Degradation Of VX Research Articles

Fluoride Product Inhibition: New Insight into the Degradation of Nerve Agents by Zr-MOFs.

Zirconium-based metal-organic frameworks (Zr-MOFs) have shown remarkable efficacy in catalytically degrading neurotoxic agents in recent years. However, the catalytic activity of Zr-MOFs can be inhibited due to the binding of phosphate degradation products to the Zr nodes. Here, we reported the inhibition effect of a nonphosphate substance, fluoride, which can deactivate Zr-MOF nodes for the degradation of GD and VX and simulate DEPPT. The experimental and theoretical calculation results reveal that the fluoride product during GD degradation shows much more significant suppression than phosphate. The phosphate products can depart from the Zr nodes completely by adding H2O molecules on the Zr nodes to reduce the energy barrier. However, the fluoride can replace the bridged μ3-OH groups and terminal -OH groups on Zr-oxo clusters irreversibly, changing the electric density of Zr nodes and eliminating the terminal -OH. Without the terminal -OH, the five-coordinate phosphorus intermediate cannot be formed, resulting in the inactivation of Zr-O-Zr sites. This study provides new insights into Zr-MOF catalyst deactivation mechanisms and may help to develop a new strategy to design MOFs with high anti-inhibition efficiency for the degradation of nerve agents.

Determination of tissue distribution of VX and its metabolites EMPA and EA-2192 in various rat tissues by LC-ESI-MS/MS after phosphotriesterase treatment

Phosphotriesterases (PTE) are a new and promising approach for the treatment of organophosphate poisoning, since the current therapy of such intoxications shows some limitations. A previous rat in vivo study confirmed the therapeutic effect of PTE, which were specifically designed for VX breakdown, and demonstrated rapid degradation of VX in whole blood samples. The present study now focuses on the degradation of VX and its distribution in organ tissues of the animals used in the aforementioned study. In order to gain a broader overview, we have extended the investigations to the VX metabolites EA-2192 and EMPA by using methods developed for an LC-ESI-MS/MS system. Applying these methods, we were able to verify the effectiveness of the PTE treatment and gained an overview of VX tissue distribution in poisoned but untreated rats.

Decontamination of mustard sulfur and VX by sodium percarbonate complexed with 1-acetylguanidine as a novel activator.

The peroxide-based decontaminants had attracted great attention for degradation of chemical warfare agents (CWAs) because of their high performance, non-corrosive and environmental-friendly merits. Hydrogen peroxide can be activated by some organic activators to enhance the oxidation ability. In this work, a novel formula based on sodium percarbonate (SPC) complexed with 1-acetylguanidine (ACG) was investigated for decontamination of sulfur mustard (HD) and VX as CWAs. In the experimental results, the active species acetyl peroxide imide acid in the formula aqueous solution was detected in situ by Raman and 13C NMR spectroscopy. The optimized conditions of the decontamination formula (SPC/ACG) were suggested that, the molar ratio of active oxygen and activator ([O]/[ACG]) was 1:1 while the pH value of the formula aqueous solution was about 9. To achieve the decontamination percentage over 99%, the molar ratio of active oxygen to CWA ((O)/(CWA)) needed to be at least 3 for HD and 7 for VX. Meanwhile, the degradation products detected by gas chromatography/mass spectrometry (GC/MS), liquid chromatography/mass spectrometry (LC/MS) and ion chromatography (IC) indicated that the oxidation and elimination reactions should have occurred on HD molecule, while the degradation of VX mainly originate from the nucleophilic substitution and oxidation reactions.

Catalytic degradation of CWAs with MOF-808 and PCN-222: Toward practical application

