doi:10.1111/iej.
12787
Properties of NeoMTA Plus and MTA Plus cements
for endodontics
F. Siboni1 , P. Taddei2, C. Prati3 & M. G. Gandolfi1
1
Laboratory of Biomaterials and Oral Pathology, Dental School; 2Unit of Biochemistry; and 3Endodontic Clinical Section, Dental
School, Department of Biomedical and NeuroMotor Sciences, University of Bologna, Bologna, Italy
Abstract
Siboni F, Taddei P, Prati C, Gandolfi MG. Properties
of NeoMTA Plus and MTA Plus cements for endodontics.
International Endodontic Journal, 50, e83–e94, 2017.
Aim To test a novel calcium silicate cement mixed
with a water-based gel (NeoMTA Plus) with regard to
chemical–physical properties and apatite-forming abil-
ity.
Methodology NeoMTA Plus (Avalon Biomed Inc.
Bradenton, FL, USA; lot. 2014090301) and a com-
mercial MTA-based material with similar properties
(MTA Plus, Prevest Denpro Limited, Jammu, India;
lot. 41001) were tested for ion-releasing ability, initial
and final setting times, radiopacity, open and impervi-
ous porosity and apparent porosity, water sorption,
weight loss, solubility, ability to nucleate calcium
phosphates (CaP) after immersion in HBSS (Hank’s
Balanced Salt Solution) by ESEM-EDX and micro-
Raman spectroscopy. The results were analysed statis-
tically with the ANOVA test (P < 0.05).
Introduction
Mineral Trioxide Aggregate (MTA) cements are
hydrophilic materials developed for a number of clini-
cal applications in endodontic therapy such as pulp
capping, pulpotomy, apexification, apicogenesis, repair
of furcation perforations, root perforations, root-end
filling and recently for orthograde canal filling (Tora-
binejad & Chivian 1999, Hegde 2009, Parirokh &
Correspondence: Prof. Maria Giovanna Gandolfi, Laboratory of
Biomaterials and Oral Pathology, Department of Biomedical
and NeuroMotor Sciences, University of Bologna, Via San
Vitale 59, 40125 - Bologna, Italy (e-mail: mgiovanna.gandolfi@
unibo.it).
© 2017 International Endodontic Journal. Published by John Wiley & Sons Ltd
Results NeoMTA Plus had a prolonged setting time
(315 min) and a satisfactory radiopacity (3.76 mm
Al). Calcium and hydroxyl ion release was signifi-
cantly greater and more prolonged in comparison
with MTA Plus (P < 0.05). Both NeoMTA Plus and
MTA Plus had high values of open porosity and solu-
bility. ESEM-EDX and micro-Raman confirmed the
ability to nucleate calcium phosphates on their sur-
face after immersion in HBSS.
Conclusion NeoMTA Plus is a new calcium sili-
cate-based cement for root filling with an adequate
radiopacity and prolonged setting time. The ion
release and CaP-forming ability could increase stabil-
ity of the root filling and promote endodontic and
periodontal tissue regeneration, enhancing the bioac-
tivity and biocompatibility of the material.
Keywords: apatite nucleation, biointeractivity,
calcium silicate endodontic cements, MTA Plus,
NeoMTA Plus, porosity.
Received 7 November 2016; accepted 25 April 2017
Torabinejad 2010, Vitti et al. 2013, Prati et al. 2014,
Prati & Gandolfi 2015, Zhou et al. 2015, Carvalho
et al. 2017). The leaching of calcium and hydroxyl
ions allows MTA to promote regeneration and rem-
ineralization of hard tissues and enhance its sealing
ability by deposition of calcium and phosphate crys-
tals into voids and potential spaces between dentine
and the root filling material (Martin et al. 2007, Gan-
dolfi et al. 2013a). Moreover, the high solubility and
the enhancement of environmental pH (>11.0) may
create antibacterial activity reducing the bacteria in
unior et al. 2013, Kim et al. 2015).
biofilms (Faria-J
However, the difficult handling and challenges in
adapting the original MTA-based products to the root
canal prevented the achievement of the low film
International Endodontic Journal, 50, e83–e94, 2017 e83
 Novel endodontic polymeric-gel MTA Siboni et al.
thickness needed for endodontic sealers (Soheilipour
et al. 2009).
NeoMTA Plus is a new finer powder tricalcium silicate
material and has tantalum oxide (Ta2O5) as a radiopaci-
fying agent that is mixed with a water-based gel that
imparts good handling properties (Avalon Biomed
2017). The powder-to-gel mixing ratio can be varied and
a thin consistency can be used as an orthograde sealer or
a thick mixture for root-end filling. The manufacturer
