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Metal-organic frameworks (MOFs) are a class of hybrid materials that offer a promising platform for a range of catalytic reactions. Due to their complex structure, MOFs offer unique opportunities to serve as novel catalysts, or as host to improve the properties of previously studied species. However, while other catalytic approaches have been studied for many decades, the recency of their discovery means that significant work is still needed to develop MOFs as a viable option for large scale application. Herein, we aimed to advance the field of MOFs as both novel catalysts, and as host platforms for other catalytic species. To this end, we studied synthetic pathways to produce favorable MOF properties such as higher porosity and active site concentration through introduction of defects and macromorphological control, as well as utilization of molecular catalysts imbedded in the MOF structure for multicomponent, light driven reactivity. Chapter 1 introduces the history MOFs and the pursuit of the stable structures commonly associated with MOF chemistry. The synthesis process for zirconium-based MOFs will be discussed, with specific attention given to the modulated synthesis process which can harnessed to change MOF properties and improve catalysis. Two specific reactions will be introduced which serve as a basis for study in this work. First, the hydrolysis of organophosphate nerve agents by MOFs acting as novel catalysts will be introduced. The mechanism of reaction, as well as previous work in this field will be discussed. Finally, water oxidation as part of artificial photosynthesis through incorporated molecular catalysts will be introduced. Chapter 2 presents a modulator screening study on a zirconium-based MOF, UiO-66. One of the most commonly studied MOFs, UiO-66 provides an excellent platform for synthetic modulation. Particle size and defect level were measured of 26 synthetic variations and synthetic conditions were found to isolate changes in defect level

Metal-organic frameworks (MOFs) are a class of hybrid materials that offer a promising platform for a range of catalytic reactions. Due to their complex structure, MOFs offer unique opportunities to serve as novel catalysts, or as host to improve the properties of previously studied species. However, while other catalytic approaches have been studied for many decades, the recency of their discovery means that significant work is still needed to develop MOFs as a viable option for large scale application. Herein, we aimed to advance the field of MOFs as both novel catalysts, and as host platforms for other catalytic species. To this end, we studied synthetic pathways to produce favorable MOF properties such as higher porosity and active site concentration through introduction of defects and macromorphological control, as well as utilization of molecular catalysts imbedded in the MOF structure for multicomponent, light driven reactivity. Chapter 1 introduces the history MOFs and the pursuit of the stable structures commonly associated with MOF chemistry. The synthesis process for zirconium-based MOFs will be discussed, with specific attention given to the modulated synthesis process which can harnessed to change MOF properties and improve catalysis. Two specific reactions will be introduced which serve as a basis for study in this work. First, the hydrolysis of organophosphate nerve agents by MOFs acting as novel catalysts will be introduced. The mechanism of reaction, as well as previous work in this field will be discussed. Finally, water oxidation as part of artificial photosynthesis through incorporated molecular catalysts will be introduced. Chapter 2 presents a modulator screening study on a zirconium-based MOF, UiO-66. One of the most commonly studied MOFs, UiO-66 provides an excellent platform for synthetic modulation. Particle size and defect level were measured of 26 synthetic variations and synthetic conditions were found to isolate changes in defect level

Since first discovered some two decades ago, metal-organic frameworks (MOFs) have shown interesting properties with regard to storage, separation, and catalysis applications. While MOFs have shown promise in these arenas over the years, a major shortcoming of these materials is their inherently crystalline form factor which hinders their applicational. To circumvent this issue, we have turned to the hybridization of MOFs with polymers in an effort to form a material that has the desired properties of the MOF and the flexibility of the polymer. In particular, we seek to develop novel textile based (nylon based or spray coated) MOF-polymer hybrid materials that are catalytically active against harmful organophosphorus chemical warfare agents (CWAs). Chapter 2 describes the synthesis of a MOF-nylon hybrid material through and interfacial postsynthetic polymerization (PSP) method. The hybrid material contains 29 weight percent MOF and shows catalytic activity against a CWA simulant. Importantly, the covalent MOF-nylon material displays about a seven-fold increase in activity compared to physically mixed controls. In Chapter 3, we screened a wide range of MOFs with varying organic functional groups to establish structure activity relationships (SAR) between MOF functional groups and CWA simulant degradation. The Zr-based MOF UiO-66 (UiO = University of Oslo) was synthesized with either mixed ligand functional groups or halogenated functional groups. We determined that the mixed ligand approach improves CWA activity by three-fold whereas the UiO-66-Iodine MOF displays a fourfold increase in activity. Through theoretical calculations, the increased activity in UiO-66-I was determined to be an artifact of halogen bonding with the CWA simulant. In Chapter 4, we combined the approaches from Chapter 2 and 3, by using the commonly known pseudohalogen isothiocyanate (NCS) functional group in UiO-66 to improve the catalytic activity against CWAs and covalent PSP sites. The UiO-66

Since first discovered some two decades ago, metal-organic frameworks (MOFs) have shown interesting properties with regard to storage, separation, and catalysis applications. While MOFs have shown promise in these arenas over the years, a major shortcoming of these materials is their inherently crystalline form factor which hinders their applicational. To circumvent this issue, we have turned to the hybridization of MOFs with polymers in an effort to form a material that has the desired properties of the MOF and the flexibility of the polymer. In particular, we seek to develop novel textile based (nylon based or spray coated) MOF-polymer hybrid materials that are catalytically active against harmful organophosphorus chemical warfare agents (CWAs). Chapter 2 describes the synthesis of a MOF-nylon hybrid material through and interfacial postsynthetic polymerization (PSP) method. The hybrid material contains 29 weight percent MOF and shows catalytic activity against a CWA simulant. Importantly, the covalent MOF-nylon material displays about a seven-fold increase in activity compared to physically mixed controls. In Chapter 3, we screened a wide range of MOFs with varying organic functional groups to establish structure activity relationships (SAR) between MOF functional groups and CWA simulant degradation. The Zr-based MOF UiO-66 (UiO = University of Oslo) was synthesized with either mixed ligand functional groups or halogenated functional groups. We determined that the mixed ligand approach improves CWA activity by three-fold whereas the UiO-66-Iodine MOF displays a fourfold increase in activity. Through theoretical calculations, the increased activity in UiO-66-I was determined to be an artifact of halogen bonding with the CWA simulant. In Chapter 4, we combined the approaches from Chapter 2 and 3, by using the commonly known pseudohalogen isothiocyanate (NCS) functional group in UiO-66 to improve the catalytic activity against CWAs and covalent PSP sites. The UiO-66

Organophosphorus esters (OPs) were originally developed as pesticides but were repurposed as easily manufactured, inexpensive, and highly toxic chemical warfare agents. Acute OP toxicity is primarily due to inhibition of acetylcholinesterase (AChE), an enzyme in the central and peripheral nervous system. OP inhibition of AChE can be reversed using oxime reactivators but many show poor CNS penetration, indicating a need for new clinically viable reactivators. However, challenges exist on how to best measure restored AChE activity in vivo and assess the reactivating agent efficacy. This work reports the development of molecular imaging tools using radiolabeled OP analog tracers that are less toxic to handle in the laboratory, yet inhibit AChE in a similar fashion to the actual OPs. Carbon-11 and fluorine-18 radiolabeled analog tracers of VX and sarin OP agents were prepared. Following intravenous injection in normal Sprague-Dawley rats (n = 3-4/tracer), the tracers were evaluated and compared using noninvasive microPET/CT imaging, biodistribution assay, and arterial blood analyses. All showed rapid uptake and stable retention in brain, heart, liver, and kidney tissues determined by imaging and biodistribution. Lung uptake of the sarin analog tracers was elevated, 2-fold and 4-fold higher uptake at 5 and 30 min, respectively, compared to that for the VX analog tracers. All tracers rapidly bound to red blood cells (RBC) and blood proteins as measured in the biodistribution and arterial blood samples. Analysis of the plasma soluble activity (nonprotein/cell bound activity) showed only 1-6% parent tracer and 88-95% of the activity in the combined solid fractions (RBC and protein bound) as early as 0.5 min post injection. Multivariate analysis of tracer production yield, molar activity, brain uptake, brain area under the curve over 0-15 min, and the amount of parent tracer in the plasma at 5 min revealed the [18F]VX analog tracer had the most favorable values for each metr

