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Objectives. The aim of this study was to assess the resin matrix monomer composition of
selected bulk-ll and conventional resin-composite materials using reverse phase liquid
2 March 2015
Material and methods. Six bulk-ll (SureFil SDR, Venus Bulk Fill, X-tra base, Filtek Bulk Fill
owable, Sonic Fill, and Tetric EvoCeram Bulk Fill) and eight conventional resin-composites
(Grandioso Flow, Venus Diamond Flow, X-Flow, Filtek Supreme XTE, Grandioso, Venus Diamond, TPH Spectrum, and Filtek Z250) were tested. For assessment of resin composition and
Keywords:
relative monomer amounts, uncured resin-composites were analysed with reverse phase
Monomer
Liquid chromatography
Mass spectrometry
reverse phase liquid chromatography retention time was explored. Data were analysed with
Bulk-ll
one-way ANOVA, Tukey post hoc test, Pearson correlation and regression analyses at = 0.05.
Resin-composites
Results. The main monomers detected were BisGMA, UDMA, TEGDMA, and BisEMA.
Monomers were detected at variable combinations in different materials with signicantly
different relative amounts. Other monomers were detected including HDDMA, DEGDMA,
TCD-DI-HEA, and SDR-UDMA in Grandioso ow, X-ow, Venus Diamond, and SureFil SDR
respectively. A positive correlation between log P and reverse phase liquid chromatography
retention time was detected (r2 = 0.62, p = 0.004).
Conclusions. Resin composition of bulk-ll resin-composites is comparable to that of conventional materials with the exception of SureFil SDR. The relative hydrophobicity of dental
monomers can be determined by their reverse phase liquid chromatography retention time.
2015 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.
Corresponding author at: School of Dentistry, The University of Manchester, Manchester M13 9PL, UK. Tel.: +44 1612756747.
E-mail address: nick.silikas@manchester.ac.uk (N. Silikas).
http://dx.doi.org/10.1016/j.dental.2015.03.010
0109-5641/ 2015 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.
712
1.
d e n t a l m a t e r i a l s 3 1 ( 2 0 1 5 ) 711720
Introduction
2.
2.1.
2.2.
713
d e n t a l m a t e r i a l s 3 1 ( 2 0 1 5 ) 711720
Table 1 Test resin-composite materials and manufacturers: six bulk-ll (light gray) and eight conventional
resin-composite materials (dark gray).
Material
Code
Type
Shade
Filler (wt%)
Lot number
SureFil SDR ow
SDR
Universal
68
10211
VBF
Universal
65
010101
X-tra base
XB
Universal
75
1208392
FBF
Universal
64
N370958
TEC
SF
Universal A shade(IVA)
A2
77
83
R04686
4964921
Grandioso Flow
GRF
Conventional, owable
A2
81
1305362
VDF
Conventional, owable
A3
65
010104
X-Flow
XF
Conventional, owable
A2
60
1267
FF
Conventional, owable
A3
65
N522058
Grandioso
GR
Conventional, regular
A2
89
1304304
Venus Diamond
VD
Conventional, regular
A2
81
010046
TPH 3 Spectrum
TPH
Conventional, regular
A2
75
1301000713
FiltekTM Z250
Z250
Conventional
A2
79
N458477
Manufacturer
DENTSPLY Caulk,
USA
Heraeus Kulzer
GmbH, Germany
VOCO GmbH,
Germany
3M ESPE GmbH,
Germany
Ivoclar Vivadent
Kerr Corporation,
USA
VOCO GmbH,
Germany
Heraeus Kulzer
GmbH, Germany
DENTSPLY Caulk,
USA
3M ESPE GmbH,
Germany
VOCO GmbH,
Germany
Heraeus Kulzer
GmbH, Germany
DENTSPLY Caulk,
USA
3M ESPE GmbH,
Germany
reference compounds. For compounds with no available reference, the molecular weight was calculated from the highest
intensity m/z value and compared with data in the literature.
To compare the quantity of each compound in different
resin-composite materials, the chromatogram peak area%
of each compound in relation to the total chromatogram
area was calculated. Log P values (octanolwater partition
coefcient) of identied non-fragmented compounds with
known structural formula were computationally obtained
using the ACD/ChemSketch (version 11.02) software.
2.3.
Statistical analysis
3.
Results
3.1.
