Synthesis of new microsensor coatings and their response to test vapors 2,4,6-trisubstituted-1,3,5-triazine derivatives

Novel 1,3,5-triazine derivatives were spray-coated onto surface acoustic wave (SAW) devices and exposed to vapors of dimethyl methylphosphonate (DMMP), chloroethyl ethyl sulfide (CEES) and water. Changes in chemiresistor and SAW responses were monitored and recorded by computer-controlled data-acquisition techniques. All the derivatives tested showed little or no chemiresistor or SAW responses to water vapor. The largest reversible chemiresistor response to DMMP vapor was observed with the dicarboxylic acid derivative. The largest SAW response to DMMP was with the dithione, and the dichloro-octylthio derivative showed the largest response to CEES.     

Synthesis and response of new microsensor coatings-II Acridinium betaines and anionic surfactants

Four acridinium betaines and two ionic surfactants were synthesized, and evaluated as chemical microsensor coatings by exposure to vapors of chloroethyl ethyl sulfide (CEES) and dimethyl methylphosphonate (DMMP). Two of the acridinium betaines showed selective and reversible responses (of 9.8 and 6.8 kHz) as SAW (surface acoustic wave) coatings in the detection of CEES vapor: there appears to be a connection between the long alkyl chain (C-12 and C-14) in the acridinium molecules and the response. Response times were generally less than 30 sec but desorption was significantly slower. The ionic surfactant coatings show small SAW changes (> 0.5 kHz) in response to DMMP vapor, and somewhat greater responses (20- and 68-fold), as chemiresistors, to CEES vapor. In each case the response occurred within 3 min, with return nearly to baseline levels within 6 min of cessation of exposure to the vapor. The responses were reproducible within +/- 5%.     

Structure and fragmentation of dimethyl methylphosphonate and trimethyl phosphite

The structures and fragmentation pathways of two isomeric organophosphorus esters, dimethyl methylphosphonate (DMMP) and trimethyl phosphite (TMP) have been determined. The long-lived, low-energy molecular ions of DMMP were found to undergo a keto-to-enol isomerization prior to collision-induced dissociation. This isomerization was established through the comparison of the collision spectra from DMMP, TMP, isotopically labeled DMMP and a model precursor ion. Electron ionization and charge exchange reactions were used to study the isomerization as a function of the internal energy of the molecular ion. The structure of the TMP molecular ion retained the structure of the neutral molecule. The daughter ion spectra of the isomeric fragment ions from DMMP and TMP were used to infer the fragment ion structures. Negative ions of DMMP and TMP were also studied, and their collision spectra were found to be indistinguishable.     

Facility monitoring of chemical warfare agent simulants in air using an automated, field-deployable, miniature mass spectrometer

Vapors of four chemical warfare agent (CWA) stimulants, 2-chloroethyl ethyl sulfide (CEES), diethyl malonate (DEM), dimethyl methylphosphonate (DMMP), and methyl salicylate (MeS), were detected, identified, and quantitated using a fully automated, field-deployable, miniature mass spectrometer. Samples were ionized using a glow discharge electron ionization (GDEI) source, and ions were mass analyzed with a cylindrical ion trap (CIT) mass analyzer. A dual-tube thermal desorption system was used to trap compounds on 50:50 Tenax TA/Carboxen 569 sorbent before their thermal release. The sample concentrations ranged from low parts per billion [ppb] to two parts per million [ppm]. Limits of detection (LODs) ranged from 0.26 to 5.0 ppb. Receiver operating characteristic (ROC) curves are presented for each analyte. A sample of CEES at low ppb concentration was combined separately with two interferents, bleach (saturated vapor) and diesel fuel exhaust (1%), as a way to explore the capability of detecting the simulant in an environmental matrix. Also investigated was a mixture of the four CWA simulants (at concentrations in air ranging from 270 to 380 ppb). Tandem mass (MS/MS) spectral data were used to identify and quantify the individual components.     

