993-13-5Relevant academic research and scientific papers
Binding and hydrolysis of soman by human serum albumin
Li, Bin,Nachon, Florian,Froment, Marie-Therese,Verdier, Laurent,Debouzy, Jean-Claude,Brasme, Bernardo,Gillon, Emilie,Schopfer, Lawrence M.,Lockridge, Oksana,Masson, Patrick
, p. 421 - 431 (2008)
Human plasma and fatty acid free human albumin were incubated with soman at pH 8.0 and 25°C. Four methods were used to monitor the reaction of albumin with soman: progressive inhibition of the aryl acylamidase activity of albumin, the release of fluoride ion from soman, 31P NMR, and mass spectrometry. Inhibition (phosphonylation) was slow with a bimolecular rate constant of 15 ± 3 M-1 min-1. MALDI-TOF and tandem mass spectrometry of the soman-albumin adduct showed that albumin was phosphonylated on tyrosine 411. No secondary dealkylation of the adduct (aging) occurred. Covalent docking simulations and 31P NMR experiments showed that albumin has no enantiomeric preference for the four stereoisomers of soman. Spontaneous reactivation at pH 8.0 and 25°C, measured as regaining of aryl acylamidase activity and decrease of covalent adduct (pinacolyl methylphosphonylated albumin) by NMR, occurred at a rate of 0.0044 h -1, indicating that the adduct is quite stable (t1/2 = 6.5 days). At pH 7.4 and 22°C, the covalent soman-albumin adduct, measured by MALDI-TOF mass spectrometry, was more stable (t1/2 = 20 days). Though the concentration of albumin in plasma is very high (about 0.6 mM), its reactivity with soman (phosphonylation and phosphotriesterase activity) is too slow to play a major role in detoxification of the highly toxic organophosphorus compound soman. Increasing the bimolecular rate constant of albumin for organophosphates is a protein engineering challenge that could lead to a new class of bioscavengers to be used against poisoning by nerve agents. Soman-albumin adducts detected by mass spectrometry could be useful for the diagnosis of soman exposure.
METHYLIDENEPHOSPHINE
Pellerin, Bruno,Guenot, Pierre,Denis, Jean-Marc
, p. 5811 - 5814 (1987)
Methylidenephosphine 1 was formed by gas-phase or liquid-phase HCl-elimination from chloromethylphosphine 2 and unambiguously characterized by chemical trapping and spectroscopic analysis (MS, IR, 31P NMR).
A Peanut-Like Sb-Embedded Polyoxoniobate Cage for Hydrolytic Decomposition of Chemical Warfare Agent
Wu, Yan-Lan,Zhong, Zhuo-Hao,Wu, Ping-Xin,Sun, Yan-Qiong,Li, Xin-Xiong,Zheng, Shou-Tian
, p. 1505 - 1509 (2021)
A Sb-embedded polyoxoniobate has been originally synthesized under hydrothermal conditions. Particularly, the peanut-like [Sb2Nb24O72]18? cluster cage in 1 with C2h symmetry is composed of two 9-nuclear {SbNb9O33} motifs and one {Nb6O24} crown-shaped ring. The compound 1 present the novel structure of Sb-substituted sandwich-type polyoxoniobate with antimoniobate cluster cage. Decomposition catalytic studies indicate that compound 1 exhibits good hydrolytic activity and stability on the degradation of nerve agent simulant dimethylphosphonate (DMMP).