states the indications include the application of this
material for vital pulp therapies (pulp capping, pulpo-
tomy or cavity liner/base), root apexification, root repair
(resorption or perforation), root-end filling and sealing of
root canals (Avalon Biomed 2017).
As reported in a previous study, bismuth oxide
(Bi2O3), a radiopacifying agent contained in most
MTA-based cements such as MTA Plus (Gandolfi et al.
2014), plays a crucial role in the hydration processes
of calcium silicates (Camilleri 2008) as well as in
potential tooth discoloration, especially when in con-
tact with sodium hypochlorite (Camilleri 2014).
The present study compared the calcium and
hydroxyl ion release, solubility, water sorption, poros-
ity, surface morphology and apatite-forming ability of
two current MTA-based cements, i.e. NeoMTA Plus
and MTA Plus, containing different radiopacifying
agents, namely Ta2O5 and Bi2O3, respectively. The
null hypothesis was that despite the different composi-
tion, the two tested materials have the same physi-
cal–chemical properties and apatite-forming ability.
Materials and methods
Materials
NeoMTA Plus (Avalon Biomed Inc. Bradenton, FL,
USA; lot. 2014090301) and MTA Plus (Prevest Denpro
Limited, Jammu, India; lot. 41001) were tested. Both
the materials are commercial cements proposed for
sealing and filling root canals. NeoMTA Plus and MTA
Plus were mixed according to the manufacturer
instructions (one scoop of powder and one small drop
of gel) for 30 s on a glass slab.
Calcium release and alkalizing activity (pH of
storage water)
The freshly mixed pastes were compacted into
polyvinyl chloride moulds (8  0.1 mm diameter;
1.6  0.1 mm height), and the excess was removed.
The filled moulds (n = 10 for each material) were
immediately immersed in 10 mL of deionized water
e84 International Endodontic Journal, 50, e83–e94, 2017
(pH 6.8) in polypropylene sealed containers and
stored at 37 °C. The storage water was replaced at
each end-point (3 h and 1, 3, 7, 14, 28 days), and
the collected water was analysed for pH by a poten-
tiometric method under magnetic stirring at room
temperature (24 °C) using a selective electrode (Sen
Tix Sur; WTW, Weilheim, Germany) connected to a
multiparameter laboratory meter (inoLab 750;
WTW) previously calibrated with standard solutions.
The amount of calcium ions was measured using a
calcium probe (calcium ion electrode; Eutech Instru-
ments Pte Ltd, Singapore) after addition of 0.200 mL
(2%) of ionic strength adjuster (ISA; 4 mol L 1 KCl;
WTW).
Physical properties
The initial and final setting time were measured by
evaluating the absence of indentation caused by Gill-
more needles (initial Gillmore tip 113.4 g weight and
2.12 mm diameter and final Gillmore tip 453.6 g
weight and 1.06 mm diameter) on the cement paste
stored at 37 °C and 99  5% relative humidity in a
polyvinyl mould of 10 mm diameter and 2 mm
thickness in accordance with ASTM C 226-07
(Standard Specification for Air-Entraining Additions
for Use in the Manufacture of Air-Entraining Hydrau-
lic Cement).
The radiopacity was measured following ISO
6876:2012 (Dental root canal sealing materials), and
completely set samples (10  0.1 mm diameter;
1.0  0.1 mm height) were radiographed using a X-
ray (Myray Cefla, Imola, Italy) with a reference alu-
minium step wedge (60 mm long, 10 mm wide). The
radiographic unit was set at 3 cm distance, 0.13 s
exposure at 70 KVp and 8 mA. The film (Kodak den-
tal film, Eastman Kodak Company, Carestream Health
Inc., Rochester, New York, NY, USA) was processed
(automatic developer, 4 min at 30 °C) and scanned.
The radiographic density (colour intensity) data were
converted (software Image J) into aluminium step-
wedge equivalent thickness (mm Al). A radiopacity
equal or higher than 3 mm Al is required by the ISO
6876:2012.
For the porosity assessments, the freshly mixed
pastes were compacted into polyvinyl chloride moulds
(8  0.1 mm diameter; 1.6  0.1 mm height), and
the excess was removed. The filled moulds (n = 10
samples for each material) were placed at 37 °C and
99% relative humidity for a period of 50% longer
than the final setting time according to ISO
6876:2012, then demoulded.
© 2017 International Endodontic Journal. Published by John Wiley & Sons Ltd

