Metal coordination complexes were formed directly from liquid surfaces using desorption electrospray ionization (DESI) mass spectrometry, in which the analyte solutions were furnished by a target capillary that protrudes into the ESI spray. The approach is attractive because it separates complexities of ESI spray droplet formation from delivery of the analyte solution, and thereby gets around difficulty resulting from alteration of the spray process by changes in solution chemistry. Cs+, Ba2+, and La3+ coordination complexes were formed using 18-crown-6 (18c6) and triethylphosphate (TEP) as ligands (L), that had the general formula [Mn+(NO3-)(n-1)(L)(m)](+). Formation of singly charged cation complexes was preferred, with charge reduction at the metal site accomplished by attachment of nitrate. Using TEP as a model phosphoryl ligand, alkali metals coordinate with up to three ligands, with Cs+ preferring fewer than Na+center dot Ba2+ and La3+ are formed as ion pair complexes [Ba(NO3)](+) and [La(NO3)(2)](+), and both will coordinate with up to four TEP ligands. Using 18c6, Cs+ forms a bis-ligand complex. In contrast, [Ba(NO3)](+) prefers a single 18c6 ligand, while La forms mainly [La(NO3)(2)(18c6)](+), for which DFT calculations suggested a structure in which the nitrate ligands occupy pseudo-axial positions on opposing sides of the crown. Lower abundances of bis-18c6 complexes were also formed together with doubly charged [La(NO3)(18c6)(n)](2+) complexes (n = 2-4). The results suggest an alternative strategy for probing metal speciation in solution that is less perturbed by the droplet formation and ionization mechanisms operating in conventional electrospray ionization mass spectrometry. (C) 2010 Elsevier B.V. All rights reserved.

Wavelength-selective infrared multiple photon photo-dissociation (IRMPD) was used to generate spectra of anionic nitrate complexes of UO22+ and Eu3+ in the mid-infrared region. Similar spectral patterns were observed for both species, including splitting of the antisymmetric O-N-O stretch into high and low frequency components with the magnitude of the splitting consistent with attachment of nitrate to a strong Lewis acid center. The frequencies measured for [UO2(NO3)(3)](-) were within a few cm(-1) of those measured in the condensed phase, the best agreement yet achieved for a comparison of IRMPD with condensed phase absorption spectra. In addition, experimentally-determined values were in good general agreement with those predicted by DFT calculations, especially for the antisymmetric UO2 stretch. The spectrum from the [UO2(NO3)(3)](-) was compared with that of [Eu(NO3)(4)](-), which showed that nitrate was bound more strongly to the Eu3+ metal center, consistent with its higher charge. The spectrum of a unique uranyl-oxo species having an elemental composition [UO9N2](-) was also acquired, that contained nitrate absorptions suggestive of a [UO2(NO3)(2)(O)](-) structure; the spectrum lacked bands indicative of nitrite and superoxide that would be indicative of an alternative [UO2(NO3)(NO2)(O-2)](-) structure.

Gas-phase complexes containing dioxouranium(V) cations ([UO(2)](+)) ligated with two or three sigma-donating acetone ligands reacted with dioxygen to form [UO(2)(A)(2,3)(O(2))](+), where A is acetone. Collision-induced dissociation studies of [UO(2)(A)(3)(O(2))](+) showed initial loss of acetone, followed by elimination of O(2), which suggested that O(2) was bound more strongly than the third acetone ligand, but less strongly than the second. Similar behavior was observed for complexes in which water was substituted for acetone. Binding of dioxygen to [UO(2)](+) containing zero, one, or four ligands did not occur, nor did it occur for analogous ligated U(IV)O(2) or U(VI)O(2) ions. For example, only addition of acetone and/or H(2)O occurred for the U(VI) species [UO(2)OH](+), with the ligand addition cascade terminating in formation of [UO(2)OH(A)(3)](+). Similarly, the U(IV) species [UOOH](+) added donor ligands, which produced the mixed-ligand complex [UOOH(A)(3)(H(2)O)](+) as the preferred product at the longest reaction times accessible. Since dioxygen normally functions as an electron acceptor, an alternative mode for binding dioxygen to the cationic U(V)O(2) center is indicated that is dependent on the presence of an unpaired electron and donor ligands in the uranyl valence orbitals.