Tidigare undersökningar i dumpningsområdet utanför Måseskär har visat på spår av nedbrytningsprodukter av de kemiska stridsmedlen Clark I och/eller Clark II i biota. Provfiske skedde i de östra delarna av dumpningsområdet utanför Måseskär som tidigare inte undersökts, samt i Gotlandsdjupet där gasbomber har identifierats genom visuella studier. Kemiska analyser av fångade organismer utfördes av the Finnish Institute for Verification of the Chemical Weapons Convention, University of Helsinki (VERIFIN). Målarter har valts baserat på deras kommersiella betydelse och ekologiska levnadssätt. På västkusten fångades och analyserades havskräfta, nordhavsräka och pirål. På östkusten fångades och analyserades torsk och skrubbskädda. Provfisket utfördes med passiva redskap så som burar, fällor och garn. I Gotlandsdjupet provtogs och analyserades även sediment. Resultatet från de kemiska analyserna i biota visade på spår av nedbrytningsprodukter från de kemiska stridsmedlen Clark I och/eller Clark II samt från Arsinolja. Nedbrytningsprodukter detekterades i ett samlingsprov från pirål fångad nedströms vraket BAL141 på västkusten samt bland två av sex samlingsprov av torsk fångad i Gotlandsdjupet. Samtliga sedimentprover från Gotlandsdjupet innehöll nedbrytningsprodukter från Clark I och/eller II i form av difenylarsinoxid (3O) och från Arsinolja i form av trifenylarsinoxid (4O) samt metylerade former av Adamsit (2.1) och Clark (3.1). Mängderna var mätbara men under gränsen för kvantifiering. Riskerna för spridning av innehållet i de dumpade kemiska stridsmedlen ökar med tiden på grund av korrosion av inkapslande höljen. Naturliga strömförhållanden leder till höga risker nedströms påverkade områden, något som ytterligare kan förvärras av bottenaktiviteter så som trålning i områdena. I Gotlandsdjupet innehöll samtliga sedimentprover produkter av kemiska stridsmedel vilket tyder på att stora delar av området är påverkat. Samma ämnen som detekterades i sedimentet gick också att fin, Marine Monitoring AB has by the request of the Swedish Agency for Marine and Water Management conducted an investigation about how widespread the contamination of dumped chemical warfare agents (CWAs) are in the dumping areas of Måseskär and the Gotland Basin. Earlier investigation in the area outside of Måseskär has shown traces of degradables from the CWAs Clark I and/or Clark II in biological samples. Sample fishing has been done in the eastern parts of the dumping area outside of Måseskär that has not previously been studied, as well as in the Gotland Basin wherein gas bombs has been visually identified. Chemical analyses were done by the Finnish Institute for Verification of the Chemical Weapons Convention, University of Helsinki (VERIFIN). Suitable target species were picked based on their commercial value and their ecology. On the west coast Norwegian lobsters, northern prawn and hagfish were captured and analysed. On the east coast cod and European flounder were captured and analysed. The sample fishing was conducted using passive gear such as cages, traps and nets. Sediment samples were also collected in the Gotland Basin. The results from the chemical analyses of the biological samples showed traces of CWA in the form of Clark I and/or Clark II as well as Arsine oil. Traces of CWA occurred in a bulk sample of hagfish caught downstream of the wreck BAL141 on the west coast and in two of the six bulk samples of cod captured in the Gotland Basin. All of the sediment samples contained traces of Clark I and/or Clark II in the form of diphenylarsinic acid (3O) and of Arsine oil in the form of triphenylarsine oxide (4O) as well as methylated forms of Adamsite (2.1) and Clark (3.1). The samples contained measurable concentrations however below the limits of quantitation. The risks of spreading of the content of the dumped CWAs rise as time passes because of corrosion of encapsulating shells. Natural currents lead to higher risks downstream of affected areas, somet

Tidigare undersökningar i dumpningsområdet utanför Måseskär har visat på spår av nedbrytningsprodukter av de kemiska stridsmedlen Clark I och/eller Clark II i biota. Provfiske skedde i de östra delarna av dumpningsområdet utanför Måseskär som tidigare inte undersökts, samt i Gotlandsdjupet där gasbomber har identifierats genom visuella studier. Kemiska analyser av fångade organismer utfördes av the Finnish Institute for Verification of the Chemical Weapons Convention, University of Helsinki (VERIFIN). Målarter har valts baserat på deras kommersiella betydelse och ekologiska levnadssätt. På västkusten fångades och analyserades havskräfta, nordhavsräka och pirål. På östkusten fångades och analyserades torsk och skrubbskädda. Provfisket utfördes med passiva redskap så som burar, fällor och garn. I Gotlandsdjupet provtogs och analyserades även sediment. Resultatet från de kemiska analyserna i biota visade på spår av nedbrytningsprodukter från de kemiska stridsmedlen Clark I och/eller Clark II samt från Arsinolja. Nedbrytningsprodukter detekterades i ett samlingsprov från pirål fångad nedströms vraket BAL141 på västkusten samt bland två av sex samlingsprov av torsk fångad i Gotlandsdjupet. Samtliga sedimentprover från Gotlandsdjupet innehöll nedbrytningsprodukter från Clark I och/eller II i form av difenylarsinoxid (3O) och från Arsinolja i form av trifenylarsinoxid (4O) samt metylerade former av Adamsit (2.1) och Clark (3.1). Mängderna var mätbara men under gränsen för kvantifiering. Riskerna för spridning av innehållet i de dumpade kemiska stridsmedlen ökar med tiden på grund av korrosion av inkapslande höljen. Naturliga strömförhållanden leder till höga risker nedströms påverkade områden, något som ytterligare kan förvärras av bottenaktiviteter så som trålning i områdena. I Gotlandsdjupet innehöll samtliga sedimentprover produkter av kemiska stridsmedel vilket tyder på att stora delar av området är påverkat. Samma ämnen som detekterades i sedimentet gick också att fin, Marine Monitoring AB has by the request of the Swedish Agency for Marine and Water Management conducted an investigation about how widespread the contamination of dumped chemical warfare agents (CWAs) are in the dumping areas of Måseskär and the Gotland Basin. Earlier investigation in the area outside of Måseskär has shown traces of degradables from the CWAs Clark I and/or Clark II in biological samples. Sample fishing has been done in the eastern parts of the dumping area outside of Måseskär that has not previously been studied, as well as in the Gotland Basin wherein gas bombs has been visually identified. Chemical analyses were done by the Finnish Institute for Verification of the Chemical Weapons Convention, University of Helsinki (VERIFIN). Suitable target species were picked based on their commercial value and their ecology. On the west coast Norwegian lobsters, northern prawn and hagfish were captured and analysed. On the east coast cod and European flounder were captured and analysed. The sample fishing was conducted using passive gear such as cages, traps and nets. Sediment samples were also collected in the Gotland Basin. The results from the chemical analyses of the biological samples showed traces of CWA in the form of Clark I and/or Clark II as well as Arsine oil. Traces of CWA occurred in a bulk sample of hagfish caught downstream of the wreck BAL141 on the west coast and in two of the six bulk samples of cod captured in the Gotland Basin. All of the sediment samples contained traces of Clark I and/or Clark II in the form of diphenylarsinic acid (3O) and of Arsine oil in the form of triphenylarsine oxide (4O) as well as methylated forms of Adamsite (2.1) and Clark (3.1). The samples contained measurable concentrations however below the limits of quantitation. The risks of spreading of the content of the dumped CWAs rise as time passes because of corrosion of encapsulating shells. Natural currents lead to higher risks downstream of affected areas, somet