Each sample was weighed to determine the initial
mass (I) and immediately immersed vertically in
20 mL of distilled water at 37 °C. After 24 h of
immersion, the specimens were removed from the
water, and the specimen mass whilst suspended in
water (S) was measured. The excess water from the
surface of each sample was removed using a moist-
ened filter paper, and the saturated mass (M) was
recorded. Finally, the samples were dried at 37 °C
until the weight was stable, and the final dry mass
(D) was recorded. Each weight measurement was
repeated three times using an analytic balance (Bel
Engineering series M, Monza, Italy) and determined to
the nearest 0.001 g.
The water sorption A (A = [(M D)/D] 9 100)
and the solubility S (S = [(I D)/D] 9 100) were cal-
culated as percentage of the original weight. ISO
4049 (polymer-based restorative materials) was used
because both materials are hydraulic self-curing mate-
rials and their setting is achieved by the water in the
mixing liquid.
The exterior volume V (V = M S), the volume of
open pores VOP (VOP = M D), the volume of the
impervious portion VIP (VIP = D S) and the appar-
ent porosity P (P = [(M D)/V] 9 100) were calcu-
lated in cm3 and in percentage, following
Archimedes’ principle (ASTM C373-88, Unosson et al.
2015, Gandolfi et al. 2015, Hea et al. 2016), as vol-
ume of fluid displaced by the immersed sample.
All the porosity, solubility and water sorption tests
were repeated after ageing the samples for 7 days at
37 °C and 99% RH, to allow setting and strengthen-
ing of the specimens.
Statistical analysis
A two-way ANOVA followed by RM Student–Newman–
Keuls test (P < 0.05) was used for the ion release test
and a one-way ANOVA followed by Student–Newman–
Keuls test (P < 0.05) for setting time, radiopacity, sol-
ubility, water sorption and porosity.
Surface characterization and test of calcium
phosphate nucleation in simulated body fluid:
SEM-EDX and micro-Raman spectroscopy
An environmental scanning electron microscope
(ESEM, Zeiss EVO 50; Carl Zeiss, Oberkochen, Ger-
many) connected to a secondary electron detector for
elemental dispersive X-ray microanalysis (EDX; Oxford
Instruments, Abingdon, UK) was used to examine the
© 2017 International Endodontic Journal. Published by John Wiley & Sons Ltd
Siboni et al. Novel endodontic polymeric-gel MTA
unhydrated powders, freshly mixed samples and sam-
ples after immersion in simulated body fluid in wet
conditions without any previous preparation.
Freshly mixed materials were immersed upright in
20 mL of Hank’s Balanced Salt Solution (HBSS, Lonza
Walkersville, Inc., Walkersville, MD, USA) and stored
at 37 °C for 28 days following ISO 23317. The HBSS
was replaced weekly. Operating conditions: low vac-
uum (100 Pascal), accelerating voltage of 20 kV,
working distance 8.5 mm, 0.5 wt% detection level,
133 eV resolution, amplification time 100 ls, mea-
suring time of 60 s for spectra.
EDX provided microchemical spectra and semi-
quantitative compositional data (weight % and atomic
% of the elemental composition).
Micro-Raman spectra were measured on the surface
of the powders, fresh samples and samples after ageing
in HBSS for 28 days. The spectra were obtained using
a Jasco NRS-2000C instrument (Jasco Inc., Easton,
MD, USA) in back-scattering conditions with 4 cm 1
spectral resolution, using the 532-nm green diode-
pumped solid state (DPSS) laser driver (RgBLase LLC,
Fremont, CA, USA) with a power of ca. 25 mW, prop-
erly filtered. A 160 K cooled digital CCD (Spec-10:
100B; Roper Scientific Inc., Trenton, NJ, USA) was
used as the detector. A microscope of 1009 magnifica-
tion with a confocal pinhole with an aperture diameter
of 3000 lm was utilized. All the Raman measurements
were made in a fully nondestructive way, without sam-
ple manipulation. All the reported spectra are an aver-
age of at least five measurements.
Results
Alkalizing activity (pH of storage water) and
calcium release
Both materials induced the alkalization of the storage
water (>11.0) after 3 h of immersion. The pH
decreased starting at 3 days (Table 1) continuing
until the last test at 28 days. No significant differ-
ences were detected between the materials during the
first hours after immersion; MTA Plus was associated
with a more rapid decrease in alkalization activity.
Similarly, the release of Ca2+ ions began immedi-
ately after sample immersion and after only 3 h, the
greatest amount of calcium leakage was recorded
(Table 1). As shown in Table 1, NeoMTA Plus pro-
duced a significantly greater (P < 0.05) amount of
leached Ca2+ during the first 3 days of immersion.
Calcium release decreased for both materials after
International Endodontic Journal, 50, e83–e94, 2017 e85
 Novel endodontic polymeric-gel MTA Siboni et al.

