Fabrication of micellar heteropolyacid catalysts for clean production of monosaccharides from polysaccharides

Article abstract of DOI:10.1016/j.catcom.2011.06.003

A micellar heteropolyacids (HPAs) catalyst had been prepared using surfactant cetyltrimethyl ammonium bromide (CTAB) and H₃PW ₁₂O₄₀ as precursors. These micellar [C₁₆H ₃₃N(CH₃)₃]_xH_{3 - x}PW ₁₂O₄₀ had been characterized to be micellar structure and the catalytic activity was evaluated by the hydrolysis of polysaccharides to the reducing sugars. The best catalytic activity was obtained over [C ₁₆H₃₃N(CH₃)₃]H₂PW ₁₂O₄₀ (abbreviated as (C₁₆TA)H₂PW), which showed 100% conversion and 99.6% selectivity within 60 min at 80 °C for hydrolysis of sucrose. And it was also active for the conversion of starch and cellulose. The leaching test showed that the HPA micellar catalysts have an excellent stability and can be used as heterogeneous catalysts for six times.

Full text of DOI:10.1016/j.catcom.2011.06.003

Catalysis Communications 12 (2011) 1483–1487
Contents lists available at ScienceDirect
Catalysis Communications
journal homepage: www.elsevier.com/locate/catcom
Short Communication
Fabrication of micellar heteropolyacid catalysts for clean production of
monosaccharides from polysaccharides
Mingxing Cheng, Tian Shi, Shengtian Wang, Hongyu Guan ⁎, Chunyan Fan, Xiaohong Wang ⁎
Key Lab of Polyoxometalate Science of Ministry of Education, Faculty of Chemistry, Northeast Normal University, Changchun 130024, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
A micellar heteropolyacids (HPAs) catalyst had been prepared using surfactant cetyltrimethyl ammonium
Received 3 March 2011
Received in revised form 28 May 2011
Accepted 6 June 2011
bromide (CTAB) and H
characterized to bemicellarstructure and the catalytic activity was evaluated bythe hydrolysisof polysaccharides
to the reducing sugars. The best catalytic activity was obtained over [C16 33N(CH ]H PW12 40 (abbreviated as
16TA)H PW), which showed 100% conversion and 99.6% selectivity within 60 min at 80 °C for hydrolysis of
3 3 3 x
PW12O40 as precursors. These micellar [C16H33N(CH ) ] H3−xPW12O40 had been
H
)
3 3
2
O
Available online 13 June 2011
(C
2
sucrose. And it was also active for the conversion of starch and cellulose. The leaching test showed that the HPA
micellar catalysts have an excellent stability and can be used as heterogeneous catalysts for six times.
© 2011 Elsevier B.V. All rights reserved.
Keywords:
Heteropolyacids
Micellar catalysis
Polysaccharides
Hydrolysis
Monosaccharides
1
. Introduction
Heteropolyacids (HPAs) exhibit unmatched physical and chemical
which is one of the key technologies for the full use of biomass,
especially for the food industry [16,17], sustainable fuels and
chemicals in the future [16,18,19]. Herein three main innovations
are proposed: (1) The assembly of HPAs into a micellar system with
Brønsted acidity, allowing the conversion of polysaccharides into
monosaccharide; (2) Overcoming the shortage of local concentration
in aqueous solution and promoting the reaction rate by HPA micellar
catalyst; (3) Easily handling this catalyst.
properties, which could act as reliable building blocks in the formation
of new materials especially in a nanomaterial area [1]. HPAs with
nanostructure could be assembled by surfactant encapsulation [2,3] as
formation of vessels, quantum dots and micelles for special devices
such as luminescence [4] and catalysis [5]. In the area of catalysis, the
utilization of HPA micelles is the most often strategy to significantly
accelerate the rate in a micellar medium [6,7]. Amphiphilic quaternary
ammonium of HPAs with surfactant core and HPA surface can form
supramolecular micellar assemblies ranging from the nanoscale to
microscale in aqueous solution, which could possibly afford high local
concentrations of the reactants near the catalysts. By now, amphi-
philic HPA catalysts have been successfully used in various oxidation
reactions [5,8–13] in emulsion or microemulsion system. However,
few studies have been made to develop amphiphilic HPA micellar
catalysts for the hydrolysis of polysaccharides into the reducing
sugars. By now, Arai investigated the hydrolysis of sucrose in the
2. Experimental
2.1. Material
Sucrose, starch and cellulose were all analytical reagents and
purchased from J&K SCIENTIFIC LTD, which were used without further
purification. Na
purchased from Sinopharm Chemical Reagent Co. Ltd.
