title: Broad-Spectrum Liquid- and Gas-Phase Decontamination of Chemical Warfare Agents by One-Dimensional Heteropolyniobates.
abstract: A wide range of chemical warfare agents and their simulants are catalytically decontaminated by a new one-dimensional polymeric polyniobate (P-PONb), K12 [Ti2 O2 ][GeNb12 O40 ]⋅19 H2 O (KGeNb) under mild conditions and in the dark. Uniquely, KGeNb facilitates hydrolysis of nerve agents Sarin (GB) and Soman (GD) (and their less reactive simulants, dimethyl methylphosphonate (DMMP)) as well as mustard (HD) in both liquid and gas phases at ambient temperature and in the absence of neutralizing bases or illumination. Three lines of evidence establish that KGeNb removes DMMP, and thus likely GB/GD, by general base catalysis: a) the k(H2 O)/k(D2 O) solvent isotope effect is 1.4; b) the rate law (hydrolysis at the same pH depends on the amount of P-PONb present); and c) hydroxide is far less active against the above simulants at the same pH than the P-PONbs themselves, a critical control experiment.
authors.affiliation: Department of Chemistry, Cherry L. Emerson Center for Scientific Computation, Emory University, 1515 Dickey Dr., Atlanta, Georgia, 30322, USA.|X-ray Crystallography Center, Emory University, 1515 Dickey Dr., Atlanta, Georgia, 30322, USA.
authors.forename: Weiwei
authors.initials: W
authors.lastname: Guo
authors.forename: Hongjin
authors.initials: H
authors.lastname: Lv
authors.affiliation: Department of Chemistry, Cherry L. Emerson Center for Scientific Computation, Emory University, 1515 Dickey Dr., Atlanta, Georgia, 30322, USA.|X-ray Crystallography Center, Emory University, 1515 Dickey Dr., Atlanta, Georgia, 30322, USA.
authors.forename: Kevin P
authors.initials: KP
authors.lastname: Sullivan
authors.affiliation: U.S. Army Edgewood Chemical Biological Center, APG, MD, 21010-5424, USA.
authors.forename: Wesley O
authors.initials: WO
authors.lastname: Gordon
authors.affiliation: U.S. Army Edgewood Chemical Biological Center, APG, MD, 21010-5424, USA.
authors.forename: Alex
authors.initials: A
authors.lastname: Balboa
authors.affiliation: U.S. Army Edgewood Chemical Biological Center, APG, MD, 21010-5424, USA.
authors.forename: George W
authors.initials: GW
authors.lastname: Wagner
authors.affiliation: Department of Chemistry, Cherry L. Emerson Center for Scientific Computation, Emory University, 1515 Dickey Dr., Atlanta, Georgia, 30322, USA.
authors.forename: Djamaladdin G
authors.initials: DG
authors.lastname: Musaev
authors.affiliation: X-ray Crystallography Center, Emory University, 1515 Dickey Dr., Atlanta, Georgia, 30322, USA.
authors.forename: John
authors.initials: J
authors.lastname: Bacsa
authors.affiliation: Department of Chemistry, Cherry L. Emerson Center for Scientific Computation, Emory University, 1515 Dickey Dr., Atlanta, Georgia, 30322, USA. chill@emory.edu.|X-ray Crystallography Center, Emory University, 1515 Dickey Dr., Atlanta, Georgia, 30322, USA. chill@emory.edu.
authors.forename: Craig L
authors.initials: CL
authors.lastname: Hill
keywords: catalysis; chemical warfare agents; decontamination; heteropolyniobates; hydrolysis