Chemical warfare agents, such as nerve agents (GD and VX) and blister agents (HD), have strong toxicities to mankind. In recent years, zirconium-based metal-organic frameworks have been found to be attractive materials for chemical warfare agent degradation. Among them, metal-organic framework-808 (MOF-808) and porous coordination network-222 (PCN-222) were the best. However, few papers pay attention to their practical application. In this work, we prepared MOF-808 and PCN-222 using water phase and organic solvothermal methods, respectively. Their performance for the catalytic degradation of chemical warfare agents under practical decontamination conditions was studied. The results showed that MOF-808 displayed a high potency for catalytic hydrolysis of VX (10,000 mg L−1) in unbuffered solution. PCN-222 exhibited weaker reactivity with a half-life ( t1/2) of 28.8 min. Their different performances might stem from the different connectivity of the Zr6 nodes and framework structures. The results illustrated that the hydrolysis of high-concentration GD required a strong alkaline buffer to neutralize the hydrolysis product of hydrofluoric acid (HF) to avoid catalyst poisoning. When H2O2 was used as the oxidant instead of O2, both zirconium-based metal-organic frameworks performed with effective catalytic potency for HD degradation without any special lighting and so was suitable for practical application, whereas the products obtained from HD, such as HDO2 and V-HDO2, still possessed vesicant toxicity. Overall, MOF-808 prepared via a water-phase synthesis performed with effective catalysis for the degradation of high-concentration VX, GD, and HD with t1/2 of < 0.5, 3.1 and 2.2 min, respectively, exhibiting its potential for practical applications.

In vitro human skin decontamination efficacy of MOF-808 in decontamination lotion following exposure to the nerve agent VX

Metal-organic frameworks (MOFs) have shown promising properties for removal of chemical warfare agents, in particular for material decontamination and functionalized fabrics. The MOF-properties could also be beneficial for skin decontamination, especially when exposed to highly toxic and low volatile nerve agents. In such exposures, efficient decontamination is crucial for adequate medical management. In the present study, seven zirconium-based MOFs were evaluated for their ability to degrade VX and subsequently tested in vitro for decontamination of VX on human dermatomed skin.Of the MOFs evaluated, MOF-808 showed the greatest ability to degrade VX in an alkaline buffer with complete degradation of VX within 5 min. PCN-777, Zr-NDC and NU-1000 displayed degradation half-lives of approximately 10 min. When including MOF-808 in a skin friendly carrier with slightly acidic pH, a decreased agent degradation rate was observed, requiring over 24 h to reach complete degradation. In skin decontamination experiments, MOF-808 enhanced the efficacy compared to the carrier alone, essentially by improved agent absorption. Adding MOF-808 to Reactive Skin Decontamination Lotion (RSDL) did not improve the high effectiveness of RSDL alone. The present study showed that including MOF in skin decontamination lotions could be beneficial. Further studies should include optimizing the particulates and formulations.

Degradation and Detection of the Nerve Agent VX by a Chromophore-Functionalized Zirconium MOF

Nerve agents are among the most toxic substances known to man. Recent events in Syria, Malaysia, and the UK illustrate that the threat of these substances is real and actual. The timely detection and identification of nerve agents is of great importance to facilitate timely decontamination or medical countermeasures. In this work, an effective and sensitive detection system, based on the metal–organic framework (MOF) NU-1000, was developed for the disclosure of V-agents, a class of nerve agents that is very persistent, highly toxic, and difficult to detect. NU-1000 is a zirconium-based MOF that can hydrolyze VX into a nontoxic phosphonic acid and the thiol 2-(diisopropylamino)ethanethiol. In this work, it was hypothesized that the four noncoordinating sites that are present on each Zr-building brick of this MOF could be functionalized with the two carboxylates present in 5,5′-di-thio-bis(2-nitrobenzoic acid), DTNB. This dimeric (RS-SR) compound efficiently reacts with thiols by S–S bond exchange and results in the release of the chromophore RS-H. Thus, the target hybrid material (DTNB@NU-1000) was expected to degrade VX and at the same time give a visual color response upon reaction of the thiol-containing degradation product of VX with MOF-bound DTNB. We here report that DTNB@NU-1000 can be readily synthesized and that it is surprisingly active in the degradation of VX in neutral buffer. Moreover, the degradation of VX resulted in a color response, the intensity of which showed linear correlation with the VX concentration used. The applicability of this material was illustrated by a proof-of-concept detection kit for VX-contaminated surfaces, as exemplified with VX-contaminated metal panels coated with military paint [chemical agent resistant coating]. This procedure requires minimal training burden, and VX contamination down to a level of about 1–2 μg/cm2 could be reliably visually established, during a total handling time of 20 min.

