An integrated nanocatalyst combining enzymatic and metal-organic framework catalysts for cascade degradation of organophosphate nerve agents

Article abstract of DOI:10.1039/C8CC06727A

An integrated nanocatalyst (INC), denoted OPH@MIL-100(Fe), was synthesized by immobilizing a biocatalyst onto a metal-organic framework (MOF)-based catalyst, which can cascadingly degrade organophosphate nerve agents to 4-aminophenol (4-AP) and result in a sharp decrease of their toxicity up to 208-fold.

Full text of DOI:10.1039/C8CC06727A

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An integrated nanocatalyst combining enzymatic and metal-
organic frameworks catalysis for cascade degradation of
organophosphate nerve agents
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
a
a
a
a
a b
DOI: 10.1039/x0xx00000x
Haibin Li , Li Ma , Liya Zhou , Jing Gao *, Zhihong Huang ,Ying He and Yanjun Jiang
*
www.rsc.org/
1
1,12
An integrated nanocatalyst (INC), named as OPH@MIL-100(Fe), the hydrolysis of organophosphorus nerve agents.
Generally,
was synthesized via immobilizing a biocatalyst onto a metal- the hydrolytic products of paraoxon and parathion usually include
1
3-15
organic framework (MOF)-based catalyst, which can cascade 4-nitrophenol (4-NP).
However, as a highly toxic chemical, 4-NP
degrade the organophosphate nerve agents to 4-aminophenol (4- is not only one of the most refractory pollutant but also would be
AP) and result in a sharp decrease of its toxicity up to 208-fold.
highly hazardous for human body including damage to blood cells,
1
6
nervous system, kidneys and liver. Recently, many nanocatalysts
17
Owing to the synergistic effect of multiple catalysts, the cascade
reactions can perform novel syntheses or degradation sequences of
complex molecules. Over past decades, successful examples of
cascade reactions for multistep syntheses and degradation have
such as transition metal nanoparticles, porous organic polymer
1
8
and MOFs have been synthesized and the hydrogenation of 4-NP
is often used to evaluate their catalytic performance. For example,
MIL-100(Fe), an iron(III) carboxylate MOF with structure formula
1
,2
III
.
.
been substantially increased.
Especially, the example of
Fe
3 2 2 6 3 2 3 2 2
O(H O) F {C H (CO ) } nH O (n~14.5), has been demonstrated
chemoenzymatic cascade process, which combines the obvious
advantages of chem- and biocatalysis, has been gaining increasing
to be an effective and eco-friendly catalyst for hydrogenation of 4-
1
9
NP to 4-aminophenol (4-AP) in the presence of NaBH
4
. 4-AP is not
3,4
interest from investigators. Metal-organic frameworks (MOFs),
which can provide uniform and confined catalytic sites, size-, shape-
and enantio-selectivities thanks to the extremely large surface
areas, appropriate micro-porous pores and highly ordered
crystalline structures, have been recognized as ideal candidates for
only a notable chemical intermediate for synthesis of dyes, drugs,
20
and additives, but more importantly, it is nearly 1.86-fold less
toxic than 4-NP (Table S1). Therefore, developing novel
decontaminants that can degrade organophosphate nerve agents
into 4-AP will be innovative and powerful tools for the treatment of
this deadly toxin.
5,6
heterogeneous catalysis. However, the incorporation of MOFs-
based catalysts and biocatalysts is challenging but attractive for
catalytic cascade reactions.
Thus, an integrated nanocatalyst (INC) incorporating both
MOFs-based catalyst and enzyme was successfully developed by
immobilizing OPH onto MIL-100(Fe). The obtained INC was defined
as OPH@MIL-100(Fe), which can degrade organophosphate nerve
agents into 4-AP through one-pot cascade reaction that contains
both hydrolysis and hydrogenation steps (Scheme1). Especially, in
this INC, OPH can hydrolyze organophosphate nerve agents into 4-
NP and MIL-100(Fe) can hydrogenate 4-NP into 4-AP. MIL-100(Fe)
Organophosphate nerve agents, which can inhibit the activity
of acetylcholinesterase and ultimately lead to asphyxiation or even
7
death, were widely used as insecticides in the mid-20th century.
However, degradation of the organophosphate residuals become a
world-wide concerning problem and much effort has been
8
,9
proceeded to address this issue. Organophosphorus hydrolase
OPH) as biocatalyst can hydrolyze wide range of
(
a
a
organophosphate nerve agents, such as paraoxon and parathion,
and has received broad interest because of its environment-friendly
10,11
and cost-effective properties.
