Chemical warfare agents, organophosphorus

Discovered in the late 1930s in Germany as improved poisonous insecticides, organophosphorus ChEIs were developed as chemical warfare agents (e.g. sarin, soman, and tabun) and were more recently employed in the 1995 terrorist attack in the Tokyo subway system [5]. 

All the enzymes discussed above belong to the class of dimetalloenzymes. In this context, it should be mentioned that serine-type hydrolases are irreversibly inhibited by organophosphorus esters, among them highly toxic chemical warfare agents. However, in some cases, for example of human butyrylcholi-noesterase, the inhibited enzyme could be reactivated by proper mutations." Moreover, such mutahons were found to confer phosphotriesterase activity in this... 

HYDROXYLAMINES, HYDROXAMATES AND OXIMATES AS ANTIDOTES FOR INTOXICATION BY ORGANOPHOSPHORUS TOXINS (CHEMICAL WARFARE AGENTS) AND... 

Model compounds (simulants) are often used to estimate the reactivity of organophosphorus pesticides and warfare agents toward potential remediation technologies because of their availability and ease of handling [5-18]. The structures of select organophosphorus pesticides, chemical warfare agents, and model compounds (simulants) are presented in Fig. 1. 

The basic experimental studies of the interactions between organophosphorus compounds and metal oxide surfaces have been carried out intensively during the last several years. Metal oxides, such as MgO, AI2O3, FeO, CaO, Ti02 a-Fe203, ZnO, and WO3, are currently under consideration as destructive adsorbents for the decontamination of chemical warfare agents [46, 47], For example, several studies have addressed adsorption of dimethyl methylphosphonate (DMMP) (a widely used model compound for the simulation of interactions of phosphate esters with a surface) on the surface of these metal oxides [48-60], In most of these works, the authors have observed that, at first, DMMP is adsorbed molecularly via hydrogen... 

U.A.Th. Brinkman, Verification of nonproduction of chemical warfare agents I. Determination of organophosphorus compounds by microcolumn liquid chromatography with flame photometric or thermionic detection, J. Microcol. Sep., 4, 465-475 (1992). 

R.M. Black and R.W. Read, Analysis of degradation products of organophosphorus chemical warfare agents and related compounds by liquid chromatography-mass spectrometry using electrospray and atmospheric pressure chemical ionization, J. Chromatogr A, 794, 233-244 (1998). 

J. Enqvist (Ed.), Systematic Identification of Chemical Warfare Agents, B.l Identification of Organophosphorus Warfare Agents. An Approach for the Standardization of Techniques and Reference Data, The Ministry for Foreign Affairs of Finland, Helsinki, 1979. 

R.M. Black and J.M. Harrison, The chemistry of organophosphorus chemical warfare agents, in The Chemistry of Organophosphorus Compounds, Vol. 4, F.R. Hartley (Ed.), John Wiley Sons, Ltd, 781-840, 1996. 

Figure 4. APCI (left) and ESI spectra of isopropyl ethylphosphonic acid, illustrating the lower abundance of adduct ions with APCI ions at mlz, 143 and 185 are adduct ions with MeOH mlz 175 is [M + Na]+. (Reprinted from Journal of Chromatography A, 794, R.M. Black and R.W. Read, Analysis of degradation products of organophosphorus chemical warfare agents and related compounds by liquid chromatography-mass spectrometry using electrospray and atmospheric pressure chemical ionisation, pp. 233-244 (1998), with permission from Elsevier)...

Richardson, D.D., Sadi, B.B.M., and Caruso, J.A. Reversed phase ion-pairing HPLC-ICP-MS for analysis of organophosphorus chemical warfare agent degradation products. J. Anal. Atom. Spectrom. 2006, 21, 396-403. 

Smith, J.R., Schlager, J.J. (1996). Gas chromatographic separation of the stereoisomers of organophosphorus chemical warfare agents using cyclodextrin capillary columns. J. High Resol. Chromatogr. 19 151-4. 

Organophosphorus compounds have agricultural and industrial applications and some are potent chemical warfare agents. Gas-phase reactions in a mass spectrometer are excellent for rapid detection and quantification of such compounds. In the gas phase, phosphonium ions were shown to undergo a Meerwein reaction with thiiranes to form oxathiophospholanium ions (87 and analogs) that undergo collision-induced dissociation (CID) to afford the... 

The organophosphosphates represent another extremely important class of organic insecticides. They were developed during World War II as chemical warfare agents. Early examples included the powerful insecticide schradan, a systemic insecticide, and the contact insecticide parathion. Unfortunately, both of these compounds are highly poisonous to mammals and subsequent research in this field has been directed toward the development of more selective and less poisonous insecticides. In 1950, malathion, the first example of a wide-specUnm organophosphorus insecticide combined with very low mammalian toxicity, was developed. And at about the same time the phenoxyacetic acid herbicides were discovered. These systemic compounds ate extremely valuable for the selective control of broad-leaved weeds in cereal crops. These compounds have a relatively low toxicity to mammals and are therefore relatively safe to use. 

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