Availability of Zr-Based MOFs for the degradation of nerve agents in all humidity conditions

Abstract Organophosphate-based nerve agents are among the most toxic chemical compounds known to mankind. In this report, we studied the degradation of soman (GD) and VX, two of the major nerve agents, by Zr(OH)4 and Zr-based Metal-Organic Frameworks (MOFs) such as MOF-808, UiO-66 and UiO-66-NH2 in the neat condition and in non-buffered aqueous solution at room temperature. Unlike Zr(OH)4, relatively less hydrophilic Zr-based MOFs were found to maintain excellent nerve agent decomposition ability, even under high relative humidity and in water. This study's results demonstrated that these Zr-based MOFs are all-weather materials that can be used to decompose nerve agents in all humidity conditions and even in water. The enhancement effect by the amine group of UiO-66-NH2 was not observed for decomposition of nerve agents in the present study, unlike the results obtained in alkaline buffered solution, which were reported previously. It was also demonstrated that MOF-808 with a pore size larger than the UiO-66 series had a better ability to degrade nerve agents.

RSDL decontamination of human skin contaminated with the nerve agent VX

Dermal exposure to low volatile organophosphorus compounds (OPC) may lead to penetration through the skin and uptake in the blood circulation. Skin decontamination of toxic OPCs, such as pesticides and chemical warfare nerve agents, might therefore be crucial for mitigating the systemic toxicity following dermal exposure. Reactive skin decontamination lotion (RSDL) has been shown to reduce toxic effects in animals dermally exposed to the nerve agent VX. In the present study, an in vitro flow-through diffusion cell was utilized to evaluate the efficacy of RSDL for decontamination of VX exposed to human epidermis. In particular, the impact of timing in the initiation of decontamination and agent dilution in water was studied. The impact of the lipophilic properties of VX in the RSDL decontamination was additionally addressed by comparing chemical degradation in RSDL and decontamination efficacy between the VX and the hydrophilic OPC triethyl phosphonoacetate (TEPA). The epidermal membrane was exposed to 20, 75 or 90% OPC diluted in deionized water and the decontamination was initiated 5, 10, 30, 60 or 120min post-exposure.Early decontamination of VX with RSDL, initiated 5–10min after skin exposure, was very effective. Delayed decontamination initiated 30–60min post-exposure was less effective but still the amount of penetrated agent was significantly reduced, while further delayed start of decontamination to 120min resulted in very low efficacy. Comparing RSDL decontamination of VX with that of TEPA showed that the decontamination efficacy at high agent concentrations was higher for VX. The degradation mechanism of VX and TEPA during decontamination was dissected by 31P NMR spectroscopy of the OPCs following reactions with RSDL and its three nucleophile components. The degradation rate was clearly associated with the high pH of the specific solution investigated; i.e. increased pH resulted in a more rapid degradation. In addition, the solubility of the OPC in RSDL also influenced the degradation rate since the degradation of VX was significantly faster when the NMR analysis was performed in the organic solvent acetonitrile compared to water.In conclusion, we have applied the in vitro flow-through diffusion cell for evaluation of skin decontamination procedures of human epidermis exposed to OPCs. It was demonstrated that early decontamination is crucial for efficient mitigation of epidermal penetration of VX and that almost complete removal of the nerve agent from the skin surface is possible. Our data also indicate that the pH of RSDL together with the solubility of OPC in RSDL are of primary importance for the decontamination efficacy.

The combined action of methanolysis and heterogeneous photocatalysis in the decomposition of chemical warfare agents.

We report the applicability of a hybrid system comprising a La3+-based catalyst and an Au/TiO2 photocatalyst in the decomposition of chemical weapons. This system is able to perform complete degradation of soman, sarin and VX in less than 1 minute under low basic conditions and visible light irradiation.

Detoxification of chemical warfare agents by CuBTC

The detoxification of chemical warfare agents by the metal–organic framework CuBTC (HKUST-1) was studied using nuclear magnetic resonance spectroscopy. All agents were shown to hydrolyze within the substrate. The degradation of VX and soman (GD) was determined to be relatively slow, with half-lives over 1 day, while the half life of distilled mustard (HD) was determined to be about 13 h. HD half lives, measured by MAS NMR, were dependant on spinning speed, with observed half lives decreasing at higher spinning speeds.

