the breakup of a
chromophore, and that destruction of one or more of
the double bonds within the conjugated system is
probably involved. Thus, the dominant theory on the

*Associate Professor, Department of Operative Dentistry, University of Iowa College of Dentistry & Dental Clinics, Iowa City, IA, USA

Professor, Oral Pathology, Radiology and Medicine, Dows Institute for Dental Research, University of Iowa College of Dentistry & Dental Clinics, Iowa City, IA, USA

240 Vol 27 No 5 240257 2015 Journal of Esthetic and Restorative Dentistry DOI 10.1111/jerd.12152 2015 Wiley Periodicals, Inc.

whitening mechanism is that stain molecules are
oxidized into colorless compounds.
The mechanism that results in changed perception of
tooth color can be subdivided into three distinct phases
(Figure 1): rst, movement of the whitening agent into
the tooth structure; second, interaction of the
whitening agent with the stain molecules; and third,
alteration of the tooth structure surface such that it
reects light dierently. The outcome of this sequence
of events would be the nal color change of the tooth
after whitening. Ideally, whitening procedures will
optimize whitening and at the same time minimize
concurrent damage to the tooth structure.
Here, we integrate the current literature on the
diusion of whitening agents, their interactions with
stain molecules, and changes to the tooth surface, with
the aim of establishing a better understanding of the
FIGURE 1. Illustration of the dynamics of diffusion and
interaction of whitening agents and surface changes at the
tooth surface.
Upper inset: Diffusion of Rhodamine B at the dentino-enamel
junction imaged with Zeiss 710 confocal laser scanning
microscope (Carl Zeiss Microimaging GmbH, Jena, Germany).
Middle inset: Intratubular collagen fibers imaged with Hitachi
S-3400 scanning electron microscope (Hitachi High-Tech,
Tokyo, Japan) and possible interaction with hydrogen peroxide
molecules. Lower inset: Surface changes associated with tooth
whitening material imaged with Bruker Multimode 8 atomic
force microscope (Bruker Corp., Billerica, MA, USA).
2015 Wiley Periodicals, Inc. DOI 10.1111/jerd.12152
THE MECHANISM OF TOOTH WHITENING Kwon and Wertz
mechanism underlying tooth whitening. It is important
to point out that this review focused on the mechanism
of peroxide-based whitening limiting the topic
specically to oxidative processes within the hard
dental tissues and did not include whitening by means
of mechanical measures nor the eect of
peroxide-based materials on the soft tissue.
This study was initiated with an electronic search of the
PubMed database using various combinations of search
terms selected from the Medical Subject Headings
(MeSH) for PubMed. These search terms were: Tooth
Bleaching, Tooth Bleaching Agent, Hydrogen Peroxide,
Pharmacokinetics, Tooth Permeability,
Oxidation-Reduction, Tooth Demineralization, and
Color. This search was restricted to articles in English
and published between 1968 and May 2014. Two other
articles that date back to the late 1800s were found
from a reference and included for this review.
Additionally, textbooks related to biochemistry and
tooth whitening were utilized. From a total of 2,885
titles, 379 abstracts were retrieved and considered for
inclusion by two reviewers. Among the study materials
represented, a total of 112 articles are covered in this
review.
TOOTH WHITENING AGENT
The quest for the ideal agent for whitening of
discolored teeth began in the 1800s. At that time, all
agents employed for tooth whitening were mixed in the
dentists oce and consisted of direct or indirect
oxidizers that acted not only on the chromogen but
also on the organic portion of the tooth.3 The variety of
whitening agents used reects the diverse nature of
discoloration: oxalic acid was used for the removal
of iron stains associated with pulp necrosis and
hemorrhage; chlorine was indicated for silver
and copper stains produced in the process of
amalgam-based restoration;4 and cyanide of potassium
could be used to remove the most resistant stains that
arose from metallic restorations, although this was not
recommended due to its highly poisonous nature.5 In
1884, Harlan published what is believed to be the rst
report of the use of hydrogen peroxide, which he called
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 THE MECHANISM OF TOOTH WHITENING Kwon and Wertz
TABLE 1. Whitening agents used in dental applications
Whitening agent Chemical Molar
formula mass
Hydrogen peroxide H2O2 34.01 g/mol
Carbamide peroxide CH6N2O3 94.07 g/mol
Sodium perborate NaBO3 99.82 g/mol
Chlorine dioxide ClO2 67.45 g/mol
hydrogen dioxide.6 Although a wide variety of
whitening products are currently available, in most
cases, hydrogen peroxide is the active agent.7 Hydrogen
peroxide may be applied directly or produced in a
chemical reaction from sodium perborate or
carbamide.8 Common whitening agents and their
dental applications are described below and their
properties are summarized in Table 1.
Hydrogen peroxide (H2O2) is a colorless liquid, is slightly
more viscous than water, and has a molar mass of
34.01 g/mol.9 Because of its low molecular weight, it can
penetrate dentin, where it releases oxygen and thereby
breaks the double bonds of the organic and inorganic
compounds inside the dentinal tubules.10 In dentistry,
hydrogen peroxide is used at concentrations ranging
from 5% to 35%.11 It acts as a strong oxidizing agent,
producing reactive oxygen molecules and hydrogen
peroxide anions. Hydrogen peroxide is naturally
produced, controlled, used, and destroyed during
normal function of the body. Indeed, the human body
can protect itself against oxidative stress by harnessing
the glutathione redox cycle, catalase, ascorbate,
superoxide dismutase, prostaglandin E1, glutathione
peroxidase, vitamin E, and plasma peroxidase.12
Carbamide peroxide (CH6N2O3) is a white crystalline
solid that releases oxygen when it comes into contact
with water.13 The concentrations used for bleaching
ranges from 10% to 35%. A 10% carbamide peroxide
solution breaks down into 3.35% hydrogen peroxide and
6.65% urea.14 The urea further breaks down into
ammonia and water, which may provide some benecial
side eects because it tends to increase the pH of the
solution.15 Additionally, urea has proteolytic properties
242 Vol 27 No 5 240257 2015 Journal of Esthetic and Restorative Dentistry
Range of Mode of Free radical
percentage action
540 Oxidation OH, OOH, O2
1035 Oxidation OH, OOH, O2
NA Oxidation OH, OOH, O2
0.07 Oxidation ClO2
that may aect the eciency of tooth whitening.16,17
Carbamide peroxide products usually contain either a
carbopol or a glycerin base. The carbopol base slows
down the release of hydrogen peroxide and is thus
eective over a longer period of time.18
Sodium perborate (NaBO3) is a white, odorless,
water-soluble chemical compound available as a
powder.13 It has been employed as an oxidizer and
whitening agent, especially in washing powders and
other detergents, since 1907.19 Although it is stable
when dry, in the presence of acid, warm air, or water, it
breaks down to form sodium metaborate, hydrogen
peroxide, and oxygen.11 Sodium perborate comes in
various formsmonohydrate, trihydrate, and
tetrahydratewhich dier in oxygen content and thus
have dierent whitening ecacy.20 A mixture of sodium
perborate and distilled water (2 g/1 mL) has an eect
equivalent to that of 16.3% hydrogen peroxide.21
Chlorine dioxide (ClO2) is a potent and useful oxidizing
agent and is commonly used in water treatment and
bleaching. Nondental establishments in the United
Kingdom introduced the use of chlorine dioxide, which
raised concerns with respect to safety.2 Despite the
safety concerns, an in vitro study showed that 0.07%
chlorine dioxide eectively whitened teeth at a faster
rate than 35% hydrogen peroxide.22
DIFFUSION
Tooth whitening is based on the premise that hydrogen
peroxide penetrates into the enamel and dentin to
interact with the organic chromophores. It is well
DOI 10.1111/jerd.12152 2015 Wiley Periodicals, Inc.