{Nb288O768(OH)48(CO3)12}: A Macromolecular Polyoxometalate with Close to 300 Niobium Atoms
Wu, Yan-Lan,Li, Xin-Xiong,Qi, Yan-Jie,Yu, Hao,Jin, Lu,Zheng, Shou-Tian
, p. 8572 - 8576 (2018)
A protein-sized (ca. 4.2×4.2×3.6 nm3) non-biologically derived molecule {Nb288O768(OH)48(CO3)12} (Nb288) containing up to 288 niobium atoms has been obtained, which is by far the largest and the highest nuclearity polyoxoniobate (PONb). Particularly, in terms of metal nuclearity number, Nb288 is the second largest cluster so far reported in classic polyoxometalate chemistry (V, Mo, W, Nb, and Ta). Nb288 can be described as a giant windmill-like cluster aggregate of six nanoscale high-nuclearity PONb units {Nb47O128(OH)6(CO3)2} (Nb47) joined together by six additional Nb ions. Interestingly, the 47-nuclearity Nb47 units generated in situ can be isolated and bridged by copper complexes to form an inorganic–organic hybrid three-dimensional PONb framework, which exhibits effective catalytic activity for hydrolyzing nerve agent simulant of dimethyl methylphosphonate. The unique Nb47 cluster also provides a new type of topology to very limited family of Nb-O clusters.
Wet and dry processes for the selective transformation of phosphonates to phosphonic acids catalyzed by br?nsted acids
Li, Chunya,Saga, Yuta,Onozawa, Shun-Ya,Kobayashi, Shu,Sato, Kazuhiko,Fukaya, Norihisa,Han, Li-Biao
, p. 14411 - 14419 (2020/12/29)
A "wet"process and two "dry"processes for converting phosphonate esters to phosphonic acids catalyzed by a Bronsted acid have been developed. Thus, in the presence of water, a range of alkyl-, alkenyl-, and aryl-substituted phosphonates can be generally hydrolyzed to the corresponding phosphonic acids in good yields catalyzed by trifluoromethyl sulfonic acid (TfOH) at 140 °C (the wet process). On the other hand, with specific substituents of the phosphonate esters, the conversion to the corresponding phosphonic acids can be achieved under milder conditions in the absence of water (the dry process). Thus, the conversion of dibenzyl phosphonates to the corresponding phosphonic acids took place smoothly at 80 °C in toluene or benzene in high yields. Moreover, selective conversion of benzyl phosphonates RP(O)(OR′)(OBn) to the corresponding mono phosphonic acids RP(O)(OR′)(OH) can also be achieved under the reaction conditions. The dealkylation via the generation of isobutene of ditert- butyl phosphonate, and the related catalysis by TfOH took place even at room temperature to give the corresponding phosphonic acids in good to high yields. Nafion also shows high catalytic activity for these reactions. By using Nafion as the catalyst, phosphonic acids could be easily prepared on a large scale via a simple process.
Synthesis of the Tripeptides Tyr-Thr-Lys Phosphorylated with Isopropyl Methyl- and (Deuteromethyl)phosphonochloridates as Reference Standards for the Analysis of Biomedical Samples
Rodin,Baygildiev,Krylov,Osipov,Krylov,Yashkir,Rybalchenko
, p. 2103 - 2107 (2019/11/29)
A procedure for the phosphorylation of the tripeptide Tyr-Thr-Lys with isopropyl methyl- or (deuteromethyl)phosphonochloridate is developed. The phosphorylated tripeptides are intended for use as reference standards in the analysis of blood samples of people suspected to have been exposed to acetylcholinesterase inhibitors. Conditions of hromatographic separation and purification of the synthesized compounds are determined and optimized, which ensures the preparation of high-purity phosphorylated tripeptides.
Magnesium Exchanged Zirconium Metal-Organic Frameworks with Improved Detoxification Properties of Nerve Agents
Gil-San-Millan, Rodrigo,López-Maya, Elena,Platero-Prats, Ana E.,Torres-Pérez, Virginia,Delgado, Pedro,Augustyniak, Adam W.,Kim, Min Kun,Lee, Hae Wan,Ryu, Sam Gon,Navarro, Jorge A. R.
supporting information, p. 11801 - 11805 (2019/08/28)
UiO-66, MOF-808 and NU-1000 metal-organic frameworks exhibit a differentiated reactivity toward [Mg(OMe)2(MeOH)2]4 related to their pore accessibility. Microporous UiO-66 remains unchanged while mesoporous MOF-808 and hierarchical micro/mesoporous NU-1000 materials yield doped systems containing exposed MgZr5O2(OH)6 clusters in the mesoporous cavities. This modification is responsible for a remarkable enhancement of the catalytic activity toward the hydrolytic degradation of P-F and P-S bonds of toxic nerve agents, at room temperature, in unbuffered aqueous solutions.