Treatment of chemical warfare agents by combined sodium percarbonate with tetraacetylethylenediamine solution

Treatment of chemical warfare agents (CWAs) including soman (GD), mustard (HD) and VX by combined sodium percarbonate and tetraacetylethylenediamine (SPC/TAED) solution was investigated. The optimal pH value for the degradation of HD and VX were about 7.5–9.0 and 8.5–9.5, respectively. The decontamination efficiency of GD increased as the pH value increases. To obtain a decontamination percentage of >99%, the molar ratio between active oxygen and CWAs needed to be at least 3, 2, 10 for GD, HD and VX, respectively. The SPC/TAED aqueous solution was used to effectively decompose CWAs in the temperature range between 0°C and 45°C. As indicated by the products analysis using gas chromatography/mass spectrometry (GC/MS), liquid chromatography/mass spectrometry (LC/MS) and ion chromatography (IC), the degradation of GD was revealed to be a perhydrolysis process; oxidation of C and S atoms and elimination of HCl were involved during the degradation of HD, while VX degradation process was through oxidation of C, S and N atoms and cleavage of CC, CN, CS and PS bonds. The porous and non-porous materials (e.g., concrete, alkyd paint coating, glaze floor, etc.) contaminated by CWAs could be decontaminated by the SPC/TAED aqueous solution.

Degradation of GD and VX over Oxides Mixing with Bleaching Powder

Nanosize oxides with acidic or basic sites could neutralize the droplets of chemical warfare agents. Refined bleaching powder was added to increase the reactivity of the nanosize oxides for degradation of GD(3,3-dimethyl-2-butyl methylphophonofluoridate or Soman) and VX(O-ehtyl S-2-(diisopropylamino)ethyl methyl-phosphonothioate). It was found that all the studied decontaminant powders exhibited room-temperature reactivity for GD and VX droplets which depends on their surface acid–base property. Decontaminant powders with basicity like nanosize MgO have the best activity towards GD and the degradation rate was improved obviously for N-MgO due to the adding of refined bleaching powder. However, surface acidity was very important for neutralizing VX over the decontaminant powders.

Role of the P–F Bond in Fluoride-Promoted Aqueous VX Hydrolysis: An Experimental and Theoretical Study

Following our ongoing studies on the reactivity of the fluoride ion toward organophosphorus compounds, we established that the extremely toxic and environmentally persistent chemical warfare agent VX (O-ethyl S-2-(diisopropylamino)ethyl methylphosphonothioate) is exclusively and rapidly degraded to the nontoxic product EMPA (ethyl methylphosphonic acid) even in dilute aqueous solutions of fluoride. The unique role of the P-F bond formation in the reaction mechanism was explored using both experimental and computational mechanistic studies. In most cases, the "G-analogue" (O-ethyl methylphosphonofluoridate, Et-G) was observed as an intermediate. Noteworthy and of practical importance is the fact that the toxic side product desethyl-VX, which is formed in substantial quantities during the slow degradation of VX in unbuffered water, is completely avoided in the presence of fluoride. A computational study on a VX-model, O,S-diethyl methylphosphonothioate (1), clarifies the distinctive tendency of aqueous fluoride ions to react with such organophosphorus compounds. The facility of the degradation process even in dilute fluoride solutions is due to the increased reactivity of fluoride, which is caused by the significant low activation barrier for the P-F bond formation. In addition, the unique nucleophilicity of fluoride versus hydroxide toward VX, in contrast to their relative basicity, is discussed. Although the reaction outcomes were similar, much slower reaction rates were observed experimentally for the VX-model (1) in comparison to VX.

Oxidative degradation of chemical warfare agents in water by bleaching powder

Degradation of sulfur mustard (HD), S-2-(di-isopropylamino)ethyl O-ethyl methylphosphonothioate (VX) and Soman (GD) in water by bleaching powder was investigated. The degradation products were comprehensively analyzed by gas chromatography/mass spectrometry (GC/MS), liquid chromatography/mass spectrometry (LC/MS) and ion chromatography. Degradation pathways were deduced based on the identified products. The product analysis results indicated that HD could be degraded through oxidation and chlorination reactions, and a small portion of sulfur atoms could be mineralized into SO(4)(2-) ion. Oxidative degradation of VX could finally generate O-ethyl methylphosphonate acid (EMPA), sulfonic acids, SO(4)(2-) and NO(3)(-) ions. GD would be converted into non-toxic pinacolyl methylphosphonate via nucleophilic substitution.

