J Inorg Organomet Polym (2017) 27:1014–1021
DOI 10.1007/s10904-017-0549-1
Can Spherical Vaterite Be Biomimetic Synthesized by Using
Histidine-Grafted-Chitosan as an Organic Matrix?
Zhangxu Chen1 · Xianxue Li1 · Bingyun Zheng1
Received: 6 March 2017 / Accepted: 13 April 2017 / Published online: 18 April 2017
© Springer Science+Business Media New York 2017
Abstract Extensive application of vaterite in ceramics,
biomedical implanting, encapsulation and drug delivery
require the effectively controlling the size, morphology and
polymorph of the obtained calcium carbonate. For this purpose, vaterite was synthesized by using histidine-graftedchitosan (NHCS) as an organic matrix in this research.
The effects of the initial concentration of NHCS, and the
aging time on the morphology and polymorph were investigated. The prepared vaterite was characterized by fieldemission scanning electron microscope, Fourier transform
infrared spectrometer and X-ray diffraction. The result
showed vaterite has presented as an advantage phase over
calcite phase in presence of NHCS system, and the 91.6
Electronic Supplementary Material The online version
of this article (doi:10.1007/s10904-017-0549-1) contains
supplementary material, which is available to authorized users.
* Zhangxu Chen
xuzhangchen@163.com
1
Fujian Provincial Key Laboratory of Ecology‑Toxicological
Effects & Control for Emerging Contaminants,
College of Environmental and Biological Engineering,
Putian University, Putian 351100, Fujian,
People’s Republic of China
13
Vol:.(1234567890)
wt% percentage of vaterite can be achieved when the initial
concentration of NHCS is 1.000 mg ­L−1. Prolonging aging
time from 0 to 24 h, the percentage of vaterite would be
deduced from 94.4 to 86.2 wt%, in which the flaky-floret
and multilayered vaterite transforms to calcite slowly. In
contrast, a single crystalline rhombohedral calcite phase
can only be obtained without adding NHCS in pure water
system. The possible growth mechanism has been proposed
by investigating the transition of crystal phase and formation of the vaterite during the growth process. The result
indicates that NHCS is an effective template to biomimetic
synthesis of vaterite, and provides a novel method for controlling synthesis other biomaterials.
J Inorg Organomet Polym (2017) 27:1014–1021
1015
Graphical Abstract
Molecular Recognition
Electrostatic Interaction
NHCS
Formation Nucleus
CO3 2-
(a)
0h
(b)
(c)
(d)
Aggreation
DissolutionReprecipitation
DissolutionReprecipitation
DissolutionReprecipitation
Limited Growth
Limited Growth
Limited Growth
(i)
(h)
Ca2+
CO32-
Keywords Vaterite · Biomimetic synthesis · Histidinegrafted-chitosan · Template · Initial concentration · Aging
time
1 Introduction
Biomineralization and related bio-related processes are
multifactorial, fantastic and complex processes that often
become a nice guide for fabrication of functional materials and keys for understanding of biophenomena [1–3].
Biomineralization process can be effectively for biomimetic synthesis of vaterite, which plays an important role
in biomedical implanting, encapsulation and drug delivery because it exhibits unique properties, such as higher
dispersion, higher solubility, and smaller specific gravity
than aragonite and calcite [4–6]. As is well known, calcite,
aragonite and vaterite are the three common anhydrous
polymorphic forms of calcium carbonate, and the thermodynamic stability decreases from calcite, aragonite to vaterite. Therefore, there is a big challenge to preparation of sole
vaterite minerals in aqueous phases [7]. Up to date, mineralization of vaterite with various strategy has been studied. Among these, stable vaterite crystals biomimetic synthesized in presence of organic matrix, such as poly(lactic
acid) [8], dopamine [9], phospholipids [10], dendrimers [6,
11], sodium bis-2-ethylhexyl-sulfosuccinate [12], protein
[13], silk [14], chitosan [15–17] and amino acid [18–23]
have been reported. In organic phases, organic matrix plays
important roles in preventing the transformation to stable
calcite. It is worthwhile to mention that both chitosan and
amino acid have been independently used as organic matrix
for biomimetic synthesis vaterite [18–23]. However, a clear
understanding of the fundamental processes controlling the
specific crystallization of calcium carbonate is still lacking.