Investigating the breakdown of the nerve agent simulant methyl paraoxon and chemical warfare agents GB and VX using nitrogen containing bases
Wilson, Craig,Cooper, Nicholas J.,Briggs, Michael E.,Cooper, Andrew I.,Adams, Dave J.
supporting information, p. 9285 - 9291 (2019/01/03)
A range of nitrogen containing bases was tested for the hydrolysis of a nerve agent simulant, methyl paraoxon (MP), and the chemical warfare agents, GB and VX. The product distribution was found to be highly dependant on the basicity of the base and the quantity of water used for the hydrolysis. This study is important in the design of decontamination technology, which often involve mimics of CWAs.
Methylphosphonic Acid Biosynthesis and Catabolism in Pelagic Archaea and Bacteria
Ulrich, Emily C.,Kamat, Siddhesh S.,Hove-Jensen, Bjarne,Zechel, David L.
, p. 351 - 426 (2018/05/16)
Inorganic phosphate is essential for all life forms, yet microbes in marine environments are in near constant deprivation of this important nutrient. Organophosphonic acids can serve as an alternative source of inorganic phosphate if microbes possess the appropriate biochemical pathways that allow cleavage of the stable carbon–phosphorus bond that defines this class of molecule. One prominent source of inorganic phosphate is methylphosphonic acid, which is found as a constituent of marine-dissolved organic matter. The cycle of biosynthesis and catabolism of methylphosphonic acid by marine microbes is the likely source of supersaturating levels of methane in shallow ocean waters. This review provides an overview of the rich biochemistry that has evolved to synthesize methylphosphonic acid and catabolize this molecule into Pi and methane, with an emphasis on the reactions catalyzed by methylphosphonic acid synthase MpnS and the carbon–phosphorus lyase system. The protocols and experiments that are described for MpnS and carbon–phosphorus lyase provide a foundation for studying the structures and mechanisms of these and related enzymes.
Decontamination of 2-chloro ethyl ethyl sulphide and dimethyl methyl phosphonate from aqueous solutions using manganese oxide nanostructures
Verma, Monu,Chandra, Ramesh,Gupta, Vinod Kumar
, p. 285 - 292 (2016/01/09)
Current study investigates the efficiency of reactive adsorbent composed of MnO2 nanoparticles and nanorods for the detoxification of 2-chloro ethyl ethyl sulphide (CEES) and dimethyl methyl phosphonate (DMMP), well-known simulants of sulphur mustard and sarin, respectively. The MnO2 nanoparticles and nanorods were synthesised using novel reactive magnetron sputtering technique and then characterised by powder XRD, Raman spectroscopy, FE-SEM, TEM, BET, FT-IR and Thermogravimetry (TG) analysis. Powder XRD and Raman results confirm the formation of pure tetragonal phase of MnO2 nanostructure material. The FE-SEM and TEM analysis exhibited the formation of aggregate MnO2 nanoparticles and nanorods. The surface area of the synthesised aggregate MnO2 nanoparticles and nanorods (164.28 m2/g) was found to be enhanced significantly in comparison with what was reported in the literature. Decontamination reactions of synthesised nanostructure material were examined by GC equipped with FID and the products obtained after reaction were analysed by GC-MS and FT-IR techniques. It was observed that the currently synthesised MnO2 nanoparticles and nanorods exhibit much better decontamination results towards CEES as well as DMMP in comparison to or as per existing solid decontaminants. The reactions exhibited pseudo first order kinetic behaviour with rate constant and half life value 0.267 h- 1 and 2.58 h for CEES and 0.068 h- 1 and 10.10 h for DMMP, respectively. The data exhibits the formation of non-toxic hydrolysis products in the detoxification of CEES as well as DMMP.
