Effective, Facile, and Selective Hydrolysis of the Chemical Warfare Agent VX Using Zr6-Based Metal-Organic Frameworks

Article abstract of DOI:10.1021/acs.inorgchem.5b01813

The nerve agent VX is among the most toxic chemicals known to mankind, and robust solutions are needed to rapidly and selectively deactivate it. Herein, we demonstrate that three Zr₆-based metal-organic frameworks (MOFs), namely, UiO-67, UiO-67-NH₂, and UiO-67-N(Me)₂, are selective and highly active catalysts for the hydrolysis of VX. Utilizing UiO-67, UiO-67-NH₂, and UiO-67-N(Me)₂ in a pH 10 buffered solution of N-ethylmorpholine, selective hydrolysis of the P-S bond in VX was observed. In addition, UiO-67-N(Me)₂ was found to catalyze VX hydrolysis with an initial half-life of 1.8 min. This half-life is nearly 3 orders of magnitude shorter than that of the only other MOF tested to date for hydrolysis of VX and rivals the activity of the best nonenzymatic materials. Hydrolysis utilizing Zr-based MOFs is also selective and facile in the absence of pH 10 buffer (just water) and for the destruction of the toxic byproduct EA-2192.

Full text of DOI:10.1021/acs.inorgchem.5b01813

Article
pubs.acs.org/IC
Effective, Facile, and Selective Hydrolysis of the Chemical Warfare
Agent VX Using Zr ‑Based Metal−Organic Frameworks
6
†
‡
§
‡
‡,∥
Su-Young Moon, George W. Wagner, Joseph E. Mondloch, Gregory W. Peterson, Jared B. DeCoste,
†
,†,⊥
Joseph T. Hupp, and Omar K. Farha*
†
Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States
‡
Edgewood Chemical Biological Center, U.S. Army Research, Development, and Engineering Command, 5183 Blackhawk Road,
Aberdeen Proving Ground, Maryland 21010, United States
§
Department of Chemistry, University of WisconsinStevens Point, 2001 Fourth Avenue, Stevens Point, Wisconsin 54482, United
States
∥
Leidos, Inc., P.O. Box 68, Gunpower, Maryland 21010, United States
⊥
Department of Chemistry, Faculty of Science, King Abdulaziz University, Jeddah, Saudi Arabia
S Supporting Information
*
ABSTRACT: The nerve agent VX is among the most toxic chemicals known
to mankind, and robust solutions are needed to rapidly and selectively
deactivate it. Herein, we demonstrate that three Zr -based metal−organic
6
frameworks (MOFs), namely, UiO-67, UiO-67-NH , and UiO-67-N(Me) , are
2
2
selective and highly active catalysts for the hydrolysis of VX. Utilizing UiO-67,
UiO-67-NH , and UiO-67-N(Me) in a pH 10 buffered solution of N-
2
2
ethylmorpholine, selective hydrolysis of the P−S bond in VX was observed. In
addition, UiO-67-N(Me) was found to catalyze VX hydrolysis with an initial
2
half-life of 1.8 min. This half-life is nearly 3 orders of magnitude shorter than
that of the only other MOF tested to date for hydrolysis of VX and rivals the
activity of the best nonenzymatic materials. Hydrolysis utilizing Zr-based
MOFs is also selective and facile in the absence of pH 10 buffer (just water)
and for the destruction of the toxic byproduct EA-2192.
INTRODUCTION
capture and destruction of chemical warfare agents in
applications that demand robust solutions.
In this regard, we have recently focused on the destruction of
CWAs (and their simulants, vide infra) utilizing a class of
■
(
17−19
Because of the extreme toxicity of chemical warfare agents
CWAs) containing phosphonate linkages, such as Sarin (GB),
Soman (GD), and VX (Figure 1), their detoxification has been
1
,2
MOFs built from Zr -based nodes and multitopic organic
6
extensively explored. Destruction and decontamination of
CWAs have received renewed attention given the recent
conflict and subsequent disarmament of Syria’s chemical
20−23
linkers.
Our studies have been driven by the casual link
between the structure of the PTE enzyme active site and the
20,22
3
,4
structure of the Zr -based nodes.