known that the dental hard tissues are highly permeable
to uids, and that the greatest uid ow in the enamel
and dentin is in the interprismatic spaces and dentinal
tubules, respectively.2325 Therefore, enamel and dentin
are expected to act as semipermeable membranes and
that they allow hydrogen peroxide to move according
to Ficks second law of diusion, which describes that
the diusion of a molecule is proportional to the
surface area, diusion coecient, and concentration,
and that it is inversely proportional to the diusion
distance.26
Despite the fact that peroxide-based tooth whitening
was introduced in the 1800s, it was in 1987 that
hydrogen peroxide penetration into the pulp cavity was
rst detected and quantied.27 In this study, extracted
teeth were exposed to 30% hydrogen peroxide, and
spectrophotometric measurement of sub-microgram
amounts of hydrogen peroxide was performed based
on the use of leucocrystal violet and horseradish
peroxidase, a well-established, accurate, selective, and
sensitive analytical method.28 This in vitro model
proved useful for further studies investigating various
factors that might inuence hydrogen peroxide
penetration of the pulp cavity. These studies and the
results are summarized in Table 2.
Overall, hydrogen peroxide penetration was found to be
enhanced by the following: higher hydrogen peroxide
concentrations;27,31,34,40 prolonged application;29,31
increased temperature;27,29 the large size of the openings
of dentinal tubules in young teeth;36 variations in the
tooth structure due to location, acid-etching or
restorations;33,37,39,44,48 and light activation.38 Penetration
was also improved by specic formulations and delivery
systems.30,32,35,42,46 The results of all reviewed studies are
basically in accordance with Ficks second law of
diusion.
The clinical relevance of these studies is not clear
because the model system did not fully replicate the
dynamics of the oral cavity; in particular, the presence
of the positive outward pulpal pressure associated with
vital teeth was not emulated. Nonetheless, it has been
cautioned to increase eciency to the point where
hydrogen peroxide penetrates the pulp cavity, due to
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THE MECHANISM OF TOOTH WHITENING Kwon and Wertz
potentially adverse and cytotoxic eects, especially in
patients with existing hypersensitivity, gingival
recession, attrition, cervical abrasion, and leaking
restorations.31
Particularly noteworthy ndings include the observation
that the dynamics of hydrogen peroxide diusion were
constant over a prolonged period, even when the
material was not replenished.43,45,49 Also, the inclusion of
chemical activators resulted in signicantly enhanced
whitening ecacy even though it was associated with a
reduction in penetration that has been attributed to
exhaustion of the hydrogen peroxide molecules within
the tooth structure.41 The latter observation is
consistent with the nding that overall hydrogen
peroxide penetration does not correlate with whitening
ecacy.45 Thus, low penetration does not necessarily
imply increased whitening ecacy and vice versa.
The relationship between the diusion of hydrogen
peroxide into the enamel and dentin and its interaction
with the dentin structure also showed that diusion does
not result in merely physical passage but rather in a
concentration gradient that is determined by its
particular chemical anity for each dental tissue.47
Notably, hydrogen peroxide does not interact only solely
with chromophores during diusion but also with sound
tooth structure. Therefore, it seems prudent to identify
optimal concentration and application times, i.e., those
that minimize penetration of the pulp cavity by
hydrogen peroxide without compromising whitening
ecacy.
INTERACTION
Traditionally, tooth whitening mechanism has been
represented by the chromophore theory, which is
based mainly on the interaction of hydrogen peroxide
with organic chromophores within the tooth structure.
Organic chromophores are colored molecules that
consist of either conjugated pi systems, such as
aromatic compounds that have electron-rich areas, or
bioinorganic metallic complexes, such as chelates.50
When reactive oxygen species encounter stain
molecules, they convert the chains of the latter into
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 THE MECHANISM OF TOOTH WHITENING Kwon and Wertz

