共查询到20条相似文献,搜索用时 15 毫秒
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Dr. Stefano Marchesi Dr. Matteo Guidotti Prof. Leonardo Marchese Claudio Evangelisti Prof. Fabio Carniato Prof. Chiara Bisio 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(14):4723-4730
For the first time, the co-presence in the saponite structure of luminescent EuIII and catalytic NbV metal sites was exploited for the simultaneous detection and catalytic abatement of sulfur-containing blister chemical warfare agents. Metal centers were introduced in structural positions of the saponite (in the interlayer space or inside the inorganic framework) following two different synthetic methodologies. The functionalized saponites were able to reveal the presence of a sulfur mustard simulant (2-chloroethyl)ethyl sulfide (CEES) after few seconds of contact time and more than 80 % of the substrate was catalytically decomposed after 24 h in the presence of aqueous hydrogen peroxide. 相似文献
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Broad‐Spectrum Liquid‐ and Gas‐Phase Decontamination of Chemical Warfare Agents by One‐Dimensional Heteropolyniobates 下载免费PDF全文
Weiwei Guo Dr. Hongjin Lv Kevin P. Sullivan Wesley O. Gordon Alex Balboa George W. Wagner Dr. Djamaladdin G. Musaev Dr. John Bacsa Prof. Craig L. Hill 《Angewandte Chemie (International ed. in English)》2016,55(26):7403-7407
A wide range of chemical warfare agents and their simulants are catalytically decontaminated by a new one‐dimensional polymeric polyniobate (P‐PONb), K12[Ti2O2][GeNb12O40]?19 H2O ( 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(H2O)/k(D2O) 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. 相似文献
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Nunzio Tuccitto Luca Spitaleri Giovanni Li Destri Andrea Pappalardo Antonino Gulino Giuseppe Trusso Sfrazzetto 《Molecules (Basel, Switzerland)》2020,25(23)
Real-time sensing of chemical warfare agents by optical sensors is today a crucial target to prevent terroristic attacks by chemical weapons. Here the synthesis, characterization and detection properties of a new sensor, based on covalently functionalized carbon nanoparticles, are reported. This nanosensor exploits noncovalent interactions, in particular hydrogen bonds, to detect DMMP, a simulant of nerve agents. The nanostructure of the sensor combined with the supramolecular sensing approach leads to high binding constant affinity, high selectivity and the possibility to reuse the sensor. 相似文献
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《Electroanalysis》2003,15(14):1149-1159
After the September 11 tragedies of 2001, scientists and law‐enforcement agencies have shown increasing concern that terrorist organizations and their “rogue” foreign government‐backers may resort to the use of chemical and/or biological agents against U.S. military or civilian targets. In addition to the right mix of policies, including security measures, intelligence gathering and training for medical personnel on how to recognize symptoms of biochemical warfare agents, the major success in combating terrorism lies in how best to respond to an attack using reliable analytical sensors. The public and regulatory agencies expect sensing methodologies and devices for homeland security to be very reliable. Quality data can only be generated by using analytical sensors that are validated and proven to be under strict design criteria, development and manufacturing controls. Electrochemical devices are ideally suited for obtaining the desired analytical information in a faster, simpler, and cheaper manner compared to traditional (lab‐based) assays and hence for meeting the requirements of decentralized biodefense applications. This articler presents a review of the major trends in monitoring technologies for chemical and biological warfare (CBW) agents. It focuses on research and development of sensors (particularly electrochemical ones), discusses how advances in molecular recognition might be used to design new multimission networked sensors (MULNETS) for homeland security. Decision flow‐charts for choosing particular analytical techniques for CBW agents are presented. Finally, the paths to designing sensors to meet the needs of today's measurement criteria are analyzed. 相似文献
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Mechanistic Insights into the Luminescent Sensing of Organophosphorus Chemical Warfare Agents and Simulants Using Trivalent Lanthanide Complexes 下载免费PDF全文
Genevieve H. Dennison Dr. Martin R. Johnston 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(17):6328-6338