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.

Desferrioxamine (DEF) is a trihydroxamate siderophore typical of those produced by bacteria and fungi for the purpose of scavenging Fe3+ from environments where the element is in short supply. Since this class of molecules has excellent chelating properties, reaction with metal contaminants such as actinide species can also occur. The complexes that are formed can be mobile in the environment. Because the natural environment is extremely diverse, strategies are needed for the identification of metal complexes in aqueous matrices having a high degree of chemical heterogeneity, and electrospray ionization mass spectrometry (ESI-MS) has been highly effective for the characterization of siderophore-metal complexes. In this study, ESI-MS of solutions containing DEF and either UO22+, Fe3+ or Ca2+ resulted in generation of abundant singly charged ions corresponding to [UO2(DEF-H)](+), [Fe(DEF-2H)](+) and [Ca(DEF-H)](+). In addition, less abundant doubly charged ions were produced. Mass spectrometry/mass spectrometry (MS/MS) studies of collision-induced dissociation (CID) reactions of protonated DEF and metal-DEF complexes were contrasted and rationalized in terms of ligand structure. In all cases, the most abundant fragmentation reactions involved cleavage of the hydroxamate moieties, consistent with the idea that they are most actively involved with metal complexation. Singly charged complexes tended to be dominated by cleavage of a single hydroxamate, while competitive fragmentation between two hydroxamate moieties increased when the doubly charged complexes were considered. Rupture of amide bonds was also observed, but these were in general less significant than the hydroxamate fragmentations. Several lower abundance fragmentations were unique to the metal examined: abundant loss of H2O occurred only for the singly charged UO22+ complex. Further, NH3 was eliminated only from the singly charged Fe3+ complex; this and fragmentation of C-C and C-N bonds derived from neither the hydroxamate nor the amide groups suggested that Fe3+ insertion reactions were competing with ligand complexation. In no experiments were coordinating solvent molecules observed, attached either to the intact complexes or to the fragment ions, which indicated that both intact DEF and its fragments were occupying all of the coordination sites around the metal centers. This conclusion was based on previous experiments that showed that undercoordinated UO22+ and Fe3+ readily added H2O and methanol in the ESI quadrupole ion trap mass spectrometer that was used in this study. Copyright (C) 2004 John Wiley Sons, Ltd.

We demonstrate, by way of multi-stage tandem mass spectrometry and extensive deuterium labeling, that 2-propanol is converted to acetone, and 2-propoxide to acetaldehyde, when monopositive 2-propanol-coordinated uranyl-ligand cations are subjected to collision-induced dissociation in the gas-phase environment of an ion trap mass spectrometer. A species with formula [(UO2OCH(CH3)2)(HOCH(CH3)2)]+, derived from dissociation of the gas-phase precursor [(UO2NO3)(HOCH(CH3)2)3]+ eliminates two H atoms and CH3 in consecutive stages to generate a monopositive complex composed of the U(V) species UO2+ coordinated by acetone and acetaldehyde, i.e. [UO2+(OC(CH3)2)(OC(H)CH3)]. Dissociation of this latter ion resulted in elimination of the two coordinating carbonyl ligands in two consecutive dissociation stages to leave UO2+. Analogous reactions were not observed for uranyl complexes containing 1-propanol or 2-methyl-2-propanol, or for cationic complexes with divalent metals such as Ni2+, Co2+, Pb2+ and Ca2+. One explanation for these reactions is bond insertion by the metal center in the bis-ligated uranyl complex, which would be expected to have an LUMO consisting of unoccupied 6d-orbitals that would confer transition metal-like behavior on the complex.

Electrospray ionization was used to generate mono-positive gas-phase complexes of the general formula [UO2A(S)n]+ where A = OH, Cl, Br, I or ClO4, S = H2O, CH3OH or CH3CH2OH, and n = 1-3. The multiple-stage dissociation pathways of the complexes were then studied using ion-trap mass spectrometry. For H2O-coordinated cations, the dissociation reactions observed included the elimination of H2O ligands and the loss of HA (where A = Cl, Br or I). Only for the Br and ClO4 versions did collision-induced dissociation (CID) of the hydrated species generate the bare, uranyl-anion complexes. CID of the chloride and iodide versions led instead to the production of uranyl hydroxide and hydrated UO2+. Replacement of H2O ligands by alcohol increased the tendency to eliminate HA, consistent with the higher intrinsic acidity of the alcohols compared to water and potentially stronger UO2-O interactions within the alkoxide complexes compared to the hydroxide version.

