Virus Size Analysis by Gas-Phase Mobility Measurements: Resolution Limits.

Electrospraying (ES) dissolved viral particles, followed by charge reduction and size analysis with a differential mobility analyzer (DMA), offers a flexible size-analysis tool for small particles in solution. The technique relies on pioneering work by Kaufman and colleagues, commercialized by TSI, and often referred to as GEMMA. However, viral studies with TSI's GEMMA have suffered from limited resolving power, possibly because of imperfections in either the instrument (DMA or charge reduction) or the sample solution preparation. Here, we explore the limits of the resolution achievable by GEMMA, taking advantage of (i) cleaner charge reduction methods and (ii) DMAs of higher resolving power. Analysis of the literature provides indications that mobility peak widths (fwhm) of 2% or less may be achieved by combining careful sample preparation with improved instrumentation. Working with purified PP7 bacteriophage particles small enough to be classifiable by existing high-resolution DMAs, we confirm that fairly narrow viral mobility peaks may be obtained (relative full width at half-maximum fwhm <5%). Comparison of spectra of a given apian virus sample obtained with TSI's GEMMA and our improved instrumentation confirms that one critical limitation is the DMA. This is further verified by narrow peaks from murine parvovirus, norovirus, and encephalomyelitis virus samples, obtained in our improved GEMMA with little sample preparation, directly from infected cell cultures. Classification of purified large (60 nm) coliphage PR772 particles leads to broad peaks, due to both viral degradation and limited intrinsic resolution of the DMAs used to cover the range of such large particles. We conclude that improved DMAs suitable for high-resolution analysis of particles larger than 30 nm need to be developed to determine the intrinsic mobility width of viral particles.

Reaching a Vapor Sensitivity of 0.01 Parts Per Quadrillion in the Screening of Large Volume Freight.

The feasibility of detecting explosives in the atmosphere at concentrations as low as 0.01 ppq hinges on the poorly known question of what interfering species exist at these or higher concentrations. To clarify the issue, hundreds of samples of ambient air, either clean or loaded with explosives (from lightly contaminated environments) have been collected in fiberglass/stainless steel filters coated with Tenax-GR, thermally desorbed at variable temperature, and ionized with Cl- via secondary electrospray (SESI). They are analyzed with a narrow-band mobility filter (SEADM's P5 DMA) and a triple quadrupole mass spectrometer (Sciex's 5500), configured in series to transmit precursor and fragment ions of the explosives Nitroglycerin, PETN, RDX, and TNT. Blanks were sampled outdoors at a rural site (Boecillo, Valladolid, Spain), and loads were sampled at diverse locations. For RDX and TNT, atmospheric background inhibits detection below 1 part/trillion (ppt) without mobility filtering. This interference was drastically reduced by the DMA, allowing detection up to 1 part/quadrillion (ppq). Further sensitivity increase was achieved by scanning over a mobility region several percent around that of the target explosive, to separate various isobaric compounds by Gaussian deconvolution. (i) All four MS/MS channels analyzed exhibit several background peaks within the narrow mobility intervals investigated. At least one of these interferents is much stronger than the instrument background at the explosive's mobility, making DMA separation most helpful. (ii) For Nitroglycerin and PETN the combined filtering techniques have not lowered ambient chemical noise down to 0.01 ppq. (iii) Interferents are greatly reduced for TNT and RDX, resulting in minimal chemical noise: 322 blank tests for RDX yielded mean signal of 0.0012 ppq and standard deviation σ = 0.0035 ppq (mean + 3σ detection limit of 0.01 ppq).

Modulations in the abundance of salt clusters in electrosprays

The abundance of tetraheptylammonium bromide clusters produced from formamide solutions by electrospray ionization (ESI) is investigated. It exhibits a wavy pattern when plotted as a function of cluster size, successive waves being ordered according to the initial cluster charge z. This structure confirms the ion evaporation mechanism of Iribarne and Thomson and simplifies drastically the determination of the distribution of cluster charge z and radius R, from which the kinetics of ion evaporation from charged drops can be inferred.

Charge-induced unfolding of multiply charged polyethylene glycol ions.

The electrical mobility of mass-selected single poly(ethylene glycol) (PEG) chains of mass m (<14 kDalton) and charge state z (+1 to +5) reveals a near-spherical shape above a critical mass m(z) approximately z(2). The abrupt unfolding observed at m < m(z) shows that the polymer molecules behave as liquid drops upon reaching the Rayleigh limit, with an apparent surface energy of 0.026 N/m at ion diameters from 1.7 to 3.2 nm. Other nonspherical shape families with structures independent of charge, and with charge-dependent stability domains, are observed. Highly charged ions adopt approximately linear highly stretched configurations where the mobility depends only on m/z, independently of z. An operational definition of the surface energy of a single long chain molecule that is computable and agrees with the measured surface energy is provided.