TABLE 2. Studies that quantified hydrogen peroxide penetration levels

Bowles and Ugwuneri 198727

Specimen Human maxillary anterior teeth (N = 58)

Quantification method Leucocrystal violet and horseradish peroxidase

Concentrations used 1, 10, 30% HP for 15 minutes at 37 and 50C

Result and comments The amount of HP penetration was concentration and temperature dependent

Rotstein and colleagues 199129

Specimen Human premolar teeth (N = 24)

Quantification method Ferrous ammonium chloride and potassium thiocyanate to form ferrithiocyanate complex

Concentrations used 30% HP for 5, 20, 40, 60 minutes at 24, 37, and 47C

Result and comments No penetration at 5 minutes regardless of temperature. Radicular penetration was time and temperature dependent.

Cooper and colleagues 199230

Specimen Human anterior teeth (N = 40)

Quantification method Leucocrystal violet and horseradish peroxidase

Concentrations used 10% and 15% CP, 5% and 30% HP for 15 minutes at 37C

Result and comments Less penetration from CP sources than the same HP equivalent

Hanks and colleagues 199331

Specimen Dentin discs (N = 6)

Quantification method Leucocrystal violet and horseradish peroxidase

Concentrations used 3% and 10% HP, 10%, 15% CP for 15 minutes, 1 and 6 hours at 37C

Result and comments The amount of HP penetration was concentration and time dependent

Thitinanthapan and colleagues 199932

Specimen Human premolars (N = 70)

Quantification method Leucocrystal violet and horseradish peroxidase

Concentrations used 10% CP from three different formulations for 25 minutes at 37C

Result and comments Penetration of whitening products were different though the products were all labeled to have 10% CP

Benetti and colleagues 200433

Specimen Bovine lateral incisors (N = 60)

Quantification method Leucocrystal violet and horseradish peroxidase

Concentrations used 10% and 35% CP in sound and restored teeth for 60 minutes at 37C

Result and comments Penetration was concentration dependent with higher HP penetration in restored teeth

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 THE MECHANISM OF TOOTH WHITENING Kwon and Wertz

TABLE 2. Continued

Gkay and colleagues 200434

Specimen Human maxillary central incisors (N = 24)

Quantification method Leucocrystal violet and horseradish peroxidase

Concentrations used 6.5% and 14% HP for 30 minutes at 37C

Result and comments Significant HP penetration with whitening strips which was concentration dependent

Gkay and colleagues 200535

Specimen Human maxillary central incisors (N = 50)

Quantification method Leucocrystal violet and horseradish peroxidase

Concentrations used 5.3% HP, 19% NPP, 18% CP, 8.7% HP for 30 minutes at 37C

Result and comments HP from whitening strips and paint on whiteners readily penetrates into the pulp chamber at various amounts

Camps and colleagues 200736

Specimen Human premolars (N = 36)

Quantification method Ferrous ammonium chloride and potassium thiocyanate to form ferrithiocyanate complex

