Effective Cleavage of β-1,4-Glycosidic Bond by Functional Micelle with l-Histidine Residue

Article abstract of DOI:10.1007/s10562-016-1745-2

Abstract: A novel functional surfactant N^α-dodecyl-l-histidine (NDH) was synthesized and its micelle was used as mimic of β-1,4-endoglucanase to catalyzed the hydrolysis of methyl-β-d-cellobioside (MCB) under relatively low temperatures (80–110?°C). The results showed that the micelle of NDH displayed excellent catalytic activity for the cleavage of β-1,4-glycosidic bond and the formation of l-histidine-5-d-glucopyranosyl. The micelle-catalyzed first-order reaction rate constant k_m of degradation of MCB was calculated. The conversion of MCB and selectivity of reducing sugars (glucose and fructose) could reach 58.9 and 87.1?%, respectively, for a reaction time of 10?h at pH 4.0 and 110?°C. In NDH micelle-catalyzed reaction sugar ester was deduced as the chief product. The reaction pathways of MCB hydrolysis were proposed and the activation energy Ea for the hydrolysis was calculated. Graphical Abstract: [Figure not available: see fulltext.]

Full text of DOI:10.1007/s10562-016-1745-2

Catal Lett
DOI 10.1007/s10562-016-1745-2
Effective Cleavage of b-1,4-Glycosidic Bond by Functional Micelle
with L-Histidine Residue
Xiao-Hong Liao1 Ying Liu1,2 Xiao Peng1 Chun Mi1 Xiang-Guang Meng1
•
•
•
•
Received: 31 March 2016 / Accepted: 3 April 2016
Ó Springer Science+Business Media New York 2016
Abstract A novel functional surfactant Na-dodecyl-L-
histidine (NDH) was synthesized and its micelle was used
as mimic of b-1,4-endoglucanase to catalyzed the hydrol-
ysis of methyl-b-D-cellobioside (MCB) under relatively
low temperatures (80–110 °C). The results showed that the
micelle of NDH displayed excellent catalytic activity for
the cleavage of b-1,4-glycosidic bond and the formation of
L-histidine-5-D-glucopyranosyl. The micelle-catalyzed
first-order reaction rate constant km of degradation of MCB
was calculated. The conversion of MCB and selectivity of
reducing sugars (glucose and fructose) could reach 58.9
and 87.1 %, respectively, for a reaction time of 10 h at pH
4.0 and 110 °C. In NDH micelle-catalyzed reaction sugar
ester was deduced as the chief product. The reaction
pathways of MCB hydrolysis were proposed and the acti-
vation energy Ea for the hydrolysis was calculated.
Graphical Abstract
OH
O
HO
HO
HO
OH
OH
OCR
O
HO
HO
OCH3
90oC
O
,
pH4.0
O
OH
O
OH
OH
o C
25
,
H25
C12
NH
pH12.0
Glucose
+
N
Fructose
HOOC
N
H
Selectivity>97%
Keywords Kinetics Á Cellulose Á Biomass Á Catalysis Á
Hydrolysis
1 Introduction
The efficient utilization of lignocellulosic biomass is of
great practical significance to solve the problems of
resource shortage, energy depletion and environmental
pollution [1–3]. Cellulose is generally the main component
of lignocellulosic biomass [4, 5]. Glucose is an important
platform compound to produce biofuel, chemicals and
polymer materials [6–8]. At present, hydrolysis of cellulose
into glucose is still one of the bottlenecks and challenging
problems in the field of utilization of biomass [9, 10]. In
recent years, some researchers have reported the hydrolysis
of cellulose into glucose through acid catalysts [11–13],
subcritical and supercritical water [14–16] and ionic liquid
[17–19]. However the problems of low activity and/or
selectivity, severe reaction conditions and potential
Electronic supplementary material The online version of this
article (doi:10.1007/s10562-016-1745-2) contains supplementary
material, which is available to authorized users.
& Xiang-Guang Meng
mengxgchem@163.com
1
Key Laboratory of Green Chemistry and Technology,
Ministry of Education, College of Chemistry, Sichuan
University, Chengdu 610064, People’s Republic of China
2
College of Chemical Engineering, Guizhou Institute of
Technology, Guiyang 550003, People’s Republic of China
123

X.-H. Liao et al.