Table 1 pH of soaking water and calcium released. Different capital letters represent significant differences (P < 0.05) in the
same line, whilst different small letters represent differences in the same-column (two-way ANOVA followed by RM Student–New-
man–Keuls with P < 0.05, n = 10 samples per group)

pH and Calcium released in soaking water

3h 1 day 3 days 7 days 14 days 28 days

pH
NeoMTA Plus 11.2  0.2Aa 11.6  0.2Aa 11.2  0.5Aa 10.8  0.4Aa 9.1  0.3Ba 8.7  0.1Ba
MTA Plus gel 11.9  0.4Ab 11.7  0.8Aa 10.6  0.8Ba 8.7  0.7Cb 8.7  0.5Ca 8.4  0.4Ca

0–3 h 3 h–1 day 1 day–3 days 3–7 days 7–14 days 14–28 days
Calcium released
NeoMTA plus 142.9  27.2Aa 126.0  20.7Ba 71.4  21.2Ca 27.1  10.9 Da 17.8  9.6 Da 10.7  1.8 Da
MTA Plus gel 115.6  22.6Ab 46.2  17.8Bb 51.3  19.7Bb 25.2  6.2Ca 18.5  9.0Ca 15.7  6.6Ca

7 days, but was still occurring at 28 days to demon-
strate long-term activity.
Physical properties
MTA Plus had a final setting time significantly shorter
than NeoMTA Plus (55 min vs. 315 min, P < 0.05
Table 2).
MTA Plus had a radiopacity value significantly
higher than NeoMTA Plus (P < 0.05 Table 2); how-
ever, both materials met the ISO requirement for
more than 3 mm of equivalent Al.
The values for porosity and solubility were high
when the material was tested at setting time plus
50% (Table 3); significantly lower values were mea-
sured after 7 days of pre-setting. A similar amount of
water sorption was detected for both test conditions
(P < 0.05 Table 3).
Surface characterization and test of calcium
phosphate nucleation in simulated body fluid:
SEM-EDX and micro-Raman spectroscopy
Figure 1a shows dry MTA Plus powder with gran-
ules that varied in size from 2 to 10 lm; EDX spec-
tra included carbon (C), oxygen (O), aluminium
Table 2 Initial, final setting time (min) and radiopacity (mm
Al). Different letters represent significant differences
(P < 0.05) in the same-column (one-way ANOVA followed by
RM Student–Newman–Keuls with P < 0.05, n = 3 samples
per group)
Initial setting Final setting
time (min) time (min)
NeoMTA Plus 130  5a 315  5a
MTA Plus gel 45  5b 55  5b
(Al), silicon (Si), sulphur (S), calcium (Ca) and bis-
muth (Bi). The Ca/Si atomic ratio calculated by
EDX was 3.71.
The freshly mixed paste had a surface where the
powder granules were still noticeable and displayed
an increase of C and the appearance of nitrogen
(N), deriving from the organic phase of the mixing
gel.
After soaking in HBSS, a coating of small spheru-
lites was observed on the surface; EDX detected
sodium (Na), magnesium (Mg), phosphorus (P), chlo-
rine (Cl) and a marked decrease in Si and Bi (unde-
tectable). The Ca/P atomic ratio was 2.48 after
28 days.
As seen in Fig. 1b, NeoMTA Plus dry powder had
more regular granules approximately smaller than 10
microns, EDX revealed C, O, Al, Si, S, Ca and Tan-
talum (Ta) as radiopacifying agent. The Ca/Si atomic
ratio calculated by EDX was 2.95.
The freshly mixed paste of NeoMTA Plus had a sur-
face where the powder granules were still noticeable
and displayed an increase of C, derived from the
organic component of the mixing gel.
After soaking in HBSS, a homogenous and thick
coating of small aggregated spherulites was observed
on the surface; EDX detected N, Na, high Mg, P, Cl
and a marked decrease of Si and Ta. The Ca/P atomic
ratio was 5.28 at 28 days.
Figure 2 shows the average micro-Raman spectra
for the powder and freshly mixed MTA Plus
cement. Both the samples had bands ascribable to
crystalline alite and belite (Conjeaud & Boyer
Radiopacity 1980), calcium sulphate as anhydrite and gypsum
(mm Al)
(Sarma et al. 1998), calcite (Martinez-Ramirez et al.
(ISO > 3)
2003) and bismuth oxide. The freshly mixed sample
3.76  0.13a had bands of the organic component present in the
6.94  0.72b
gel.

e86 International Endodontic Journal, 50, e83–e94, 2017 © 2017 International Endodontic Journal. Published by John Wiley & Sons Ltd
 Siboni et al. Novel endodontic polymeric-gel MTA

After ageing in HBSS (Fig. 3), calcite (Martinez- Figure 4 shows the average micro-Raman spectra
Ramirez et al. 2003) and apatite (Nelson & Featherstone recorded on the NeoMTA Plus, powder and freshly
1982) deposits were observed; the bands due to the mixed cement. The spectra of the powder as well as of
underlying cement were still detectable. the freshly mixed cement were similar to those of MTA

Table 3 Porosity, water sorption and solubility after 50% setting time (ISO 6876) and after 7 days at 37 °C 99%RH. Different
letters represent statistically significant differences (P < 0.05) in the same-column (one-way ANOVA followed by Student–New-
man–Keuls with P < 0.05, n = 10 samples per group)

Exterior volume Volume of open Volume of impervious Apparent Water sorption Solubility
(V, cm3) pores (Vop, cm3) portion (Vip, cm3) porosity (P %) (A %) (S %)

Setting time + 50% at 37 °C 99% RH before test

NeoMTA plus 0.0983  0.0227a 0.0483  0.0097a 0.0500  0.0108a 49.1  2.6a 35.6  3.7a 16.7  2.4a
MTA plus 0.1052  0.0132a 0.0582  0.0060b 0.0469  0.0062a 45.41  1.6a 40.0  2.5a 18.5  2.7a
7 days at 37 °C 99% RH before test
NeoMTA plus 0.0919  0.0105a 0.0476  0.0035a 0.0421  0.0098a 44.6  5.7a 36.7  4.1a 8.9  1.9b
MTA plus 0.1036  0.0058a 0.0448  0.0047a 0.0587  0.0063a 43.3  4.8a 39.7  3.6a 8.1  1.3b

Figure 1 (a) ESEM images and EDX microanalysis of MTA Plus powder, freshly mixed and after 28 days in HBSS. The image shows
the surface morphology and the composition of the powder and freshly mixed cement; the QBSD reveals the presence of the radiopaci-
fying agent (Bi). After immersion in HBSS the coating of small spherulites of Ca and P appears on the sample surface. (b) ESEM images
and EDX microanalysis of NeoMTA Plus powder, freshly mixed and after 28 days in HBSS. The surface morphology showed the pres-
ence of granules in the powder and freshly mixed paste, and the presence of the radiopacifying agent (Ta) in the QBSD. After immer-
sion in HBSS a homogenous and thick coating of small aggregated spherulites of Ca and P appears on the sample surface.