Ripening
1h
6h
12 h
24 h
0.5 h
(g)
NHCS
(f)
Calcite
(e)
Vaterite
Especially, the mechanism and kinetics of sole vaterite
phase or coexistence of vaterite–calcite phases remain a
longstanding challenge in biomimetic synthesis.
To approach these problems, histidine-grafted-chitosan
(NHCS) can be used as a matrix for biomimetic synthesis
of vaterite. In our previous research, histidine was used to
modify chitosan with 1-(3-dimethylamino propyl)-3-ethyl
carbodiimide hydrochloride and N-hydroxysuccinimide for
preparation of NHCS powers in order to improve the solubility of chitosan and expend its application over it’s wide
pH range. Furthermore, effect of the pH value on the morphology and polymorph of calcium carbonate, and mechanism of formation and stabilization at different pH values in
the presence of NHCS were investigated [24]. As expected,
NHCS is an effective template and pH responsive for biomimetic synthesis of vaterite. In order to supplement preparation parameters of biomimetic synthesis vaterite in presence of NHCS for providing a novel method to synthesize
other biomaterials, the effects of the initial concentration of
NHCS, and the aging time on the morphology and polymorph of calcium carbonate are investigated in this manuscript. The possible growth mechanism of crystal phase and
formation of the vaterite during the growth process (altering aging time) has been proposed, which might provide a
novel method for controlling synthesis other biomaterials.
2 Experimental Section
2.1 Materials
Histidine-grafted-chitosan powder (NHCS) is synthesized
according to our previously report (Supplementary Fig.
S1 and Fig. S2). Sodium carbonate ­
(Na2CO3), absolute
ethanol ­(C2H5OH), calcium chloride ­(CaCl2) and ammonia
13
1016
J Inorg Organomet Polym (2017) 27:1014–1021
­(NH3·H2O) are all of analytical reagent and are purchased
from Sinopharm Chemical Reagent Co., Ltd. (China).
2.2 Method of Preparing Calcium Carbonate Crystals
in Absence or Presence of NHCS
The calcium carbonate crystals were obtained in pure
water system [24]. In a typical synthesis, 20.00 mL of
­CaCl2 (0.10 mol L−1) was adjusted to 7.0 using ammonia with constant stirring. Then, 20.00 mL of N
­ a2CO3
(0.10 mol L−1) solution was drop wise added into the above
solution at room temperature, stirred for 10 min and aged
for 1.0 h. Finally, the obtained white precipitates were
separated by centrifugation, rinsed several times with double distilled water and absolute ethanol, respectively, and
then dried under vacuum oven until a constant weight is
achieved. The as-synthesized product was denoted sample
0 (S0).
To investigate the effect of NHCS on the crystallization
of calcium carbonate, different samples (S1–S4, S5–S9)
were prepared by using histidine-grafted-chitosan as a
matrix at different initial concentration of NHCS and aging
time by following the same procedures of sample 0 (S0)
except that ­CaCl2 solution was replaced with NHCS/CaCl2
aqueous solutions. In detail, firstly, a series of solutions of
different concentrations of NHCS (0.125, 0.250, 0.500 and
1.000 mg L−1) were prepared at 25.0 °C and pH of 7.0. Second, the different aging times of 0, 0.5, 1, 6, 12 and 24 h
were applied respectively. The detailed preparation parameters were listed in the Table 1.
2.3 Characterization
of 1 wt% in KBr powder) were performed and recorded
with a Fourier transform infrared spectrometer (BRUKER
TENSON 27, Germany) between 4000 and 400 cm−1 with
a resolution of 4 cm−1. The X-ray diffraction (XRD) patterns were obtained on SmartLab 3 kW, X-ray diffractometer (Rigaku, Japan) using Cu Kα radiation at a scan rate of
4° min−1 was used to determine the identity of crystalline
phase. The accelerating voltage and applied current were
30 kV and 40 mA, respectively.
3 Results and Discussion
3.1 Influence of NHCS Concentration on Calcium
Carbonate
Figures 1 and 2 presented the infrared spectra and XRD
patterns of the calcium carbonate crystals (S0–S4) produced with different initial concentration of NHCS (0,
0.125, 0.250, 0.500 and 1.000 mg L−1) at 25.0 °C for aging
1 h, respectively.