Application of laccase-mediator system (LMS) for the degradation of organophosphorus compounds

Degradation of organophosphorus compounds was achieved in the presence of purified fungal laccase from Trametes versicolor and a small molecular weight redox mediator (ABTS). This laccase-mediator system (LMS) catalyzed degradation of VX, PhX and VR while had no apparent effect on CVX, ecothiophate or demeton. Inhibition of ABTS oxidation was shown with VX, PhX, VR and CVX. Results with CVX suggest either no degradation subsequent to interaction with the laccase active site or the formation of a new toxic compound. PhX degradation was also monitored by mass spectroscopy, a method that allowed us to identify certain intermediates formed during OP degradation. Altogether, results underline the importance of the OP nitrogen atom at β-position and of its substituents, even though the intimate mechanism of laccase-catalyzed degradation is not yet known.

Evaporation and Degradation of VX on Silica Sand

The evaporation and degradation of VX (O-ethyl S-[2-N,N-(diisopropylamino)ethyl] methylphosphonothioate) on silica sand and borosilicate glass were measured using vapor analysis and 31P solid state magic angle spinning nuclear magnetic resonance (SSMAS NMR) spectroscopy. 31P SSMAS NMR studies of VX degradation on crushed glass, air-dried sand, and oven-dried sand at a variety of temperatures showed that the final product was nontoxic ethyl methylphosphonic acid (EMPA), produced via the toxic diethyl dimethylpyrophosphonate intermediate. The reaction exhibited a lag time that depended upon the quantity of water and EMPA that were present in the initial sample of VX and was autocatalytic; EMPA was both the catalyst and product for the degradation of VX. 31P SSMAS NMR studies of VX on moist sand at a variety of temperatures showed that the final product was nontoxic EMPA; observed intermediates were protonated VX, O-ethyl methylphosphonothioic acid, and toxic EA-2192 (S-[2-N,N-(diisopropylamino)ethyl methylp...

Degradation Kinetics of VX on Concrete by Secondary Ion Mass Spectrometry

At trace coverages on concrete surfaces, the nerve agent VX (O-ethyl S-2-diisopropylaminoethyl methyl phosphonothiolate) degrades by cleavage of the P-S and S-C bonds, as revealed by periodic secondary ion mass spectrometry (SIMS). The observed kinetics were (pseudo-) first-order, with a half-life of 2-3 h at room temperature. The rate increased with surface pH and temperature, with an apparent second-order constant of k(OH) = 0.64 M(-1) min(-1) at 25 degrees C and an activation energy of 50-60 kJ mol(-1). These values are consistent with a degradation mechanism of alkaline hydrolysis within the adventitious water film on the concrete surface. Degradation of bulk VX on concrete would proceed more slowly.

Effect of drop size on the degradation of VX in concrete.

The effect of drop size on the degradation rate of VX, O-ethyl S-[2-(diisopropylamino)ethyl]methylphosphonothioate, in fresh concrete has been examined using (31)P NMR. Drops of neat VX, ranging in size from 4 microL to 0.2 microL, applied to small concrete coupons (8 mm x 15 mm) were observed to degrade at different rates, with the 1 microL and smaller drops reacting in less than 4 days, and the larger droplets reacting in less than 11 days. Additionally, 4 microL VX predissolved in hexane to evenly spread it over the concrete coupon likewise reacted faster, degrading in less than 5 days. The fresh concrete, less than 2 months old, exhibited significantly faster VX degradation for all drop sizes than that observed for "aged" concrete in a previous study where VX persisted for months. The enhanced reactivity of the "fresh" concrete for VX was maintained for at least a 1-year period. The pH of water containing crushed "fresh" and "aged" concrete was 10.0 and 9.0, respectively. The higher pH of the "fresh" concrete is one reason for its enhanced reactivity toward VX. An additional contribution to the enhanced reactivity of the "fresh" concrete is suggested by the increased mobility of its sorbed VX as evidenced by its significantly narrower peak in (31)P NMR spectra.

Degradation of VX and sulfur mustard by enzymatic haloperoxidation.