We report on the synthesis and characterization of TiO2/Nanodiamond (ND) nanocomposites for rapid decontamination of chemical warfare agents (CWA) and toxic industrial compounds prepared by a simple water-based, low-temperature method using urea as a homogeneous precipitating agent. The excellent water-compatibility of NDs promoted their good dispersion within the TiO2 matrix resulting in intergrown TiO2/ND nanostructures. NDs with an abundance of oxygen-containing surface moieties increased the porosity of the composites resulting in their three times more efficient spontaneous degradation of the CWA soman in solution compared to pure TiO2. In situ DRIFT spectroscopy revealed the enhanced reactive adsorption and solar light photodecomposition of dimethyl methyl phosphonate vapor on TiO2/ND. The charge transfer across TiO2/ND interfaces that hinder recombination of photo-excited electron-hole pairs was inferred from surface potential measurements. The results indicate that well-dispersed NDs forming heterojunctions together with their high porosity contribute to the reactive properties of the nanocomposites., Correction in: APPLIED CATALYSIS B-ENVIRONMENTAL, Volume: 261, Article Number: 118263, DOI: 10.1016/j.apcatb.2019.118263

With recent advances in ionization sources and instrumentation, ion mobility spectrometers (IMS) have transformed from a detector for chemical warfare agents and explosives to a widely used tool in analytical and bioanalytical applications. This increasing measurement task complexity requires higher and higher analytical performance and especially ultra-high resolution. In this review, we will discuss the currently used ion mobility spectrometers able to reach such ultra-high resolution, defined here as a resolving power greater than 200. These instruments are drift tube IMS, traveling wave IMS, trapped IMS, and field asymmetric or differential IMS. The basic operating principles and the resulting effects of experimental parameters on resolving power are explained and compared between the different instruments. This allows understanding the current limitations of resolving power and how ion mobility spectrometers may progress in the future.

The threat of chemical warfare agent (CWA) attacks has persisted into the 21st century due to the actions of terror groups and rogue states. Traditional filtration strategies for soldier protection rely on high surface area activated carbon, but these materials merely trap CWAs through weak physisorption. Metal-organic frameworks (MOFs) have emerged as promising materials to catalyze the degradation of CWAs into significantly less toxic byproducts. The precise synthetic control over the porosity, defect density, and chemical functionality of MOFs offer exciting potential of for use in CWA degradation as well as a wide variety of other applications. Developing a molecular-level understanding of gas-MOF interactions can allow for the rational design of MOFs optimized for CWA degradation. Our research investigated the fundamental interfacial interactions between CWA simulant vapors, specifically sulfur mustard (HD) simulants, and zirconium-based MOFs (Zr-MOFs). Utilizing a custom-built ultrahigh vacuum chamber with infrared spectroscopic and mass spectrometric capabilities, the adsorption mechanism, diffusion energetics, and diffusion kinetics of HD simulants were determined. For 2-chloroethyl ethyl sulfide (2-CEES), a widely used HD simulant, infrared spectroscopy revealed that adsorption within Zr-MOFs primarily proceeded through hydrogen bond formation between 2-CEES and the bridging hydroxyls on the secondary building unit of the MOFs. Through the study of 1-chloropentane and diethyl sulfide adsorption, we determined that 2-CEES forms hydrogen bonds through its chlorine atom likely due to geometric constraints within the MOF pore environment. Temperature-programmed desorption experiments aimed at determining desorption energetics reveal that 2-CEES remain adsorbed within the pores of the MOFs until high temperatures, but traditional methods of TPD analysis fail to accurately measure both the enthalpic and entropic interactions of 2-CEES desorption from a single ads

OBJECTIVE: This study investigated how European first responders and hospital personnel, along with CBRN experts, approach an overwhelming surge situation after a chemical incident. Surge capacity and capability bottlenecks were discussed.MATERIALS AND METHODS: Two chemical warfare agent (CWA) scenarios were developed: in the first, a nerve agent was released indoors; in the second, there was an outdoor explosion containing a blister agent. CBRNE experts, first responders and hospital specialists from across Europe participated in a two-day table-top exercise to discuss pre-hospital and hospital CBRNE preparedness, triage, surge capacity and communication issues. This was followed by a medical response exercise at a level 2 Emergency Department in Italy.RESULTS: Several surge capacity challenges and lessons were identified. Critical resources were rapidly exhausted and sourcing from national/international medical stockpiles was not feasible in the time critical scenarios. Secondary contamination in the blister agent scenario was considered plausible and hospitals are currently unprepared for this situation. The medical response exercise highlighted further training needs.CONCLUSIONS: The majority of the lessons are not new and have been reported in North American studies. However, this study is the first to describe these CWA challenges from a European perspective. Medical facilities across the region should consider these lessons to evaluate and improve their surge capacity, capability and response.

Two water-based methods were used to produce TiO2/graphene oxide (GO) nanocomposites with 1 and 2 wt.% GO. Both procedures exclude the use of organometallic precursors, as well as the high-pressure and high-temperature treatments, which facilitate pure and energy efficient synthesis amenable for larger scale synthesis. Nanocomposites with narrow (< 10 nm) and long spindle-like (< 100 nm) TiO2 nanoparticles supported on GO flakes were obtained (TiO2/GO), and their properties for reactive destruction of the organophosphorus simile chemical warfare agent (CWA) dimethyl methylphosphonate (DMMP) were investigated by in situ DRIFTS spectroscopy. Both synthesis procedures yielded highly reactive nanocomposites with markedly different properties compared to similarly prepared pure TiO2 nanoparticles. GO also induced morphology and texture changes, which were observed to have a significant impact on the adsorption and reactivity of the nano composites, and which were strongly related to synthesis procedure. In particular, the reduction state of GO, as measured by Raman spectroscopy, was observed to play a major role for the reactivity of the TiO2/GO nano composites.

We report on a new longwave infrared optical parametric source, and its implementation for long range or medium range standoff detection of gaseous chemical warfare agents., QC 20181023

Fatalities from organophosphate (OP) insecticide result from both occupational and deliberate exposure; significantly impacting human health. Like nerve agents, insecticides are neurotoxins which target and inhibit acetylcholinesterases (AChE) in central and peripheral synapses in the cholinergic nervous system. Post-exposure therapeutic countermeasures generally include administration of atropine with a pyridinium aldoxime e.g. pralidoxime, to reactivate the OP-inhibited AChE. However, commonly used oximes inefficiently cross the bloodbrain barrier and are rapidly cleared and their benefit is debated. Recent findings have demonstrated the ability of a novel zwitterionic, centrally acting, brain penetrating oxime (RS194B) to reverse severe symptoms and rapidly reactivate sarin-inhibited AChE in macaques, but it has not been tested following OP pesticide poisoning. In the present study, the symptoms following a lethal dose of inhaled paraoxon (100ug/kg), were shown to mimic those in insecticide poisoned individuals and were also rapidly reversed in macaques by post-exposure IM administration of 80mg/kg of RS194B. This occurred with a concomitant reactivation of AChE to 40-100% in<1hr and BChE (40% in 8h). These findings will be used to develop a macaque model with RS194B as a post-exposure treatment for insecticide poisoning and generate efficacy data for approval under the FDA Animal rule.