As well known, band assignment for FTIR of calcium
carbonate polymorphs was well established [25–27]. These
absorption bands correspond to symmetric C–O stretching mode ­
(v1), ­CO32− out-of-plane bending mode ­
(v2),
doubly degenerated asymmetric C–O stretching mode ­(v3)
and doubly degenerated in-plane OCO deformation bending mode ­
(v4). The spectral region between 2000 and
600 cm−1 was selected for qualitative analysis, because
of severe peak overlapping of the different polymorphs of
calcium carbonate in other spectral regions [28, 29]. As
a
The sizes and morphologies of calcium carbonate crystals
were investigated by FESEM (NovaNanoSEM230, American). Calibrated pellets of calcium carbonate (in proportion
b
c
Table 1 Preparation conditions of calcium carbonate products with
sample names
d
Sample name
Initial concentration
of NHCS (mg L−1)
Temperature
Aging time (h)
e
S0
S1
S2
S3
S4
S5
S6
S7
S8
S9
0
0.125
0.250
0.500
1.000
0.250
0.250
0.250
0.250
0.250
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
1.0
1.0
1.0
1.0
1.0
0.0
0.5
6.0
12.0
24.0
13
745
712
876
2000
1800
1600
1400
1200
1000
800
600
-1
Wavenuber/ cm
Fig. 1 FT-IR spectra of calcium carbonate particles biomimetic
synthesized with different initial concentration of NHCS for aging
time 1 h (a 0, b 0.125 mg L−1, c 0.250 mg L−1, d 0.500 mg L−1, e
1.000 mg L−1)
1017
C018
C116
C202
C110
C113
C 113
V 114
a
C 110
C006
V 112
V 110
C 012
C012
C104
J Inorg Organomet Polym (2017) 27:1014–1021
b
c
d
e
20
30
40
50
60
70
2-Theta /degrees
Fig. 2 XRD patterns of calcium carbonate particles biomimetic
synthesized with different initial concentration of NHCS for aging
time 1 h (a 0, b 0.125 mg L−1, c 0.250 mg L−1, d 0.500 mg L−1, e
1.000 mg L−1)
Table 2 Weight percentages of different polymorphs of calcium carbonate in presence (or absence) of NHCS
Sample name
Vaterite (%)
Calcite (%)
S0
S1
S2
S3
S4
S5
S6
S7
S8
S9
0
61.8
89.2
91.4
91.6
94.4
93.5
87.9
86.8
86.2
100.0
38.2
10.8
8.6
8.4
5.6
6.5
12.1
13.2
13.8
of NHCS remarkably increased, which was favorable to
the growth of vaterite. In addition, the higher of the initial
concentration of NHCS, the more vaterite amounts present,
and the higher intensity ratio of bands at 746 and 712 cm−1
(I746/I712) responded in FTIR spectrum of the obtained calcium carbonate.
The same observation can also be found by XRD analysis. The diffraction peaks occurred at 2θ = 23.0°, 29.4°,
39.4° and 47.5°, corresponding to calcite crystal face (012),
(104), (113) and (018), respectively (JCPDS No. 05-0586).
It indicated that calcite was also formed with different initial concentration of NHCS. Compared with S0 obtained in
pure water (initial concentration of NHCS is 0, Fig. 2a), the
new diffraction peaks occurred at 2θ = 24.9°, 27.0°, 32.8°
and 43.8°, corresponding to vaterite crystal face (110),
(112), (114) and (300), respectively (JCPDS No. 33-0268),
showed that vaterite phase can be prepared (S1–S4 in
Fig. 2b–e) at different initial concentration of NHCS. With
increasing the initial concentration of NHCS, the intensity
of the (104) face diffraction peak of calcite reduced quickly,
but the intensity of the (110) face diffraction peak of vaterite increased gradually.
The relative amounts of the polymorphic composition
were calculated from the relative areas of the vaterite (110)
and calcite (104) by using Kontoyannis equation [33] and
were presented in Table 2. It can be seen that the percentage of vaterite (with the remainder being calcite) in S0–S4
were ca. 0 wt%, 61.8, 89.2, 91.4 and 91.6%, respectively.
It is clear that the content of vaterite can be controlled by
varying the dosage of NHCS. It increases from 61.8 to
91.6 wt% when the initial concentration of NHCS changes
from 0.125 to 1.000 mg L−1. These results are in agreement
with those obtained by FTIR. The above results suggest
that NHCS is an effective organic matrix to biomimetic
synthesis of vaterite.