Organophosphorus chemical warfare agents (OP CWAs) are potent acetylcholinesterase inhibitors that can cause incapacitation and death within minutes of exposure, and furthermore are largely undetectable by the human senses. Fast, efficient, sensitive and selective detection of these compounds is therefore critical to minimise exposure. Traditional molecular‐based sensing approaches have exploited the chemical reactivity of the OP CWAs, whereas more recently supramolecular‐based approaches using non‐covalent interactions have gained momentum. This is due, in part, to the potential development of sensors with second‐generation properties, such as reversibility and multifunction capabilities. Supramolecular sensors also offer opportunities for incorporation of metal ions allowing for the exploitation of their unique properties. In particular, trivalent lanthanide ions are being increasingly used in the OP CWA sensing event and their use in supramolecular sensors is discussed in this Minireview. We focus on the fundamental interactions of simple lanthanide systems with OP CWAs and simulants, along with the development of more elaborate and complex systems including those containing nanotubes, polymers and gold nanoparticles. Whilst literature investigations into lanthanide‐based OP CWA detection systems are relatively scarce, their unique and versatile properties provide a promising platform for the development of more efficient and complex sensing systems into the future. 相似文献
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Dr. Su‐Young Moon Emmanuel Proussaloglou Gregory W. Peterson Dr. Jared B. DeCoste Morgan G. Hall Dr. Ashlee J. Howarth Prof. Joseph T. Hupp Prof. Omar K. Farha 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(42):14864-14868
Owing to their high surface area, periodic distribution of metal sites, and water stability, zirconium‐based metal–organic frameworks (Zr6‐MOFs) have shown promising activity for the hydrolysis of nerve agents GD and VX, as well as the simulant, dimethyl 4‐nitrophenylphosphate (DMNP), in buffered solutions. A hurdle to using MOFs for this application is the current need for a buffer solution. Here the destruction of the simulant DMNP, as well as the chemical warfare agents (GD and VX) through hydrolysis using a MOF catalyst mixed with a non‐volatile, water‐insoluble, heterogeneous buffer is reported. The hydrolysis of the simulant and nerve agents in the presence of the heterogeneous buffer was fast and effective. 相似文献
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Jin Young Lee Yong Han Lee Yong Gwan Byun 《Phosphorus, sulfur, and silicon and the related elements》2013,188(5):641-649
Abstract A new (E)-pyrene-1-carbaldehyde O-tert-butyldimethylsilyl oxime 3 was synthesized for the detection of chemical warfare nerve agents, O-isopropyl methylphosphonofluoridate (GB) and O-pinacolyl methylphosphonofluoridate (GD). 1H NMR spectrum showed that the tert-butyldimethylsilyl (TBDMS) group was deprotected using TBAF and the oximate supernucleophile was made. Upon addition of chemical warfare agents (GB and GD) (50 mol%), the reaction was completely finished within 5 min and also the color change of reaction mixture was observed under a hand-held UV lamp with the naked eye. 相似文献
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Dr. Emmanuel Oheix Dr. Edmond Gravel Dr. Eric Doris 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(1):54-68
Research on the decontamination of the chemical warfare agent sulfur mustard pursues several objectives that include the neutralization of spared ammunition, the cleaning of affected areas, and also the development of protective equipment or tools. Neutralization of vesicant sulfur mustard involves different chemical routes such as hydrolysis, dehydrochlorination, oxidation, or complete mineralization. This review weighs the pros and cons associated with the different systems reported in the literature, with an emphasis on catalytic procedures, to selectively convert sulfur mustard or its simulants into harmless products. 相似文献
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Jon A. Ashley Chao-Hsiung Lin Peter Wirsching Kim D. Janda 《Angewandte Chemie (International ed. in English)》1999,38(12):1793-1795
Methylphosphonic acid (MPA) is the degradation product of many chemical warfare agents. The convenient detection of this substance would aid in field testing to confirm illicit manufacture and use of banned chemical weapons. Efficient functionalization of MPA with an aromatic diazo compound allowed binding by monoclonal antibodies elicited by using an analogous hapten (see scheme). An ELISA assay was rapid, sensitive, and specific. 相似文献
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Junjie Zhao Dennis T. Lee Robert W. Yaga Morgan G. Hall Heather F. Barton Ian R. Woodward Christopher J. Oldham Howard J. Walls Gregory W. Peterson Prof. Gregory N. Parsons 《Angewandte Chemie (International ed. in English)》2016,55(42):13224-13228
The threat associated with chemical warfare agents (CWAs) motivates the development of new materials to provide enhanced protection with a reduced burden. Metal–organic frame‐works (MOFs) have recently been shown as highly effective catalysts for detoxifying CWAs, but challenges still remain for integrating MOFs into functional filter media and/or protective garments. Herein, we report a series of MOF–nanofiber kebab structures for fast degradation of CWAs. We found TiO2 coatings deposited via atomic layer deposition (ALD) onto polyamide‐6 nanofibers enable the formation of conformal Zr‐based MOF thin films including UiO‐66, UiO‐66‐NH2, and UiO‐67. Cross‐sectional TEM images show that these MOF crystals nucleate and grow directly on and around the nanofibers, with strong attachment to the substrates. These MOF‐functionalized nanofibers exhibit excellent reactivity for detoxifying CWAs. The half‐lives of a CWA simulant compound and nerve agent soman (GD) are as short as 7.3 min and 2.3 min, respectively. These results therefore provide the earliest report of MOF–nanofiber textile composites capable of ultra‐fast degradation of CWAs. 相似文献