PurposeNitrogen mustard (NM), which simulates the effects of sulfur mustard (SM), is a potent vesicant known to cause irreversible corneal damage. This study investigates the mechanisms by which NM induces corneal damage by examining the impact of NM exposure on the morphology and lipidome of the cornea.MethodsIntact ex vivo rabbit eyes were placed in serum-free DMEM organ culture. NM (0, 1, 2.5, 5 or 10 mg/ml) was applied to the central cornea for 5, 10 or 15 min using a 5 mm filter disk and subsequently rinsed with DMEM. Corneas were then cultured for 3, 24, or 48 h before being fixed for morphological analysis or for 24 h before being snap frozen for lipidomic analysis.ResultsNo morphological changes were detected 3 h after NM exposure. Twenty-four h after exposure, 1 mg/ml NM caused erosion of the corneal epithelium, but no damage to the underlying stroma. Damage caused by 2.5 mg/ml NM extended almost two thirds through the corneal stroma, while 5 mg/ml completely penetrated the corneal stroma. An altered lipid profile occurred 24 h after corneas were exposed to NM. Specific sphingomyelins, ceramides, and diacylglycerols were increased up to 9-, 60- and 10-fold, respectively.ConclusionsNM induces concentration- and exposure time-dependent damage to the cornea that increases in severity over time. Alterations in the sphingomyelin-ceramide pathway may contribute to the damaging effects of NM exposure.

Chemical attribution signatures (CAS) associated with different synthetic routes used for the production of Russian VX (VR) were identified. The goal of the study was to retrospectively determine the production method employed for an unknown VR sample. Six different production methods were evaluated, carefully chosen to include established synthetic routes used in the past for large scale production of the agent, routes involving general phosphorus-sulfur chemistry pathways leading to the agent, and routes whose main characteristic is their innate simplicity in execution. Two laboratories worked in parallel and synthesized a total of 37 batches of VR via the six synthetic routes following predefined synthesis protocols. The chemical composition of impurities and byproducts in each route was analyzed by GC/MS-EI and 49 potential CAS were recognized as important markers in distinguishing these routes using Principal Component Analysis (PCA). The 49 potential CAS included expected species based on knowledge of reaction conditions and pathways but also several novel compounds that were fully identified and characterized by a combined analysis that included MS-CI, MS-EI and HR-MS. The CAS profiles of the calibration set were then analyzed using partial least squares discriminant analysis (PLS-DA) and a cross validated model was constructed. The model allowed the correct classification of an external test set without any misclassifications, demonstrating the utility of this methodology for attributing VR samples to a particular production method. This work is part one of a three-part series in this Forensic VSI issue of a Sweden-United States collaborative effort towards the understanding of the CAS of VR in diverse batches and matrices. This part focuses on the CAS in synthesized batches of crude VR and in the following two parts of the series the influence of food matrices on the CAS profiles are investigated., Funding agencies: the Swedish Civil Contingencies Agency (under Contract 2014–5170) and the Department of Homeland Security, Science and Technology Directorate, Chemical Forensic Program (under Contract # HSHQPM-10-X-00014 and HSHQPM-11-X-00247), United States

Ultra-sensitive in-field measurements of most forensic substances still today remain a challenge for first responders and forensic investigators. Handheld Raman spectroscopy equipment is getting more and more routinely used in the field for evidence collection, however, restricted to measurements of pure or high concentration samples. Here, surface-enhanced Raman scattering (SERS) sensing of common forensic substances with commercially available SERS substrates and handheld spectrometers, have been investigated. 3D Finite Element Method (FEM) and Density Functional Theory (DFT) simulations were used to interpret the high SERS enhancement of the Ag nanopillar substrate and the detection of the substances, respectively. The forensic generality and high performance of the analytical method were demonstrated by explicit detection of close to unprecedented amounts, down to femtograms, of Cyclosarin, RDX, Amphetamine and Picric acid. Implications are ultra-sensitive in-field SERS detection of these substances with commercial equipment.

Надходження в арсенали озброєнь фосфорорганічних отруйних речовин (ОР) нервово-паралітичної дії знаменувало апогей розвитку хімічної зброї. У 1939 р. було отримано зарин, а наприкінці 1944 р. — зоман, що належали до нового класу смертельних ОР нервово-паралітичної дії й у багато разів перевершували за своєю токсичністю ОР часів Першої світової війни. Промислове виробництво зарину почалося в 1952 р. В середині 1961 р. у США почали виробляти малолетючу стійку фосфорорганічну ОР під шифром VХ, особливо небезпечну при потраплянні навіть невеликих кількостей її на шкіру. За роки Другої світової війни в США на 17 технологічних установках було вироблено 135 тис. т різних ОР, з яких більше половини припадало на іприт. Останнім було споряджено близько 5 млн снарядів і 1 млн хімічних авіаційних бомб. Результатом робіт у галузі ОР, що впливають на центральну нервову систему людини, стало детальне дослідження до 1962 р. 3-хінуклідинілового ефіру бензилової кислоти, що має шифр ВZ. Вона перебувала на озброєнні американської армії і в експериментальному варіанті застосовувалася у В’єтнамі. У післявоєнні роки в армії США на зміну старих речовин подразнюючої дії були прийняті нові речовини — СS і СR, що стали результатом спільних англо-американських досліджень. За подразнюючою дією речовина CS значно перевершує іританти часів Першої світової війни. У 1993 р. було прийнято Міжнародну конвенцію про заборону хімічної зброї, що набрала чинності 29 квітня 1997 р., Поступление в арсеналы вооружений фосфор­органических отравляющих веществ (ОВ) нервно-паралитического действия знаменовало апогей развития химического оружия. В 1939 г. были получены зарин, а в конце 1944 г. — зоман, принадлежавшие к новому классу смертельных ОВ нервно-паралитического действия и во много раз преобладавшие по своей токсичности ОВ времен Первой мировой войны. Промышленное производство зарина началось в 1952 г. В середине 1961 г. в США начали производить малолетучее стойкое фосфор­органическое ОВ под шифром VХ, особенно опасное при попадании даже небольшого количества его на кожу. За годы Второй мировой войны в США на 17 технологических установках было произведено 135 тыс. тонн различных ОВ, из которых более половины приходилось на иприт. Последним были снаряжены около 5 млн снарядов и 1 млн химических авиационных бомб. Результатом работ в области ОВ, влияющих на центральную нервную систему человека, стало детальное исследование до 1962 г. 3-хинуклидинилового эфира бензиловой кислоты, имеющего шифр ВZ. Оно находилось на вооружении американской армии и в экспериментальном варианте применялось во Вьетнаме. В послевоенные годы в армии США на смену старых веществ раздражающего действия были приняты новые вещества — СS и СR, которые стали результатом совместных англо-американских исследований. По раздражающим действиям вещество CS значительно превосходит ирританты времен Первой мировой войны. В 1993 г. была принята Международная конвенция о запрещении химического оружия, вступившая в силу 29 апреля 1997 г., Entering the arsenals of weapons of organophosphorus compounds marked the apogee in the development of chemical weapons. In 1939, sarin was obtained, and by the end of 1944 — soman, belonging to a new class of lethal nerve agents, whose toxicity was much higher than that of chemical warfare agents in World War I. Industrial production of sarin began in 1952. In mid-1961, the United States began producing low-volatile persistent organophosphorus compounds under the code VX, especially dangerous if you get even a small amount of it on the skin. During World War II, in the United States on 17 processing plants, there were produced 135 thousand tons of chemical warfare agents, of which more than half was mustard gas. The last were filled in about 5 million chemical bombs. The result of the work in the field of chemical warfare agents affecting the central nervous system has been a detailed study in 1962 of 3-quinuclidinyl benzyl ester acid, which has the code BZ. It was in service with the US Army, and an experimental version was used in Vietnam. CS and CR — new substances adopted in the postwar years by the US Army to replace the old irritating substances. Both agents are the result of joint Anglo-American studies. As irritating substance, CS exceeds the irritants of World War I. International Chemical Weapons Convention adopted in 1993 entered into force on 29 April 1997.

