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      A Chromogenic Probe for the Selective Recognition of Sarin and Soman Mimic DFP**

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          Abstract

          The synthesis, characterization and sensing features of a novel probe 1 for the selective chromogenic recognition of diisopropylfluorophosphate (DFP), a sarin and soman mimic, in 99:1 ( v/ v) water/acetonitrile and in the gas phase is reported. Colour modulation is based on the combined reaction of phosphorylation of 1 and fluoride-induced hydrolysis of a silyl ether moiety. As fluoride is a specific reaction product of the reaction between DFP and the −OH group, the probe shows a selective colour modulation in the presence of this chemical. Other nerve agent simulants, certain anions, oxidant species and other organophosphorous compounds were unable to induce colour changes in 1. This is one of the very few examples of a selective detection, in solution and in the gas phase, of a sarin and soman simulant versus other reactive derivatives such as the tabun mimic diethylcyanophosphate (DCNP).

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          Most cited references63

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          Fluorescent detection of chemical warfare agents: functional group specific ratiometric chemosensors.

          Indicators providing highly sensitive and functional group specific fluorescent response to diisopropyl fluorophosphate (DFP, a nerve gas (G-agent) simulant) are reported. Nonemissive indicator 2 reacts with DFP to give a cyclized compound 2+A- that shows a high emission due to its highly planar and rigid structure. Very weak emission was observed by the addition of HCl. Another indicator based on pyridyl naphthalene exhibits a large shift in its emission spectrum after reaction with DFP, which provides for quantitative ratiometric detection.
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            Fluorescent sensors for organophosphorus nerve agent mimics.

            We present a small molecule sensor that provides an optical response to the presence of an organophosphorus (OP)-containing nerve agent mimic. The design contains three key features: a primary alcohol, a tertiary amine in close proximity to the alcohol, and a fluorescent group used as the optical readout. In the sensor's rest state, the lone pair of electrons of the basic amine quenches the fluorescence of the nearby fluorophore through photoinduced electron transfer (PET). Exposure to an OP nerve agent mimic triggers phosphorylation of the primary alcohol followed rapidly by an intramolecular substitution reaction as the amine displaces the created phosphate. The quaternized ammonium salt produced by this cyclization reaction no longer possesses a lone pair of electrons, and a fluorescence readout is observed as the nonradiative PET quenching pathway of the fluorophore is shut down.
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              Biosensor based on self-assembling acetylcholinesterase on carbon nanotubes for flow injection/amperometric detection of organophosphate pesticides and nerve agents.

              A highly sensitive flow injection amperometric biosensor for organophosphate pesticides and nerve agents based on self-assembled acetylcholinesterase (AChE) on a carbon nanotube (CNT)-modified glassy carbon (GC) electrode is described. AChE is immobilized on the negatively charged CNT surface by alternatively assembling a cationic poly(diallyldimethylammonium chloride) (PDDA) layer and an AChE layer. Transmission electron microscopy images confirm the formation of layer-by-layer nanostructures on carboxyl-functionalized CNTs. Fourier transform infrared reflectance spectrum indicates the AChE was immobilized successfully on the CNT/PDDA surface. The unique sandwich-like structure (PDDA/AChE/PDDA) on the CNT surface formed by self-assembling provides a favorable microenvironment to keep the bioactivity of AChE. The electrocatalytic activity of CNT leads to a greatly improved electrochemical detection of the enzymatically generated thiocholine product, including a low oxidation overvoltage (+150 mV), higher sensitivity, and stability. The developed PDDA/AChE/PDDA/CNT/GC biosensor integrated into a flow injection system was used to monitor organophosphate pesticides and nerve agents, such as paraoxon. The sensor performance, including inhibition time and regeneration conditions, was optimized with respect to operating conditions. Under the optimal conditions, the biosensor was used to measure as low as 0.4 pM paraoxon with a 6-min inhibition time. The biosensor had excellent operational lifetime stability with no decrease in the activity of enzymes for more than 20 repeated measurements over a 1-week period. The developed biosensor system is an ideal tool for online monitoring of organophosphate pesticides and nerve agents.
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                Author and article information

                Journal
                ChemistryOpen
                ChemistryOpen
                open
                ChemistryOpen
                Blackwell Publishing Ltd (Oxford, UK )
                2191-1363
                2191-1363
                August 2014
                09 July 2014
                : 3
                : 4
                : 142-145
                Affiliations
                [[a] ]Centro de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Unidad Mixta Universidad Politécnica de Valencia, Universidad de Valencia (Spain)
                [[b] ]Departamento de Química, Universidad Politécnica de Valencia, Camino de Vera s/n 46022 Valencia (Spain) E-mail: rmaez@ 123456qim.upv.es
                [[c] ]CIBER de Bioingeniería Biomateriales y Nanomedicina (CIBER-BBN)
                [[d] ]Departamento de Química Orgánica, Universitat de València Dr. Moliner 50, 46100 Burjassot, Valencia (Spain) E-mail: ana.costero@ 123456uv.es
                Author notes
                [**]

                This article is part of the Virtual Special Issue “Molecular Sensors”

                Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/open.201402014.

                Article
                10.1002/open.201402014
                4232269
                25478309
                37762df4-d52a-4b52-8612-72edd21a4ff9
                © 2014 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

                This is an open access article under the terms of the Creative Commons Attribution-NonCommercial-NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.

                History
                : 07 May 2014
                Categories
                Communications

                chromogenic probe,diisopropylfluorophosphate,nerve agents,sarin,soman

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