Concentrations used 20% CP measured at 1, 24, 48, 120 hours at a temperature not specified in the methods

Result and comments Maximal HP diffusion and diffusive flux through dentin was higher for young than old teeth

Camargo and colleagues 200737

Specimen Human third molars (N = 70), bovine lateral incisors (N = 70)

Quantification method Leucocrystal violet and horseradish peroxidase

Concentrations used 38% HP for 40 minutes at a temperature not specified in the methods

Result and comments HP penetration was higher in human teeth for any experimental situation

Camargo and colleagues 200938

Specimen Bovine lateral incisors (N = 48)

Quantification method Leucocrystal violet and horseradish peroxidase

Concentrations used 35% HP with LED and Nd:YAG laser activation for 20 minutes at not-specified temperature

Result and comments LED and Nd:YAG laser activation increased HP penetration in bovine teeth

Camps and colleagues 201039

Specimen Human premolars (N = 46)

Quantification method Ferrous ammonium chloride and potassium thiocyanate to form ferrithiocyanate complex

Concentrations used 35% HP measured at 24, 48, 168 hours at not-specified temperature

Result and comments Higher HP penetration when acid-etching of dentin was performed

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 THE MECHANISM OF TOOTH WHITENING Kwon and Wertz

TABLE 2. Continued

Palo and colleagues 201040

Specimen Bovine lateral incisors (N = 72)

Quantification method Leucocrystal violet and horseradish peroxidase

Concentrations used Variations of Walking Bleach technique: 35% HP, 35% CP, SP, SP + HP, SP + CP for 7 days at 37C

Result and comments There was direct correlation between the presence of oxidative agents and HP penetration potential

Torres and colleagues 201041

Specimen Bovine incisors (N = 104)

Quantification method 4-aminoantipyrine and phenol with HP catalyzed with peroxidase

Concentrations used 35% HP and manganese gluconate, manganese chlorite, ferrous sulfate, ferrous chloride, mulberry root extract

Result and comments Chemical activation using metal salts increased whitening efficacy and decreased HP penetration levels

Pignoly and colleagues 201242

Specimen Bovine teeth (N = 30)

Quantification method Peroxi kit (Sigma Chemical Co, St. Louis, MO, USA)

Concentrations used 30% HP pH 3.0; 35% HP pH 5.0; 38% HP pH 7.0 measured every 10 minutes for 1 hour at not-specified temperature

Result and comments No difference in whitening efficacy among different groups and no effect of pH on HP diffusion coefficient

Kwon and colleagues 201243

Specimen Human canines (N = 20)

Quantification method Leucocrystal violet and horseradish peroxidase

Concentrations used 40% HP measured every 10 minutes for 1 hour at 25C

Result and comments Time course diffusion kinetics of HP penetration showed constant HP penetration over an hour period

Palo and colleagues 201244

Specimen Bovine teeth (N = 50)

Quantification method Leucocrystal violet and horseradish peroxidase

Concentrations used Walking Bleach technique with 35% HP for 7 days at not-specified temperature

Result and comments HP penetrated through enamel, dentin and cementum with cementum being the least permeable dental tissue

Kwon and colleagues 201345

Specimen Human canines (N = 80)

Quantification method Leucocrystal violet and horseradish peroxidase

Concentrations used 38% HP for 1 hour with the use of conventional versus sealed bleaching technique (SBT) at 25C

Result and comments SBT that does not require replenishment of material provided same whitening efficacy with lower HP penetration

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 THE MECHANISM OF TOOTH WHITENING Kwon and Wertz

TABLE 2. Continued

Ubaldini and colleagues 201347

Specimen Human premolars (N = 18)

Quantification method Micro-Raman spectroscopy (MRS) and Fourier transform infrared photoacoustic spectroscopy (FTIR-PAS) to measure
spectra of specimens

Concentrations used 25% HP for 1 hour at room temperature

Result and comments MRS showed that HP crossed enamel had a marked concentration at the DEJ and accumulated in dentin

FTIR-PAS showed that HP modified dentins organic compounds demonstrated by a decrease in amides I, II, III absorption
band intensities

Patri and colleagues 201348

Specimen Human incisors (N = 60)

Quantification method Leucocrystal violet and horseradish peroxidase

Concentrations used 10% CP for 1 hour at 37C

Result and comments HP penetration in restored teeth was higher than in sound teeth

Marson and colleagues 201449

Specimen Bovine teeth (N = 75 specimens)

Quantification method Leucocrystal violet and horseradish peroxidase

Concentrations used 3538% HP for 45 minutes three times at not-specified temperature

Result and comments Whitening gels maintain more than 86% of their initial concentration of HP after 45 minutes without replenishment

CP = carbamide peroxide; HP = hydrogen peroxide; LED = Light Emitting Diode; Nd:YAG = Neodymium-Doped Yttrium Aluminium Garnet;
NPP = sodium percarbonate peroxide; SP = sodium perborate.

