UNIVERSIDADE ESTADUAL PAULISTA
JÚLIO DE MESQUITA FILHO”
Instituto de Ciência e Tecnologia
Campus de São José dos Campos
ORIGINAL ARTICLE DOI: https://doi.org/10.4322/bds.2023.e3945
1
Braz Dent Sci 2023 Oct/Dec;26 (4): e3945
Light-curing of calcium hydroxide-based liners: pH analysis and
calcium ion release
Fotoativação de forradores a base de hidróxido de cálcio: análise de pH e liberação de íons cálcio
Paulo Fermino da COSTA NETO
1
, Mariana Bena GELIO
1
, Joissi Ferrari ZANIBONI
1
, Jardel Camilo do Carmo MONTEIRO
1
,
Adirson JORGE JÚNIOR
1
, Milton Carlos KUGA
1
1 - Universidade Estadual Paulista Júlio de Mesquita Filho, Faculdade de Odontologia de Araraquara, Departamento de Odontologia
Restauradora, Araraquara, SP, Brazil.
How to cite: Costa PF No, Gelio MB, Zaniboni JF, Monteiro JCC, Jorge A Jr, Kuga MC. Light-curing of calcium hydroxide-based liners:
pH analysis and calcium ion release. Braz Dent Sci. 2023;26(4):e3945. https://doi.org/10.4322/bds.2023.e3945
ABSTRACT
Objective: Compare the pH values and calcium ion release of calcium hydroxide-based liner materials before
and after light-curing. Material and Methods: The materials evaluated were: hydrox-cal white (HW), hydrox-
cal dentin (HD), Biocal (BC) and UltraBlend Plus (UB). 120 samples of the liner materials were inserted into
a PVC tube (n=15). The samples from HW+A, HD+A, BC+A and UB+A were subjected to photoactivation.
The other groups HW+N, HD+N, BC+N and UB+N were only inserted in a glass tube with deionized water.
The pH was measured 24 hours and 14 days after the inclusion of the samples with the aid of a pH meter. The
calcium release was analyzed with the aid of an atomic absorption spectophotometer at 24h and 14 days. The
results were submitted to the Shapiro-Wilk test, followed by ANOVA and Tukey test (p=0.05). Results: In 24h,
the groups that were not light cured showed the highest pH values (p<0.05). In 14 days, BC+N and BC+A
demonstrated the lowest pH values. The groups that were not light cured also showed higher calcium release
values in 24h and 14 days (p<0.05). Conclusion: Photoactivation of calcium hydroxide-based liner materials
negatively interferes with calcium ion release, as well as with pH.
KEYWORDS
Acidication; Alkalinization; Calcium hydroxide; Hydrogen-ion concentration; Light-curing.
RESUMO
Objetivo: Comparar os valores de pH e liberação de íons cálcio de materiais forradores à base de hidróxido de
cálcio antes e depois da fotopolimerização. Material e métodos: Os materiais avaliados foram: Hidrox-cal branco
(HW), Hidrox-cal dentina (HD), Biocal (BC) e UltraBlend Plus (UB). 120 amostras dos materiais de revestimento
foram inseridas em um tubo de PVC (n=15). As amostras de HW +A, HD+A, BC+A e UB+A foram submetidas à
fotoativação. Os demais grupos HW +N, HD+N, BC+N e UB+N foram inseridos apenas em um tubo de vidro com
água deionizada. O pH foi medido 24 horas e 14 dias após a inclusão das amostras com o auxílio de um medidor
de pH. A liberação de cálcio foi analisada com o auxílio de um espectrofotômetro de absorção atômica em 24h e
14 dias. Os resultados foram submetidos ao teste de Shapiro-Wilk, seguido de ANOVA e teste de Tukey (p=0,05).
Resultados: Em 24h, os grupos não fotopolimerizados apresentaram os maiores valores de pH (p<0,05). Em 14 dias,
BC+N e BC+A apresentaram os menores valores de pH. Os grupos não fotopolimerizados também apresentaram
maiores valores de liberação de cálcio em 24h e 14 dias (p<0,05). Conclusão: A fotoativação de materiais de
revestimento à base de hidróxido de cálcio interfere negativamente na liberação de íons cálcio e no pH.