Fluorescent dendritic polymers and nanostructured coatings for the detection of chemical warfare agents and other analytes

Polyamidoamine (PAMAM) dendrimers of generations zero (G0) to four (G4), and a hyperbranched polyurea (HB‐PU), were functionalized with 1,5‐dansyl (1,5‐D), 2,5‐dansyl (2,5‐D), 2,6‐dansyl (2,6‐D) and nitrobenzofurazan (NBD) fluorophores that change their fluorescence emission wavelength in response to chemical environment, and the resulting dendritic polymers were characterized by MALDI‐TOF mass spectrometry, ¹H NMR, ¹³C NMR, and fluorescence spectroscopy. Fluorophore‐functionalized dendritic polymers were then reacted further with 3‐acryloxypropyldimethoxymethylsilane (AOP‐DMOMS) at various fluorophore to DMOMS substitution ratios. The resulting materials were cast onto glass slides, and cured into robust nanostructured coatings. Coatings with 50% fluorophore–50% DMOMS substitution showed the strongest fluorescence and the best physical properties. Coated coupons were tested against a wide range of analytes including the chemical warfare agent simulants dimethyl methylphosphonate (DMMP) and chloroethylethylsulfide (CEES), and the water‐methanol‐ethanol series. It was found that the ability of the coatings to distinguish between analytes decreased with increasing cross‐link density for both dendrimer and hyperbranched polymer‐based coatings. It was also found that the percent fluorophore substitution and the type of dendritic polymer carrying the fluorophore had no significant effect upon fluorescence emission wavelength, but fluorescence emission wavelength became less dependent upon solvent with increasing dendrimer generation and molecular mass. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5101–5115, 2009     

TiO2 photocatalytic degradation of dimethyl- and diethyl- methylphosphonate, effects of catalyst and environmental factors

Dimethyl methylphosphonate (DMMP) and diethyl methylphosphonate (DEMP) are readily mineralized by photoexcited titanium dioxide (TiO₂). Intermediate products include low molecular weight organic acids and methylphosphonic acid. Complete mineralization yields phosphate and carbon dioxide. The photoactivities of different types of TiO₂ were investigated. The decomposition kinetics of DMMP and effects of DMMP and catalyst concentration, sonication, solar irradiation, oxygen concentration, temperature, and hydrogen peroxide on the rate of decomposition are reported. The degradation rates increase with simultaneous sonication, addition of hydrogen peroxide, and at higher temperatures.     

Preparation and application of the sol-gel-derived acrylate/silicone co-polymer coatings for headspace solid-phase microextraction of 2-chloroethyl ethyl sulfide in soil

Three types of novel acrylate/silicone co-polymer coatings, including co-poly(methyl acrylate/hydroxy-terminated silicone oil) (MA/OH-TSO), co-poly(methyl methacrylate/OH-TSO) (MMA/OH-TSO) and co-poly(butyl methacrylate/OH-TSO) (BMA/OH-TSO), were prepared for the first time by sol-gel method and cross-linking technology and subsequently applied to headspace solid-phase microextraction (HS-SPME) of 2-chloroethyl ethyl sulfide (CEES), a surrogate of mustard, in soil. The underlying mechanisms of the coating process were discussed and confirmed by IR spectra. The selectivity of the three types of sol-gel-derived acrylate/silicone coated fibers was studied, and the BMA/OH-TSO coated fibers exhibited the highest extraction ability to CEES. The concentration of BMA and OH-TSO in sol solution was optimized, and the BMA/OH-TSO (3:1)-coated fibers possessed the highest extraction efficiency. Compared with commercially available polyacrylate (PA) fiber, the sol-gel-derived BMA/OH-TSO (3:1) fibers showed much higher extraction efficiency to CEES. Therefore, the BMA/OH-TSO (3:1)-coated fibers were chosen for the analysis of CEES in soil matrix. The reproducibility of coating preparation was satisfactory, with the RSD 2.39% within batch and 3.52% between batches, respectively. The coatings proved to be quite stable at high temperature (to 350 degrees C) and in different solvents (organic or inorganic), thus their lifetimes (to 150 times) are longer than conventional fibers. Extraction parameters, such as the volume of water added to the soil, extraction temperature and time, and the ionic strength were optimized. The linearity was from 0.1 to 10 microg/g, the limit of detection (LOD) was 2.7 ng/g, and the RSD was 2.19%. The recovery of CEES was 88.06% in agriculture soil, 92.61% in red clay, and 101.95% in sandy soil, respectively.     