simpler structures or alter their optical properties such
that the appearance of the stain is diminished.51 These
reactions will also yield products that are both more
polar and lower in molecular weight than the original
stain molecule. Both of these properties will make the
products easier to remove in an aqueous environment.
Although it remains to be determined how the
whitening agent interacts with the stain molecules,
chemical oxidation is thought to be involved. As such,
it will be important to understand the roles of pH,
chemical activators, temperature, and light activation at
various wavelengths.52
The rate of decomposition and the type of active oxygen
formed are dependent on the temperature and
concentration of the peroxide, as well as on the pH and the
presence of co-catalysts and metallic reaction partners.53 In
addition, depending on which chemical bond breaks,
hydrogen peroxide can give rise to a number of reactive
oxygen species. These include the hydroxyl radical,
hydroperoxyl radical, hydroperoxyl radical anion,
superoxide radical anion, and superoxide radical cation. In
an aqueous environment, the peroxyl radical will be in
equilibrium with the superoxide radical. The reactive
oxygen species produced from hydrogen peroxide depend
on factors such as pH and the presence of metal cations.
These reactive oxygen species are generally capable of
abstracting hydrogen atoms from biological molecules.12
These sorts of chemical reactions can cause damage to
biological membranes, but can also cause the degradation
of stain molecules.
Despite the well-established chemistry of hydrogen
peroxide, central issues remain to be addressed. For