© 2017 International Endodontic Journal. Published by John Wiley & Sons Ltd International Endodontic Journal, 50, e83–e94, 2017 e87
 Novel endodontic polymeric-gel MTA Siboni et al.
Figure 1 Continued.
Plus with bands of crystalline alite and belite (Con-
jeaud & Boyer 1980), anhydrite (Sarma et al. 1998),
calcite (Martinez-Ramirez et al. 2003). However, no
bismuth oxide was observed, although tantalum oxide
bands were seen (Dobal et al. 2000). The organic com-
ponent detectable in the fresh cement had bands anal-
ogous to those observed in fresh MTA Plus. After
ageing in HBSS (Fig. 5), a calcite (Martinez-Ramirez
et al. 2003) deposit was observed; the bands due to
the underlying cement were hardly detectable.
Discussion
This study compared the physical and chemical
properties of two MTA-based materials modified
with a polymer gel when observed in a laboratory set-
ting.
A surface characterization of both materials after
immersion in HBSS was performed by Camilleri
(2015) with similar results, but in this study, the
superficial changes and bioactivity were correlated to
e88 International Endodontic Journal, 50, e83–e94, 2017
the ability to release ions, the physical stability (solu-
bility, water sorption) and the porosity of the material
after immersion.
The ESEM and micro-Raman analysis revealed that
both MTA Plus and NeoMTA Plus contain a fine pow-
der of tricalcium silicate (alite), dicalcium silicate (be-
lite), calcium sulphate (as anhydrite). However,
bismuth oxide is present in MTA Plus, as confirmed
by Gandolfi et al. (2014), and tantalum oxide (Ta2O5)
is the radiopacifying agent in NeoMTA Plus. The
water-based gel contains accelerators for setting and
film-forming polymers, but no salts (Govindaraju et al.
2016). Silica, which is reported in the EDX of MTA
Plus powder, was not detected by micro-Raman spec-
troscopy, as its main band (at about 500 cm 1) was
obscured by a stronger band of bismuth oxide. Both
cements contained a small amount of calcite, proba-
bly due to a certain hydration in storage that leads to
the formation of calcium hydroxide, which forms cal-
cium carbonate when exposed to air. The exposure to
humidity previously reported (Taddei et al. 2011) also
© 2017 International Endodontic Journal. Published by John Wiley & Sons Ltd

Figure 2 Average micro-Raman spectra recorded on the MTA Plus powder and freshly mixed cement. The bands ascribable to
the organic component (OR), alite (A), belite (B), anhydrite (An), gypsum (G), calcite (C) and bismuth oxide (Bi) are indicated.
explains the presence of gypsum in MTA Plus (formed
upon hydration of anhydrite or hemihydrate).
Despite the use of different radiopacifying agents,
both materials had a radiopacity greater than 3 mm
Al as required by ISO 6876:2012. As shown by the
EDX and micro-Raman analyses, MTA Plus contains
bismuth oxide in the powder as a radiopacifier (Gan-
dolfi et al. 2014), which plays an active role in
cement hydration (Camilleri 2008), but has been
reported to discolour in contact with sodium
hypochlorite (Camilleri 2014). NeoMTA Plus contains
tantalum oxide as radiopacifier, but its influence on
hydration is unknown.
The study confirmed that the ion release values
(Ca2+ and OH ) were higher than conventional
MTA (Gandolfi et al. 2014, 2015). The continued
release of calcium ions over 28 days has been
demonstrated to be a key factor in promoting
endodontic and periodontal tissue regeneration
(Bonson et al. 2004, Al-Rabeah et al. 2006, Hakki
et al. 2009, Matsumoto et al. 2013) that will
enhance the bioactivity and biocompatibility of the
material (Prati & Gandolfi 2015).
© 2017 International Endodontic Journal. Published by John Wiley & Sons Ltd
Siboni et al. Novel endodontic polymeric-gel MTA
Alkaline pH promotes antibacterial activity
(Siqueira & Lopes 1999, Al-Hezaimi et al. 2006,
Reston & Souza Costa 2009, Poggio et al. 2015,) and
accelerates apatite nucleation (Gandolfi et al. 2013b).
As shown in Fig. 1a–b, after soaking for 28 days in
HBSS, both test materials formed a Ca-P layer. Micro-
Raman spectroscopy gave more insight into the bioac-
tivity of the two cements. Figure 3 shows that the
deposit formed on MTA Plus was composed of calcite
(main component) and apatite, whilst only calcite
was found on NeoMTA Plus (Fig. 5). This result is in
agreement with Camilleri (2015), who disclosed a
more extensive calcium phosphate deposit on MTA
Plus than on NeoMTA Plus. On the other hand, that
study reported the presence of calcium hydroxide on
the surface of the latter cement. This phase was not
revealed in the present study, in agreement with pre-
vious investigations (Taddei et al. 2009a,b, 2011),
which have detected this component only in the inte-
rior of the specimens, due to its release into the age-
ing medium.
The EDX data agree with micro-Raman analyses.
After ageing in HBSS, both cements had Ca/P molar
International Endodontic Journal, 50, e83–e94, 2017 e89
 Novel endodontic polymeric-gel MTA Siboni et al.
Figure 3 Average micro-Raman spectra recorded on the MTA Plus cement before (i.e. fresh) and after ageing in HBSS for
28 days. The bands ascribable to the organic component (OR), alite (A), belite (B), anhydrite (An), gypsum (G), bismuth oxide
(Bi), calcite (C) and apatite (Ap) are indicated.
ratio higher than hydroxyapatite (Ca10(PO4)6
(OH)2, Ca/P = 1.67), indicating the contribution of
calcite (CaCO3), revealed on both cements by micro-
Raman spectroscopy (Gandolfi et al. 2011b). Actually,
the presence of this phase determines an increase in
the Ca/P ratio. It is interesting to note that the
NeoMTA Plus cement had more calcite after soaking
in HBSS and had a higher Ca/P ratio (i.e. 5.28); on
the other hand, the MTA Plus cement had detectably
higher apatite by micro-Raman spectroscopy, with a
lower Ca/P ratio (2.48).
The use of a finer Ca-Si-O powder and the applica-
tion of an organic gel increased the porosity, water
sorption, ion release and solubility when compared
with traditional MTA materials (Gandolfi et al. 2014).
In the present study, the solubility was calculated as
weight loss, according to the ISO 6876 standard for
root canal sealers, leaving the samples to set at 37 °C
and 98–100% relative humidity for a period 50%
longer than the final setting time before testing. The
same test was performed leaving the samples at
e90 International Endodontic Journal, 50, e83–e94, 2017
37 °C and 98–100% relative humidity for 7 days to
allow more complete hydration. As reported in
Table 3, the solubility decreased significantly after
7 days of setting, which parallels the ion release, but
no significant differences were recorded for porosity
and water sorption between the two test conditions.
This result may be explained by considering that the
hydration and setting of both the materials do not
affect the morphology and allow the same superficial
porosity and liquid sorption when immersed in dis-
tilled water.
The solubility of set hydraulic calcium silicate mate-
rials depends on several factors, including porosity
(Gandolfi et al. 2015). Both NeoMTA Plus and MTA
Plus (Gandolfi et al. 2014) had high values of open
porosity; in the past, this finding has been related to
voids and structural defects in set endodontic sealers
which, associated with a high solubility, have been
linked to a lack of integrity, stability, durability and
impermeability of the sealer, a pivotal component of
root fillings (Mutal & Gani 2005, Uyanik et al. 2010).
© 2017 International Endodontic Journal. Published by John Wiley & Sons Ltd