Both contain a bimetallic,
6
weapons program. CWAs containing phosphonothioate and
related units (see Figure 1c) are particularly insidious; they
effectively inhibit the enzyme acetylcholine esterase, shutting
down pulmonary muscle control and causing death by oxygen
Lewis acidic moiety linked by a bridging hydroxide that
facilitates substrate binding and subsequent phosphorus−
24,25
oxygen bond hydrolysis.
In addition, Zr -based MOFs
6
5
−8
have been found to be remarkably robust, showing excellent
deprivation within minutes.
While enzymes such as
26−32
thermal, mechanical, and chemical stability.
phosphotriesterase (PTE) are extremely effective at hydrolyzing
9
−12
Our initial work was focused on identifying Zr -based MOFs
6
these agents,
enzymes often lack the robustness necessary
capable of rapidly hydrolyzing CWA simulants, such as
dimethyl 4-nitrophenyl phosphonate [DMNP (Figure 1a)]
for many practical and nonbiological applications. Therefore,
new materials are needed for chemical filtration and
detoxification as well as bulk destruction of these agents.
20,21
10,13
that can be safely handled in academic laboratories.
A
handful of Zr -based MOFs were found to effectively hydrolyze
Metal−organic frameworks (MOFs) are a rapidly growing
6
23
DMNP, some of them with half-lives of <1 min. More
class of permanently porous and crystalline solid-state
1
4−16
recently, we demonstrated that one of these Zr -based MOFs,
materials.
MOFs have great potential as adsorbents and
6
NU-1000, is also capable of cataltyically degrading the G-agent
catalysts given a high concentration of well-dispersed metal-
based nodes, their periodic structures, and their exceptionally
large surface areas, permanent porosity, and tunable chemical
pores. Given these attributes, MOFs are uniquely suited for the
Received: August 18, 2015
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.5b01813
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
Figure 2. (a) Crystalline topology of UiO-67 (Zr, green; O, red; C,
gray; H, white) and (b) chemical structures of ligands for UiO-67 and
its derivatives used in this study.
21
UiO-66. Herein we report that UiO-67, UiO-67-NH , and
2
UiO-67-N(Me) are selective and highly active catalysts for the
destruction of the CWA VX. The selectivity and activity are
present not only in a buffered solution but also in pure water.
2
Figure 1. Stoichiometric hydrolysis reactions of representative
phosphonate-based simulants and nerve agents: (a) dimethyl 4-
nitrophenyl phosphonate (DMNP, simulant), (b) O-pinacolyl
methylphosphonofluoridate (GD, G-agent), and (c) O-ethyl S-[2-
These Zr -based MOFs are also active for the hydrolysis of the
6
highly toxic byproduct, EA-2192.
(
diisopropylamino)ethyl] methylphosphonothioate (VX, V-agent).
EXPERIMENTAL SECTION
Synthesis of the Zr-MOF Catalyst. All reagents were purchased
from commercial sources and used without further purification. UiO-
■
6
O-pinacolyl methylphosphonofluoridate [GD (Figure 1b)] with
remarkable speed and efficacy (Figure 1b). In addition, density
functional theory (DFT) calculations indicated that the Zr6
clusters of NU-1000 were also favored to selectively hydrolyze
O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphono-
thioate [VX (Figure 1c)] to the nontoxic products EMPA
7, UiO-67-NH , and UiO-67-N(Me) were synthesized according to
2 2
39
literature procedures. An 8-dram vial was loaded with ZrCl (67 mg,
4
0
.29 mmol), DMF (5 mL), and concentrated HCl (0.5 mL) before
being sonicated for 20 min until the solids were fully dissolved. The
ligand (107 mg, 0.38 mmol) and DMF (10 mL) were then added, and
the mixture was sonicated for an additional 20 min before being heated
at 80 °C overnight. The resulting solid was washed first with DMF (2
(
(
ethyl methylphosphonic acid) and DESH [2-
diisopropylamino)ethanethiol] by cleavage of the P−S bond.