Бойові отруйні речовини задушливої та подразнюючої дії були першим видом хімічної зброї, що застосована під час Першої світової війни. Основні отруйні речовини (задушливі — газоподібний фосген, рідкий дифосген; подразнюючої дії — хлорпікрин) поширювалися за допомогою газометів. Усі ці сполуки викликали тяжкі ураження органів дихання, шкірних покривів. Усього з квітня 1915 р. по листопад 1918 р. відбулося понад 50 німецьких газобалонних атак. У цей же період проти німецьких військ було здійснено 150 англійських і 20 французьких газопусків. Французькі війська 15 травня 1916 р. застосовували артилерію з сумішшю фосгену з чотирихлористим оловом і трихлористим миш’яком, хлорпікрином, а також суміш синільної кислоти з трихлористим миш’яком, чотирихлористим оловом у хлороформі (форма венсеніту). Хлорціан і синільна кислота — бойові отруйні речовини загальноотруйної дії. Вперше іприт як шкірно-наривна бойова отруйна речовина був застосований 12 липня 1917 р. під м. Іпр (Бельгія) в артилерійських снарядах. Застосування бойових отруйних речовин у Першій світовій війні викликало протест світової громадськості. Після закінчення війни за Версальським мирним договором (1919) Німеччині та її військовим союзникам було заборонено проводити дослідження, розробку і взяття бойових отруйних речовин на озброєння., Боевые отравляющие вещества удушающего и раздражающего действия были первым видом химического оружия, примененного во время Первой мировой войны. Основные ядовитые вещества (удушающие — газообразный фосген, жидкий дифосген; раздражающего действия — хлорпикрин) применялись с помощью газометов. Все эти соединения вызывали тяжелые поражения органов дыхания, кожных покровов. Всего с апреля 1915 г. по ноябрь 1918 г. прошло более 50 немецких газобаллонных атак. В этот же период против немецких войск было осуществлено 150 английских и 20 французских газопусков. Французские войска 15 мая 1916 г. применяли артиллерию со смесью фосгена с четыреххлористым оловом и треххлористым мышьяком, хлорпикрином, а также смесь синильной кислоты с треххлористым мышьяком, четыреххлористым оловом в хлороформе (форма венсенита). Хлорциан и синильная кислота — боевые отравляющие вещества общеотравляющего действия. Впервые иприт как кожно-нарывное отравляющее вещество был применен 12 июля 1917 года в г. Ипр (Бельгия) в артиллерийских снарядах. Применение боевых отравляющих веществ в Первой мировой войне вызвало протест мировой общественности. После окончания войны по Версальскому мирному договору (1919) Германии и ее военным союзникам были запрещены исследования, разработка и взятие боевых отравляющих веществ на вооружение., Chemical warfare agents with suffocating and irritating action were the first type of chemical weapon used during the World War I. The main toxic substances used by a gas projector were suffocating ones — gas-like phosgene, liquid diphosgene and irritating toxic substance — chloropicrin. All of these compounds caused severe damage to the respiratory system, skin. In total, from April 1915 to November 1918, there were more than 50 German cloud attacks. For the same period, 150 English and 20 French gas discharges were carried out against the German troops. French troops on May 15, 1916 used artillery with a mixture of phosgene and tin tetrachloride and arsenic trichloride, chloropicrin, as well as a mixture of hydrogen cyanide and arsenic trichloride, tin tetrachloride in chloroform in the form of vincennite. Cyanogen chloride and hydrogen cyanide — chemical warfare agents with general poisonous effect. For the first time, mustard gas as a blister agent was used on July 12, 1917 outside the town of Ypres in Belgium in artillery shells. The use of chemical warfare agents in the World War I caused the protest of the world community. After the war, according to the Treaty of Versailles (1919), Germany and its military allies were prohibited from researching, developing and adopting chemical warfare agents.

Ambient pressure in situ synchrotron-based spectroscopic techniques have been correlated to illuminate atomic-level details of bond breaking and formation during the hydrolysis of a chemical warfare nerve agent simulant over a polyoxometalate catalyst. Specifically, a Cs-8[Nb6O19] polyoxoniobate catalyst has been shown to react readily with dimethyl methylphosphonate (DMMP). The atomic-level transformations of all reactant moieties, the [Nb6O19](8)-polyanion, its Cs+ counterions, and the DMMP substrate, were tracked under ambient conditions by a combination of X-ray absorption fine structure spectroscopy, Raman spectroscopy, and X-ray diffraction. Results reveal that the reaction mechanism follows general base (in contrast to specific base) hydrolysis. Together with computational results, the work demonstrates that the ultimate fate of DMMP hydrolysis at the Cs-8[Nb6O19] catalyst is strong binding of the (methyl) methylphosphonic acid ((M) MPA) product to the polyanions, which ultimately inhibits catalytic turnover.

Exposure to organophosphorus nerve agents, the most deadly chemical warfare agents, is possible in a variety of situations, such as destruction of chemical warfare agents, terrorist attacks, armed conflicts or accidents in research laboratories and storage facilities. Hundreds of thousands of tons of chemical munitions were disposed of at the sea in the post World War II period, with European, Russian, Japanese and US coasts being the most affected. Sulfur mustard, Lewisite and nerve agents appear to be the most frequently chemical warfare agents disposed of at the sea. Addressing the overall environmental risk, it has been one of the priorities of the world community since that time. Aside from confirming exposure to nerve agents in the alleged use for forensic purposes, the detection and identification of biological markers of exposure are also needed for the diagnosis and treatment of poisoning, in addition to occupational health monitoring for specific profiles of workers. When estimating detrimental effects of acute or potential chronic sub-lethal doses of organophosphorus nerve agents, released accidentally or intentionally into the environment, it is necessary to understand the wide spectra of physical, chemical and toxicological properties of these agents, and predict their ultimate fate in environmental systems.

In the article the author in his memoirs ponders the military-political aspects of the presence of toxic substances in the Gulf War in 1990-1991, measured by chemists from the 1st Czechoslovak independent chemical protection battalion. The thesis provides a comprehensive look at the history of its origin, its own deployment of in the war, and access to public administrations to its members after returning from the war.

Motivated by recent experiments in gas-surface chemistry, we report our results from computational investigations of heterogeneous systems relevant to atmospheric chemistry and protection against chemical weapons. To elucidate findings of ultra-high vacuum experiments that probe the oxidation of carbon-carbon double bonds on model surfaces, we used electronic structure and QM/MM methods to study the reaction of ozone with C60-fullerene and the products of nitrate addition to a vinyl-terminated self-assembled monolayer. In the first system, we followed a reaction pathway beginning with primary ozonide formation through the formation of stable products. Theoretical vibrational spectra were used to identify a ketene product in prior experimental work. Next, through the construction of a multilayer model for the initial addition product of a nitrate radical to a chain embedded within a self-assembled monolayer, we report theoretical spectra that are consistent with experimental results. We then examined the fundamentals of the hydrolysis mechanism for nerve agents by a catalyst of interest in the development of filtration materials for chemical-warfare-agent defense. By following the gas-surface reaction pathway of the nerve agent Sarin on the Lindqvist polyoxoniobate Cs8Nb6O19, we determined that the rate-limiting step is the transfer of a proton from an adsorbed water molecule to the niobate surface, concomitant with the nucleophilic addition of the nascent hydroxide to the phosphorus atom in Sarin. Our results support a general base hydrolysis mechanism, though high product-adsorption energies suggest that thermal treatment of the system is required to fully regenerate the catalyst. We report similar mechanisms for the simulants dimethyl methylphosphonate and dimethyl chlorophosphate, though the latter may serve as a better simulant in studies of this type. Finally, an investigation of Sarin hydrolysis with solvated Cs8Nb6O19 shows an increase in the rate-limiting ba

Ambient pressure in situ synchrotron-based spectroscopic techniques have been correlated to illuminate atomic-level details of bond breaking and formation during the hydrolysis of a chemical warfare nerve agent simulant over a polyoxometalate catalyst. Specifically, a Cs-8[Nb6O19] polyoxoniobate catalyst has been shown to react readily with dimethyl methylphosphonate (DMMP). The atomic-level transformations of all reactant moieties, the [Nb6O19](8)-polyanion, its Cs+ counterions, and the DMMP substrate, were tracked under ambient conditions by a combination of X-ray absorption fine structure spectroscopy, Raman spectroscopy, and X-ray diffraction. Results reveal that the reaction mechanism follows general base (in contrast to specific base) hydrolysis. Together with computational results, the work demonstrates that the ultimate fate of DMMP hydrolysis at the Cs-8[Nb6O19] catalyst is strong binding of the (methyl) methylphosphonic acid ((M) MPA) product to the polyanions, which ultimately inhibits catalytic turnover.