The formation of adduct ions consisting of uranium oxycations and water was studied using an ion trap-secondary ion mass spectrometer. The U(IV) and U(V) species [UO(OH)](+) and [UO2](+) were produced by bombarding the surface of UO3 using molecular primary ions, and the U(VI) species [UO2(OH)](+) was generated by O-2 oxidation of [UO(OH)](+) in the gas phase. All three ions formed H2O adducts by termolecular association reactions: [UO(OH)](+) (a U(IV) species) added three water molecules, for a total of five ligands; [UO2](+) (U(V)) added three or four water molecules, for a total of five or six ligands; and [UO2(OH)](+) (U(VI)) added four water molecules for a total of six ligands. Addition of a seventh ligand was not observed in any of the systems. These analyses showed that the optimum extent of ligation increased with increasing oxidation state of the uranium metal. Hard kinetic models were fit to the time-dependent mass spectral data using adaptive simulated annealing (ASA) to estimate reaction rates and rate constants from kinetic data sets. The values determined were validated using stochastic kinetic modeling and resulted in rate data for all forward and reverse reactions for the ensemble of reactive ions present in the ion trap. A comparison of the forward rate constants of the hydration steps showed that in general, formation of the monohydrates was slow, but that hydration efficiency increased upon addition of the second H2O. Addition of the third H2O was less efficient (except in the case Of [UO2](+)), and addition of the fourth H2O was even more inefficient and did not occur at all in the [UO2(OH)](+) system. Reverse rate constants also decreased with increasing ligation by H2O, except in the case of [UO(OH)(H2O)(4)](+), which prefers to quickly revert to the trihydrate. These findings indicate that stability of the hydrate complexes [UOyHz(H2O)(n)](+) increases with increasing n, until the optimum number of ligands is achieved. The results enable correlation of uranium hydration behavior with oxidation state.

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.

Detection of the blister agent HD [bis(2-chloroethyl)sulfide] or distilled mustard directly on the surface of soil particles using ion trap secondary ion mass spectrometry in the static mode is demonstrated. HD by its very nature is adsorptive; this attribute makes detection of surface adsorbed HD by gas-phase approaches difficult, but renders the compound amenable to surface detection. Two different ion trap (IT) mass spectrometers, modified to perform secondary ionization mass spectrometry using a ReO4− primary ion beam, were employed in the present study. Sputtered ions were trapped in the gas phase in the IT, where they could be scanned out (MS1), or isolated and fragmented (MS2). The intact HD molecular ion was not observed, however an abundant ion corresponding to [HD − Cl]+ was formed, as were lower mass fragment ions, and ions derived from the chemical background. Ab initio calculations were used to propose structures of the fragment ions. At 0.5 monolayers surface coverage, [HD − Cl]+ and lower mass HD fragment ions were significantly more abundant than the background. At lower concentrations, however, the HD secondary ion signal became masked by the background. Sensitivity and selectivity were significantly improved in the MS2 mode of operation. MS2 of [HD − Cl]+ resulted in production of analytically diagnostic C2H4SH+ and other S- and Cl-bearing fragment ions. HD was detected at 0.07 monolayers using the MS2 approach, which corresponds to 108 ppm on a mass/mass basis.

The nitrogen blister agents HN-2 (bis(2-chloroethyl)methylamine) and HN-3 (tris(2-chloroethyl)amine) were directly analyzed on the surface of soil samples using ion trap secondary ion mass spectrometry (SIMS). In the presence of water, HN-1 (bis(2-choroethyl)ethylamine), HN-2 and HN-3 undergo hydrolysis to form N-ethyldiethanolamine, N-methyldiethanolamine and triethanolamine (TEA), respectively; these compounds can be readily detected as adsorbed species on soil particles. When soil samples spiked with HN-3 in alcohol were analyzed, 2-alkoxyethylamine derivatives were observed on the sample surfaces. This result shows that nitrogen blister agents will undergo condensation reactions with nucleophilic compounds and emphasizes the need for an analytical methodology capable of detecting a range of degradation and condensation products on environmental surfaces. The ability of ion trap SIMS to isolate and accumulate ions, and then perform tandem mass spectrometric analysis improves the detection of low-abundance surface contaminants and the selectivity of the technique. Utilizing these techniques, the limits of detection for HN-3 were studied as a function of surface coverage. It was found that HN-3 could be detected at a surface coverage of 0.01 monolayer, which corresponds to 20 ppm (mass/mass) for a soil having a surface area of 2.2 m(2) g(-1). TEA, the exhaustive hydrolysis product of HN-3, was detected at a surface coverage of 0.001 monolayer, which corresponds to 0.86 ppm.