Previous reports have developed
various methods to improve the catalytic performance of OPH for
Scheme 1. The schematic illustration of cascade reaction on
OPH@MIL-100(Fe).
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also can act as support for OPH immobilization, which makes OPH covalently immobilized on the MIL-100(Fe) via the same process.
can be separated and reused easily. Most remarkably, an up to 208- The green fluorescence dots confirmed the successful
fold decrease in toxicity of organophosphate nerve agents was immobilization of OPH onto MIL-100(Fe). To further confirm that
observed after degradation by INC (Table S1). Firstly, MIL-100(Fe) the OPH was immobilized by covalent bond rather than physical
nanoparticles were synthesized and characterized by SEM and XRD. adsorption, the OPH@MIL-100(Fe) was washed with sodium
Fig.1a shows that the MIL-100(Fe) presents typical octahedral dodecyl sulfate, which can remove the physically adsorbed enzymes
2
9
morphology with an average size of approximately 600nm. As from the support surface. After that, the obtained OPH@MIL-
illustrated in Fig.1b, the characteristic peaks (2θ~2°, 3.6° and 10.6°) 100(Fe) was acid treated (soaked in 0.1M HCl solution for 12h) to
of the XRD pattern of the synthesized MIL-100(Fe) are matched well dissolve the support and release OPH molecules. The free OPH,
with those of simulated MIL-100(Fe), which indicate that the MIL- sodium dodecyl sulfate solution that washed the OPH@MIL-100(Fe)
2
1,22
1
00(Fe) was successfully synthesized.
The survey XPS data and acid-treated OPH@MIL-100(Fe) solution were analyzed by SDS-
(
Fig.S1a) indicate that MIL-100(Fe) contains three elements of Fe, O, PAGE. As shown in Fig.S2, protein bands corresponding to the
and C. The Fe 2p spectrum (Fig.S1b) can be deconvoluted into four molecular weight of OPH appeared on the gel for both free OPH
peaks centered at 725.8, 712.6, 717.7, and 731.6 eV, corresponding and acid treated OPH@MIL-100(Fe) samples (lane 1 and 2). In
to the peaks of Fe 2p1/2 and Fe 2p3/2 and the two satellite peaks contrast, no obvious band was observed for sodium dodecyl sulfate
of Fe 2p3/2 and Fe 2p1/2, respectively. These results indicate that solution that washed the OPH@MIL-100(Fe) (lane 3). These results
3
+
the Fe exists in MIL-100(Fe), which is consistent with previous confirmed that OPH was immobilized covalently instead of being
2
3,24
reports.
the INC can be prepared by immobilizing OPH on activated MIL-
Since the free carboxyl groups present in MIL-100(Fe), adsorbed on the surface of MIL-100(Fe).
The feasibility of OPH@MIL-100(Fe) for the cascade
00(Fe) through covalent combination. The FTIR spectra of OPH, degradation of organophosphate nerve agents was intuitively
MIL-100(Fe) and OPH@MIL-100(Fe) are shown in Fig.1c. The bands evaluated by dividing the cascade reaction into independent two
2
5
1
−1
at 1649 and 1546 cm are ascribed to amide I and II of OPH, steps. The first step of the cascade reaction was the hydrolysis of
−1
respectively, which are shifted to 1628 and 1570 cm in OPH@MIL- parathion-methyl into 4-NP and dimethyl phosphorothinate, which
2
6
−1
1
00(Fe). The bands at 1125, 1081, 1026 cm are ascribed to was demonstrated by OPH@MOF-808-loaded filter. MOF-808, a
carbohydrate moiety, which broaden the peak centered at 1033 MOF with free carboxyl group, cannot catalyze any reaction in this
−1
27
cm in OPH@MIL-100(Fe). Additionally, for MIL-100(Fe), the cascade process. Fig.S3 showed that the parathion-methyl solution
−1
peaks located at 1451, 1380 and 711 cm correspond to the became yellow after passing through the OPH@MOF-808 filter,
bending of O-H, va(C-O) and vas(Fe O). These peaks also appear in which is consistent well with the colour of 4-NP solution. The GC-
3
2
8
OPH@MIL-100(Fe). The results of FTIR confirm that OPH was MS spectrum (Fig.S4) of the yellow solution demonstrated that
immobilized on MIL-100(Fe) successfully. Subsequently, as shown in parathion-methyl has been converted to 4-NP partially. In the
Fig.1d, fluorescently labeled OPH (FITC-OPH) molecules were also second step, the MIL-100(Fe)-loaded filter was used to demonstrate
the hydrogenation of 4-NP to 4-AP. As shown in Fig.S5, the 4-NP
solution containing NaBH4 turned into colorless after passing
through the MIL-100(Fe) filter. The GC-MS spectrum (Fig.S6)
demonstrated that the colorless solution contains 4-AP and 4-NP,
suggesting the hydrogenation that catalyzed by MIL-100(Fe)
occurred. Finally, the OPH@MIL-100(Fe)-loaded filter as reactor for
degradation of parathion-methyl in the presence of NaBH (Fig.S7)
4
was also investigated. The GC-MS spectrum (Fig.S8) demonstrated
that the degradation product includes 4-AP and 4-NP. The above
results confirmed the feasibility of this cascade degradation, where
the INC can degrade organophosphate nerve agents into 4-AP.