3.2 Influence of Aging Time on Calcium Carbonate
evident from Fig. 1, the sample 0 (S0) prepared in pure
water system only showed three characteristic bands for
calcite, ­v2 at 876 cm−1, ­v3 at 1435 cm−1 and ­v4 at 712 cm−1.
Increasing the dosage of NHCS of 0.125, 0.250, 0.500 and
1.000 mg L−1 (S1, S2, S3 and S4), ­v2 at 876 cm−1, overlapping of vaterite and calcite absorption bands can
be observed, but new bands of ­
v4 at 746 cm−1, ­v1 at
−1
−1
1090 cm , ­v3 at 1450 cm corresponding to vaterite also
appeared [30–32]. This confirmed that NHCS is an effective template to biomimetic synthesis of vaterite. It can be
explained as following: –OH and –COO− groups of NHCS
can chelate ­Ca2+ to form ­Ca2+-NHCS structure, in which
­Ca2+ can further attract C
­ O32− ions by electrostatic interaction. As a result, the number of nucleus on the surface
In order to study the effect of aging time on the morphology and polymorph of calcium carbonate in presence of
NHCS at the same initial concentration of NHCS (0.250
mg L−1). Different samples (S5, S6, S2, S7–S9) were prepared in presence of NHCS at different aging times of 0,
0.5, 1, 6, 12 and 24 h, respectively.
Figures 3, 4 and 5 show the infrared spectra, XRD patterns and FESEM images of the as-prepared samples (S5,
S6, S2, S7–S9) obtained by using histidine-grafted-chitosan
as an organic matrix at different aging times, respectively.
As shown from Fig. 3, the calcite characteristic bands
of ­v2 at 876 cm−1 and v­4 at 712 cm−1 appeared in the
above samples. Also, vaterite characteristic bands of
­v4 at 746 cm−1, ­v1 at 1090 cm−1, ­v3 at 1450 cm−1 can be
13
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J Inorg Organomet Polym (2017) 27:1014–1021
a
b
c
d
e
f
876
2000
1800
1600
1400
1200
1000
Wavenumber /cm-1
746
712
800
600
V300
V114
V110
V112
V104
Fig. 3 FT-IR spectra of calcium carbonate particles obtained by
using NHCS as an organic matrix at different aging times (a 0 h, b
0.5 h, c 1 h, d 6 h, e 12 h, f 24 h)
b
C113
C012
a
c
d
e
f
20
30
40
50
60
70
2-Theta /degrees
Fig. 4 XRD patterns of calcium carbonate particles obtained by
using NHCS as an organic matrix at different aging times (a 0 h, b
0.5 h, c 1 h, d 6 h, e 12 h, f 24 h, C calcite, V vaterite)
observed. The different ratios of vaterite to calcite formed
at different aging times can be indicated from I746/I712 too.
Compared with S0 obtained without addition of NHCS
(S0 in Fig. 2a), vaterite phase can be successfully achieved.
with NHCS as an organic matrix It is found that vaterite is
the major crystal phase of calcium carbonate (S5, S6, S2,
S7–S9 in Fig. 4) at different aging times with the representative crystal face for vaterite. In presence of NHCS system,
the diffraction peak intensity of the (104) face of calcite
increased gradually with the prolonging of the aging time.
13
To certify the ratio changes of vaterite and calcite, the
percentage of each polymorph obtained at different aging
times was calculated by using Kontoyannis equation [33]
and are showed in Table 2. As can be seen, the percentage
of vaterite in S5, S6, S2, and S7–S9 at different times are
ca. 94.4, 93.5, 89.2, 87.9, 86.8 and 86.2 wt% at different
aging times of 0, 0.5, 1, 6, 12 and 24 h, respectively. It is
clear that the percentage of vaterite was affected by varying aging time. It decreases from 94.4 to 86.2 wt% after
24 h, in which a nearly constant percentage of vaterite was
attained.