2.2 Synthesis of Na-dodecyl-L-Histidine (NDH)
environmental pollution have not been resolved [20, 21].
Cellulase-catalyzed way shows fast reaction rate and high
selectivity of glucose for the hydrolysis of cellulose under
mild conditions. However, the high cost and instability of
the enzyme restrict its further application [22]. There are
three kinds of cellulase for hydrolysis of cellulose by
synergistic action: endo-b-1,4-glucanase; exo-b-1,4-glu-
canase; b-glucosidases [23].
Endo-b-1,4-glucanase hydrolyzes internal glycosidic
bonds in cellulose with a random, on–off fashion [24, 25].
And the catalytic mechanism of endo-b-1,4-glucanase was
believed to consist of two reaction steps involving glyco-
sylation and deglycosylation steps [26, 27].
NDH surfactant was synthesized by a modification of
published procedures as described in Scheme 1 [32]: lau-
raldehyde (3.11 ml, 14 mmol) was dissolved in hot abso-
lute ethanol (30 ml), then it was added into 30 ml absolute
methanol solution of L-histidine (1.5516 g, 10 mmol) with
NaOH powder (0.52 g, 13 mmol). The mixture was heated
to 45 °C and stirred for 10 h, then the solution was cooled
with an ice bath and NaBH4 (0.49 g, 13.0 mmol) was
added in small portions. The mixture was stirred about 12 h
at 0 °C. The solvent was evaporated, the resulting solid
was dissolved in ethyl acetate and washed by the saturated
sodium chloride solution to remove the remainder histi-
dine. The organic solvent was evaporated and the write
solid was dissolved in acetone. Then it was acidified with
37 % HCl up to the isoelectric point of histidine to obtain
the desired product as white powder (1.45 g, 45 %). IR
(KBr, cm-1) 3670–2000, 1578, 1457, 1398, 1138, 1111,
984, 940, 841, 811, 752, 667, 628, 553. MS (ESI, H2O/
CH3OH): m/z: calc.: 323.47 [M?H]?; Found: 324.26.
Elemental analysis calc. for C18H33N3O2: C, 66.83; H,
10.28; N, 12.99 %. Found: C, 66.80; H, 10.26; N, 13.02 %.
1HNMR (300 MHz, D2O–NaOH, dppm): 0.64 (t, J = 7.5,
3H, CH3), 1.10–1.50 (m, 20H, 10CH2), 2.11–2.36 (m, 2H,
NCH2), 2.63 (d, J = 6.6, 2H, *CHCH2), 3.11 (t, J = 6.6,
1H, *CH), 6.65 (s, 1H, Im-5H), 7.40 (s, 1H, Im-2H).
Functional micelle, a new kind of self-assembly
supramolecular system, which possesses hydrophilic and
hydrophobic chemical functional groups and could simulate
the active center and the hydrophobic microenvironment of
enzyme, attracts many attentions of chemists and biologists
[28–30]. In this work, a novel functional surfactant with L-
histidine (His) residue was synthesized and its micelle was
used as mimic of endo-b-1,4-glucanase to catalyzed the
hydrolysis of methyl-b-D-cellobioside, which is regarded as a
good structural unit model of cellulose, in weakly acidic
aqueous solution at relatively low temperatures (80–110 °C).
This micelle displayed excellent catalytic activity and selec-
tivity of reducing sugar for MCB hydrolysis.
2 Experimental Section
2.3 Methods
2.1 Materials and Instruments
The hydrolysis of MCB was carried out for two reaction
steps. Typically, the first step, the reaction solution of pH
4.0, containing 2.0 9 10-3 mol L-1 MCB and
2.0 9 10-4 mol L-1 catalyst, was heated and kept at
desired temperature; the second step, the reaction solution
was adjusted to pH 12 and kept at 25 °C for 10 h. Before
heating, N2 gas was passed into the solution for 30 min
for the cases of reaction at temperature below 100 °C. For
the cases of reaction above 100 °C the N2 was passed into
reaction solution until the reaction was completed. The
sample was extracted from the reactor periodically, the
concentrations of MCB and products were determined by
HPLC with external standard method. The pH of solution
was adjusted by H2SO4 or NaOH. On a carbon basis, the
conversion of MCB X was calculated as X = (C0-Ct)/
C0), yield of reducing sugar Y was calculated as Y = Ct0/
C0 and the selectivity of reducing sugar S was calculated
as S = Y/X. Where C0, Ct are the concentrations of MCB
at reaction time t = 0 and t = t, respectively. Ct0 is the
total concentration of reducing sugars (glucose, fructose)
at time t.
