TY - JOUR
T1 - Catalytic degradation of an organophosphorus agent at Zn-OH sites in a metal-organic framework
AU - Mian, Mohammad Rasel
AU - Islamoglu, Timur
AU - Afrin, Unjila
AU - Goswami, Subhadip
AU - Cao, Ran
AU - Kirlikovali, Kent O.
AU - Hall, Morgan G.
AU - Peterson, Gregory W.
AU - Farha, Omar K.
N1 - Funding Information:
The authors gratefully acknowledge support from the Defense Threat Reduction Agency (HDTRA1-18-1-0003). Use was made of the IMSERC X-ray facility at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the State of Illinois, and the International Institute for Nanotechnology (IIN). This work made use of the EPIC facility of Northwestern University’s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSFECCS-1542205), the MRSEC program (NSF DMR-1720139) at the Materials Research Center, the International Institute for Nanotechnology (IIN), the Keck Foundation, and the State of Illinois through the IIN. K.O.K. gratefully acknowledges support from the IIN Postdoctoral Fellowship and the Northwestern University International Institute for Nanotechnology.
PY - 2020/8/25
Y1 - 2020/8/25
N2 - Chemical warfare agents (CWAs), and in particular organophosphorus nerve agents, still pose a significant threat to society due to their continued use despite international bans. While nature has constructed a variety of enzymes that are capable of rapidly hydrolyzing organophosphorus substrates, the poor stability of enzymes outside of buffered solutions has limited their use in practical applications, such as in filters or on protective suits. As a result, we have explored the use of metal-organic frameworks (MOFs) as robust and tunable catalytic materials in which the nodes can be tailored to resemble the active sites found in these enzymes. We identified the Zn-based MOF, MFU-4l, as a promising hydrolysis catalyst due to the presence of Zn(II)-OH groups on the nodes, which are structurally reminiscent of the active sites in carbonic anhydrase (CA), a Zn-based enzyme that has been shown to efficiently catalyze the hydrolysis of phosphate esters. Indeed, MFU-4l can rapidly hydrolyze both the organophosphorus nerve agent, GD, and its simulant, DMNP, with half-lives as low as <1 min, which is competitive with the some of best heterogeneous hydrolysis catalysts reported to date.
AB - Chemical warfare agents (CWAs), and in particular organophosphorus nerve agents, still pose a significant threat to society due to their continued use despite international bans. While nature has constructed a variety of enzymes that are capable of rapidly hydrolyzing organophosphorus substrates, the poor stability of enzymes outside of buffered solutions has limited their use in practical applications, such as in filters or on protective suits. As a result, we have explored the use of metal-organic frameworks (MOFs) as robust and tunable catalytic materials in which the nodes can be tailored to resemble the active sites found in these enzymes. We identified the Zn-based MOF, MFU-4l, as a promising hydrolysis catalyst due to the presence of Zn(II)-OH groups on the nodes, which are structurally reminiscent of the active sites in carbonic anhydrase (CA), a Zn-based enzyme that has been shown to efficiently catalyze the hydrolysis of phosphate esters. Indeed, MFU-4l can rapidly hydrolyze both the organophosphorus nerve agent, GD, and its simulant, DMNP, with half-lives as low as <1 min, which is competitive with the some of best heterogeneous hydrolysis catalysts reported to date.
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U2 - 10.1021/acs.chemmater.0c02373
DO - 10.1021/acs.chemmater.0c02373
M3 - Article
AN - SCOPUS:85089974439
VL - 32
SP - 6998
EP - 7004
JO - Chemistry of Materials
JF - Chemistry of Materials
SN - 0897-4756
IS - 16
ER -