Dimethyl methylphosphonate decomposition on Cu surfaces: supported Cu nanoclusters and films on TiO2(110)

The thermal decomposition of dimethyl methylphosphonate (DMMP), which is a simulant molecule for organophosphorus nerve agents, has been investigated on Cu clusters as well as on Cu films deposited on a TiO(2)(110) surface. Scanning tunneling microscopy studies were conducted to characterize the cluster sizes and surface morphologies of the deposited Cu clusters and films. Temperature-programmed desorption experiments demonstrated that the surface chemistry of DMMP is not sensitive to the size of the Cu clusters over the range studied in this work. DMMP reaction on an annealed 40 monolayer Cu film resulted in the desorption of H(2), methane, methyl, formaldehyde, methanol, and molecular DMMP, and reaction on the small (4.4 +/- 0.9 nm diameter, 1.8 +/- 0.6 nm height) and large (10.7 +/- 1.9 nm diameter, 4.8 +/- 1.0 nm height) Cu clusters generated similar products. Formaldehyde and methane production is believed to occur via a methoxy intermediate on the Cu surface. These products are favored on the higher coverage Cu films that completely cover the TiO(2) surface since competing reaction pathways on TiO(2) are suppressed. X-ray photoelectron spectroscopy studies showed that DMMP begins to decompose on the Cu clusters upon adsorption at room temperature and that atomic carbon, atomic phosphorus, and PO(x) remain on the surface after DMMP decomposition.     

[EMIm]NTf_2中Fe~(2+)催化氧化芥子气模拟剂CEES研究

合成并表征了3种不同烷基链长的1-烷基-3-甲基咪唑双三氟甲基磺酰亚胺([CnMIm]NTf_2,n=2、4、6)离子液体及金属催化剂双三氟甲基磺酰亚胺铁二水合物(Fe(NTf_2)_2·2H_2O),对H_2O_2/离子液体消毒芥子气模拟剂2-氯乙基乙基硫醚(CEES)的能力进行了研究.通过HPLC考察了H_2O_2/CEES摩尔比、H_2O_2浓度、反应温度、时间、离子液体再生次数对H_2O_2/[EMIm]NTf_2/Fe~(2+)消毒CEES能力的影响,并采用GC-MS、CL对反应产物、活性氧物种及反应机制进行了分析.结果表明:基于离子液体的类Fenton体系消毒CEES时,具有H_2O_2/CEES摩尔比小、消毒速率快、低温消毒效果良好、离子液体可循环利用等的优点,在毒剂洗消领域具有极大的应用前景.     

Adsorption and thermal reaction of DMMP in nanocrystalline NaY

In this study, FTIR spectroscopy and solid-state magic angle spinning (MAS) NMR were used to investigate the adsorption and thermal reaction of the nerve gas simulant dimethyl methylphosphonate (DMMP) in nanocrystalline NaY with a crystal size of approximately 30 nm. DMMP adsorbs molecularly in nanocrystalline NaY at 25 degrees C. Gas-phase products of the reaction of DMMP and oxygen in nanocrystalline NaY at 200 degrees C were monitored by FTIR spectroscopy and determined to be carbon dioxide (major product), formaldehyde, and dimethyl ether. In the presence of water, the thermal reaction of DMMP in nanocrystalline NaY at 200 degrees C yielded methanol (major product), carbon dioxide, and dimethyl ether. When the thermal reaction of DMMP in nanocrystalline NaY at 200 degrees C was conducted in the presence of water and oxygen, the predominant products were methanol and carbon dioxide. Hydroxyl sites located on the external zeolite surface were consumed during the DMMP thermal reactions as monitored by FTIR spectroscopy and were therefore determined to be the active sites in this reaction. 31P solid-state MAS NMR experiments were used to identify the surface-bound phosphorus complexes. The reactivity per gram of zeolite was comparable to other recently studied metal oxides such as MgO, Al2O3, and TiO2, and was found to have comparable, if not higher reactivity. Future improvements in reactivity may be achieved by incorporating a reactive transition metal ion or metal oxide nanocluster into the nanocrystalline NaY to enhance reaction rates and to achieve complete reaction of DMMP.     