The hydrolysis of VX under mild conditions is particularly
22
×
30 mL) and then with EtOH (2 × 30 mL). UiO-67, UiO-67-
challenging. This is in large part a selectivity issue; the P−O,
10
N(Me) , and UiO-67-NH were desolvated and activated by
2
2
P−S, and C−O bonds can all be hydrolyzed, which is due to
4
0−42
supercritical CO2.
the number of potential modes of binding of VX to the catalyst
Monitoring the Hydrolysis of VX in Buffer or Water. To a 5
mm NMR tube was added 2.5 mg (1.1 μmol of Zr -based nodes)
catalyst [formula weights, UiO-67, 2120.8; UiO-67-NH , 2210.8; UiO-
3
3
active site. Exacerbating this problem, hydrolysis of the P−O
6
bond produces the toxic byproduct EA-2192 [S-2-
2
(
diisopropylamino)ethyl O-hydrogen methylphosphono-
6
7-N(Me) , 2373.2] followed by 47 μL of N-ethylmorpholine and 0.7
2
thioate]. Instead, hydrolysis of the P−S bond is desired as
the resultant products, EMPA and DESH, are much less toxic.
While many materials have been examined for the degradation
mL of water [0.5 M N-ethylmorpholine (pH 10)] for buffered
experiments. For nonbuffered experiments, 0.75 mL of water was used
(
no N-ethylmorpholine); 3.9 μL (14.7 μmol) of VX was then added
1
,2
and the tube capped, and the tube was vigorously shaken before being
placed in the NMR magnet for monitoring by 31P NMR. Initial
reaction half-lives (t1/2) were extracted by plotting the natural log of
the concentration versus time; for a pseudo-first-order process, the
slope (m = −k) is related to the half-life by the equation t = ln 2/k.
of VX, some of the most facile and selective materials
developed to date include metal oxides and hydroxides [e.g.,
3
4
TiO2 and Zr(OH) ] as well as fluoride ion-exchange
resins.
4
3
5,36
Unfortunately, these materials are often tested
1
/2
stoichiometrically (or substoichiometrically) and/or have
inhibitively slow degradation kinetics that have limited their
Monitoring the Hydrolysis of the VX/EA-2192 Mixture in
Buffer or Water. VX (3.9 μL, 14.7 μmol) was added to a 5 mm NMR
tube followed by 47 μL of N-ethylmorpholine and 0.7 mL of water
[0.5 M N-ethylmorpholine (pH 10)] for buffered experiments. After 6
days, 2.5 mg (1.1 μmol) of catalyst was added to a NMR tube and
vigorously shaken before the tube was placed in the NMR magnet for
monitoring by 31P NMR. For nonbuffered experiments, 0.75 mL of
water was used (no N-ethylmorpholine). After 7 days, 2.5 mg of
catalyst was added to a NMR tube and vigorously shaken before the
37
real-world implementation. Thus, there is still a compelling
need to develop new materials, particularly catalysts, that can
selectively and rapidly hydrolyze VX (and other CWAs) under
1
0
mild conditions.
We sought to determine if a series of Zr -based MOFs,
6
namely, UiO-67, UiO-67-NH , and UiO-67-N(Me) (Figure
2
2
2
), are capable of selectively and actively hydrolyzing VX.
31
tube was placed in the NMR magnet for monitoring by P NMR.
Earlier DFT calculations based on Zr6 node-bound VX
Initial reaction half-lives (t1/2) were extracted by plotting the natural
log of the concentration versus time; for a pseudo-first-order process,
the slope (m = −k) is related to the half-life by the equation t1/2 = ln
indicated a significant thermodynamic preference for hydro-
−1
lyzing the P−S bond (−123 kJ mol ) of VX versus the P−O
−
1
2
/k.
bond (−79 kJ mol ). Our selection of Zr -based MOFs was
6
further motivated by their high activity toward the DMNP
but also based on the ease of synthesis as well as
their known stability in H O. We speculated that the biphenyl
2
0,21,38
RESULTS AND DISCUSSION
The hydrolysis of VX was conducted under conditions similar
to those previously reported for the DMNP simulant as well as
simulant
■
39
2
dicarboxylate (BPDC) linker in UiO-67 prevents steric
20,22
crowding about the Zr -based node and facilitates hydrolysis
GD (see the Experimental Section for additional details).