Figure 4 Average micro-Raman spectra recorded on the NeoMTA Plus gel, powder and freshly mixed cement. The bands ascrib-
able to the organic component (OR), alite (A), belite (B), anhydrite (An), calcite (C) and tantalum oxide (Ta) are indicated.
However, Gandolfi et al. (2011a) demonstrated that
the solubility of calcium silicate-containing materials
immersed in biological-like saline solutions is lower
compared to its solubility in deionized water as inter-
national standards recommend.
The translation to the clinic of laboratory studies
and particularly for tests such as solubility requires
some consideration. A high value of solubility in dis-
tilled water of the early set materials is associated
with high Ca2+ and OH release, which leaves voids.
On the other hand, when immersed in body fluids,
the calcium and hydroxyl ions from the materials
combine with the phosphate of the surrounding fluids
(Gandolfi et al. 2013b) causing the precipitation of a
superficial layer of calcium phosphate able to fill the
open voids. This apatite-forming ability may improve
the sealing ability at the dentine–cement interface
(Gandolfi et al. 2013a).
For these reasons, the solubility and porosity of tri-
calcium silicate (MTA-type) materials in distilled
water do not predict the real stability and integrity of
© 2017 International Endodontic Journal. Published by John Wiley & Sons Ltd
Siboni et al. Novel endodontic polymeric-gel MTA
such materials under in vivo conditions. This is a limi-
tation of the present study and in general of all labo-
ratory studies. In addition, the international
specifications for testing materials (such as ISO or
ASTM) are not always ideal, as often the test methods
are different from the clinical situation. Longer times
of setting and different soaking media could be helpful
to investigate their in vivo physical properties.
Conclusion
NeoMTA Plus is a new calcium silicate-based
cement with an adequate radiopacity and prolonged
setting time for root filling. The calcium and hydro-
xyl ion release was greater and more prolonged in
comparison with MTA Plus, maintaining the ability
to form a calcium phosphate layer. This CaP-form-
ing ability could be helpful to increase the stability
in the root canal, but further studies are necessary
to investigate the sealing ability associated with
gutta-percha.
International Endodontic Journal, 50, e83–e94, 2017 e91
 Novel endodontic polymeric-gel MTA Siboni et al.

Figure 5 Average micro-Raman spectra recorded on the NeoMTA Plus cement before (i.e. fresh) and after ageing in HBSS for
28 days. The bands ascribable to the organic component (OR), alite (A), belite (B), anhydrite (An), tantalum oxide (Ta) and
calcite (C) are indicated.