Membrane introduction mass spectrometry (MIMS) has made large strides in capability improvement since its introduction. The main progress has been in systematic design changes that has allowed this technique to measure analytes in the parts-per-trillion range, samples that have had no special handling or pre-treatment. In spite of these improvements, however, the most important component of MIMS—the membrane—has not been optimized. In this paper, the results of testing two polyphosphazene polymers is reported and compared with those of silicone rubber. The results show that the rich chemical diversity possible with the phosphazene materials and their tailorability, make them good candidates for MIMS applications.

A variety of paint and fingernail polish samples, which were visually similar, but had different chemical compositions and formulations, was analyzed using quadrupole static secondary ion mass spectrometry (SIMS). Coating distinction was easily achieved in many cases because of the presence of dominant ions derived from the components of the coating, which could be observed in the SIMS spectra. In other instances, coating distinction was difficult within a product line because of spectral complexity; for this reason and because of the large numbers of spectra generated in this study, multivariate statistical techniques were employed, which allowed the meaningful classification and comparison of spectra. Partial Least Squares (PLS) and Principal Component Analysis (PCA) were applied to quadrupole SIMS data. PCA showed distinct spectral differences between most spectral groups, and also emphasized the reproducibility of the SIMS spectra. When using PLS analysis, reasonably accurate coating identification was achieved with the data. Overall, the PLS model is more than 90% effective in identifying the spectrum of a particular coating, and nearly 100% effective at telling which coating components represented in the PLS models are not present in a spectrum. The level of spectral variation caused by sample bombardment in the SIMS analysis was investigated using Fourier transform infrared spectroscopy (FT-IR) and quadrupole static SIMS. Changes in the FT-IR spectra were observed and were most likely a result of a number of factors involving the static SIMS analysis. However, the bulk of the sample is unaltered and may be used for further testing.

The direct detection of the nerve agent VX (methylphosphonothioic acid, S-[2-[bis(1-methylethyl)amino]ethyl] O-ethyl ester) on milligram quantities of soil particles has been achieved using ion trap secondary ion mass spectrometry (IT-SIMS). VX is highly adsorptive toward a wide variety of surfaces; this attribute makes detection using gas-phase approaches difficult but renders the compound very amenable to surface detection. An ion trap mass spectrometer, modified to perform SIMS, was employed in the present study. A primary ion beam (ReO4-) was fired on axis through the ion trap, where it impacted the soil particle samples. [VX + H]+, [VX + H]+ fragment ions, and ions from the chemical background were sputtered into the gas-phase environment of the ion trap, where they were either scanned out or isolated and fragmented (MS2). At a surface concentration of 0.4 monolayer, intact [VX + H]+, and its fragment ions, were readily observable above background. However, at lower concentrations, the secondary ion signal from VX became obscured by ions derived from the chemical background on the surface of the soil particles. MS2 analysis using the ion trap was employed to improve detection of lower concentrations of VX: detection of the 34S isotopic ion of [VX + H]+, present at a surface concentration of approximately 0.002 monolayer, was accomplished. The study afforded the opportunity to investigate the fragmentation chemistry of VX. Semiempirical calculations suggest strongly that the molecule is protonated at the N atom. Deuterium labeling showed that formation of the base peak ion (C2H4)N(i-C3H7)2+ involves transfer of the amino proton to the phosphonothioate moiety prior to, or concurrent with, C-S bond cleavage. To manage the risk associated with working with the compound, the vacuum unit of the IT-SIMS was located in a hood, connected by cables to the externally located electronics and computer.