Transport and time dependent small angle X‐ray morphology in metal cation and polymer modified perfluorocarbon ionomers

Transport and absorption in metal cation exchanged and polyvinylpyrrolidone (PVP) modified Nafion® films were studied by various techniques. To understand the microscopic basis for permeation, time resolved small angle X‐ray scattering (SAXS) was used to characterize the ionic domain morphology while films were exposed to vapors of water, dimethyl methylphosphonate (DMMP), or triethyl phosphate. Macroscopic weight uptake studies of DMMP vapor into PVP‐Nafion® were also used to help explain the SAXS absorption studies and DMMP permeation properties. The SAXS results were correlated with macroscopic permeation rates of DMMP, Soman, and water through several different membranes. To provide additional basis for the SAXS derived morphologies, tapping‐mode AFM was also used to image the 3–5 nm diameter ionic domains. A goal for protective suit applications is to find films with a balance of high moisture permeation rate for comfort, and low DMMP permeation. The best balance of properties in this context was found with PVP‐ and zirconyl‐modified films. In another extreme, the permeation rates of both water and DMMP through cesium‐modified Nafion® were low. SAXS studies were used to explain this where the ionic domains of cesium‐modified Nafion® did not “expand” when exposed to DMMP or water vapor. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 284–298, 2009     

Bi‐phase flame‐retardant effect of dimethyl methylphosphonate and modified ammonium polyphosphate on rigid polyurethane foam

The flame‐retardant rigid polyurethane foams (RPUFs) with dimethyl methylphosphonate (DMMP) and modified ammonium polyphosphate (MAPP) were prepared. The results showed that the limiting oxygen index (LOI) value was improved by adding DMMP into RPUF/MAPP composite; 10 wt% of DMMP addition can increase the LOI value from 24.3% to 26.0%, where the commercial application standard of RPUF is achieved. Further benefits of using DMMP/MAPP system included restraining of total heat and smoke release, improvement of thermal stability, and char yield of RPUF. The thermogravimetric analysis (TGA)‐gas chromatography‐mass spectrometer (GC‐MS) results indicated that DMMP/MAPP could continuously release PO₂ and PO·free radicals in the gas phase. In addition, DMMP/MAPP exhibited the charring effect and barrier effect in the condensed phase, such bi‐flame retardant effect exerted by DMMP/MAPP resulted in the enhanced flame retardant property of RPUF.     

A Dual Read-out Molecularly Imprinted Composite Membrane Sensor Based on Zinc Porphyrin for the Detection of Dimethyl Methylphosphonate

Molecularly imprinted membrane-zinc porphyrin-mathacrylate(MIM-Zn-MAA), a dual read-out sensor based on a molecularly imprinted membrane, was developed to recognize and detect dimethyl methylphosphonate (DMMP) as an intermediate molecule of organophosphorus pesticides. The membranes were prepared via thermal polymerization of two functional monomers(zinc porphyrin and mathacrylate) on the surface of a glass slide functionalized with ethylene glycol dimethacrylate and azobisisobutyronitrile. The morphology of the as-synthesized MIM-Zn-MAA was determined with scanning electronic microscopy. The composite membranes exhibited macrovoid morphologies, which were affected by the functional monomers. These membranes were selectively adsorbed onto the template molecule and displayed higher adsorbing capacity toward DMMP compared with their structural analogs. Changes in the fluorescent spectra were qualitatively and quantitatively monitored via fluorescence photometry. Difference maps were also obtained using colorimetry before and after the reaction between MIM-Zn-MAA and DMMP at various concentrations. The maps showed a wide linear range varying from 0.1 μmol/L to 10 mmol/L with a low detection limit of 0.1 μmol/L. These preliminary results demonstrate that the as-fabricated dual read-out sensor displays good sensitivity and selectivity toward DMMP, indicating its considerable potential in DMMP detection in practical applications.     