6
in comparison to Zr -based MOFs with shorter linkers such as
The reactions were conducted in the presence of N-
6
B
DOI: 10.1021/acs.inorgchem.5b01813
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
ethylmorpholine to buffer the reaction solution at pH 10. The
hydrolysis of VX was monitored by P NMR spectroscopy, an
example of which is shown in Figure 3a (see Figure S2 of the
Next, we sought to see if the UiO-67 derivatives could
hydrolyze VX in the absence of buffer. [It is known that VX
slowly hydrolyzes in the absence of buffer; however, the rate is
3
1
extremely slow. The t
solution, and the reaction is not selective, forming a mixture
of EMPA and EA-2192 (Figure S5 and S15).] Building off our
is 4.8 days in a dilute aqueous
1/2
49
8
VX results in buffered pH 10 solution, we placed UiO-67-
N(Me) in water (no buffer, pH 4.5) and added VX (see the
2
Experimental Section for details). Again, monitoring the
reaction via 31P NMR spectroscopy revealed that UiO-67-
N(Me) was quantitatively selective for P−S bond cleavage
2
(
Figure 4a and Figure S7), while no evidence of the presence of
Figure 3. (a) 31P NMR spectra indicating the progress of selective
hydrolysis of 14.7 μmol of VX (62.5 ppm) to the nontoxic EMP (27.5
ppm) in the presence of 1.1 μmol of UiO-67-NMe in a buffer solution
2
and a 0.5 M 4-ethylmorpholine solution (pH 10) at room temperature.
31
(
b) Hydrolysis profile, calculated by comparing the integrated
P
peaks, of VX to EMP in the presence of UiO-67-NMe in a buffer
2
solution based on 31P NMR spectra.
Supporting Information for additional 31P NMR spectra with
Figure 4. 31P NMR spectra in the absence of buffer indicating (a) the
progress of hydrolysis of 14.7 μmol of VX (62.5 ppm) to EMPA (27.5
31
UiO-67 and UiO-67-NH as the catalyst). Importantly, the
P
2
NMR spectra reveal that UiO-67, UiO-67-NH , and UiO-67-
2
ppm) with 1.1 μmol of UiO-67-NMe at room temperature and (b)
2
N(Me) all selectively hydrolyze the P−S bond in VX (δ 62.5)
the percent conversion of VX to EMPA in the presence of UiO-67-
2
to the nontoxic ethyl methylphosphonate (EMP) anion (δ
NMe in water.
2
2
7.5) and DESH. Notably, the toxic byproduct EA-2192
cleavage at the P−O bond, δ 43.1) was not observed. These
results are consistent with the DFT-derived estimates of bond-
(
EA-2192 could be detected (Figure S3). The initial t1/2 was
again extracted and found to be about 7 min in the absence of
added buffer (Figure 5), while the background reaction was
negligible over the same period (Figures S11 and S15).
22
specific hydrolysis energies mentioned above.
The percent conversion, calculated by comparing the
integrated 31P peaks for VX (δ 62.5) to that of EMP (δ
2
7.5), for UiO-67-N(Me) , is shown in Figure 3b. Conversion
2
of VX to EMP is complete within 15 min [for UiO-67-N(Me)2]
to approximately 50 min (for UiO-67 and UiO-67-NH )
2
43
(
Figure S6). The initial t1/2 values are 1.8 min [UiO-67-
N(Me) ], 6.0 min (UiO-67-NH ), and 7.9 min (UiO-67)
2
2
(
Figures S8−S10). Notably, the background reaction in the
absence of a catalyst is negligible over the same time period in
buffered solutions (Figure S15). Albeit under different reaction
conditions, the half-life with UiO-67-N(Me) represents an
2
∼
970-fold enhancement over that for the only other MOF
shown to be capable of hydrolyzing VX (HKUST-1; t = 29
1/2
44
h). Notably, the 1.8 min half-life is similar to that yielded by
the most active abiotic catalysts described to date.