PALAVRAS-CHAVE
Acidicação; Alcalinização; Concentração de íons de hidrogênio; Fotopolimerização; Hidróxido de cálcio.
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Braz Dent Sci 2023 Oct/Dec;26 (4): e3945
Costa Neto PF et al.
Light-curing of calcium hydrox ide-based liners: pH analysis and calcium ion r elease
Costa Neto PF et al.
Light-curing of calcium hydroxide-based liners: pH analysis
and calcium ion release
INTRODUCTION
Calcium hydroxide was introduced in
dentistry in 1920 and is highly recommended as a
protective agent for the dentin-pulp complex [1].
The material has high solubility and slow release
of calcium and hydroxyl ions [2] when in contact
with humid environment [1]. The presence of
calcium ions in dentin promotes remineralization,
while the hydroxyl ion inhibits the action of
microorganisms and alkalizes the pH of the
region [3], thus promoting the formation of hard
tissue [1].
Several materials are proposed in the
literature as protective agents of the dentin-
pulp complex. The objective of using these
materials is to prevent pulpal exposure in cases of
extensive and deep caries, besides favoring dental
remineralization by the formation of restorative
dentin in the region [4]. Calcium hydroxide is
still one of the main materials of choice for this
procedure due to alkalinization, biocompatibility
and remineralization, which provides formation
of tertiary dentin [4,5].
However, their high solubility, poor
mechanical properties, and lack of adhesion
to dentinal tissue make them unviable. As a
solution to the problem, some calcium hydroxide-
based materials that allow photoactivation have
appeared in the market [5,6]. The addition
of polymerizable methacrylates allowed their
physical properties, chemical stability and
solubility to be improved [7-9], making their
clinical use more favorable and practical.
Although photoactivation replaces the
deficiencies that calcium hydroxide cements
had, its use may prevent or reduce the release of
calcium and hydroxyl ions into the tooth tissue,
besides not achieving a good pH stability, thus
affecting dentin remineralization [3]. However,
there are controversies about this change in
pH and ion release using light-cured calcium
hydroxide-based materials [6]. Therefore, it
is of interest to evaluate whether light-curing
interferes with the beneficial properties of
calcium hydroxide-based materials. Therefore,
it is necessary to compare the pH values and the
presence of calcium ions before and after light
curing.
The aim of this study was to evaluate
the hydrogen potencial and calcium release
of cavity luting cements containing calcium
hydroxide (Hydrox-cal white, Hydrox-cal dentin,
Biocal and Ultra-Blend Plus) before and after
photoactivation, at 24 hours and 14 days, by
measuring pH with a pH meter and by atomic
absorption spectroscopy to evaluate calcium
ions. The null hypotheses (H0) there were no
differences in relation to pH and calcium release
in the calcium hydroxide cements with or no
photoactivation.
MATERIAL AND METHODS
The analyses were performed by a single
operator who did not know which groups were
being evaluated. Table I shows the materials
used, manufactures and chemical composition.
Evaluated groups
- HW+N (Hydrox-cal white, not
photoactivated): the material was directly
inserted into the polyethylene tube and
immediately immersed in distilled water; -
HW+A (Hydrox-cal white, photoactivated):
After the material was inserted in the
polyethylene tubes, the set underwent
photoactivation using a LED unit (Valo;
South Jordan, UT, USA) at potency of
1200mW/cm
2
, positioned 5 mm apart for 20
Table I - Liner materials, manufacturer and chemical composition
Materials Manufacturer Chemical compositiom
Hidrox-cal white Maquira, (Maringá, PR, BR)
Calcium hydroxide (7.5%), UDMA, Tetraethylene glycol dimethacrylate,
Subtle Hydroxy Toluene, Camphorquinone, Chivacure EPD, 1.0µm glass
filler
Hidrox-cal dentin Maquira, (Maringá, PR, BR)
Calcium Hydroxide (7.5%), UDMA, Tetraethylene Glycoldimethacrylate,
Subtle Hydroxy Toluene, Camphorquinone, Chivacure EPD, 1.0 µm Glass
Filler, Yellow Iron Oxide, Red Iron Oxide, Titanium Dioxide
Biocal Biodinâmica (Ibiporã, PR, BR)
Calcium hydroxide, UDMA, inorganic particles, barium sulfate,
photoactivator and pigments
Ultra-Blend Plus Ultradent (South Jordan, UT, USA) UDMA, calcium hydroxide
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Braz Dent Sci 2023 Oct/Dec;26 (4): e3945
Costa Neto PF et al.