PW12 40·23H O was prepared according to the literature method
[20] and was calcinated at 300 °C for 6 h to obtain H PW12 40·6H O.
2 4 3 4
WO , H PO (80%), diethyl ether and HCl(37%) were
H
3
O
2
3
O
2
presence of H
4
SiW12
O
40 as a homogeneous catalyst [14]. And Shimizu
3,5-Dinitrosalicylic acid (DNS) reagent was prepared according
Ref. [21], which is used to determine the amount of total reducing
sugar.
et al. [15] studied the Lewis and Brønsted acidity of HPAs catalysts on
the hydrolysis reactions for cellobiose and cellulose.
As a continuation of our work, we designed and synthesized
micellar HPAs [C16
H
3 3
33N(CH ) ]
x
H
3 − xPW12
O
40 in catalyzing hydroly-
2.2. Physical measurements
sis of polysaccharides into monosaccharide (glucose and fructose),
Elemental analysis was carried out using a Leeman Plasma Spec (I)
ICP-ES and a PE 2400 CHN elemental analyzer. FTIR spectra (4000–
−
1
4
00 cm ) were recorded in KBr discs on a Nicolet Magna 560 IR
⁎
Corresponding authors at: Northeast Normal University, 5268 Renmin Street,
spectrometer. TEM image was measured on JOEL JEM-2100F micro-
scope. The leaching concentrations of the catalysts during the reaction
Changchun, Jilin Province, PR China. Tel.: +86 431 88930042; fax: +86 431 85099759.
E-mail address: guanhy534@nenu.edu.cn (H. Guan).
1566-7367/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.catcom.2011.06.003

1484
M. Cheng et al. / Catalysis Communications 12 (2011) 1483–1487
were also measured through analyzing the dissolved concentration of
W in aqueous solution using a Leeman Plasma Spec (I) ICP-ES. The
2.6. Adsorption experiments
critical micellar concentration (CMC) of (C16TA)H
mined by conductivity versus concentration plot using conductome
ter model DDS-11A.
The titration was used to evaluate the acidity characteristics of the
solids [22]. 0.1 g of solid suspended in 20 mL sodium chloride solution
2
PW was deter-
Adsorption experiments were carried out to determine the
adsorption capacity of catalysts for polysaccharides. In the simulta-
neous adsorption experiments, 1.6 g of sucrose and 0.08 mmol of
catalyst were mixed in a steal autoclave for 15 min at 80 °C in order to
determine the adsorption effect by the IR spectroscopy.
(
2.0 M) was stirred for 24 h. Then, the titration was carried out by a
solution of sodium hydroxide (0.006 M) with the indicator
phenolphthalein.
2.7. Total reducing sugars (TRS) analysis [26]
Sucrose's conversion was quantitative by thin-layer chromatogra-
phy (TLC, DENSITOMETER CD 60) with tungsten lamp, and the scan
wavelength was 418 nm. The concentration of monosaccharides was
measured in the aqueous phase by high-performance liquid chroma-
tography (HPLC), which conducted on a system equipped with a
refractive index detector (Shimadzu LC-10A, HPX-87H column).
A mixture that contained 2 mL of DNS regent and 1 mL of reaction
sample was heated for 2 min in a boiling water bath, then cooled to
room temperature by flowing water, and mixed with deionized water
to 25 mL. The color intensity of the mixture was measured in a
UV757CRT Model spectrophotometer at 540 nm. The concentration of
total reducing sugars was calculated based on a standard curve
obtained with glucose.