In the article the author in his memoirs ponders the military-political aspects of the presence of toxic substances in the Gulf War in 1990-1991, measured by chemists from the 1st Czechoslovak independent chemical protection battalion. The thesis provides a comprehensive look at the history of its origin, its own deployment of in the war, and access to public administrations to its members after returning from the war.

Exposure to organophosphorus nerve agents, the most deadly chemical warfare agents, is possible in a variety of situations, such as destruction of chemical warfare agents, terrorist attacks, armed conflicts or accidents in research laboratories and storage facilities. Hundreds of thousands of tons of chemical munitions were disposed of at the sea in the post World War II period, with European, Russian, Japanese and US coasts being the most affected. Sulfur mustard, Lewisite and nerve agents appear to be the most frequently chemical warfare agents disposed of at the sea. Addressing the overall environmental risk, it has been one of the priorities of the world community since that time. Aside from confirming exposure to nerve agents in the alleged use for forensic purposes, the detection and identification of biological markers of exposure are also needed for the diagnosis and treatment of poisoning, in addition to occupational health monitoring for specific profiles of workers. When estimating detrimental effects of acute or potential chronic sub-lethal doses of organophosphorus nerve agents, released accidentally or intentionally into the environment, it is necessary to understand the wide spectra of physical, chemical and toxicological properties of these agents, and predict their ultimate fate in environmental systems.

As a result of the disarmament of Germany after the Second World War, 65,000 tons of chemical munitions were dumped in the Baltic Sea. Approximately 13,000 tons containing chemical warfare agents (CWAs) of which 11,000 tons were dumped in the Bornholm Basin east of Bornholm. This paper addresses the ecotoxicity of compounds actually present in the Bornholm dumpsite by obtaining novel acute ecotoxicity data. EC50 values were successfully obtained for 12 CWAs from acute tests using Allivibrio fischeri (Microtox™). The three most toxic compounds were α-chloroacetophenone, 2-chlorovinylarsonic acid and 1,2,5-trithiepane having EC50 values of 11.20, 31.20 and 1170 μg L−1, respectively. A. fischeri demonstrated hormesis when exposed to triphenylarsine and triphenylarsine oxide at concentrations of 100 and 50 mg L−1, respectively. Four different mixtures were assessed including compounds which were dissolvable; a mixture of sulphur mustard degradation products, a mixture of the three most toxic sulphur mustard compounds, a mixture of organoarsenical degradation products and a mixture of all compounds. The mixtures deviate by a factor of 1.5–2.5 from the prediction of the concentration addition model and hence, the mixtures demonstrate no sign of synergism or antagonism. The compounds presented in this study are mainly CWA.

Chemical Munitions Search & Assessment (CHEMSEA) project has performed studies on chemical weapon (CW) detection, sediment pollution and spreading as well as biological effects of chemical warfare agents (CWAs) dumped in the Baltic Sea. Results suggest that munitions containing CWAs are more scattered on the seafloor than suspected, and previously undocumented dumpsite was discovered in Gdansk Deep. Pollution of sediments with CWA degradation products was local and close to the detected objects; however the pollution range was larger than predicted with theoretical models. Bottom currents observed in the dumpsites were strong enough for sediment re-suspension, and contributed to the transport of polluted sediments. Diversity and density of the faunal communities were poor at the dumping sites in comparison to the reference area, although the direct effects of CWA on benthos organisms were difficult to determine due to hypoxic or even anoxic conditions near the bottom. Equally, the low oxygen might have affected the biological effects assessed in cod and caged blue mussels. Nonetheless, both species showed significantly elevated molecular and cellular level responses at contaminated sites compared to reference sites.

Anti-retroviral drugs suppress HIV-1 plasma viremia to undetectable levels; however, latent HIV-1 persists in reservoirs within HIV-1-infected patients. The silent provirus can be activated through the use of drugs, including protein kinase C activators and histone deacetylase inhibitors. This "shock" approach is then followed by "kill" of the producing cells either through direct HIV-1-induced cell death or natural immune mechanisms. However, these mechanisms are relatively slow and effectiveness is unclear. Here, we develop an approach to specifically target and kill cells that are activated early in the process of virus production. We utilize a novel nanocapsule technology whereby the ricin A chain is encapsulated in an inactive form within a polymer shell. Specificity for release of the ricin A toxin is conferred by peptide crosslinkers that are sensitive to cleavage by HIV-1 protease. By using well-established latent infection models, J-Lat and U1 cells, we demonstrate that only within an HIV-1-producing cell expressing functional HIV-1 protease will the nanocapsule release its ricin A cargo, shutting down viral and cellular protein synthesis, and ultimately leading to rapid death of the producer cell. Thus, we provide proof of principle for a novel technology to kill HIV-1-producing cells without effects on non-target cells.

Test strips that in combination with a portable fluorescence reader or digital camera can rapidly and selectively detect chemical warfare agents (CWAs) such as Tabun (GA), Sarin (GB), and Soman (GD) and their simulants in the gas phase have been developed. The strips contain spots of a hybrid indicator material consisting of a fluorescent BODIPY indicator covalently anchored into the channels of mesoporous SBA silica microparticles. The fluorescence quenching response allows the sensitive detection of CWAs in the mu g m(-3) range in a few seconds.

Test strips that in combination with a portable fluorescence reader or digital camera can rapidly and selectively detect chemical warfare agents (CWAs) such as Tabun (GA), Sarin (GB), and Soman (GD) and their simulants in the gas phase have been developed. The strips contain spots of a hybrid indicator material consisting of a fluorescent BODIPY indicator covalently anchored into the channels of mesoporous SBA silica microparticles. The fluorescence quenching response allows the sensitive detection of CWAs in the mu g m(-3) range in a few seconds.

Mesoporous silica nanoparticles loaded with rhodamine B and capped with acetylcholinesterase are able to be selectively opened and deliver their cargo in the presence of nerve agent simulant diisopropyl fluorophosphate (DFP).

Anti-retroviral drugs suppress HIV-1 plasma viremia to undetectable levels; however, latent HIV-1 persists in reservoirs within HIV-1-infected patients. The silent provirus can be activated through the use of drugs, including protein kinase C activators and histone deacetylase inhibitors. This "shock" approach is then followed by "kill" of the producing cells either through direct HIV-1-induced cell death or natural immune mechanisms. However, these mechanisms are relatively slow and effectiveness is unclear. Here, we develop an approach to specifically target and kill cells that are activated early in the process of virus production. We utilize a novel nanocapsule technology whereby the ricin A chain is encapsulated in an inactive form within a polymer shell. Specificity for release of the ricin A toxin is conferred by peptide crosslinkers that are sensitive to cleavage by HIV-1 protease. By using well-established latent infection models, J-Lat and U1 cells, we demonstrate that only within an HIV-1-producing cell expressing functional HIV-1 protease will the nanocapsule release its ricin A cargo, shutting down viral and cellular protein synthesis, and ultimately leading to rapid death of the producer cell. Thus, we provide proof of principle for a novel technology to kill HIV-1-producing cells without effects on non-target cells.