b-D-(?)-Cellobiose purchased from J&K Corp company.
methanol, ethanol, sodium chloride, concentrated sulfuric
acid, sodium hydroxide, potassium sodium tartrate, sodium
borohydride, ethyl acetate, sodium sulfate, acetone, L-his-
tidine, dodecyl sulfate, hexadecyl trimethyl ammonium
bromide, Polyoxyethylene (23) lauryl ether, all of the
reagents were analytical grade and purchased from Kelong
reagent company and used after certain purification. MCB
was prepared according to previously reported procedures
[31], the characterization data was provided in Supporting
Information (SI).
NMR (AM-400, Bruker, Switzerland). Pulsed ampero-
metric detection and mass spectrometry (PAD-MS)
(LCMS-IT-TOF, Shimadzu, Japan). Elemental analyses
were implemented with an elemental analyzer (MOD 1106,
Carlo Erba company, Italy). Conductivity meter (Ban-
te950-DH, Shanghai HeChen Company, China). High
Performance Liquid Chromatography (HPLC) (LC-10T,
Shodex, Japan) with a RI detector (RI-201R, Shodex,
Japan) and a sugar-D chromatographic column.
123

Effective Cleavage of b-1,4-Glycosidic Bond by Functional Micelle with L-Histidine Residue
Scheme 1 Synthesis of Na-
dodecyl-L-histidine
O
O
O
N
N
N
C11H23CHO
CH3OH
OH
OH
NaBH4
OH
NH2
N
HN
HN
HN
CH2C11H23
HN
CHC11H23
3.2 Comparison of Catalytic Activity
3 Results and Discussion
MCB is stable and difficult to hydrolyze at pH 3–11 and
90 °C in aqueous solution. It was observed that MCB could
be efficiently degraded only under strong acidic conditions
in aqueous solution (Fig. S1 in the SI). However histidine
and NDH micelle systems can catalyze the hydrolysis of
MCB. The conversion of MCB and yield of reducing sugar
for the MCB hydrolysis catalyzed by different systems at
pH 4.0, 90 °C and reaction for 10 h were listed in Table 1.
From Table 1 we can see that in the absence of catalyst
MCB could degrade only 0.37 % and the yield of reducing
sugar was just 0.36 % under this work’ conditions, the
NDH micelle showed excellent catalytic activity even at
relatively low concentration. In previous reports it was
found that the hydrophobic microenvironment of micelle
played an important role in activating substrates, as well as
changing the catalytic activity of catalysts [37, 38]. From
Table 1 we found that the conventional micelles SDS,
CTAB and Brij35 indeed promoted the catalytic activity of
histidine. However the activity was obviously less than that
of NDH micelle. In latest study, we found metallomicelle
La(DMBO)2 with N–OH functional group displayed
excellent catalytic activity for conversion of cellobiose and
the selectivity of monosaccharides (glucose, fructose and
1,6-anhydroglucose) reached 71 % in weakly alkaline
aqueous solutions [39]. From Table 1 we can see that for
NDH micelle catalyzed system, through two step processes
the final hydrolysis products were glucose and fructose and
the selectivity of monosaccharide reached 96.8 %. This is
an ideal selectivity, which is even better than those caused
by natural enzymes [40, 41].
3.1 Critical Micelle Concentration of Surfactant
Surfactant molecules can aggregate to form micelles above
the critical micelle concentration (cmc). The characteristics
and the self-assembly supramolecular structure of micelle
are far different from its monomer [33, 34]. In this work,
the cmc of surfactant NDH was measured with the elec-
trical conductivity method. From the plots of electric
conductivity versus concentrations of NDH (Fig. 1), it can
be seen that although the electric conductivity increased
with increasing temperature at the same concentration, the
shape of plots of j versus c were similar at three temper-
atures. The values of cmc1 were evaluated as 8.6 9 10-6
,
9.4 9 10-6 and 1.0 9 10-5 mol L-1, respectively. And the
values of cmc2 were evaluated as 9.8 9 10-5, 9.9 9 10-5
and 1.1 9 10-4 mol L-1, respectively. It was possible that
the aggregate state of NDH micelle changed with
increasing concentration, and this resulted in two cmc. The
phenomenon of several aggregate states appeared in
aqueous solution were also reported by many researchers
[35]. The increased effect of temperature on cmc may
contribute to the destruction of the water structure sur-
rounding the hydrophobic groups [36].