714
Trivial name
MW
[M+Na]+
Bisphenol A
Glycidyl
Methacrylate
512
UDMA
Urethane
dimethacrylate
Triethylene
glycol dimethacrylate
Diethylene glycol
di-methacrylate
1,6-Hexanediol
di-methacrylate
2-Hydroxyethyl methacrylate
Bis-(acryloyloxymethyl)
tricyclo[5.2.1.0.sup.2,6] decane
Ethoxylated bis-phenol A
dimethacrylate
Ethoxylated Bis-phenol A
Diacrylate
SDR-urethane dimethacrylate
4-Dimethyl aminobenzoic acid
ethyl ester
Methyl methacrylate
1,3,7-Trimethylxanthine
(caffeine)
470
DEGDMA
HDDMA
HEMA
TCD-DI-HEA
BISEMA
EBPADA
SDR-UDMA
DMABEE
MMA
CF (internal standard)
a
b
242
535
476 [MC4 H5 O+Na]+
399 [MC8 H10 O2 +Na]+
519 [MOH+Na]+
493
425 [MC4 H5 O+Na]+
479 [MCH2 +Na]+ a
309
241 [MC4 H5 O+Na]+
353 [M+C2 H4 O+Na]+ b
265
254
277
130
478
131
501
447 [MC3 H3 O+Na]+
381 [MC6 H10 O+Na]+
536 (CH2 CH2 O)n
427 (CH2 CH2 O)n
481 (CH2 CH2 O)n
871
286
1700
468
848
193
100
194
[M+H]+
[M+NH4 ]+
Predicted
log P ()
48.2
13.0
6.3
11.4
34.6
10.2
2629
16.3
5.7
15.7
17.3
5.53 (0.48)
255
68.0
4.06 (0.3)
0.5 (0.28)
4.18 (0.42)
194
6.7
18.526.6
8.510.2
6, 69.4
2869
10.2
2429
48.6
26.2
195
10.1
6.1
530
471
474 [MCH2 +NH4 ]+
304
Reverse phase LC
average retention
time (min)
457[MCH2 +H]+
153
Not detected by MS
5.06 (0.46)
1.81 (0.43)
2.17 (0.35)
6.99 (0.4)
5.89 (0.35)
NA
3.14 (0.24)
1.35 (0.25)
0.13 (0.37)
d e n t a l m a t e r i a l s 3 1 ( 2 0 1 5 ) 711720
BisGMA
TEGDMA
MS numbers (m/z)
d e n t a l m a t e r i a l s 3 1 ( 2 0 1 5 ) 711720
715
3.2.
LC/MS analysis of the methanol extract of different resincomposite materials showed variable combinations of
monomers with different relative amounts between materials (Table 3 and Fig. 3). In addition to the reference monomers
that were analysed, other monomers and compounds were
detected.
All materials showed TEGDMA on LC/MS except XF. TPH
showed a signicantly higher chromatogram peak area% of
TEGDMA (75.35%, SD 7.36) than other materials. TEC, FBF, VDF,
VBF, XB, and Z250 showed comparable TEGDMA area% which
was signicantly lower than other materials (0.196.26%).
Ethoxylated TEGDMA (TEGDMA+ CH2 CH2 O) with a molecular weight of 330 was detected in both FBF and FF. DEGDMA
was detected as a main component of XF with 67.97% chromatogram peak area. Only a small amount of DEGDMA was
detected in XB with a peak area of 2.82%.
BisGMA was detected in TEC, FF, GR, SF, Z250, FBF, GRF, and
TPH. The highest chromatogram peak area% of BisGMA was
shown by TEC (70.27%) followed by FF (62.59%) and GR and
(62.38%). TPH showed the lowest BisGMA chromatogram peak
area of 4.59%. UDMA was detected in VDF, VBF, FBF, SDR, Z250,
VD, TEC, and XB. VDF and VBF showed signicantly higher
UDMA area% than other materials (80.12% and 78.07% respectively). XB showed the lowest UDMA area% of 3.75%.
BisEMA was detected in all materials but was not quantiable for TEC. BisEMA chromatogram peak areas for GRF, FBF, FF,
GR, XF, Z250, VD, and TPH were not signicantly different and
ranged from 0.33 to 3.24%. SF, VBF, VDF, and SDR showed higher
BisEMA chromatogram peak area% which ranged from 11.60
to 16.91%. XB showed a signicantly higher chromatogram
peak area% of BisEMA (55.42%) compared to other materials.