In Fig. 5, FESEM images of the calcium carbonate
particles obtained at various aging times clearly showed
the growth process of the calcite and vaterite. The crystal phases of calcium carbonate evolved in presence of
NHCS are obviously different from those in pure water
system (Supplementary Fig. S3). Sole calcite particles
were formed with morphologies of stacked rhombohedral
in pure water system. In contrast, when NHCS was added
in the medium, the as-prepared particles eventually exhibited unusual mixture of calcium carbonate with rhombohedral morphologies and spherical morphologies. When the
aging time was 0 h, “flaky-floret” and multilayered calcium
carbonate particles (S5, Fig. 5a) were observed with diameters and thicknesses of about 1.0–2.5 and 0.1–2.2 μm,
respectively. Increasing the aging time from 0 to 0.5 h, the
morphology of obtained calcium carbonate particles (S6,
Fig. 5b) was similar to S5. Besides flaky-floret and multilayered crystallites, the rhombohedral calcium carbonate
of about 1.9 μm × 1.9 μm × 1.9 μm in size appeared. It is
worthwhile to note that the amount of multilayered crystallites decreased in this stage. With the aging time extended,
the “flaky-floret” or multilayered structure disappeared
completely. More and more rhombohedral calcium carbonate are obtained (S2, Fig. 5c). Meanwhile, the sizes of
spherical and rhombohedral particles increased with the
increase of aging time from 1.0 to 6.0 h (S7, Fig. 5d), and
some spherical particles embedded in the rhombohedral
ones. Aging for 12.0 h would lead to the decrease of spherical calcium carbonate, but the increase of rhombohedral
calcium carbonate, which can be seen in (Fig. 5e). As the
time prolonging up to 24.0 h, the morphology of the calcium carbonate tended to be stabilized (S9, Fig. 5f), rhombohedral like calcium carbonate with an average length of
4.0 μm was obtained.
From the Table 2, indicated from the XRD data, large
percentage of vaterite were all obtained in the as-prepared samples. It is reasonable to assign that calcite is
with rhombohedral morphologies and vaterite is with
flaky-floret, multilayered structure and spherical eventually. The similar results can also be found in the reported
researches [34, 35]. The growth process of the stacked
rhombohedral calcite and microspherical vaterite can be
J Inorg Organomet Polym (2017) 27:1014–1021
1019
Fig. 5 FESEM images of
calcium carbonate particles
obtained by using NHCS as an
organic matrix at different aging
times (a 0 h, b 0.5 h, c 1 h, d
6 h, e 12 h, f 24 h, the scale bar
is 500 nm)
explained by Ostwald ripening mechanism [36]. Lengthening the aging time introduced the decrease of spherical like calcium carbonate, but the increase of rhombohedral like calcium carbonate. Moreover, the content of
the vaterite in the obtained calcium carbonate decreases,
and part of the vaterite begins to dissolve and transfer
to calcite. Therefore, it indicates that NHCS is a good
matrix to control biomimetic synthesis of vaterite by
using it as soft template within aging time of 24 h.
4 Proposed Mechanism of Vaterite
A possible illustration is proposed in Fig. 6 for the the transition of crystal phase and formation of the vaterite at different aging times. As shown, the mechanism of “molecular recognition”–“electrostatic interaction”–“formation nuc
leus”–“aggregation”–“ripening”–“dissolution-reprecipitation–limited growth” is proposed to explain the development of crystal phases and formation of the vaterite during
13
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J Inorg Organomet Polym (2017) 27:1014–1021
Molecular Recognition
Electrostatic Interaction
NHCS
Formation Nucleus
CO3 2-
(a)
0h
(b)
(c)
(d)
Aggreation
DissolutionReprecipitation
DissolutionReprecipitation
DissolutionReprecipitation
Limited Growth
Limited Growth
Limited Growth
(i)
(h)
Ca2+
CO32-
Ripening
1h
6h
12 h
24 h
0.5 h
(g)
NHCS
(f)
Calcite
(e)
Vaterite
Fig. 6 Schematic sequence illustrating the transition of crystal phase and formation of the vaterite at different aging times
the growth process. First, the pI of NHCS is 6.54 (Supplementary Fig. S4). In addition, the pKa of chitosan is 6.30
and the pKa of active-center histidine imidazole group is
6.00 [37, 38]. When the pH value of NHCS system is 7.0
(pH > pI(NHCS)), deprotonation of hydroxyl group, imidazole group and amino groups leads to the whole NHCS carrying with negative charges (−10.8 mV) [24], this presents
that a specific interaction does exist between NHCS and
calcium ions. As a result, NHCS can capture and collect
­Ca2+ ion from ­CaCl2 solution (Fig. 6a) by molecular recognition (Fig. 6b), which leads to the enrichment of ­Ca2+
near the surface of NHCS. Meanwhile, these calcium ions
can further attract more ­CO32− ions by electrostatic interaction, thus remarkably increasing the number of nucleus
(Fig. 6c).