55
50
45
40
35
30
3.3 Micelle-Catalyzed Kinetics for the Hydrolysis
of MCB
cmc2
25
20
15
10
5
In aqueous solution, micelle forms a pseudophase. Reac-
tion can occur simultaneously in the micellar pseudophase
and aqueous solution phase. The reaction kinetics of
micelle catalysis was generally dealt with phase separation
model [42], as described in Scheme 2. In micellar pseu-
dophase, micelle M associates firstly substrate S to form an
micelle-substrate complex MS with association constant
Ks, then MS reacts to product P with rate constant km and
releases simultaneously M. In aqueous solution phase,
substrate S spontaneously reacts with rate constant kw. The
cmc1
0
0
5
10
15
20
25
30
105cL / (mol·L )
-1
Fig. 1 Plots of electrical conductivity versus concentration of Na-
Dodecyl-L-histidine (NDH) at pH 4.0 and temperature 25 °C
(square), 50 °C (circle), 90 °C (triangle)
123

X.-H. Liao et al.
Table 1 Comparison of
catalytic activity for various
systems
Systems
Conversion of
MCB/ %
Yield of reducing sugar
Selectivity of
reducing sugar/%
Glucose/%
Fructose/%
Bulk solution
His
0.37
4.60
15.4
9.4
0.36
3.40
11.2
6.59
5.44
4.53
–
97.3
97.8
96.8
96.2
96.7
96.5
1.10
3.70
2.45
2.10
1.84
NDH
SDS-His
CTAB-His
Brij35-His
7.80
6.60
[MCB]0 = 2.0 9 10-3 mol L-1
,
[NDH] = 2.0 9 10-4 mol L-1
,
[His] = 2.0 9 10-4 mol L-1
,
[SDS] = 1.0 9 10-2 mol L-1, [CTAB] = 5.0 9 10-3 mol L-1, [Brij35] = 1.0 9 10-3 mol L-1, pH 4.0,
90 °C, 10 h
SDS-His, CTAB-His and Brij35-His are mixture systems of histidine with micelles SDS, CTAB and Brij35,
respectively
first-order rate constants kobsd increased with increasing
ks
km
MS
P
+
S
S
P M
M
+
concentration of surfactant. According to Eq. (1) the values
of km and N/ks can be calculated from slope and intercept of
the plot of 1/(kobsd-kw) versus 1/(cD-cmc), as shown in
Fig. 3. The km and N/ks was evaluated as 6.13 9 10-6 s-1
and 2.21 9 10-5 mol L-1, respectively. The linear corre-
lation coefficient was above 0.98. The values of km/
kw = 4.23 9 105 was very large, which indicated that
NDH micelle displayed excellent catalytic activity for the
MCB degradation.
kw
Scheme 2 Kinetic model of micelle catalysis
first-order rate constant km in micellar phase can be cal-
culated from Menger–Portnoy Eq. (1) [43, 44].
1
1
1
N
1
¼
þ
ð1Þ
kobsd À kw km À kw km À kw Ks cD À cmc
3.4 Effect of pH
Equation (1) is the kinetic treatment model of micelle
catalysis, where the kobsd is the apparent first-order rate
constants, cD is the total surfactant concentration, N is the
micelle aggregation number, cmc is the critical micelle
concentration. In this work the value of cmc is 8.79 9 10-6
mol L-1. From the Fig. 2 we can seen that the apparent
From Fig. 4 it can be seen that for the micelle catalyzed
system, pH has great influence on the yield of reducing sugar.