2
.3. Preparation of [C16
3
H33N(CH )
]H
3 2
PW12O
40
2.8. Yield and selectivity definitions
A typical reaction procedure was as follows: 10 mL, 40 mM of
hexadecyltrimethylammonium bromide (CTAB) aqueous solution
was added into 10 mL, 40 mM of H PW12 40·6H O solution with
stirring at room temperature [23]. The white precipitate formed
immediately and was collected by filtration, then was dried at 100 °C
ꢀ
ꢁ
3
O
2
A mass in product
A mass in the loaded sample
Conversionð%Þ = 1−
× 100%
for about 3 h. The resulting [C16
3 3 2
H33N(CH ) ]H PW12O40 was obtained
main product mass
A mass in the loaded sample
−
1
with yield 46%. IR (1% KBr pellet, 4000–400 cm ): 1080, 980, 896,
Yieldð%Þ =
× 100%
−
1
and 806 cm . Anal. Calcd for [C16
3 3 2
H33N(CH ) ]H PW12O40: W, 69.76;
P, 0.98; C, 7.20; H, 1.39; N, 0.44%. Found: W, 69.37; P, 1.06; C, 7.43; H,
Yield
Conversion
1
.22; N, 0.39%.
Selectivityð%Þ =
× 100%
3 3 x
The other catalysts [C16H33N(CH ) ] H3 − xPW12O40 were prepared
in the same way except that the different molar ratio of CTAB and
PW12 40·6H O was used.
Cs2.5 0.5PW12 40 was prepared according to Okuhara's method
24]. Before the reaction, the catalyst was calcined at 300 °C for 2 h.
H
3
O
H
2
A stands for sucrose, cellulose or starch.
O
[
3. Results and discussion
3.1. Characterization of the micellar catalyst
2
.4. Critical micelle concentration (CMC) determination
The CMC of (C16TA)H PW was determined at break points of
From the results of elemental analysis (Table S1), the content of
W, P, C, H and N of catalyst is agreed with the calculated values.
The IR spectra of H PW12 40 and (C16TA)H PW are shown in Fig. S1.
The IR spectrum of H PW12 40 showed four characteristic peaks at
080, 982, 888 and 803 cm , reflecting the four different vibrations of
2
nearly two straight-line portions of the specific conductivity versus
concentration plot [25].
3
O
2
3
O
−
1
1
3−
oxygen atoms of the Keggin-type structure PW12
attributed to the asymmetry vibrations P–O (internal oxygen connect-
ing P and W), W–O (terminal oxygen bonding to W atom), W–O
(edge-sharing oxygen connecting W) and W–O (corner-sharing
oxygen connecting W 13 units). The IR spectrum of (C16TA)H PW
was in good agreement with that of its parent PW12 40 , though the
peaks were slightly shifted to 1080, 980, 896 and 806 cm , showing
that (C16TA)H PW retains Keggin structure. The slight shift may be
attributed to the influence of the C16TA on PW12
of (C16TA)H PW exhibit two peaks at 2923 and 2851 cm , which are
the symmetric and asymmetric stretching vibrations of C–H of C16TA.
Compared to the spectrum of CTAB [27], the peaks are shifted, which
O40 , which are
2
.5. Catalytic procedure
a
d
b
For hydrolysis of sucrose, a mixture of sucrose (1.6 g) and catalyst
c
(
0.08 mmol) in distilled water (8 mL) were heated at 80 °C in a steal
autoclave lined with Teflon under air for 60 min with agitation
300 rpm). After the reaction, the sample was centrifuged to separate
3
O
2
3−
O
−
1
(
the catalyst and the filtered solution was used for monosaccharides
analysis by HPLC.
2
3
−
O
40 . And the spectrum
−
1
For hydrolysis of starch, a mixture of starch (0.1 g) and catalyst
2
(
0.07 mmol) in distilled water (7 mL) was heated at 120 °C in a steal
2
autoclave lined with Teflon under air for 5 h with agitation (300 rpm).
At the end of the reaction, the mixture was centrifuged to separate the
catalyst and unreacted starch and the filtered solution was used for
TRS and glucose analysis by HPLC. The conversion of starch can be
determined by the mass change of the solid mixture.
3
−
may also due to the influence of PW12
As Table S1 shows (C16TA)
capacity due to the different content of H . And for these solid acid
O
40 on C16TA.
x
H
3 − xPW12 40 exhibits different acidic
O
+
2
catalysts, the acidity of (C16TA)H PW12O40 is the highest one about
For hydrolysis of cellulose, a mixture of cellulose (0.1 g) and
catalyst (0.07 mmol) in distilled water (7 mL) was heated at 170 °C in
a steal autoclave lined with Teflon under air for 8 h with agitation
1.8 mmol/g.
The critical micelle concentration (CMC) of (C16TA)H
determined by conductivity versus concentration plot given in Fig. S2.