BackgroundWe previously reported evidence of reduced cortical gray matter (GM), white matter (WM), and hippocampal volume in Gulf War (GW) veterans with predicted exposure to low-levels of nerve agent according to the 2000 Khamisiyah plume model analysis. Because there is suggestive evidence that other nerve agent exposures may have occurred during the Gulf War, we examined the association between the self-reported frequency of hearing chemical alarms sound during deployment in the Gulf War and regional brain volume in GW veterans.MethodsNinety consecutive GW veterans (15 female, mean age: 52±8years) participating in a VA-funded study underwent structural magnetic resonance imaging (MRI) on a 3T scanner. Freesurfer (version 5.1) was used to obtain regional measures of cortical GM, WM, hippocampal, and insula volume. Multiple linear regression was used to determine the association between the self-reported frequencies of hearing chemical alarms during the Gulf War and regional brain volume.ResultsThere was an inverse association between the self-reported frequency of hearing chemical alarms sound and total cortical GM (adjusted p=0.007), even after accounting for potentially confounding demographic and clinical variables, the veterans' current health status, and other concurrent deployment-related exposures that were correlated with hearing chemical alarms. Post-hoc analyses extended the inverse relationship between the frequency of hearing chemical alarms to GM volume in the frontal (adjusted p=0.02), parietal (adjusted p=0.01), and occipital (adjusted p=0.001) lobes. In contrast, regional brain volumes were not significantly associated with predicted exposure to the Khamisiyah plume or with Gulf War Illness status defined by the Kansas or Centers for Disease Control and Prevention criteria.ConclusionsMany veterans reported hearing chemical alarms sound during the Gulf War. The current findings suggest that exposure to substances that triggered those chemical alarms

Decontamination activities may cause the release of contaminated washwater into the wastewater that eventually flows into a wastewater treatment facility. This raises concerns about the effect of chemical warfare agents (CWAs) on the microbial consortia that are responsible for cleaning the wastewater. This study investigated the impact of malathion on the microbial ecology of laboratory scale activated sludge communities. The Simpson Reciprocal Index decreased for three bioreactors operated in the absence of malathion, which showed that the microbial assemblage became less diverse during the course of the study. The species identified in the bioreactors belonged to well-known groups of heterotrophic and autotrophic bacteria, and these groups were represented in the presence and absence of malathion. Nitrospira, a key player in autotrophic nitrogen removal, decreased in relative abundance for the bioreactor exposed to 0.1 mg/L of malathion but increased in the bioreactor exposed to 3 mg/L of malathion, possibly due to interactions with heterotrophic groups that suffered inhibition. To the author???s knowledge, this study is the first to document the ecological impacts of long term malathion exposure in bioreactors carrying out COD removal and nitrification., The original document contains color images.

Decontamination activities following a chemical weapons incident may generate significant quantities of contaminated wash water that may enter the wastewater collection system either intentionally or accidentally. This raises concerns about the effect of chemical warfare agents (CWAs) on the operation of a biological wastewater treatment plant. The goal of the study was to evaluate the effect of malathion on the activity and performance of activated sludge. Malathion is an organophosphate (OP) and is considered an environmental surrogate for VX. This study employed respirometry, short term batch tests, and long term exposure experiments to investigate the effects of different concentrations of malathion on bioreactor performance. Short-term exposure to malathion may depress microbial respiration, however, short-term batch tests showed that chemical oxygen demand (COD) removal was not negatively impacted by the presence of malathion concentrations of 0.1 or 3 mg/L. Unlike COD removal, ammonia-N removal was slowed by the presence of malathion at both 0.1 and 3 mg/L with a positive correlation of the removal rate to the quantity of total suspended solids. Long-term exposure experiments demonstrated that both COD removal and Nitrate production were negatively affected at concentrations of 3.0 mg/L and unaffected at concentrations of 0.1 mg/L., The original document contains color images.

In 1917 the Bureau of Mines established the War Gas Investigations at American University, in Washington, D.C. This bibliography is a compilation of the technical reports and monographs produced in this effort. The reports were produced at the university during the time frame of 1918 to 1919, however, the date that this bibliography was compiled is unknown. It was made available for release in April 2015., Bibliography spans reports produced from 1918-1919. Actual date that this bibliography was compiled is unknown.

he interactions of the chemical warfare agent sulfur mustard with amorphous silica were investigated using electronic structure calculations. In this thesis, the binding energies of sulfur mustard and mimic species used in the laboratory were calculated using density functional theory and fully ab initio calculations. The wB97XD and B97D functionals, which include functions to account for long-range dispersion interactions, were compared to experimental trends. The hydroxylated amorphous silica surface was approximated using a gas-phase silanol molecule and clusters containing a single hydroxyl moiety. Recent temperature programmed desorption experiments performed in UHV concluded that sulfur mustard and its less toxic mimics undergo molecular adsorption to amorphous silica. Hydrogen bonding can occur between surface silanol groups and either the sulfur or chlorine atom of the adsorbates, and the calculations indicate that the binding energies for the two hydrogen bond acceptors are similar. The adsorption of sulfur mustard and its mimics on silica also exhibits the presence of significant van der Waals interactions between alkyl of the adsorbates and the surface. These interactions, in combination with the formation of a hydrogen bond between a surface silanol group and the Cl or S atoms of the adsorbates, provide remarkably large binding energies.

The paper provides a brief description of the Prague Metro focusing on the potential chemical threats by chemical warfare agents. Detailed evaluation of the possibility of abuse of chemical warfare nerve agents is presented in different conditions in the Prague Metro system as simulated by a TEREX computer program. In conclusion, the results are evaluated by a SWOT analysis referring to many domestic scientific works dedicated to the protection of population against the effects of chemical terrorism., Příspěvek podává stručnou informaci o podzemní dráze hlavního města Prahy a zaměřuje se na potenciální chemickou hrozbu v podobě chemických bojových látek. V rámci příspěvku byly vyhodnoceny možnosti zneužití chemických bojových látek v podobě nervově paralytických plynů v podmínkách pražského metra, modelované pomocí počítačového programu TEREX. V závěru jsou vyhodnoceny zjištěné výsledky pomocí analýzy SWOT a je upozorněno na na mnoho domácích vědeckých prací, které se ochraně obyvatelstva před účinky chemického terorismu věnují.

The paper provides a brief description of the Prague Metro focusing on the potential chemical threats by chemical warfare agents. Detailed evaluation of the possibility of abuse of chemical warfare nerve agents is presented in different conditions in the Prague Metro system as simulated by a TEREX computer program. In conclusion, the results are evaluated by a SWOT analysis referring to many domestic scientific works dedicated to the protection of population against the effects of chemical terrorism., Příspěvek podává stručnou informaci o podzemní dráze hlavního města Prahy a zaměřuje se na potenciální chemickou hrozbu v podobě chemických bojových látek. V rámci příspěvku byly vyhodnoceny možnosti zneužití chemických bojových látek v podobě nervově paralytických plynů v podmínkách pražského metra, modelované pomocí počítačového programu TEREX. V závěru jsou vyhodnoceny zjištěné výsledky pomocí analýzy SWOT a je upozorněno na na mnoho domácích vědeckých prací, které se ochraně obyvatelstva před účinky chemického terorismu věnují.