Light-curing of calcium hydrox ide-based liners: pH analysis and calcium ion r elease
Costa Neto PF et al.
Light-curing of calcium hydroxide-based liners: pH analysis
and calcium ion release
seconds. Immediately, the specimens were
immersed in distilled water;
- HD+N (Hydrox-cal dentin, not light cured):
similar to HW +N, but Hydrox-cal dentin
was used;
- HD+A (Hydrox-cal dentin light cured):
similar to HW+A, but Hydrox-cal dentin was
used;
- BC+N (Biocal, not light cured): similar to
HW+N, but Biocal was used;
- BC+A (Biocal, light cured): similar to
HW+A, but Biocal was used;
- UB+N (Ultra-blend Plus, not light cured):
similar to HW+N, but Ultra-blend Plus was
used;
- UB+A (Ultra-blend Plus, light cured): similar
to HW+A, but Ultra-blend Plus was used.
pH analysis
Fifteen specimens from each group were
prepared for the study, totaling 120 individualized
samples. The materials, described in Table I,
were inserted in polyethylene tubes (10 mm
length x 1 mm internal diameter) compacted
at the ends, with a spatula 24, to avoid lateral
extrusion of the materials. To standardize the
volume contained in the specimens, the set
was weighed on an analytical balance, with
precision of 0.0001g (ATY224; Shimadzu, São
Paulo, SP, BR), and maintained at a weight of
10 + 0.1 mg. After insertion and standardization
of the volume of materials in polyethylene
tubes, HW+A, HD+A, BC+A and UB+A were
subjected to photoactivation. Immediately after,
all specimens were individually immersed in glass
vials with 10 mL of distilled deionized water with
controlled pH (pH=7), sealed with a plastic cap
and kept at rest at a constant temperature of
37ºC. After 24 hours, the pH of the distilled water
was measured with a pH meter (Q-400; Quimis
Instrument, São Paulo, SP, BR), previously
calibrated with buffered solutions (pH 4.0 and
7.0), as described by Duarte et al. (2007) [9].
Calcium release analysis
After pH measurement, the solution in which
the specimens were immersed was analyzed to
quantify the presence of calcium released by
the materials. For this, an atomic absorption
spectrophotometer (Spectra 55B - Varian, Inc.,
Palo Alto, CA, USA) was used.
Initially, lanthanum oxide was added to
all samples in a proportion of 1% in relation to
the volume of the initial content, to avoid the
interference of phosphate ions on the analysis.
After calibration of the spectrophotometer with
standard solutions containing calcium at the
values of 0, 1, 2, 3, 4 and 5 ppm, the measurement
was performed.
After the pH and calcium release measurements
were completed within 24 hours, the specimens
were again immersed in 10 mL of distilled water.
The set was stored and kept in the same conditions
as previously described. After 14 days, a new
measurement of pH and calcium release in the
solution was obtained.
Statistical analysis
The results obtained from the pH and calcium
release analyses were submitted to the Shapiro-
Wilk tetes to evaluate the homoscedasticity of the
data. Then, the values were analyzed by ANOVA
and Tukey (α=0.05) tests.
RESULTS
pH analysis
After 24 h of immersion in distilled water,
HW+N, HD+N, and UB+N provided the highest
pH values (P<0.05). BC+A provided the lowest
pH value (P<0.05). On the other hand, HW+A
and HD+A provided higher pH value than BC+N
(P<0.05). There were no differences between
HW+N, HD+N and UB+N or between HW+A,
HD+A and UB+N (P>0.05).