EBPADA was detected in GRF, SF, and GR with a peak area
that ranged from 0.39% to 0.47%. EBPADA was also detected
in XB with a signicantly higher peak area (9.09%) than other
materials.
716
d e n t a l m a t e r i a l s 3 1 ( 2 0 1 5 ) 711720
Fig. 2 LC/MS of BisEMA showing total ion and UV chromatograms (top). Note the multiple peaks in both chromatograms.
Some peaks are dened and their corresponding mass spectra are shown at the bottom. At 6.0 and 69.4 min, m/z value of
381 (sodium adduct of BisEMA CH2 = C(CH3 )CO,CH3 ,CH2 ) are observed on the mass spectrum. Note the caffeine (internal
standard) m/z value of 195 and corresponding UV chromatographic peak at 6 min. Total ion and UV chromatographic peaks
between 28 and 69 min shows mass spectra with an average m/z value of 536 (44)n . They represent BisEMA molecules
having different number of ethoxy groups ( CH2 CH2 O ). Peak at 16.6 min shows a mass spectrum with m/z value of 309
which represent the sodium adduct of TEGDMA (used as a diluent for BisEMA).
Some further compounds were detected in specic materials. HDDMA was detected in GRF at 68 min with a
chromatographic peak area of 43.35%. The sodium adduct of
the co-monomer HDDMA was observed at 277 m/z value on the
mass spectrum. In SDR, UDMA was observed at a different m/z
value than the reference UDMA monomer. Sodium, ammonium, and protonated adducts of [UDMA-CH2 ] were observed
at 479, 474, and 457 m/z values respectively at 2629 min. Also,
an m/z value of 871 was detected in SDR at 48.6 min with
a chromatographic peak area of 11.37%. This high molecular weight compound could represent the sodium adduct of
two modied UDMA molecules joined by an SDR photoactive group (polymerization modulator). In VD, m/z values of
501 (18.526.6 min) and 447 (8.510.2 min) were detected. They
represent the sodium adduct of TCD-DI-HEA molecule and
TCD-DI-HEA [COCH CH2 ] respectively and account for the
56.34% peak area on VD chromatogram. In XF, an unknown
3.3.
d e n t a l m a t e r i a l s 3 1 ( 2 0 1 5 ) 711720
717
Fig. 3 The main monomer content of the different resin-composites (bulk-ll and conventional) detected by LC/MS (mean
area% of the chromatogram). Monomers with values <1 chromatogram area % are not shown.
4.
Discussion
718
91.38
83.92
89.54
91.81
89.14
70.65
96.09
89.79
83.80
90.68
89.95
62.38
(4.24)
NDa
26.73d (1.74)
NDa
NDa
NDa
1.08a (0.52)
0.47a (0.01)
NDa
1.15b,c,d (0.31)
62.59 (10.23)
NDa
23.94d (1.70)
NDa
NDa
NDa
0.88a (0.39)
NDa
NDa
1.73d (0.43)
ND
NDa
NDa
67.97b (4.38)
NDa
NDa
2.17a (0.81)
NDa
NDa
0.51a,b (0.01)
ND
80.12e (2.75)
1.44a (0.17)
NDa
NDa
NDa
14.03b (0.33)
NDa
NDa
NDa
30.68 (4.01)
NDa
14.54c (1.48)
NDa
43.35b (4.67)
NDa
0.33a (0.15)
0.39a (0.16)
NDa
0.50a,b (0.03)
55.75 (4.27)
NDa
14.56c (1.40)
NDa
NDa
NDa
11.60b (3.63)
0.41a (0.18)
NDa
1.48c,d (0.14)
70.27 (0.67)
20.22b (3.73)
0.19a (0.08)
NDa
NDa
NDa
Not quantiable
NDa
NDa
NDa
44.43 (1.00)
43.53d (4.98)
0.37a (0.26)
NDa
NDa
NDa
0.39a (0.10)
NDa
NDa
1.23b,c,d (0.23)
ND
3.75a (0.93)
2.14a (0.13)
2.82a (1.23)
NDa
NDa
55.42c (3.15)
9.09b (1.26)
NDa
6.21e (0.33)
91.90
88.28
Total
ND
78.07e (1.18)
1.47a (0.06)
NDa
NDa
NDa
12.35b (1.43)
NDa
NDa
NDa
ND
35.61c (0.70)
24.39d (0.61)
0.00a
NDa
NDa
16.91b (4.73)
NDa
11.37b (4.68)
NDa
BisGMA
UDMA
TEGDMA
DEGDMA
HDDMA
TCD-DI-HEA
BISEMA
EBPADA
SDR-UDMA
DMABEE
79.43
Z250
52.06c,d (6.54)
28.12c (1.68)
6.26a,b (0.72)
NDa
NDa
0.00a
3.05a (0.14)
NDa
NDa
1.89d (0.75)
4.59 (0.74)
NDa
75.35e (7.36)
NDa
NDa
NDa
3.24a (0.39)
NDa
NDa
0.74a,b,c (0.15)
ND
24.07b,c (1.31)
9.13b,c (1.41)
NDa
NDa
56.34b (3.53)
3.06a (0.18)
NDa
NDa
NDa
TPH
VD
GR
c.d,e
d,e
FF
XF
a
a
VDF
GRF
b
c,d
SF
TEC
e
c
FBF
XB
VBF
SDR
Compound
Table 3 Main monomer content of the different resin-composites detected by LC/MS (mean area% of the chromatogram and standard deviation). Values with same
superscript letters per row indicate statistically homogenous groups (Tukey test, = 0.05).