The degradation activity of OPH@MIL-100(Fe) was
investigated using parathion-methyl as substrate. Firstly, the effect
of OPH loading amount on the degradation activity was explored.
The OPH loading was manipulated by controlling the original OPH
concentration with constant amount of MIL-100(Fe) (Fig.S9a).
Fig.S9b showed that the degradation activity of OPH@MIL-100(Fe)
Figure 1. (a) SEM image for MIL-100(Fe) with scale bar of 500 nm.
increases with the increases of OPH loading. On the basis of the
(
b) XRD patterns of simulated MIL-100(Fe) and synthesized MIL-
Fig.S9b, the OPH loading of 53 mg/gMIL-100(Fe) and immobilization
time of 4h were chosen for the subsequent experiments. Under this
condition, 88.3% of immobilization yield (calculated by Bradford
assay), 4.62 U/gMIL-100(Fe) of specific activity and 64.9% of activity
recovery for OPH were obtained (Fig.S10). Meanwhile, Fig.S11
showed that the maximum degradation activity of 1.5 μmol/min/g
was obtained with the substrate concentration of 0.75 µmol/ml
1
1
00(Fe). (c) FTIR spectra of OPH, MIL-100(Fe) and OPH@MIL-
00(Fe). (d) CLSM image of the FITC-labelled OPH@MIL-100(Fe)
with scale bar of 2.5 µm.
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o
Parathion-methyl
(
about 197 ppm), the temperature of 40 C, the pH value of 9 and
1
00
Paraoxon-methyl
Parathion-ethyl
Paraoxon-ethyl
the NaBH concentration of 30 mg/ml.
4
The degradation activity of the mixture of free OPH and MIL-
00(Fe) (defined as OPH+MIL-100(Fe)), OPH@MIL-100(Fe), and
8
0
1
mixture of OPH@MOF-808 and MIL-100(Fe) (defined as
OPH@MOF-808+MIL-100(Fe)) were compared. As shown in Fig.2,
OPH@MIL-100(Fe) showed lower degradation activity (judging from
the slope of the curve) than OPH+MIL-100(Fe). Approximately 100%
of parathion-methyl was degraded after 50min on OPH+MIL-
60
40
20
0
100(Fe), whereas only 85% of degradation was observed on
OPH@MIL-100(Fe) even after 90min. These phenomena may be
ascribed to the following reasons: (1) For the OPH@MIL-100(Fe),
the OPH molecules are densely immobilized on the surface of MOF,
which formed steric hindrance that can limit the diffusion of the
substrate and then result in the lower hydrolytic activity of the INC
1
2
3
4
5
6
7
8
9
Recycle number
Figure 3. Relative degraded activity of OPH@MIL-100(Fe) with
four substrates after multiple degradation cycles though a plug-
flow reactor.
