Specificity enhancement by electrospray ionization multistage mass spectrometry – a valuable tool for differentiation and identification of ‘V’‐type chemical warfare agents

The use of chemical warfare agents has become an issue of emerging concern. One of the challenges in analytical monitoring of the extremely toxic ‘V’‐type chemical weapons [O‐alkyl S‐(2‐dialkylamino)ethyl alkylphosphonothiolates] is to distinguish and identify compounds of similar structure. MS analysis of these compounds reveals mostly fragment/product ions representing the amine‐containing residue. Hence, isomers or derivatives with the same amine residue exhibit similar mass spectral patterns in both classical EI/MS and electrospray ionization‐MS, leading to unavoidable ambiguity in the identification of the phosphonate moiety. A set of five ‘V’‐type agents, including O‐ethyl S‐(2‐diisopropylamino)ethyl methylphosphonothiolate (VX), O‐isobutyl S‐(2‐diethylamino)ethyl methylphosphonothiolate (RVX) and O‐ethyl S‐(2‐diethylamino)ethyl methylphosphonothiolate (VM) were studied by liquid chromatography/electrospray ionization/MS, utilizing a QTRAP mass detector. MS/MS enhanced product ion scans and multistage MS³ experiments were carried out. Based on the results, possible fragmentation pathways were proposed, and a method for the differentiation and identification of structural isomers and derivatives of ‘V’‐type chemical warfare agents was obtained. MS/MS enhanced product ion scans at various collision energies provided information‐rich spectra, although many of the product ions obtained were at low abundance. Employing MS³ experiments enhanced the selectivity for those low abundance product ions and provided spectra indicative of the different phosphonate groups. Study of the fragmentation pathways, revealing some less expected structures, was carried out and allowed the formulation of mechanistic rules and the determination of sets of ions typical of specific groups, for example, methylphosphonothiolates versus ethylphosphonothiolates. The new group‐specific ions elucidated in this work are also useful for screening unknown ‘V’‐type agents and related compounds, utilizing precursor ion scan experiments. Copyright © 2013 John Wiley & Sons, Ltd.     

Ionic diffusion in dynamically-disordered materials: Motion on a renewing, percolative lattice

Diffusion in concentrated ionic solutions involves ionic motion subject both to interionic Coulomb forces and to the fluctuating potentials arising from solvent motion. To study how these reflect themselves in the ion transport, we examine a problem in which Coulomb particles hop on a lattice that is percolative (some jumps are forbidden) and renewing (the forbidden jumps evolve in time). Diffusivity and tracer correlation are both effected by both renewal and Coulomb interaction. Coulomb effects can destroy the validity of the dynamic percolation result that the diffusivity is proportional to the renewal rate; non-exponential decay of the energy fluctuation correlation function is observed.     

Isotopic hydration of cellobiose: vibrational spectroscopy and dynamical simulations

The conformation and structural dynamics of cellobiose, one of the fundamental building blocks in nature, its C4' epimer, lactose, and their microhydrated complexes, isolated in the gas phase, have been explored through a combination of experiment and theory. Their structures at low temperature have been determined through double resonance, IR-UV vibrational spectroscopy conducted under molecular beam conditions, substituting D(2)O for H(2)O to separate isotopically, the carbohydrate (OH) bands from the hydration (OD) bands. Car-Parrinello (CP2K) simulations, employing dispersion corrected density functional potentials and conducted "on-the-fly" from ～20 to ～300 K, have been used to explore the consequences of raising the temperature. Comparisons between the experimental data, anharmonic vibrational self-consistent field calculations based upon ab initio potentials, and the CP2K simulations have established the role of anharmonicity; the reliability of classical molecular dynamics predictions of the vibrational spectra of carbohydrates and the accuracy of the dispersion corrected (BLYP-D) force fields employed; the structural consequences of increasing hydration; and the dynamical consequences of increasing temperature. The isolated and hydrated cellobiose and lactose units both present remarkably rigid structures: their glycosidic linkages adopt a "cis" (anti-? and syn-ψ) conformation bound by inter-ring hydrogen bonds. This conformation is maintained when the temperature is increased to ～300 K and it continues to be maintained when the cellobiose (or lactose) unit is hydrated by one or two explicitly bound water molecules. Despite individual fluctuations in the intra- and intermolecular hydrogen bonding pattern and some local structural motions, the water molecules remain locally bound and the isolated carbohydrates remain trapped within the cis potential well. The Car-Parrinello dynamical simulations do not suggest any accessible pathway to the trans conformations that are formed in aqueous solution and are widespread in nature.     