The CMC of (C16TA)H PW is 0.92 mM. This point confirms that
(C16TA)H PW could form micelle in aqueous solution.
The cryo-TEM image of (C16TA)H PW also showed that it could
form relatively uniform micellar droplets about 50–60 nm (Fig. 1).
2
PW was
(
300 rpm). The reaction mixture was centrifuged to separate
2
unreacted cellulose and catalyst. The clear solution was used for
analysis. The conversion of cellulose was calculated according to Ref.
2
2
[26].

M. Cheng et al. / Catalysis Communications 12 (2011) 1483–1487
1485
corresponding to the strength of their Brønsted acidity (Table S1). This
point shows that the certain Brønsted acidity must be kept for an acid
catalyst in order to promote the hydrolysis of sugar. The fact that
[
C
16
H
33N(CH
be attributed to the effect of the amount of the carbonic chain. There are
less hydrophobic tails in [C16 33N(CH 40 than (C16TA)
PW, but the acidic difference between (C16TA)H PW and [C16
CH is less. Therefore, (C16TA)H PW exhibits higher
3 3 0.5 2
) ] H2.5PW12O40 is less active than (C16TA)H PW might
H
3 3 0.5
) ] H2.5PW12O
H
(
2
2
33
H N
3
)
3 0.5
] H
2.5PW12O
4
2
activity attributed to its higher acidity and large amount of carbonic
chain.
From Table 1, micellar HPA catalysts show higher selectivity than
3 3
H PW12O40. H PW12O40 is a homogeneous acid catalyst, which is
favorable for the conversion of sucrose, but the selectivity of
monosaccharides is low owing to its high acid strength and the
ratio of glucose with fructose is 1:0.7. Cs2.5
heterogeneous acid catalyst, which exhibits high selectivity and low
conversion. The high activity of (C16TA)H PW is attributed to the
accumulation of sucrose around the catalyst. (C16TA)H PW with a
H0.5PW12O40 is a
2
Fig. 1. The cryo-TEM image of (C16TA)H
2
PW micellar catalyst.
2
quaternary ammonium-hydrophobic tail and a HPA hydrophilic head
group, exhibits amphiphilic properties and acts as both catalyst and
surfactant to assemble micelle in an aqueous solution. The IR spectrum
3
.2. Catalytic activity
2
of adsorption of sucrose on (C16TA)H PW (Fig. S1) confirms the
assembly of sucrose on the HPA head region. The spectrum of (C16TA)
−
1
The micellar HPA catalysts were used in hydrolysis of sucrose
Fig. 2), and the hydrolysis products are glucose and fructose. It can be
seen that these micellar HPA catalysts exhibit some certain catalytic
performance in this hydrolysis reaction. The active range of this series is
H
2
PW-adsorbed sucrose gives four characteristic peaks at 1080 cm
,
−
1
−1
−1
3−
(
978 cm , 895 cm , and 807 cm corresponding to PW12
tural vibrations. Comparedtothe peaks of PW12
of W–O , W–O and W–O
O
40 struc-
40 , thevibration bands
c
shift from 978 to 982, 895 to 888, 807 to
3−
O
d
−
b
1
(
H
PW12
C
16TA)H
2
PW~[C16
H
33N(CH
33N(CH
33N(CH PW12
3
)
3
]
0.5
H
2.5PW12
HPW12 40 N[C16
40. (C16TA)H
O
40 N[C16
H
33N(CH
3
)
3
]
1.5
803 cm , respectively. This result indicates that some interaction
occurs between the OH group from sucrose and the HPA molecules. In
1.5PW12
O
40 N[C16
H
3
)
3
]
2
O
H
33N(CH ) ] H
3 3 2.5
0.5
−
1
O40N[C16
H
3
)
]
3 3
O
2
PW exhibits the high-
addition, the peaks at 1486 and 1474 cm
are attributed to the C–O
est conversion and selectivity among all catalysts. This range is partially
vibration of sucrose, indicating the assembly of sucrose on the catalyst.
Therefore, sucrose is accumulated through interactions with the micelle
surface or through insertion into the micelle itself compared to the
surrounding water phase.