34,45−47
It is
plausible that the enhanced catalytic activity of UiO-67-NH2
and UiO-67-N(Me) relative to UiO-67 is due to the ability of
the amino moieties to act as a base or proton-transfer agent.
2
Figure 5. Screening of catalysts for highly selective and active
hydrolysis of nerve agent simulants and VX in water.
The tertiary amine on UiO-67-N(Me) is more basic than the
2
9
,21,48
primary amine on UiO-67-NH2.
Underivatized UiO-66
also displays selective hydrolysis of VX, albeit at a significantly
slower rate [i.e., a 90 min half-life (see Figure S12 and Table
S1)] than with underivatized UiO-67, consistent with the
Because of the persistence and toxicity of EA-2192, we also
wanted to see if the series of UiO-67-based MOFs was capable
of hydrolyzing EA-2192. EA-2192 is often present in
ammunition stockpiles and can persist in the environment
after agent deployment because of the nonselective hydrolytic
instability of VX. A mixture of VX and EA-2192 (as well as
EMPA due to nonselective hydrolysis) was prepared via aging
VX in a 0.5 M N-ethylmorpholine buffer solution for 6 days
(Figure S4a; see the Experimental Section for details).
prevention of steric crowding about the Zr cluster of the UiO-
6
6
7 series. Turnover frequencies (TOFs) based on the half-life
50
of the VX substrate (per Zr cluster) were calculated on the
6
basis of the assumption that all catalyst sites were accessible
and, alternatively, that only sites on the exterior of the MOF
surfaces were accessible, and are included in Table S1.
C
DOI: 10.1021/acs.inorgchem.5b01813
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
Decomposition of VX and EA-2192 was followed simulta-
neously via 31P NMR spectroscopy in the presence of UiO-67.
In pH 10 buffer, initial t1/2 values for decomposition of the
mixture were found to be ∼11 and ∼29 min for VX and EA-
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192, respectively (Figures S16 and S17). Complete hydrolysis
of VX was observed after 30 min, while the more persistent EA-
192 was completely hydrolyzed to MPA and DESH after 22 h
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in the buffered solution (Figures S1, S4b, and S14a). Initial
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(
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CONCLUSION
In conclusion, a series of Zr -based MOFs, including UiO-67,
■
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UiO-67-NH , and UiO-67-N(Me) , is capable of hydrolyzing
2
2
(
the CWA VX. Importantly, the P−S bond (and not the P−O
bond) is selectively hydrolyzed producing the preferred, low-
toxicity products EMPA and DESH. One of the MOFs, UiO-
(
1
(
5
(
4
6
7-N(Me) , hydrolyzes VX in a pH 10 buffered solution with
2
remarkable efficiency (initial t1/2 of 1.8 min that rivals those of
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́
why these Zr -based MOFs are so potent for the destruction of
́
6
phosphonate linkages, and those results will be reported in due
course.
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ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.5b01813.
■
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Hydrolysis mechanisms, conversion versus time data,
natural logarithm plots, NMR spectra for hydrolysis, and
dynamic light scattering data (PDF)
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(
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AUTHOR INFORMATION
Corresponding Author
E-mail: o-farha@northwestern.edu.
■
25) Ott, R.; Kram
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(
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The authors declare no competing financial interest.
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ACKNOWLEDGMENTS
■
(
(
29) Kim, M.; Cohen, S. M. CrystEngComm 2012, 14, 4096−4104.
O.K.F. and J.T.H. gratefully acknowledge DTRA for financial
support (Grant HDTRA-1-10-0023). G.W.W., G.W.P., and
J.B.D. gratefully acknowledge the Joint Science Technology
Office for Chemical and Biological Defense (JSTO-CBD) for
financial support under Program BA13PHM210. We thank Mr.
McGuirk for sharing the synthesis procedure that we used to
synthesize some of the organic linkers.
30) Mondloch, J. E.; Bury, W.; Fairen-Jimenez, D.; Kwon, S.;
DeMarco, E. J.; Weston, M. H.; Sarjeant, A. A.; Nguyen, S. T.; Stair, P.
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D
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Inorganic Chemistry
Article
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