Liposome fusion rates depend upon the conformation of polycation catalysts

Cryo-TEM and NaCl-leakage experiments demonstrated that the cationic polymer polylysine induces fusion of anionic liposomes but that the cationic polymer poly(N-ethyl-4-vinylpyridinium bromide) (PEVP) does not, although both polymers bind strongly to the liposomes. The difference was traced to the thickness of the coatings at constant charge coverage. Polylysine is believed to form planar β-sheets that are sufficiently thin to allow membrane fusion. In contrast, looping and disorganization among adsorbed PEVP molecules physically prevent fusion. A similar effect is likely to be applicable to important polycation-induced fusion of cell membranes.     

Comparison of oleyl and elaidyl isomer surfactant-counterion systems in drag reduction, rheological properties and nanostructure

Compared with quaternary ammonium cationic surfactants with saturated alkyl chains, quaternary ammonium cationic surfactants with one double-bond in their alkyl chains, when mixed with appropriate counterions (in certain molar concentration ratios, ξ), can reach much lower effective drag-reduction temperatures, while maintaining the upper drag-reduction temperature limit of the corresponding saturated drag reducing surfactant solutions. No previous study has compared the effects of cis- vs. trans-unsaturated alkyl hydrocarbon tail configurations (oleyl vs. elaidyl) trimethyl ammonium chloride cationic surfactants at different counterion/surfactant concentration ratios on micellar nanostructures, (1)H NMR spectra and on rheological and drag-reduction behavior of their solutions. Since neither pure oleyl (cis-) nor elaidyl (trans-) trimethyl ammonium chloride surfactants are commercially available, they were synthesized and their 5mM solutions with NaSal counterion at concentrations of 5mM, 7.5mM and 12.5mM were studied.     

Complexation of anionic liposomes with spherical polycationic brushes

Spherical polycationic brushes, consisting of polystyrene particles with linear cationic macromolecules grafted onto their surfaces, were electrostatically complexed with small unilamellar anionic liposomes. Complexation was monitored using a multimethod approach that included laser electrophoresis, dynamic light scattering, fluorescence, cryogenic transmission electron microscopy, and conductivity. Liposomes adsorb onto the outer edges of the brushes rather than penetrate into their dense polycationic layer. The integrity of the liposomes remains unaltered when the liposomes reside on the polycationic brushes. The resulting complexes (roughly 40 liposomes per brush) do not dissociate into their components upon exposure to physiological solutions. The system is potentially useful in that liposomes are gathered into well-defined clusters with a high encapsulating potential. Multicomponent constructs can be easily prepared if polycationic brushes are allowed to bind to a mixture of liposomes that encapsulate different guests. This work provides an example of "systems chemistry" whereby as many as eight components, each with its own particular location and function (i.e., polystyrene core, polycationic graft, egg lecithin, cardiolipin, two fluorescent dyes, water, and buffer), collectively self-assemble.     

Unusual temperature gap in turbulent drag reduction of cationic surfactants with mixed counterions

Unusual temperature gaps have previously been observed in the turbulent drag reduction effectiveness of Dobon and Habon cationic surfactant systems containing two anionic counterions of different binding strengths. Here, we report drag reduction data for a cationic surfactant with a mixture of dodecyl sulfate and tosylate counterions showing a temperature gap. Cryo-TEM images of nanostructures at different temperatures for this system support an explanation for this gap, based on the counterions’ relative binding strengths.     

On the impact and the separation approximations in the theory of multiphoton interactions ivith thermally perturbed systems

Criteria are provided for the factorization of thermal averages incuring in the calculation of cross-sections for several-photon processes, into produc     

Quadratic effects in multiphonon transition rates in solids

In this paper we explore the contribution of quadratic impurity—phonon coupling terms on nonradiative multiphonon transition rates in solids. It is demonstrated that the quadratic terms may increase substantially the transition rate and may modify quantitatively the energy gap law. Such effects will be exhibited even when the quadratic coupling is too weak to be observable in the optical spectra.     

Potential variability of decisional skills in uncertain dichotomous choice situations

The main concern of this paper is the selection of optimal decision rules for groups of individuals with identical preferences but diverse and potentially variable independent decisional skills. Employing the uncertain dichotomous choice model the main results illustrate how optimality and sensitivity analysis can be pursued while explicitly recognizing decision-making costs associated with potential variability of decisional skills. For panels of experts consisting of three members our analysis focuses on three special cases of potential variability in individual skills. The extended optimality problem is analyzed resolving the dilemma which of the two common rules, the simple majority rule or the expert rule, is the better selection for the group. The sensitivity of the two rules to variability of decisional skills is also investigated.