Camilleri J (2014) Color stability of white mineral trioxide

Conflict of interest aggregate in contact with hypochlorite solution. Journal of
The authors have stated explicitly that there are no Endodontics 40, 436–40.
conflict of interests in connection with this article. Camilleri J (2015) Staining potential of Neo MTA Plus, MTA
Plus, and Biodentine used for pulpotomy procedures. Jour-
nal of Endodontics 41, 1139–45.
References Carvalho NK, Prado MC, Senna PM et al. (2017) Do smear-
layer removal agents affect the push-out bond strength of
Al-Hezaimi K, Al-Shalan TA, Naghshbandi J, Oglesby S,
calcium-silicate based endodontic sealers? International
Simon JH, Rotstein I (2006) Antibacterial effect of two
Endodontic Journal 50, 612–9.
mineral trioxide aggregate (MTA) preparations against
Conjeaud M, Boyer H (1980) Some possibilities of Raman
Enterococcus faecalis and Streptococcus sanguis in vitro. Jour-
microprobe in cement chemistry. Cement and Concrete
nal of Endodontics 32, 1053–6.
Research 10, 61–70.
Al-Rabeah E, Perinpanayagam H, MacFarland D (2006)
Dobal PS, Katiyar RS, Jiang Y, Guo R, Bhalla AS (2000)
Human alveolar bone cells interact with ProRoot and
Raman scattering study of a phase transition in
tooth-colored MTA. Journal of Endodontics 32, 872–5.
tantalum pentoxide. Journal of Raman Spectroscopy 31,
Avalon Biomed (2017) NeoMTAPlus Directions for use. URL
1061–5.
avalonbiomed.com/wp-content/uploads/2014/04/DFU-
Faria-J
unior NB, Tanomaru-Filho M, Berbert FL, Guerreiro-
NeoMTA-Plus-REV-1601.pdf [accessed April 2017]
Tanomaru JM (2013) Antibiofilm activity, pH and solubil-
Bonson S, Jeansonne BG, Lallier TE (2004) Root-end filling
ity of endodontic sealers. International Endodontic Journal
materials alter fibroblast differentiation. Journal of Dental
46, 755–62.
Research 83, 408–13.
Gandolfi MG, Taddei P, Siboni F, Modena E, Ciapetti G, Prati
Camilleri J (2008) Characterization of hydration products of
C (2011a) Development of the foremost light-curable cal-
mineral trioxide aggregate. International Endodontic Journal
cium-silicate MTA cement as root-end in oral surgery.
41, 408–17.

e92 International Endodontic Journal, 50, e83–e94, 2017 © 2017 International Endodontic Journal. Published by John Wiley & Sons Ltd