d e n t a l m a t e r i a l s 3 1 ( 2 0 1 5 ) 711720
used [14]. In a few studies, LC/MS equipped with a soft ionization source such as electro spray ionization (ESI) has been
reliably used for the detection of high molecular weight nonvolatile cross-linking monomers such as UDMA, Bis-GMA,
and BisEMA [24,2628]. In the current study, higher molecular weight compounds and new monomers (like SDR-UDMA
(848 MW), TDC-DI-HEA (478 MW), and homologous series of
BisEMA and EBPADA) were detected intact for the rst time
using LC/MS with ESI. Also, different m/z values of UDMA and
TEGDMA were detected in some materials like SDR, FF, and
FBF compared to other resin-composites which reect variations in the chemical structure of monomers used by different
manufacturers as has been previously reported [29].
In this study, LC/MS was operated using an internal
standard (caffeine) incorporated into all samples. The use of a
suitable internal standard in conjunction with LC/MS, LC, and
GC procedures provides a means for evaluating method performance, verication, and assessing the validity of the detection
technique.
Reverse phase liquid chromatography technique is the
best separation method for non-polar compounds that constitute the majority resin-composite monomers, and also has
the advantage of separating components according to their
order of hydrophobicity [30]. This has been shown in the
current study by the positive correlation between predicted
log P values of compounds with known structural formula and
their reverse phase liquid chromatography retention time. The
same relationship was shown in a previous study when HPLC
was used for identication of monomers composing different
dentin primers and bonding agents [31]. log P (octanolwater
partition coefcient) is a widely used partition coefcient used
to measure hydrophobicity in pharmaceutical and medicinal chemistry [32]. Hydrophobicity of constituent monomers
and compounds is considered as a key factor that determines the diffusibility of a storage solution into a polymeric
structure and its solubility [33]. In a previous study, log P
was found to be a good predictor of water sorption for polymerized experimental dental resins when they were grouped
according to compositional and structural similarities [34]. In
addition, from a biological point of view, hydrophobicity of
a substance has been found to correlate with its genotoxicity [35]. In a previous study using GC/MS, the octanolwater
partition coefcient for several detected leachable compounds
from resin-composite materials were laboratory measured as
a mean for assessing their lipophilicity. Values in that study
ranged from 0.5 to 4.1, however, values for BisGMA, UDMA, and
TEGDMA were not comparable to those obtained in the current study which is attributed to the use of different partition
solutions [25].
According to the determined relative hydrophobicity of
compounds detected in this study, higher solubility and elution into polar aqueous media is expected from XF compared
to other materials since its resin is mainly composed of the
hydrophilic monomer DEGDMA. The log P values of BisEMA
and EBPADA could not be obtained because of their variable
ethylene oxide chain length resulting in different molecular
weights and structural formulae for these compounds. However, predicted log P for BisEMA and EBPADA with two ethoxy
groups were the highest compared to other materials which
indicates high hydrophobicity of these monomers.
d e n t a l m a t e r i a l s 3 1 ( 2 0 1 5 ) 711720
5.
Conclusions
1. Resin composition of bulk-ll resin-composites is generally comparable to that of conventional materials with the
exception of SDR.
2. The relative hydrophobicity of dental monomers can be
determined by their reverse phase liquid chromatography
retention time.
719
references
720
d e n t a l m a t e r i a l s 3 1 ( 2 0 1 5 ) 711720