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Catalytic Consequences of the Thermodynamic Activities at Metal Cluster Surfaces and Their Periodic Reactivity Trend for Methanol Oxidation 下载免费PDF全文
Dr. Weifeng Tu Prof. Ya‐Huei Chin 《Angewandte Chemie (International ed. in English)》2014,53(45):12148-12152
The periodic reactivity trend and the connection of kinetics to the thermodynamic activity of oxygen are established for the oxidation of methanol on metal clusters. First‐order rate coefficients are a single‐valued function of the O2‐to‐CH3OH ratio, because this ratio, together with the rate constants for O2 and CH3OH activation, determine the oxygen chemical potential, thus the relative abundance of active sites and bulk chemical state of the clusters. CH3OH activation rate constants on oxygen‐covered Ag, Pt, and Pd and on RuO2 clusters vary with the metal–oxygen binding strength in a classical volcano‐type relation, because the oxygen‐binding strength directly influences the reactivities of oxygen as H abstractors during the kinetically relevant CH3OH activation step. The differences in oxygen thermodynamic activity lead to five orders of magnitude variation in rates (Pt>Pd>RuO2>Ag, 373 K), because of its strong effects on the activation enthalpy and more prominently activation entropy in CH3OH activation. 相似文献
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WEN Xianfang YE Lin CHEN Likun KONG Lingce YUAN Ling XI Hailing ZHONG Jinyi 《高等学校化学研究》2019,35(6):1095-1104
A novel acrylate copolymer, polymethylacrylate-β-(bromoacetyl ethyl)ester-co-N,N-dimethylacrylamide[P(MABE-co-DMAA)] was synthesized by the copolymerization of N,N-dimethylacrylamide and methylacrylate-β-(bromoacetyl ethyl)ester. Subsequently, the copolymer was oximated by 4-pyridinium aldoxime(4-PAM), and was abbreviated as PAM-P(MABE-co-DMAA). A maximum oxime conversion of 53.7% was obtained. The as-prepared oximated copolymer PAM-P(MABE-co-DMAA) effectively decontaminated chemical warfare agents(CWAs) including methylphosphonofluoridate(sarin or GB), S-2-(diisopropylamino)ethyl O-ethyl methylphosphonothioate (VX), and 2,2'-dichloroethyl sulfide(sulfur mustard, or HD). The detoxification rates were 90.6% for GB, 85.7% for VX, and 90.5% for HD. Chromogenic analysis, high performance liquid chromatography-mass spectrometry (HPLC/MS) and gas chromatography-mass spectrometry(GC/MS) were used to identify the decontamination products, and the decontamination mechanism was concluded to be a combination of nucleophilic substitution and a second order Beckmann rearrangement. Furthermore, the active decontamination materials, such as decontamination cloths and covers could be made from the oximated copolymer by virtue of its processability, as well as its strong ability to degrade CWA. 相似文献
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Baptiste Picard Boris Gouilleux Dr. Thomas Lebleu Dr. Jacques Maddaluno Prof. Isabelle Chataigner Dr. Maël Penhoat Prof. François-Xavier Felpin Dr. Patrick Giraudeau Dr. Julien Legros 《Angewandte Chemie (International ed. in English)》2017,56(26):7568-7572
The fast and effective neutralization of the mustard-gas simulant 2-chloroethyl ethyl sulfide (CEES) using a simple and portable continuous flow device is reported. Neutralization takes place through a fully selective sulfoxidation by a stable source of hydrogen peroxide (alcoholic solution of urea–H2O2 adduct/MeSO3H freshly prepared). The reaction progress can be monitored with an in-line benchtop NMR spectrometer, allowing a real-time adjustment of reaction conditions. Inherent features of millireactors, that is, perfect control of mixing, heat and reaction time, allowed the neutralization of 25 g of pure CEES within 46 minutes in a 21.5 mL millireactor (tR=3.9 minutes). This device, which relies on affordable and nontoxic reagents, fits into a suitcase, and can be deployed by police/military forces directly on the attack site. 相似文献
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《Analytical letters》2012,45(10):669-673
Abstract The possibility of formation of mixed complex compound niobium(V)-pyrocatechol (PC)-thenoyltrifluoracetone (TTA) has been shown. Optimum conditions for the formation of such a compound have been found (7.5 M HCI, 0.3 MTTA, 0.4 MPC) and the molar ratio Nb (V):PC:TTA=1:2:2 has been established by the equilibrium shift method. The absorption spectrum of the chloroform extract of the Nb-PC-TTA compound has a maximum at 414 nm, ε= (7.7±0.2) × 103. The influence of other ions on extraction-photometric determination of niobium (V) with PC and TTA is discussed. 相似文献