Structure and stability of solvation complexes of trimethyl phosphate and dimethyl methyl phosphonate

The presently used electrolytes in Lithium ion batteries, dimethyl carbonate (DMC), and ethylene carbonate are flammable. Trimethyl phosphate (TMP) and dimethyl methyl phosphonate (DMMP) have been shown to be potential nonflammable electrolytes. Density functional theory is used to calculate the structure and stability of the solvation complexes of TMP and DMMP. The calculations indicate that TMP and DMMP can form a solvation complex of the form Li⁺(X)₄ where X is the TMP or DMMP molecule. Calculations of the solvation energy and bond dissociation energies to remove one TMP and DMMP from the solvation complexes are compared with the same calculations on DMC. The results indicate that TMP and DMMP are considerably more stable than DMC.     

Gas chromatographic analysis of methiocarb and its metabolites in soil and rice

Summary A new method to determine the amount of methiocarb and its two metabolites, the sulfoxide and sulfone in soil and rice plant is described. The method consists of extraction of samples with acetone, filtration, separation of methiocarb and its metabolites through a Florisil column, and gas chromatographic determination. Since the degradation of methiocarb to 3,5-dimethyl-4-methylthiophenol (DMMP) is commonly observed during GC analysis, methiocarb was converted to DMMP via chemical hydrolysis after column chromatography. Reasonable recoveries for routine analysis were obtained and the limit of quantitation (LOQ) with GC/FPD were 0.5, 2 and 2 ng for DMMP sulfoxide and sulfone, with a signal to noise ratio of 4. In all rice samples, no detectable residues were found, however DMMP and methiocarb sulfoxide were found in some straw samples. In field soil samples, no sulfone was detected in all samples and methiocarb showed typical degradation curves with a half life of 8 days after treatment. A five-fold longer half life was observed in indoor studies.     

Flower-like tungsten oxide particles: Synthesis, characterization and dimethyl methylphosphonate sensing properties

Flower-like WO₃ particles with high specific surface area were synthesized via a template/surfactant-free way. Scanning and transmission microscopies and X-ray diffraction were applied to investigate the formation mechanism of the morphology. Gas sensing characterization showed an enhanced sensitivity (70 Hz/ppm) to dimethyl methylphosphonate (DMMP) as compared with previously reported WO₃ nanoflakes (38 Hz/ppm) at a DMMP concentration of 4 ppm. Cross-sensitivity results revealed that flower-like WO₃ still showed sound sensitivity in presence of interfering agents, which benefited from its intrinsic high sensitivity. The mechanism of DMMP adsorption on the flower-like WO₃ particle was studied by in situ diffuse reflectance infrared Fourier transform spectroscopy.     

Characterization and utilization of a novel triflate ionic liquid stationary phase for use in comprehensive two-dimensional gas chromatography

A novel triflate (trifluoromethylsulfonate) ionic liquid (IL) thin film (0.08 microm) stationary phase was implemented for use within the second column of a comprehensive GC x GC configuration. The first column in the configuration had a 5% phenyl/95% dimethyl polysiloxane (DMPS) stationary phase with a 0.4 microm film. The DMPS x IL column configuration was used to separate a mixture of 32 compounds of various chemical functional classes. The GC x GC results for the IL column were compared with a commercially available polar column (with a 0.1 microm PEG stationary phase film) used as the second column instead. Additional studies focused on the rapid and selective separation of four phosphorous-oxygen (P-O) containing compounds from the 32-compound matrix: dimethyl methylphosphonate (DMMP), diethyl methylphosphonate (DEMP), diisopropyl methylphosphonate (DIMP), and triethyl phosphate (TEP). van't Hoff plots (plots of ln k vs. 1/T) demonstrated the difference in retention between the P-O containing compounds (with DMMP reported in detail) and other classes of compounds (i. e., 2-pentanol and n-dodecane as representative) using either the IL column or the commercial PEG column. The selectivity (alpha) of the triflate IL column and the commercially available PEG column were also compared. The IL column provided significantly larger selectivities between DMMP and the other two compounds (2-pentanol and n-dodecane) than the commercial PEG column. The alpha for DMMP relative to n-dodecane was 3.0-fold greater for the triflate IL column, and the alpha for DMMP relative to 2-pentanol was 1.7-fold greater for the triflate IL column than for the PEG column.     