It is known that the length of quaternary ammonium cations
n 3 3 5
[(C H2n+1)N(CH ) ] plays a vital role not only in the formation of the
micellar system but also the catalytic activity. The hydrophobic chain
must possess a certain length (NC10) to enable successful micelle
formation [28]. Therefore, the effect of carbon chain length on the
catalytic activity had been checked in Fig. 3. With the enhancement of
the length from C8 to C18, the conversion increases significantly, from
5
6.5% for (O
for (O18TA)H
The catalytic difference between (C16TA)H
PW12 40 is less. This result confirms that the length of the carbonic
chain of cations plays an important role in the formation of micelle as
well as the hydrolysis reaction. (O TA)H PW12 40, with a short
8
TA)H
2
PW12
O
40([(C
8
H
17)N(CH
3
)
3
]H
PW12
PW and (O18TA)
2
PW12
O40) to 97.5%
2
PW12
O40([(C18
H
17)N(CH
3
3
) ]H
2
O
40), respectively.
2
H
2
O
8
2
O
carbon chain comprising less than C10, has difficulty forming a micelle
and only acts as a heterogeneous catalyst, resulting in low conversion
(
56.5%). The surfactant-HPAs act as both a catalyst and a surfactant to
x
Fig. 2. Hydrolysis of sucrose by (C16TA) H3 − xPW12O40. Reaction conditions: 0.1 g of
sucrose, 0.08 mmol of catalyst and 10 mL of water for 60 min at 80 °C.
assemble micelles in water.
Table 1
The hydrolysis of sucrose by different catalysts. Reaction conditions: 80 °C, 60 min, catalyst 0.08 mmol.
1
Catalyst
PW12
Amount of sucrose/g
Amount of water/mL
Conversion of sucrose/%
Yield of mon-/%
Glu:Fru
Selectivity/%
TOF/g mmol− h−1
H
3
O
40
1.6
1.6
1.6
1.6
1.6
1.6
1.6
1.6
1.8
2.0
3.0
8
8
10
8
7
6
5
4
10
10
10
100
94.3
92.7
100
100
100
100
100
88.3
84.0
76.8
87.5
88.2
89.8
99.6
92.1
88.7
77.6
63.1
79.4
70.7
64.2
1:0.7
1:1
1:1
1:1
1:1
87.5
93.5
96.9
99.6
92.1
88.7
77.6
63.1
89.9
84.2
83.6
18.2
18.4
18.5
20.0
20.0
20.0
20.0
20.0
19.9
21.0
28.8
Cs2.5 0.5PW
H
(C
(C
(C
(C
(C
(C
(C
(C
(C
16 TA)H
16 TA)H
16TA) H
16TA) H
16TA) H
16 TA)H
16 TA)H
16 TA)H
16TA) H
2
PW
2
PW
2
PW
2
PW
2
PW
2
PW
2
PW
2
PW
2
PW
1:1
1:0.9
1:0.8
1:1
1:1
1:1

1486
M. Cheng et al. / Catalysis Communications 12 (2011) 1483–1487
From Table 1, it can be seen that the usage of sucrose influenced
the conversion and yield of monosaccharides, while the yield of
monosaccharides decreased as increasing the usage of sucrose. It can
be seen that the amount of water influenced the selectivity of
monosaccharides (Fig. S3). It is known that water is not only the
solvent, but also is a reactant. In hydrolysis reaction, a large amount of
water is favorable for the promotion of the reaction in kinetics and
equilibrium but decreases the acidic strength leading to low activity of
acid catalysts [29]. Using the same amount of sucrose and different
amount of catalyst, water content influences the conversion and the
yield. In lower usage of catalyst, decreasing the amount of water could
enhance the conversion and yield of monosaccharides. This is due to
the lower acidic sites for lower usage of catalyst, therefore, lower
amount of water provides the higher acidic strength. In higher
amount of catalyst, 8 mL of water is suitable for the hydrolysis of
sucrose into sugars with high conversion and high selectivity. At the
situation of same amount of catalyst and different usage of sucrose,
the conversion and yield increase first and then decrease, which
achieve highest at 8 mL of water.
Fig. 4. Hydrolysis of sucrose by (C16TA)H
conditions: 1.6 g of sucrose, 0.08 mmol of catalyst and 8 mL of water for 60 min.
2
PW at different temperatures. Reaction
this result, (C16TA)H
leaching amount of (C16TA)H
The regeneration of (C16TA)H
2
PW is confirmed as a heterogeneous one and the
PW is little.