3
+
than its free counterpart (Fig.S10). Meanwhile, Fe coordination
unsaturation sites (CUSs) of the MIL-100(Fe) acted as the Lewis acid
sites for catalytic hydrogenation reaction. The steric hindrance of
A simple plug-flow reactor was prepared to explore the
the OPH molecules can also block the contact between 4-NP and universal applicability and reusability of OPH@MIL-100(Fe)
3
+
Fe CUSs, leading to the lower hydrogenation activity of the (Fig.S12). To prepare the plug-flow reactor, OPH@MIL-100(Fe) (20
3
0,31
INC;
00(Fe) can promote proton transfer during the catalytic process commercial polymer membrane by filtration. A 2mL solution
(2) For the OPH+MIL-100(Fe), the carboxyl groups in MIL- mg) was dispersed in Tris-HCl solution and then loaded onto a
1
3
2
and improve the catalytic activity. However, for OPH@MIL- containing 1.5 μmol of substrate was injected through the reactor
at 0.4 ml/min. Fig.3 showed that the OPH@MIL-100(Fe) maintained
more than 50% of original degradation activity (defined as 100%)
after 9 cycles for four organophosphate nerve agents. Moreover,
100
taking parathion-methyl as substrate, the reasons such as the
stability of the OPH@MIL-100(Fe), the stability of OPH in
OPH@MIL-100(Fe) in the presence of 4-NP and 4-AP, and the effect
8
6
4
2
0
0
0
0
0
4
of NaBH on the hydrolytic activity of OPH and hydrogenation
activity of MIL-100(Fe) for the decrease of degradation activity
during multiple catalytic cycles were investigated. The crystalline
structure and purity of OPH@MIL-100(Fe) was determined by XRD
after catalytic cascade reactions. As can be seen in Fig.S13, the
crystalline structure of the fabricated OPH@MIL-100(Fe) has no
obvious change after 9 catalytic cycles. Only about total of 0.55 wt%
of Fe leaching (Fig.S14a) and negligible enzyme leaching (Fig.S14b)
were detected in the filtered reaction solution. The activity of OPH
maintained approximately 96% and 95% of the original activity after
incubated in the solution of 4-NP and 4-AP for 90 minutes (Fig.S15).
Fig.S16 showed that the hydrolytic activity of OPH and the
hydrogenation activity of MIL-100(Fe) were reduced to 53% and
OPH+MIL-100(Fe)
OPH@MIL-100(Fe)
OPH@MOF-808+MIL-100(Fe)
0
10 20 30 40 50 60 70 80 90
Time (min)
Figure 2. Degradation profiles of parathion-methyl that degraded
by OPH+MIL-100(Fe), OPH@MIL-100(Fe) and OPH@MOF-
8
08+MIL-100(Fe).
1
00(Fe), some of the carboxyl groups in MIL-100(Fe) are consumed
9
5% of the original activity after 9 catalytic cycles, respectively. On
to immobilize OPH, which may affect the proton transfer and
3
3
the basis of the above results, the decrease of degradation activity
reduce the activity of the MIL-100(Fe). However, although the
degradation activity of OPH@MIL-100(Fe) is slower, MIL-100(Fe) as
the OPH support allows its easy recovery and reusability, thereby
making it great potential in practical applications. Fig.2 also showed
that the degradation activity of OPH@MIL-100(Fe) exceeds that of
the OPH@MOF-808+MIL-100(Fe). The degradation was about 85%
on OPH@MIL-100(Fe) but only about 60% on OPH@MOF-808+MIL-
4
of the INC was mainly due to the effect of NaBH on the hydrolytic
activity of OPH.
On the basis of the above experiments, it is reasonable to
speculate that the degradation performance of INC can be
improved by shortening the contact time of INC with NaBH
NaBH was added after the hydrolysis step. When methyl parathion
was chosen as the substrate, it can be hydrolyzed completely to 4-
NP after 30 minutes (Fig.S17a). At this time, NaBH was added and
-NP can be completely hydrogenated to 4-AP after 15 minutes. In
4
. Thus,
4
1
00(Fe) at about 80min. This result might be ascribed to the more
4
complete and immediate utilization of the intermediate (4-NP) due
to the proximity of the catalytic sites of both catalysts in the
OPH@MIL-100(Fe). For the OPH@MOF-808+MIL-100(Fe), the
intermediate needs to transfer from the OPH@MOF-808 to MIL-
4
this case, 100% of methyl parathion can be degraded into 4-AP with
total reaction time of 45 minutes, which was higher than the
34
degradation (85% at 90min) that NaBH was added at the beginning
4
100(Fe).
of the cascade reaction. For the other three substrates, 100%
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degradation was also obtained through the same operations 15.
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1
1
1
1
6.
7.
8.
9.
catalyst and biocatalyst for cascade degradation of
organophosphate nerve agents was demonstrated in this work. The
integrated nanocatalyst of OPH@MIL-100(Fe) possess the ability to
degrade the organophosphate nerve agents into 4-aminophenol,
which is less toxicity than 4-nitrophenol. Moreover, OPH@MIL-
2
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00(Fe) can be effectively used as the catalytic element of the
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Conflicts of interest
There are no conflicts to declare.
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S
P
H CO
O
NO2
HO
NH2
3
OCH3
Parathion-methyl
4-aminophenol
An integrated nanocatalyst that combines the metal-organic framework-based catalyst
and biocatalyst was developed for cascade degradation of organophosphate nerve
agents.