Initially the yield of monosaccharide increased with
increasing pH and reached a maximum at pH 4.0. The
reduced sugar was detected as monosaccharides glucose and
fructose. The effect of pH is related to the pKa of two
4.0
3.5
3.0
2.5
2.0
1.5
1.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
0
5
10
105cL / (mol·L )
15
20
-1
0
1
2
3
4
5
-1
10-4
( )
cD-cmc)-1/ (L·mol
Fig. 2 Plot of the apparent first-order rate constants (kobsd) versus
concentration of surfactant NDH. [MCB]0 = 2.0 9 10-3 molÁL-1
pH 4.0, 90 °C
,
Fig. 3 Plot of 1/(kobsd-kw) versus 1/(cD-cmc)
123

Effective Cleavage of b-1,4-Glycosidic Bond by Functional Micelle with L-Histidine Residue
15
the ester is hydrolyzed, is similar to that of natural b-1,4-
endoglucanase [46]. It is noted that although NDH micelle
showed excellent catalytic activity for the cleavage of
glucosidic bond and the formation of sugar ester, it showed
very low activity for the hydrolysis of sugar ester under the
condition of pH 4.0. This conclusion can be further reached
by the quantitative analysis of concentration changes of
MCB, sugar ester and glucose during reaction process.
Figure 6 showed the HPLC profiles of reaction solution
after the first and second step reaction, respectively. From
Fig. 6 it can be seen that after hydrolysis at pH 12 and
25 °C for 10 h, the concentrations of MCB and methyl-
glucoside were almost unchanged, however the total con-
centration of monosaccharides (glucose and fructose)
obviously increased from 2.6 9 10-5 to 9.0 9 10-5
mol L-1, which was attributed to the hydrolysis of sugar
ester. The generation of fructose was owing to the iso-
merization of glucose under alkaline condition.
14
13
12
11
2
4
6
8
10
12
pH
Fig. 4 Effects of pH on yield of reducing sugar catalyzed by NDH
micelle. [MCB]0 = 2.0 9 10-3 mol L-1
,
[NDH] = 2.0 9 10-4
mol L-1, 90 °C, 10 h
3.6 Reaction Kinetics and Activation Energy
functional groups of NDH. The values of pKa1(–COOH) and
pKa2(–Imidazole) of histidine are 1.82 and 6.86, respec- Cellulose is difficult to hydrolyze because of the high
tively. Under the condition of pH 4.0, the imidazole group of
histidine exists in its protonated form, the carboxylic acid
group of histidine in its anionic form. It is considered that the
imidazole served as an acid to protonate glycosidic oxygen
reaction activation energy of b-1,4-linkages, it was repor-
ted that the rate constant k values was on the order of
10-15 s-1 at room temperature [47]. In order to accelerate
the reaction, many researches were carried out at relative
and the carboxylic anion acts as a nucleophile to attack the C1 high temperature ([200 °C) [12, 13, 18]. However the
atom. Thus this catalytic mechanism is very similar to that of defects of low selectivity and generation of lots of side-
endo-b-1,4-glucanase [45].
products obviously appeared under the elevated tempera-
ture condition. In this work we found that the reaction rate
might be accelerated by increasing reaction temperature.
And the selectivity of monosaccharide was good enough
([87 %) at the relative low temperature of less than
3.5 The Reaction Intermediate and Reaction
Pathway
In this work, the hydrolysis of MCB underwent two pro- 110 °C. The effects of temperature on conversion of MCB
cesses: the first step was the reaction of MCB with NDH
and yield of reducing sugar were described in Figs. S2 and
molecule in micellar solution at pH 4.0 and 80–110 °C; then 7, respectively. From Fig. S2 it can be observed that the
the reaction intermediate was hydrolyzed at pH 12.0 and conversion of MCB increased with increasing reaction
25 °C. In order to understand the reaction pathway, we temperature as well as reaction time. However the variation
investigated the reaction product for the first step. Owing to
of yield of reducing sugar with reaction time was complex.
the difficulty of detecting large molecule NDH and its Below 100 °C, the yield of reducing sugar increased with
derivative, a small molecule histidine was used as a substi- reaction time. Above 100 °C, initially the yield of
tute to react with MCB. After reacting 10 h at pH 4.0 and
monosaccharide increased with reaction time and reached a
90 °C, the reaction solution was checked by PAD-MS maximum for reaction about 10 h. At higher temperature
analysis. From the PAD-MS (E?) spectrum, it can be seen
products glucose and fructose would continue to degrade
that a sugar ester intermediate L-histidine-5-D-glucopyra-
and thus led to the decrease of selectivity of monosac-
nosyl ester (HDGE) which mass spectrometry peaks at 217.0 charide. In kinetics, the consecutive reaction of monosac-
obviously appeared, as shown in Fig. 5. Therefore, it can be charide would result in the appear of maximal point of
deduced that in the NDH micelle catalyzed process a sub-
yield of monosaccharide with time. The yield of reducing
stitution reaction occurred through the attack of COO- to C1 sugar were 9.7, 14.9, 27.7, 42.1, 51.3 % for a reaction time
atom and resulted in the generation of sugar ester.
of 10 h at pH 4.0 at temperature of 80, 90, 100, 105 and
110 °C, respectively.
