1. Scope of Article and Previous Related Reviews 5346 2. Introduction 5346 2.1. Destruction 5347 2.2. Sensing 5347 2.3. Historical Context 5348 2.3.1. Brief History and Molecular Structure 5348 2.4. Related Compounds and Nomenclature 5348 2.4.1. Phosphorus(V) Parent Compounds and Fundamental Chemistry 5348 2.4.2. Pesticides 5349 2.4.3. Simulants 5349 2.4.4. Decomposition Products 5350 2.5. Toxicology 5351 2.5.1. Acetylcholine Esterase (AChE) Inhibition 5351 2.5.2. Endocannabinoid System Activation 5352 2.6. Critical Needs To Decontaminate and Detect 5353 2.7. Treaties and Conventions 5354 3. Stockpile Destruction 5355 3.1. Agent Storage 5355 3.2. Protection Protocols and Logistics 5355 3.3. Background 5355 3.4. Methods Currently Employed 5355 3.4.1. Incineration 5355 3.4.2. Neutralization by Base Hydrolysis 5356 4. Decomposition Reactions 5357 4.1. Hydrolysis 5357 4.2. Autocatalytic Hydrolysis or Hydrolysis Byproducts 5358 4.3. Use of Peroxide 5359 4.4. Oxidation with Bleach and Related Reagents 5360 4.5. Alkoxide as Nucleophile 5360 4.5.1. Basic Media 5360 4.5.2. Metal-Catalyzed Reactions 5361 4.5.3. Metal-Assisted Reactions 5363 4.5.4. Biotechnological Degradation 5363 4.5.5. Cyclodextrin-Assisted Reactions 5370 4.6. Halogen as the Nucleophile 5370 4.6.1. Use of BrOx 5370 4.6.2. Use of Other Halogens 5371 4.6.3. Use of Group 13 Chelates 5371 4.7. Surface Chemistry 5371 4.7.1. Bare Metals and Solid Nanoparticles 5371 4.7.2. Metal Oxides 5371 4.7.3. Representative Elements 5372 4.7.4. d-Block (Groups 4 10) 5373 4.7.5. Solid Metal Oxides of Group 3 and the Lanthanides 5375 4.7.6. Porous Silicon and Related Systems 5375 4.7.7. Zeolites 5375 4.7.8. Comparative IR Data 5375 4.8. Other Types of Systems 5375 5. Decontamination 5376 5.1. Overview: Ability to React with All Types of Agents, Ease of Application, and Compatibility with Treated Objects 5376 6. Agent Fate and Disposal 5378 6.1. Indoor 5378 6.2. Concrete and Construction Surfaces 5378 6.3. Landfills 5379 7. Sensing and Detection 5379 7.1. Possible Metal Ion Binding Modes in Solution 5379 7.1.1. Early Reports of Phosph(on)ate [R3PdO 3 3 3M nþ] Interactions (R= Alkyl, Alkoxyl) 5380 7.1.2. Coordination Chemistry of Downstream Non-P-Containing Products of Decomposition 5380 7.2. Colorimetric Detection 5381 7.3. Chemiluminescence: Fluorescence and Phosphorescence 5382 7.3.1. Lanthanide-Based Catalysts 5382 7.3.2. Organometallic-Based Sensors 5382 7.3.3. Organic Design 5382 7.3.4. Biologically-Based Luminescence Detection 5382 7.3.5. Polymer and Bead Supports 5382 7.4. Porous Silicon 5383 7.5. Carbon Nanotubes 5383

Destruction and Detection of Chemical Warfare Agents

Yoon Jeong Jang,† Kibong Kim,† Olga G. Tsay,† David A. Atwood,‡ and David G. Churchill*,†,§ †Molecular Logic Gate Laboratory, Department of Chemistry, KAIST, Daejeon, 305-701, Republic of Korea ‡Department of Chemistry, University of Kentucky, Lexington, Kentucky 40506-0055, United States Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS), 373-1 Guseong-dong, Yuseong-gu, Daejeon, 305−701, Republic of Korea

Update 1 of: Destruction and detection of chemical warfare agents

Iron pyrite (FeS2) is a naturally abundant and nontoxic photovoltaic material that can potentially make de- vices as efficient as silicon-based ones; however existing iron pyrite photovoltaic devices contain thermodynamically un- stable FeS2 film surfaces that lead to low open circuit voltages. Wereporttherationalsynthesisofphasepure,highlycrystalline cubic FeS2 nanocrystals (NCs) using a trioctylphosphine oxide (TOPO) assisted hot-injection method. The synthesized pyrite NC films have excellent air stability over one year. In contrast, obvious surface decomposition was observed on the surface of FeS2 NCs synthesized without TOPO. A high carrier mobility of 80 cm 2 /(V s) and a strong photoconductivity were observed for the first time for pyrite films at room temperature. Our results indicate that TOPO passivates both iron and sulfur atoms on FeS2 NC surfaces, efficiently inhibiting surface decomposition.

https://www.unk.edu/academics/chemistry/Miscellaneous-files/Exstrom20_NanoLett2011.pdf

Air stable, photosensitive, phase pure iron pyrite nanocrystal thin films for photovoltaic application.

Infra-red spectroscopic detection of bridging cyanide groups

The inhibition of graphite oxidation by phosphorus additives

S>The ingrared spectra of trimethyl- and triphenylphosphine oxide and a number of their complexes with various transition-metal cations were examined. Complexformation causes the P-O stretching frequencies to shift approximately 50 cm/sup -1/ to lower values. Since a simple linematic effect would raise the frequency, an explanation in terms of a lowering of the P-O bond order is proposed. (auth)

E. Bannister

Papers

442. The effect of complex-formation by phosphine oxides on their P–O stretching frequencies