Chloroperoxidase (CPO) isolated from Caldariomyces fumago (20 U ml(-1)) together with urea hydrogenperoxide (UPER, 0.5 mM) and sodium chloride as co-substrate (NaCl, 0.5 M) caused rapid breakdown of VX (10 microM) (t((1/2)) = 8 s, 25 C, 50 mM tartarate, pH 2.75). Glucose oxidase (GOX, Aspergillus niger) and glucose were used as an alternative source for H(2)O(2). A mixture of GOX (20 U ml(-1)), glucose (GLU 0.45 M), CPO (20 U ml(-1)) and NaCl (0.5 M) caused a 3.8-fold slower degradation of VX (10 microM) (t((1/2)) = 30 s, 25 C, 50 mM tartarate, pH 2.75). The concentrations of H(2)O(2) and chlorine produced by this enzyme/substrate mixture depended mainly on the GLU concentration. Horseradish peroxidase (HRP) together with UPER (1 mM) and sodium iodide (NaI, 0.05 M) caused progressive degradation of VX that was more than 400-fold slower than with CPO (20 U ml(-1)), UPER (0.5 mM) and NaCl (0.5 M) (t((1/2)) = 55 min, 25 C, pH 8). Skin decontamination of VX by CPO was tested in pig-ear skin in vitro. The chemical agent VX (0.01 M, 100 microl) was degraded by 98% within 3 h of skin diffusion when a mixture of UPER/NaCl/CPO was applied 60 min prior to VX application. A mixture of UPER/NaCl without CPO also caused significant VX degradation (94%) during skin diffusion whereas it did not cause any VX degradation in solution. Degradation of VX in skin, obtained without exogenous CPO, may indicate involvement of endogenous intradermal haloperoxidase-like enzyme. Reagent UPER (1 mM) did not cause any degradation of VX in solution or during its skin diffusion. Furthermore, a mixture of CPO, UPER and NaCl caused rapid degradation of sulfur mustard (HD). Sulfur mustard (50 microM) incubated in the presence of CPO (4 U ml(-1)), UPER (0.05 M) and NaCl (0.5 M) at pH 2.75 and 30 C was oxidized by 97% and 99% within 5 and 10 min, respectively. The oxidation products HD sulfoxide, HD sulfone and HD sulfoxidevinyl were identified by GC/MS in the enzymatic chloroperoxidation mixture.

Hydrolysis of VX on concrete: rate of degradation by direct surface interrogation using an ion trap secondary ion mass spectrometer.

The nerve agent VX (O-ethyl S-2-diisopropylaminoethyl methylphosphonothiolate) is lethal at very low levels of exposure, which can occur by dermal contact with contaminated surfaces. Hence, behavior of VX in contact with common urban or industrial surfaces is a subject of acute interest. In the present study, VX was found to undergo complete degradation when in contact with concrete surfaces. The degradation was directly interrogated at submonolayer concentrations by periodically performing secondary ion mass spectrometry (SIMS) analyses after exposure of the concrete to VX. The abundance of the [VX + H]+ ion in the SIMS spectra was observed to decrease in an exponential fashion, consistent with first-order or pseudo-first-order behavior. This phenomenon enabled the rate constant to be determined at 0.005 min(-1) at 25 degrees C, which corresponds to a half-life of about 3 h on the concrete surface. The decrease in [VX + H]+ was accompanied by an increase in the abundance of the principal degradation product diisopropylaminoethanethiol (DESH), which arises by cleavage of the P-S bond. Degradation to form DESH is accompanied by the formation of ethyl methylphosphonic acid, which is observable only in the negative ion spectrum. A second degradation product was also implicated, which corresponded to a diisopropylvinylamine isomer (perhaps N,N-diisopropyl aziridinium) that arose via cleavage of the S-C bond. No evidence was observed for the formation of the toxic S-2-diisopropylaminoethyl methylphosphonothioic acid. The degradation rate constants were measured at four different temperatures (24-50 degrees C), which resulted in a linear Arrhenius relationship and an activation energy of 52 kJ mol(-1). This value agrees with previous values observed for VX hydrolysis in alkaline solutions, which suggests that the degradation of submonolayer VX is dominated by alkaline hydrolysis within the adventitious water film on the concrete surface.