Kinetic reaction of hydrolysis of cellulose was generally
The sugar ester HDGE can be easily hydrolyzed in
alkalic solution at room temperature. The catalytic mech-
anism, which first form sugar ester intermediate and then described as pseudo-first-order reactions [48, 49]. From the
123

X.-H. Liao et al.
Fig. 5 PAD-MS (E?) spectrum
of reaction solution of MCB
degradation catalyzed by
histidine.
6
5
4
3
2
1
0
156.0751
[MCB]0 = 2.0 9 10-3
379.1237
OH
NH2
mol L-1, [His] = 2.0 9 10-3
mol L-1, pH 4.0, 90 °C, 10 h
NH
O
HO
O
HO
N
315.9571
300
OH
O
180.0600
395.0408
217.0707
150
200
250
350
400
450
m/z
different temperature were all good linear lines. The acti-
vation energy Ea and pre-exponential factor A for MCB
conversion and generation of reducing sugar were evalu-
ated from the Arrhenius plots of lnkobsd versus 1/T, which
were obtained easily through slope and intercept of liner
respectively. As shown in Fig. 8, the correlation coefficient
of linear were above 0.99. The activation energy Ea1 and
pre-exponential factors A1 of MCB conversion were eval-
uated as 102.6 kJ mol-1 and 2.4 9 109 s-1, respectively.
The activation energy Ea2 and pre-exponential factors A2
of generation of reducing sugar catalyzed by NDH micelle
system were evaluated as 93.8 kJ mol-1 and 1.5 9 108 s-1
respectively. The activation energy Ea1 is somewhat larger
than Ea2 implied that there might be an undetectable par-
allel reaction occurred during the process of degradation of
MCB. It has been reported that the activation energies of
cellulose hydrolysis was in the range of 110–260 kJ mol-1
[50–52], and the activation energy of generation of
reducing sugar was in the range of 130–180 kJ mol-1 [53,
54]. In this work, the activation energy of MCB conversion
is relatively small, which indicated that the NDH micelle
system displayed excellent catalytic activity for the
breakage of b-1,4-glycosidic bond under mild conditions.
Fig. 6 HPLC profiles of reaction solution. [MCB]0 = 2.0 9 10-3
mol L-1 [His] = 2.0 9 10-3 mol L-1
The first step reaction
catalyzed by NDH micelle at pH 4.0, 90 °C, 10 h (black line); the
second step reaction under alkalic condition at 25 °C, 10 h (red line)
,
.
60
50
40
30
20
10
0
-10.5
-11.0
-11.5
-12.0
-12.5
-13.0
-13.5
0
10
20
30
-1
t
/h
Fig. 7 Plots of yield of reducing sugar versus reaction time t for
NDH micelle catalyzed system at pH 4.0 and temperatures 80 °C
(square), 90 °C (circle), 100 °C (up-pointing triangle), 105 °C
(down-pointing triangle), 110 °C (left-pointing triangle)
2.60
2.65
2.70
2.75
2.80
2.85
-1
103T-1 /K
Figs. S3 and S4, we can seen that the plots of -ln(1-ct/c0)
versus reaction time for the MCB conversion and genera-
tion of reducing sugar catalyzed by NDH micelle system at
Fig. 8 Plots of lnkobsd versus 1/T for MCB conversion (circle) and
generation of reducing sugar (square) catalyzed by NDH micelle
123

Effective Cleavage of b-1,4-Glycosidic Bond by Functional Micelle with L-Histidine Residue
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A novel functional surfactant NDH was synthesized and its
micelle was used to catalyzed the cleavage of b-1,4-gly-
cosidic bonds of MCB under mild conditions. The results
indicated that the micelle displayed excellent catalytic
activity for the conversion of MCB in weakly acidic
aqueous solution at relative low temperature (80–110 °C).
Interestingly, this catalysis system display outstanding
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in alkalic solution at ambient temperature. The reaction
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