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 THE MECHANISM OF TOOTH WHITENING Kwon and Wertz
example, we remain unable to detect chromophores
within the tooth structure and have yet to establish the
site-specic mechanism whereby whiteners bind to
them. Furthermore, it will be important to analyze and
quantify breakdown products associated with tooth
whitening. Studies on tooth enamel using Fourier
transform infrared (FTIR) and Raman spectroscopy
failed to detect chromophores or their breakdown
products, and as such, the chromophore theory is not
fully supported.5456
Dental enamel is the most highly mineralized and
hardest tissue of the body. It is approximately 96%
mineral, 3% water, and 1% organic matter by weight.
The enamel interface undergoes continuous dynamic
ion exchange with the oral biolm, with calcium
phosphate apatite crystals moving in both directions to
maintain a proper mineral balance. Recent evidence
indicates that some organic materials in the enamel
originate from exogenous sources and become part of
the organic matrix.57 Mature dentin is 70% mineral,
20% organic matrix, and 10% water by weight. The
mineral component of dentin consists of substituted
hydroxyapatite in the form of small plates, whereas the
organic matrix is 90% collagen and includes small
percentages of various noncollagenous matrix proteins
and lipids.58
Ideally, throughout the process of tooth penetration,
the oxidizing action of hydrogen peroxide should be
limited to the organic chromophores. However, review
of the literature suggests that hydrogen peroxide
interacts signicantly with the organic as well
as inorganic components of both enamel and
dentin.
Hydrogen peroxide penetrates the enamel mainly by
entering the interprismatic spaces, which are lled with
enamel proteins. Because the mineralized, inorganic
phase is much more compact than the organic,
penetration through the hydroxyapatite crystals and
interaction with them is probably very low.57 The
assumption that the organic matrix of enamel and
dentin is aected by hydrogen peroxide is supported by
several studies. X-ray diraction analysis of
hydroxyapatite and NMR-based measurement of
248 Vol 27 No 5 240257 2015 Journal of Esthetic and Restorative Dentistry
changes in amino acids suggested that hydrogen
peroxide and hydroxyl radicals do not inuence the
inorganic component of dentin but do inuence the
organic tissue.5961 These ndings led to speculation that
the whitening eect could result from modication of
the polypeptide chain in the organic substance rather
than from the interaction of the whitener with stain
molecules. This is also in accordance with the
observation of advanced oxidation processes, where
hydroxyl radicals interact mainly with organic matter to
produce intermediates and yield harmless species such
as carbon dioxide and water.62 Other studies using
atomic force microscopy (AFM) and FTIR showed
that the morphological changes in dentin and enamel
were due mainly to partial lysis of the tooth enamel
matrix protein or the organic matrix of the
dentin.47,57,6366 Moreover, signicant increases in the
proteolytic activities of cathepsin B and matrix
metalloproteinase after tooth whitening have been
demonstrated, suggesting a dynamic change within
the tooth.63
The change in the inorganic chemical composition of
enamel and dentin, suggesting that hydrogen peroxide
interacts with the tooth structure, has been studied
extensively using ion-selective electrode probes,
FT-Raman spectroscopy, and a combination of
scanning electron microscopy (SEM), energy-dispersive
X-ray spectrometer, and microcomputerized
tomography. Despite the fact that many studies of
peroxide-based materials have shown that these agents
do not inuence the chemistry of enamel and dentin
beyond clinical relevance or may be prevented with
addition of uoride or calcium,6772 many others have
indicated signicant changes in the calcium/phosphate
ratio, indicating that the inorganic components of
hydroxyapatite are altered.7380 Several studies using
FTIR analysis revealed that hydrogen peroxide
treatment induces loss of both carbonate and proteins
from enamel and dentin,63,81 and also alterations in
representative biological bands of hydroxyapatite.82,83
Furthermore, the use of microcomputerized
tomography showed that 35% carbamide peroxide
induced the demineralization of enamel to a depth of
250 m, although demineralization of dentin was not
observed.76,78
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Overall, these studies suggest that hydrogen peroxide
has the potential to interact with all the components of
dentin and enamel. The clinical signicance of this
interaction and how it relates to tooth whitening
remains to be assessed and evaluated in future studies.
SURFACE CHANGE AND COLOR
Perception of tooth color is inuenced by many factors,
including lighting conditions, the object being viewed,
and the viewer. Given the dynamics of these three
components, accurately recording tooth shade and
monitoring minute color changes is extremely dicult,
especially when the complex optical properties of
mineralized tissues and the combined eects of intrinsic
and extrinsic pigmentation are factored in.84,85 Optical
characteristics, such as gloss, opacity, and translucency,
and also optical phenomena such as metamerism,
opalescence and uorescence, add to the intricacy of
the color perception process.86
Most inherent tooth color is attributed to diuse
reectance from the volume of the inner dentin
through the outer translucent enamel layer. Based on
color vision, the human eye can only perceive the light
that is reected. Reection occurs at the surface and
from the volume of the object that can be further
divided into specular reection and diuse reection,
summing up into the total reection.87 A study
evaluated the tooth color and reectance as related to
light scattering and enamel hardness. It specically
compared the color of the extracted teeth before and
after removal of the labial enamel, and found that tooth
color is determined mainly by dentin; enamel plays only
a minor role, primarily through scattering at
wavelengths in the blue range.88
The fact that dentin is a predominant factor in
determining tooth color is also important when
considering the mechanism of tooth whitening. For
example, it raises the question of whether the whitening
agent interacts mainly within the dentin to change the
overall tooth color. Several studies that evaluated the
separate contributions of enamel and dentin to overall
change in tooth color during whitening concluded that
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THE MECHANISM OF TOOTH WHITENING Kwon and Wertz
the overall change was highly inuenced by that in the
subsurface dentin.89,90 However, results from other
studies emphasized the signicance of the contribution
of enamel to the overall color change and suggested
that this contribution was due mainly to the decrease in
translucency of the enamel and thus to masking of the
color of the underlying dentin.9193
The change in translucency of the enamel has been
attributed to micromorphological alterations of the
most supercial enamel through deproteinization,
demineralization, and oxidation.54,92,93 Despite the fact
that surface alterations related to tooth whitening have
been extensively investigated by SEM, prolometry, and
AFM, with many studies indicating that whitening has
no eect on surface topography,9499 there are as many
in which signicant changes in surface topography have
been documented.100108 Studies that specically related
optical properties of the tooth or changes in enamel
surface topography to tooth whitening and color
change are summarized in Table 3.
It is well known that a rough or coarse surface results
in more diuse reection, turning the object brighter,
whereas a smooth surface leads to more specular
reection, and that increased backscattering of short
wavelengths that are reected as bluish-white due to
opalescent eects at small structures plays a
considerable role in the light scattering of teeth.84
Although an increase in surface roughness
post-whitening is not necessarily anticipated, where
present, it may result in increased reectance spectra
and thus in improved digital color reading.109,113,116,117
The enhanced reection on the surface post-whitening
would, in turn, render the enamel more opaque, as can
also be observed in early carious lesions.92,93,111
Within the same context, it has been suggested that
demineralization during tooth whitening might
contribute to the whitening eect.67,70,109,118 This
possibility was supported by a report of color regression
in association with increased mineral uptake after tooth
whitening.114 However, a reduction in laser-induced
uorescence and luminescence during Raman spectral
analyses was found to be associated with tooth
whitening and has been attributed to a change in the
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 THE MECHANISM OF TOOTH WHITENING Kwon and Wertz

TABLE 3. Studies relating optical properties or a change in surface enamel to tooth color change

Kwon and colleagues 2002109

Specimen Bovine incisors (N = 5)

Methods Diffuse reflectance measurement with UVvisNIR spectrophotometer, surface topography observation with SEM

Materials used 30 % HP for 0, 1, 2 and 3 days

Result and comments Whitened samples showed slight alterations with varying degrees of surface porosity and increased reflectance spectra
compared with control

Gtz and colleagues 2007110

Specimen Human molars (N = not clear)

Methods Color measurement with digital camera, microhardness, VP-SEM, ultrastructure assessment with CLSM, micro-Raman
spectroscopy

Materials used 13% and 16% HP strips for a total exposure time of 28 hours

Result and comments Significant whitening compared with control. No changes in VHN, VP-SEM observations similar to control.