The paper provides a brief description of the Prague Metro focusing on the potential chemical threats by chemical warfare agents. Detailed evaluation of the possibility of abuse of chemical warfare nerve agents is presented in different conditions in the Prague Metro system as simulated by a TEREX computer program. In conclusion, the results are evaluated by a SWOT analysis referring to many domestic scientific works dedicated to the protection of population against the effects of chemical terrorism., Příspěvek podává stručnou informaci o podzemní dráze hlavního města Prahy a zaměřuje se na potenciální chemickou hrozbu v podobě chemických bojových látek. V rámci příspěvku byly vyhodnoceny možnosti zneužití chemických bojových látek v podobě nervově paralytických plynů v podmínkách pražského metra, modelované pomocí počítačového programu TEREX. V závěru jsou vyhodnoceny zjištěné výsledky pomocí analýzy SWOT a je upozorněno na na mnoho domácích vědeckých prací, které se ochraně obyvatelstva před účinky chemického terorismu věnují.

The paper provides a brief description of the Prague Metro focusing on the potential chemical threats by chemical warfare agents. Detailed evaluation of the possibility of abuse of chemical warfare nerve agents is presented in different conditions in the Prague Metro system as simulated by a TEREX computer program. In conclusion, the results are evaluated by a SWOT analysis referring to many domestic scientific works dedicated to the protection of population against the effects of chemical terrorism., Příspěvek podává stručnou informaci o podzemní dráze hlavního města Prahy a zaměřuje se na potenciální chemickou hrozbu v podobě chemických bojových látek. V rámci příspěvku byly vyhodnoceny možnosti zneužití chemických bojových látek v podobě nervově paralytických plynů v podmínkách pražského metra, modelované pomocí počítačového programu TEREX. V závěru jsou vyhodnoceny zjištěné výsledky pomocí analýzy SWOT a je upozorněno na na mnoho domácích vědeckých prací, které se ochraně obyvatelstva před účinky chemického terorismu věnují.

Manuel Valls, the French Prime Minister, has warned about the possibility of terrorist use of chemical or bacteriological weapons by DAESH. In the sense of considering this possibility as an "extremely limited" but credible risk against which had to be prepared. These statements would be based on the interest shown by terrorist organizations with Jihadist inspiration to possess and use WMDs to achieve its operational and strategic objectives. In the case of biological agents, but also chemical warfare agents, this interest is facing the reality of having to overcome a series of interconnected steps must overcome, some dependent on others, to achieve the operational capacity of dissemination., Manuel Valls, el primer ministro francés, ha informado sobre la posibilidad de empleo terrorista de armas químicas o bacteriológicas por parte de DAESH. Estas declaraciones estarían basadas en el interés demostrado por las organizaciones terroristas de inspiración yihadista en poseer y utilizar Armas de Destrucción Masiva para alcanzar sus objetivos operacionales y estratégicos. En el caso particular de los agentes biológicos, pero también los agentes químicos de guerra, este interés se enfrenta a la realidad de tener que superar una serie de pasos de obligado cumplimiento, unos dependientes de otros, para alcanzar la capacidad operacional de diseminación.

The paper provides a brief description of the Prague Metro focusing on the potential chemical threats by chemical warfare agents. Detailed evaluation of the possibility of abuse of chemical warfare nerve agents is presented in different conditions in the Prague Metro system as simulated by a TEREX computer program. In conclusion, the results are evaluated by a SWOT analysis referring to many domestic scientific works dedicated to the protection of population against the effects of chemical terrorism., Příspěvek podává stručnou informaci o podzemní dráze hlavního města Prahy a zaměřuje se na potenciální chemickou hrozbu v podobě chemických bojových látek. V rámci příspěvku byly vyhodnoceny možnosti zneužití chemických bojových látek v podobě nervově paralytických plynů v podmínkách pražského metra, modelované pomocí počítačového programu TEREX. V závěru jsou vyhodnoceny zjištěné výsledky pomocí analýzy SWOT a je upozorněno na na mnoho domácích vědeckých prací, které se ochraně obyvatelstva před účinky chemického terorismu věnují.

The primary objectives of this work have been to: (1) characterize the chemistry of chemical warfare agents (CWAs) on metal, oxide, and polymeric surfaces, (2) make the first direct comparisons of the surface chemistry of CWA simulants and the agents themselves, including GB, VX, and HD, and (3) explore the chemistry of surface decontamination strategies including exposure to vaporous H2O2 and ClO2. These goals have been addressed through a concerted research effort along two fronts: CWA simulant studies at Virginia Tech and a new comprehensive effort that provides unique capabilities at the Edgewood Chemical Biological Center (ECBC) for studying the surface chemistry of CWAs. Specifically, a new state-of-the-art surface science instrument was developed at ECBC, which is the first of its kind to couple precision CWA dosing capabilities with mass spectrometry, infrared surface spectroscopy, photoelectron spectroscopy, and temperature programmed desorption methods. These techniques are providing time-resolved studies of CWA surface chemistry on important materials including those found in buildings or vehicles, within sensitive equipment, and on new coatings designed for soldier protection.

A fundamental understanding of the surface chemistry of chemical warfare agents is needed to fully predict the interaction of these toxic molecules with militarily relevant materials, catalysts, and environmental surfaces. For example, rules for predicting the surface chemistry of agents can be applied to the creation of next generation decontaminants, reactive coatings, and protective materials for the warfighter. Here, we describe a multifunctional ultra-high vacuum instrument for conducting comprehensive studies of the adsorption, desorption, and surface chemistry of chemical warfare agents on model and militarily relevant surfaces. The system applies reflection-absorption infrared spectroscopy, x-ray photoelectron spectroscopy, and mass spectrometry to study adsorption and surface reactions of chemical warfare agents. Several novel components have been developed to address the unique safety and sample exposure challenges that accompany the research of these toxic, often very low vapor pressure, compounds. While results of vacuum-based surface science techniques may not necessarily translate directly to environmental processes, learning about the fundamental chemistry will begin to inform scientists about the critical aspects that impact real-world applications., Published in the Journal of Review of Scientific Instruments, v85 n1 p1-9, 2014. The original document contains color images.

Chemical warfare nerve agents (CWNAs) are extremely toxic organophosphorus compounds that contain a chiral phosphorus center. Undirected synthesis of G-type CWNAs produces stereoisomers of tabun, sarin, soman, and cyclosarin (GA, GB, GD, and GF, respectively). Analytical-scale methods were developed using a supercritical fluid chromatography (SFC) system in tandem with a mass spectrometer for the separation, quantitation, and isolation of individual stereoisomers of GA, GB, GD, and GF. Screening various chiral stationary phases (CSPs) for the capacity to provide full baseline separation of the CWNAs revealed that a Regis WhelkO1 (SS) column was capable of separating the enantiomers of GA, GB, and GF, with elution of the P(+) enantiomer preceding elution of the corresponding P( ) enantiomer; two WhelkO1 (SS) columns had to be connected in series to achieve complete baseline resolution. The four diastereomers of GD were also resolved using two tandem WhelkO1 (SS) columns, with complete baseline separation of the two P(+) epimers. A single WhelkO1 (RR) column with inverse stereochemistry resulted in baseline separation of the GD P( ) epimers. The analytical methods described can be scaled to allow isolation of individual stereoisomers to assist in screening and development of countermeasures to organophosphorus nerve agents., The original document contains color images. Published in Chirality, v26 n12 p817-824, 2014. Prepared in collaboration with Waters Corp., New Castle, DE and Milford, MA.

This report outlines the instrumental method development for the analysis of human biofluids, in this case urine, for the presence of metabolites of the chemical warfare agents HD, GA, GB, GD, GE, GF, VX and VR using UHPLC MSMS. It also investigates the effect of different sample preparation techniques on the recovery of the analytes, using the analysis method developed.