After 14 days, BC+N and BC+A provided
the lowest pH values (P<0.05) but were similar
to each other (P>0.05). There was no difference
among the other groups (P>0.05).
Table II shows the arithmetic mean and
standard deviation of the pH values at 24 hours
and 14 days of immersion in distilled water as a
function of photoactivation of calcium hydroxide-
containing pulp protection agents.
Calcium release analysis
After 24, HW+N, HD+N, and UB+N
provided the highest calcium release values
(P<0.05), but similar to each other (P>0.05).
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Braz Dent Sci 2023 Oct/Dec;26 (4): e3945
Costa Neto PF et al.
Light-curing of calcium hydrox ide-based liners: pH analysis and calcium ion r elease
Costa Neto PF et al.
Light-curing of calcium hydroxide-based liners: pH analysis
and calcium ion release
BC+N and BC+A provided the lowest calcium
release values (P<0.05) and similar to each other
(P>0.05). There was no difference between the
other groups (P>0.05).
After 14 days, HW+N, HD+N, and UB+N
provided the highest calcium release values
(P<0.05), whereas, BC+A provided the lowest ion
release value (P<0.05). HW+A, HD+N, and BC+N
showed similar values among themselves (P>0.05)
and different from the other groups (P<0.05).
Table III shows the arithmetic mean and
standard deviation of calcium release values (mg/L)
at 24 hours and 14 days of immersion in distilled
water as a function of photoactivation of pulp
protection agents containing calcium hydroxide.
DISCUSSION
For this study, four light-cured calcium
hydroxide-based materials were used to evaluate
calcium ion release and pH values. The null
hypotheses were rejected because there was
variation in pH and calcium release between the
groups that were subjected to the light-curing
process and those that were not.
The sample size calculation in this study was
based on previous studies that used the same
analysis methodology [8-10]. The use of pH
meter and atomic absorption spectophotometer
are methods accepted in the literature, used in
previous studies [8,11,12].
The aim of using calcium hydroxide is to
stimulate dentin remineralization [1,10] and, for
this to happen, the material must have an alkaline
pH in order to demonstrate hydrogenrogen
potential [8,13]. Moreover, the release of
calcium into the environment is essential for
remineralization to occur.
The incorporation of polymerizable
methacrylates to calcium hydroxide allows the
material to have lower solubility and adhesion
to dentin [1-3]. However, there is a signicant
difference when comparing the pH value of the
material with and without light-curing. This may
be explained by the fact that some methacrylates
do not light-cure completely [14,15]. This
justies what was found in BC+A, where the
lowest pH values were found compared to the
other groups evaluated.
For the pH value to be alkaline, hydroxyl ions
must be present [1-3]. After the photoactivation
process, the polymers formed prevent hydroxyl
ion dissociation, which explains the low pH
values of the groups that were light-cured [16].
Moreover, the pH value may be associated with
the solubility of the material. The higher the
solubility, the greater the capacity of the material
to reach alkaline pH [17,18].
Table III - Arithmetic mean and standard deviation of calcium release values (in mg/L), 24 hours and 14 days of immersion in distilled water, as
a function of photoactivation of pulp protection agents containing calcium hydroxide
HW+N HW+A HD+N HD+A BC+N BC+A UB+N UB+A
24h
x
40.16
a
3.37
b
39.26
a
4.68
b
0.16
c
0.13
c
41.82
a
4.85
b
SD 10.11 0.95 13.64 1.37 0.01 0.03 14.11 1.08
14d
x
4.79
a
0.58
a
4.80
a
0.60
b
0.41
b
0.07
c
4.84
a
0.57
b
SD 0.97 0.01 1.17 0.09 0.11 0.01 1.39 0.12
a,b,c
Different letters on the same line indicate significant differences (P < 0.05).
HW+N, non-light-cured hydroxy-cal; HW, light-cured white hydroxy-cal; HD+N, non-light cured dentin hydroxy-cal; HD+A, light-cured hydroxy-
cal; BC+N, non-light-cured Biocal; BC+A, light-cured Biocal; UB+N, non-light cured Ultra-Blend Plus; UB+A, light-cured Ultra-Blend Plus; x ,
arithmetic mean; SD, standard deviation.