Reduction of luminescence during Raman spectral analyses of enamel and dentin in samples whitened with higher
concentrations.

Vieira and colleagues 2008111

Specimen Human molar teeth (N = 14)

Methods Color measurement with spectrophotometer

Materials used 10% CP for 8 hours per day for 28 days

Result and comments For all samples, a decrease in translucency and transmittance was observed that may be due to rise in diffuse reflection on
a rougher surface

Joiner and colleagues 2008112

Specimen Human anterior and premolar teeth (N = 68)

Methods Color measurement with colorimeter, time-of-flight secondary ion mass spectrometry (TOF-SIMS)

Materials used Blue covarine containing toothpaste, brushing for 1 minute

Result and comments Blue covarine was detected on enamel surface by TOF-SIMS and resulted in a negative shift in b* and a increase in
whiteness index (WIO)

Ma and colleagues 200992

Specimen Human premolars (N = 24)

Methods Color measurement and translucency measurement with spectrophotometer

Materials used 10% and 15% CP for 8 hours per day for 14 days

Result and comments 10% and 15% CP made color changes in E-D specimens-upon removal of dentin, significant color change was observed in
enamel slabs

Translucency parameters were less for bleached enamel compared with control suggesting that enamel plays a key role in
color change related to whitening

250 Vol 27 No 5 240257 2015 Journal of Esthetic and Restorative Dentistry DOI 10.1111/jerd.12152 2015 Wiley Periodicals, Inc.
 THE MECHANISM OF TOOTH WHITENING Kwon and Wertz

TABLE 3. Continued

Markovic and colleagues 2010113

Specimen Human teeth were grouped based on maturation stage (N = 48)

Methods Total reflectance measurement with computer assisted spectrometer

Materials used 10% and15% CP for 8 hours with 14 applications, 35% HP for 24 minutes repeated three times

Result and comments Total reflectance increased post-whitening at all enamel maturation stages, for wavelength 450 and 500 nm

Whitening of enamel worked at different maturation stages even in impacted teeth

Li and colleagues 2010114

Specimen Human incisors (N = 40)

Methods Color measurement with spectrophotometer, mineral content measurements with -CT

Materials used 38% HP for 10 minutes repeated three times

Result and comments Color regression resulted by the reversal of lightness and was correlated with the presence of remineralization process
within the tooth

No color regression and mineral content change was found in the anhydrous environment

Sun and colleagues 2011115

Specimen Human premolars (N = 27)

Methods Color measurement with spectrophotometer, ATR-FTIR spectroscopy, Raman spectroscopy, AFM, microhardness test

Materials used Neutral 30% HP versus acidic 30% HP, immersion for 4 hours

Result and comments No significant difference in color change between acidic and neutral 30% HP

Significant decrease of carbonate : mineral ratio in acidic HP, LIF was significantly reduced in both HP groups

Pedreira de Freitas and colleagues 2010108

Specimen Human lower incisors (N = 3)

Methods AFM for roughness (Ra and RMS) and power spectral density (PSD)

Materials used 35% HP, four applications of 10 minutes each

Result and comments Significant increase in PSD in the range of visible light spectrum (380750 nm) with whitening procedure

The results promote more visible light scattering which leads to an opaque surface

Eimar and colleagues 201254

Specimen Human upper incisors and canines (N = 60)

Methods Color measurement with spectrophotometer, elemental analysis with SEM-EDS, crystallinity index analysis with Raman
spectrophotometer

Materials used 1 M NaOH, 0.5 M EDTA, 30% HP immersion in solution for 4 days

Result and comments Deproteinization with NaOH increased lightness, demineralization with EDTA decreased lightness and oxidation with HP
increased lightness

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 THE MECHANISM OF TOOTH WHITENING Kwon and Wertz

TABLE 3. Continued

Grundlingh and colleagues 2013116

Specimen Human incisors, canines and premolars (N = 99)

Methods Color measurement with Vitapan 3D Master Shade guide and spectrophotometer, surface roughness measurement with
AFM

Materials used Ozicure oxygen activator bleach and 35% CP three times according to each manufacturers instructions

Result and comments Surface roughness value increased twofold for 35% CP. Increased light scattering improved digital color reading.