Chemical-physical properties, bioactivity and biological
behaviour. Dental Materials 27, e134–57.
Gandolfi MG, Taddei P, Tinti A, Dorigo De Stefano E, Prati C
(2011b) Alpha-TCP improves the apatite-formation ability
of calcium-silicate hydraulic cement soaked in phosphate
solutions. Materials Science and Engineering C 31, 1412–
22.
Gandolfi MG, Parrilli AP, Fini M, Prati C, Dummer PM
(2013a) 3D micro-CT analysis of the interface voids asso-
ciated with Thermafil root fillings used with AH Plus or a
flowable MTA sealer. International Endodontic Journal 46,
253–63.
Gandolfi MG, Taddei P, Modena E, Siboni F, Prati C (2013b)
Biointeractivity-related versus chemi/physisorption-related
apatite precursor-forming ability of current root end filling
materials. Journal of Biomedical Materials Research Part B:
Applied Biomaterials 101, 1107–23.
Gandolfi MG, Siboni F, Primus CM, Prati C (2014) Ion
release, porosity, solubility, and bioactivity of MTA Plus
tricalcium silicate. Journal of Endodontics 40, 1632–7.
Gandolfi MG, Siboni F, Botero T, Boss u M, Riccitiello F, Prati
C (2015) Calcium silicate and calcium hydroxide materials
for pulp capping: biointeractivity, porosity, solubility and
bioactivity of current formulations. Journal of Applied Bio-
materials & Functional Materials 13, 43–60.
Govindaraju L, Neelakantan P, Gutmann JL (2016) Effect of
root canal irrigating solutions on the compressive strength
of tricalcium silicate cements. Clinical Oral Investigations
https://doi.org/10.1007/s00784-016-1922-0.
Hakki SS, Bozkurt SB, Hakki EE, Belli S (2009) Effects of
mineral trioxide aggregate on cell survival, gene
expression associated with mineralized tissues, and
biomineralization of cementoblasts. Journal of Endodontics
35, 513–9.
Hea D, Zhuanga C, Xub S et al. (2016) 3D printing of Mg-
substituted wollastonite reinforcing diopside porous bioce-
ramics with enhanced mechanical and biological perfor-
mances. Bioactive Materials 1, 85–92.
Hegde V (2009) Enterococcus faecalis: clinical significance
and treatment considerations. Endodontology 21, 48–52.
Kim RJ, Kim MO, Lee KS, Lee DY, Shin JH (2015) An
in vitro evaluation of the antibacterial properties of three
mineral trioxide aggregate (MTA) against five oral bacte-
ria. Archives of Oral Biology 60, 1497–502.
Martin RL, Monticelli F, Brackett WW et al. (2007) Sealing
properties of mineral trioxide aggregate orthograde apical
plugs and root fillings in an in vitro apexification model.
Journal of Endodontics 33, 272–5.
Martinez-Ramirez S, Sanchez-Cortes S, Garcia Ramos JV,
Domingo C, Fortes C, Blanco-Varela MT (2003) Micro-
Raman spectroscopy applied to depth profiles of carbonates
formed in lime mortar. Cement and Concrete Research 33,
2063–8.
Matsumoto S, Hayashi M, Suzuki Y, Suzuki N, Maeno M, Ogiso
B (2013) Calcium ions released from mineral trioxide
© 2017 International Endodontic Journal. Published by John Wiley & Sons Ltd
Siboni et al. Novel endodontic polymeric-gel MTA
aggregate convert the differentiation pathway of C2C12
Cells into osteoblast lineage. Journal of Endodontics 39, 68–
75.
Mutal L, Gani O (2005) Presence of pores and vacuoles in
set endodontic sealers. International Endodontic Journal 38,
690–6.
Nelson DG, Featherstone JD (1982) Preparation, analysis,
and characterization of carbonated apatites. Calcified Tissue
International 34, S69–81.
Parirokh M, Torabinejad M (2010) Mineral trioxide aggre-
gate: a comprehensive literature review—part III: clinical
applications, drawbacks, and mechanism of action. Journal
of Endodontics 36, 400–13.
Poggio C, Beltrami R, Colombo M, Ceci M, Dagna A, Chiesa
M (2015) In vitro antibacterial activity of different pulp
capping materials. Journal of Clinical and Experimental Den-
tistry 7, e584–8.
Prati C, Gandolfi MG (2015) Calcium silicate bioactive
cements: biological perspectives and clinical applications.
Dental Materials 31, 351–70.
Prati C, Siboni F, Polimeni A, Bossu M, Gandolfi MG (2014)
Use of calcium-containing endodontic sealers as apical
barrier in fluid-contaminated wide-open apices. Journal of
Applied Biomaterials & Functional Materials 12, 263–70.
Reston EG, Souza Costa CA (2009) Scanning electron micro-
scopy evaluation of the hard tissue barrier after pulp cap-
ping with calcium hydroxide, mineral trioxide aggregate
(MTA) or ProRoot MTA. Australian Endodontic Journal 35,
78–84.
Sarma LP, Prasad PSR, Ravikumar N (1998) Raman spec-
troscopic study of phase transitions in natural gypsum.
Journal of Raman Spectroscopy 29, 851–6.
Siqueira JF Jr, Lopes HP (1999) Mechanisms of antimicrobial
activity of calcium hydroxide: a critical review. Interna-
tional Endodontic Journal 32, 361–9.
Soheilipour E, Kheirieh S, Madani M, Akbarzadeh Baghban
A, Asgary S (2009) Particle size of a new endodontic
cement compared to Root MTA and calcium hydroxide.
Iranian Endodontic Journal 4, 112–6.
Taddei P, Tinti A, Gandolfi MG, Rossi PL, Prati C (2009a)
Ageing of calcium silicate cements for endodontic use in
simulated body fluids: a micro-Raman study. Journal of
Raman Spectroscopy 40, 1858–66.
Taddei P, Tinti A, Gandolfi MG, Rossi PL, Prati C (2009b)
Vibrational study on the bioactivity of Portland cement-
based materials for endodontic use. Journal of Molecular
Structure 924–926, 548–54.
Taddei P, Modena E, Tinti A, Siboni F, Prati C, Gandolfi MG
(2011) Vibrational investigation of calcium silicate
cements for endodontics in simulated body fluids. Journal
of Molecular Structure 993, 367–75.
Torabinejad M, Chivian N (1999) Clinical applications of min-
eral trioxide aggregate. Journal of Endodontics 25, 197–205.
Unosson EJ, Persson C, Engqvist H (2015) An evaluation of
methods to determine the porosity of calcium phosphate
International Endodontic Journal, 50, e83–e94, 2017 e93
 Novel endodontic polymeric-gel MTA Siboni et al.
cements. Journal of Biomedical Materials Research Part B:
Applied Biomaterials. 103, 62–71.
Uyanik MO, Nagas E, Cubukcu HE, Dagli F, Cehreli ZC
(2010) Surface porosity of hand-mixed, syringe-mixed and
encapsulated set endodontic sealers. Oral Surgery, Oral
Medicine, Oral Pathology, Oral Radiology, and Endodontology
109, e117–22.
e94 International Endodontic Journal, 50, e83–e94, 2017
Vitti RP, Prati C, Sinhoreti MA et al. (2013) Chemical-physi-
cal properties of experimental root canal sealers based on
butyl ethylene glycol disalicylate and MTA. Dental Materi-
als 29, 1287–94.
Zhou HM, Du TF, Shen Y, Wang ZJ, Zheng YF, Haapasalo M
(2015) In vitro cytotoxicity of calcium silicate containing
endodontic sealers. Journal of Endodontics 41, 56–61.
© 2017 International Endodontic Journal. Published by John Wiley & Sons Ltd