PW is of practical and economic
The temperature influenced the yield of monosaccharides from
hydrolysis of sucrose (Fig. 4.). It can be seen that the reaction
temperature had a large effect on the sucrose conversion and
monosaccharides yield. When reaction temperature was 70 °C, the
conversion of sucrose was 66.1% and the yield of monosaccharide was
2
2
importance. It can be easily achieved by the centrifugation of the
white solid from the reaction system. This residue was reused without
any treatment. The regenerated reagent is as reactive as the freshly
prepared catalyst. The catalytic activity of the hydrolysis of sucrose is
maintained efficiently after six repeated experiments, showing only a
6
3.5%; and when the temperature increased to 80 °C, the sucrose
conversion reached about 100% for 60 min. So the temperature played
a positive role for sucrose conversion. Enhancement of temperature
from 70 °C to 90 °C could increase monosaccharides selectivity, while
could reach the highest 99.8% at 90 °C. However, higher temperatures
slight decrease (Fig. 5) and the total amount of (C16TA)H
through six runs of the reaction reaches 143 ppm.
2
PW leaching
The hydrolysis of starch and cellulose by this micellar HPA catalyst
(C16TA)H PW was done in order to evaluate its catalytic activity. It can
be seen that the micellar (C16TA)H PW catalyst (0.07 mmol) could
catalyze the hydrolysis of starch (0.1 g) at 120 °C for 5 h with 96.1%
(
120 °C) gave rise to byproducts leading to low monosaccharides
2
selectivity (95.2%). Therefore, 80 °C was selected as the reaction
temperature. In addition, the stirring rate also influences the activity
2
−
1
−1
(
Fig. S4). At the lower stirring rate (100 rpm), the conversion of
conversion, 82.4% yield of glucose and TOF 0.274 g mmol
h
. In
sucrose and yield were only 95.7% and 91.2%, respectively. Speeded up
the stirring rate, the conversion and yield increased, but the effect
shows no significance for 300 and 500 rpm.
Heterogeneous or homogeneous one for the micellar HPA catalyst?
Therefore, the heterogeneous nature of the catalytic reaction had been
confirmed. For this purpose, a test had been performed as following:
addition, this micellar HPA catalyst (0.07 mmol) achieved the
conversion of cellulose (0.1 g) into glucose with 44.1% conversion,
−
1
−1
89.1% selectivity of glucose and TOF 0.079 g mmol
8 h.
h
at 170 °C for
4. Conclusions
2
the (C16TA)H PW is stirred in water at 80 °C (without saccharide)
within 60 min, and then the solid is separated from the aqueous phase
by an ultrafiltration membrane. To this liquid phase, the saccharide is
added and the reaction is done for further 60 min at 80 °C. The
conversion and yield are 2.5 and 2.3%, respectively. Compared to the
results of that without any catalyst (1.1% conversion and 0.7% yield,
respectively), this conversion and yield are almost the same,
indicating there is a little catalyst residual in the liquid phase. From
The micellar acid catalyst had been synthesized by using surfactant
cetyltrimethyl ammonium bromide (CTAB) and H PW12 40 as pre-
cursors. The hydrolysis of polysaccharides such as sucrose, starch and
cellulose had been achieved by a micellar HPA catalyst (C16TA)H PW.
(C16TA)H PW exhibited remarkable catalytic performance for the
3
O
2
2
hydrolysis of polysaccharides. Moreover, this catalyst can be recycled
by centrifuge and can be reused at least six times. This heterogeneous
Fig. 3. Hydrolysis of sucrose by [(C
conditions: 0.1 g of sucrose, 0.08 mmol of catalyst and 10 mL of water for 60 min at
0 °C.
n 3 3 2
H2n + 1)N(CH ) ]H PW catalysts. Reaction
Fig. 5. The life span of catalyst for sucrose hydrolysis. Reaction conditions: 1.6 g of
sucrose, 0.08 mmol of catalyst and 8 mL of water for 60 min at 80 °C.
8

M. Cheng et al. / Catalysis Communications 12 (2011) 1483–1487
1487
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This work was supported by the National Natural Science
Foundation of China (20871026, 51078066). And it was supported
by analysis and testing foundation of Northeast Normal University
and the projects of Jilin Provincial Science and Technology Depart-
ment (201105001).
[
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