Adsorption and photodegradation of dimethyl methylphosphonate vapor at TiO(2) surfaces

The adsorption and degradation of the nerve agent simulant dimethyl methylphosphonate (DMMP) over UV-irradiated TiO(2) powders and thin films has been investigated. Adsorption of vapor-phase DMMP on TiO(2) powder is characterized by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Photochemically assisted oxidation of adsorbed DMMP is carried out in situ by irradiation of samples in the DRIFTS accessory, giving kinetic data and information on specific site binding of DMMP and catalyst poisoning. Gas-phase intermediates from a static vapor phase reaction are identified by gas chromatography-mass spectrometry analysis, and surface-bound intermediates and products are analyzed by high-performance liquid chromatography-mass spectrometry, and ion chromatography of both aqueous and organic extractions from the TiO(2). Adsorbed DMMP is photodegraded in a stepwise fashion to give methylphosphonic acid, PO(4)(3-), H(2)O, and CO(2) as products. A proposed reaction pathway is consistent with a rapid degradation of DMMP but with extensive poisoning of the catalyst by surface-bound phosphonate products.     

Effect of humidity on the interaction of dimethyl methylphosphonate (DMMP) vapor with SiO2 and Al2O3 surfaces, studied using infrared attenuated total reflection spectroscopy

Infrared attenuated total reflection spectroscopy has been used to study the interaction of DMMP vapor with SiO(2), Al(2)O(3), and AlO(OH) vs relative humidity (RH) and DMMP partial pressure (P/P(0)). For SiO(2) the growth with increasing RH of ice-like and liquid-like layers is seen in agreement with previous work. H?D exchange during exposure to H(2)O and D(2)O indicates that the ice-like layer is more resistant to exchange, consistent with stronger H-bonding than in the liquid-like layer. Exposure of nominally dry SiO(2) to D(2)O indicates the existence of adsorbed H(2)O that does not exhibit an ice-like spectrum. The ice-like layer appears only at a finite RH. Exposure of SiO(2) to DMMP in the absence of intentionally added H(2)O shows the formation of a strongly bound molecular species followed by a liquid-like layer. The strong interaction involves SiO-H···O═P bonds to surface silanols and/or HO-H···O═P bonds to preadsorbed molecular H(2)O. At a finite RH the ice-like layer forms on SiO(2) even in the presence of DMMP up to P/P(0) = 0.30. DMMP does not appear to penetrate the ice-like layer under these conditions, and the tendency to form a such a layer drives the displacement of DMMP. Amorphous Al(2)O(3) and AlO(OH) do not exhibit an ice-like H(2)O layer. Both have a higher surface OH content than does SiO(2), which leads to higher coverages of H(2)O or DMMP at equivalent RH or P/P(0). At low P/P(0), for which adsorption is dominated by Al-OH···O═P bonding, a-Al(2)O(3) interacts with DMMP more strongly than does AlO(OH) as a result of the higher acidity of OH sites on the former. Up to RH = 0.30 and P/P(0) = 0.30, DMMP appears to remain bonded to the surface rather than being displaced by H(2)O. H(2)O appears to have little or no effect on the total amount of DMMP adsorbed on any of these surfaces, up to an RH of 0.30 and a P/P(0) of 0.30. The results have implications for the transport of DMMP and related molecules on oxide surfaces in the environment.     

Synergistic effect of combined dimethyl methylphosphonate with aluminum hydroxide or ammonium polyphosphate retardant systems on the flame retardancy and thermal properties of unsaturated polyester resin

A series of flame-retardant unsaturated polyester resin (UPR) were prepared by the addition of dimethyl methylphosphonate (DMMP) with various amounts of aluminum hydroxide (ATH) or ammonium polyphosphate (APP) as the flame retardants. The combustion resistance effects of ATH/DMMP and APP/DMMP systems were evaluated by limiting oxygen index test and vertical burning test (UL-94). The thermal properties of UPR were investigated by thermogravimetric analysis. The structure of char was observed by scanning electron microscopy. DMMP incorporated with ATH or APP improved the flame retardancy and thermal properties of UPR. However, the fire-retardant mechanism of these two systems were different: The ATH/DMMP system provided synergistic effect in charring property of the UPR, produced great amount of residual char, and thus revealed the excellent flame retardancy. The APP/DMMP system further improved the flame retardancy of the UPR due to the change in the residual char structure rather than the increase in the production of char.