Table II - Arithmetic mean and standard deviation of pH values, periods of 24 hours and 14 days of immersion in distilled water, as a function
of photoactivation of pulp protection agents containing calcium hydroxide
HW+N HW+A HD+N HD+A BC+N BC+A UB+N UB+A
24h
x
8.78
a
7.31
b
8.84
a
7.30
b
6.33
c
5.57
d
8.95
a
7.35
a
SD 0.27 0.16 0.31 0.21 0.33 0.12 0.38 0.39
14d
x
7.35
a
7.21
a
7.39
a
7.29
a
6.23
b
6.35
b
7.40
a
7.50
a
SD 0.18 0.40 0.15 0.38 0.43 0.18 0.20 0.75
a,b,c,d
Different letters on the same line indicate significant differences (P < 0.05). HW+N, non-light-cured hydroxy-cal; HW, light-cured white
hydroxy-cal; HD+N, non-light cured dentin hydroxy-cal; HD+A, light-cured hydroxy-cal; BC+N, non-light-cured Biocal; BC+A, light-cured Biocal;
UB+N, non-light cured Ultra-Blend Plus; UB+A, light-cured Ultra-Blend Plus; x , arithmetic mean; SD, standard deviation.
5
Braz Dent Sci 2023 Oct/Dec;26 (4): e3945
Costa Neto PF et al.
Light-curing of calcium hydrox ide-based liners: pH analysis and calcium ion r elease
Costa Neto PF et al.
Light-curing of calcium hydroxide-based liners: pH analysis
and calcium ion release
The release of calcium ions from the material
into th dentinal tissue is essential for the formation
of mineralized hard tissue [19]. It was observed
that the materials tested after photoactivation
showed lower ion values when compared to
the same material without photoactivation,
corroborating the study of Camilleri (2014) [20].
In an experimental in vivo study, the authors
observed that the use of photopolymerized
calcium hydroxide-based material did not form
mineralized tissue on the dental pulp within
15 days [21,22]. This may be explained by the
low release of calcium ion from these materials
when subjected to light-curing.
Due to the light-curing process of these
materials, there is a conversion of monomers into
polymers. This conversion leads to the formation
of a large marginal space between the dental
tissue and the protective material, preventing it
from coming into contact with moisture, leading
to a lower calcium ion release.
Efcient light-curing is one of the factors
for a correct conversion of monomers into
polymers. Therefore, it is necessary that further
studies, varying the photoactivation devices,
as well as the time and power, be performed
in order to question whether the light-curing
process effectively interferes in the effects of
these materials.
Further studies are needed to evaluate the
cytotoxicity of these monomers to pulp tissue
and the temperature increase caused by the light-
curing process.
CONCLUSION
Photoactivation of calcium hydroxide-based
dentin-pulp cements negatively interferes with
the hydrogen potential and calcium ion release.
However, these effects tend to stabilize after
14 days. Peculiarly, BC showed the worst values
in relation to the analyses performed.
Author’s Contributions
MCK: Conceptualization. PFCN, MBG,
JFZ, MCK: Methodology. PFCN, JCCM, AJJ:
Software. MBG, JFZ, MCK: Validation. PFCN,
JCCM, AJJ, MCK: Formal Analysis. PFCN, MBG,
JFZ: Investigation. JCCM, AJJ, MCK: Resources.
PFCN, MCK: Data Curation. PFCN, MBG, JFZ:
Writing – Original Draft Preparation. JCCM,
AJJ, MCK: Writing – Review & Editing. MCK:
Visualization. MCK: Supervision. PFCN, MCK:
Project Administration. MCK: Funding Acquisition.
Conict of Interest
All authors declare that they have no
conicts of interest.
Funding
None.
Regulatory Statement
None.
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Mariana Bena Gelio
(Corresponding address)
Universidade Estadual Paulista Júlio de Mesquita Filho, Faculdade de Odontologia
de Araraquara, Departamento de Odontologia Restauradora, Araraquara, SP, Brazil.
Email: marianagelio@outlook.com
Date submitted: 2023 July 05
Accept submission: 2023 Oct 10