The increase of the degree of supersaturation favors the
nucleation of precipitation according to the Gibbs–Thomson formula of classical nucleation theory [39]:
(1)
where J and S are the nucleation rate and degree of
supersaturation, respectively, and both A and B are constants. According to the Eq. (1), nucleation rate increases
along with the increase of supersaturation degree [32].
Thus, as NHCS is added into ­CaCl2 solution, numerous
nucleuses will form in the supersaturation zone on the
surface of NHCS. High supersaturation on NHCS leads
to increase of the nucleation rate as well as the nucleation
number. These nucleuses then grow into nanoflakes and
nanolayers rapidly. Large amount of crystal nucleus will
facilitate the formation of nanoflakes and nanolayers and
the refinement of precipitation. Due to their high surface
energy, the nanoflakes and nanolayers have the tendency to
aggregate. Consequently, the “flaky-floret” or multilayered
J = A exp −B(ln S)−2
13
particles by nanoflakes and nanolayers are observed in
Fig. 5a in the initial stage (at aging time 0 h, Figs. 5a, 6d).
As time progresses (aging time 0.5 h), these metastable
vaterite phase bounded by NHCS aggregate continuously
into “spherical-like” vaterite particles. On the other hand,
those crystal nucleuses unbounded by NHCS or its surface
grows into rhombohedral calcite phase (Figs. 5b, 6e). With
the aging time going, metastable vaterite can transform into
calcite through a solvent-mediate process [40]. Considering
Ostwald ripening mechanism [36] and the solubility products of the different polymorphs (vaterite, 1.22 × 10−8 M2;
aragonite, 4.61 × 10−9 M2; calcite, 3.31 × 10−9 M2 at 25 °C,
respectively) [41], the phase transformation of vaterite to
calcite is a thermodynamically feasible process. Thus, the
“dissolution-reprecipitation-limited growth” will take place
and the metastable vaterite particles begin to dissolve as
aging time progresses (Fig. 6f). After aging for 1.0 h, the
dissolved particles reprecipitated again and its surface is
adsorbed by NHCS molecular, so the initial crude “flakyfloret” or multilayered vaterite disappeared completely during ripening. It is worth noting that lots of crude elliptical
or spherical vaterite structures are formed by the reprecipitated particles and get more smooth and regular, and the
crystallite size of the metastable vaterite structures is making up of large crude spherulites increased from ~100 nm
to ~2 μm. Meanwhile, those unbounded crystal nucleuses
lead to the simultaneous growth of few rhombohedral calcite phase (Figs. 5c, 6f). In summary, morphology and polymorph of the coexistence of vaterite-calcite is controlled
by NHCS and leads to limited growth near the surface of
NHCS. On the other hand, coexistence of vaterite–calcite growth is controlled by Ostwald ripening to keep the
thermodynamics and dissolve dynamic balance in NHCS
system (Figs. 5d–f, 6g–i). The NHCS molecule plays an
J Inorg Organomet Polym (2017) 27:1014–1021
important role in the formation and stabilization of vaterite
within aging time of 24 h.
5 Conclusion
The sole rhombohedral calcite is easily obtained in pure
water system, while spherial vaterite phase can be obtained
and can be relatively stable in presence of NHCS system. Various morphologies of vaterite can be obtained
by using organic matrix of NHCS, such as “flaky-floret”,
multilayered and crude spherical structures. As the aging
time progresses to 24 h, the percentage of vaterite reaches
86.2 wt%. The spherical vaterite can be biomimetic synthesized by using histidine-grafted-chitosan as an organic
matrix.
Acknowledgements This work is supported by the National Science Foundation of China (21103095, 21206079), Fujian Provincial
Natural Science Foundation (2015J01057, 2015J01644, 2017J01590,
2017J01710), Scientific Research Plan of Education Bureau of Fujian
Province (JAT160431), Projects of Putian University (2015060,
2016015, 2016065).
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