-CT = microcomputerized tomography; AFM = atomic force microscopy; ATR-FTIR = attenuated total reflectionFourier transform infrared
spectroscopy; CLSM = confocal laser scanning microscopy; CP = carbamide peroxide; EDS = energy dispersive spectroscopy; HP = hydrogen peroxide;
LIF = laser-induced fluorescence intensity; RMS = Root Mean Square; SEM = scanning electron microscopy; VHN = Vickers hardness number;
VP = variable pressure.

organic matrix within the enamel rather than with
surface mineral loss and changes in roughness.54,110,115,119
Eorts have also been made to assess tooth shade as it
relates to the chemical composition and crystallography
of the enamel. Based on a study using crystallography,
tooth hue was associated with the size of
hydroxylapatite (HA) crystals in the enamel, whereas
chroma was associated with the carbonization of
these HA crystals, and lightness was associated with
both the size and the carbonization of the HA crystals.
This partly explained the reduction of lightness
observed with aging, as crystal size increases with
aging.120
Other innovative approaches that have been applied
toward understanding the optical phenomenon
introduced chemicals such as covarine into whitening
agents, with the purpose of depositing a material on the
tooth surface that alters the optical properties of the
tooth. The results indicated that blue covarine
produced a greater negative shift in chroma in the
yellow blue axis and also increased the measured
whiteness index.112
All of the studies evaluating changes in the optical
properties of teeth suggest that the assumption that
the chromophore eect is dominant in tooth
whitening cannot be sustained. It seems necessary
to modify this theory to reect the complexity of
interactions and optical changes associated with
tooth whitening.
DISCUSSION AND CONCLUSIONS
With the high demand for instant whitening results
from patients in a highly appearance-driven society,
tooth whitening products continue to become ever
more prolic and diverse. To keep pace with this trend,
and to provide a solid foundation for the development
of innovative, new whitening technologies, scientists
have put great eort into elucidating the mechanism
underlying tooth whitening.
The mechanism that underlies tooth whitening,
however, has proven to be a complex phenomenon, and
no model fully integrating the details of the mechanism
that leads to the nal outcome of color change toward
increased lightness and reduced chroma has been
developed. Therefore, it is imperative to develop a stain
retention model that takes into account the amount
and type of chromophore within a given tooth. Most
studies to date have been concerned mainly with the
evaluation of tooth discoloration based on visual or
instrumental color measurements without trying to
directly assess the density of chromophore molecules
trapped within the dentition. However, it is precisely
the amount of stain intercollated within the dental hard
tissues that needs to be correlated with spectroscopic
methods in order to allow for assessment of the true
character of staining and possible changes associated
with tooth whitening. With the development of a
proper stain retention model, several signicant
outcomes become possible. For instance, if the stain has
an ultraviolet absorption spectrum, that spectrum can

252 Vol 27 No 5 240257 2015 Journal of Esthetic and Restorative Dentistry DOI 10.1111/jerd.12152 2015 Wiley Periodicals, Inc.

be used to assess the amount of stain still intercollated
in the tooth structure after the completion of tooth
whitening. This model could also be used to assess the
amount of stain or breakdown products present in both
enamel and dentin, which will lead to a better
understanding of the nature of perceived color, i.e., the
stain could be present primarily in the dentin but
perceived through the enamel even though the enamel
itself may have very little stain present. Furthermore,
surface changes and concomitant changes in optical
properties could be additionally determined through
this model. A more distant but still reachable outcome
could be the development of innovative whitening
alternatives. For instance, if the chromophore never had
an opportunity to bond with the organic or inorganic
content of the dental hard tissues by means of an
anti-staining treatment that would act like dental
Teon, a dentist could prescribe a rinse once or twice a
week that could potentially prevent tooth staining in
the rst place.
This review on the integration of three aspects of tooth
whitening mechanism covers diusion, interaction, and
surface changes related to the optical properties of the
tooth. Although a vast body of literature indicates that
surface changes and interactions with minerals in sound
tooth structures are associated with tooth whitening,
other studies suggest that they are not. Based on our
review, it is evident that tooth whitening with
peroxide-based materials is a dynamic process initiated
by the movement of the whitening material into the
tooth structure to interact with stain molecules and also
involves micromorphologic alterations on the surface
and changes within the tooth that aect its optical
properties. The interaction seems not to be limited to
the organic stain molecules, but rather an anity-based
interaction process that also accompanies eects on
sound enamel and dentin structures.
The clinical relevance and signicance of these minute
alterations remain to be investigated in further detail.
The conclusions of this review underline that careful
monitoring and supervision by dental health
professionals as recommended by the ADA Council on
Scientic Aairs is critical to achieving a successful and
safe tooth whitening outcome.2
2015 Wiley Periodicals, Inc. DOI 10.1111/jerd.12152
THE MECHANISM OF TOOTH WHITENING Kwon and Wertz
DISCLOSURE AND ACKNOWLEDGEMENT
The authors declare no potential conicts of interest
with respect to the authorship and/or publication of
this article. The authors express their sincere gratitude
to University of Iowa College of Dentistry librarian
Christine White for her assistance in the database
search. Special thanks also to Patricia Conrad at
Technology & Media Services for her help with the
illustration.
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Reprint requests: So Ran Kwon, DDS, MS, PhD, Department of Operative
Dentistry, University of Iowa College of Dentistry & Dental Clinics, 801
Newton Road #45, S235 DSB, Iowa City, IA 52242-1001, USA; Tel.:
319-335-8871; Fax: 319-335-7267; email: soran-kwon@uiowa.edu
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