Time-Resolved Ion Mobility Spectrometry with a Stop Flow Confined Volume Reaction Region.

An ion source concept is described where the sample flow is stopped in a confined volume of an ion mobility spectrometer creating time-dependent patterns of ion patterns of signal intensities for ions from mixtures of volatile organic compounds and improved signal-to-noise rate compared to conventional unidirectional drift gas flow. Hydrated protons from a corona discharge were introduced continuously into the confined volume with the sample in air at ambient pressure, and product ions were extracted continuously using an electric field for subsequent mobility analysis. Ion signal intensities for protonated monomers and proton bound dimers were measured and computationally extracted using mobilities from mobility spectra and exhibited distinct times of appearance over 30 s or more after sample injection. Models, and experimental findings with a ternary mixture, suggest that the separation of vapors as ions over time was consistent with differences in the reaction rate for reactions between primary ions from hydrated protons and constituents and from cross-reactions that follow the initial step of ionization. The findings suggest that the concept of stopped flow, introduced here for the first time, may provide a method for the temporal separation of atmospheric pressure ions. This separation relies on ion kinetics and does not require chromatographic technology.

A PYP chromophore acts as a 'photoacid' in an isolated hydrogen bonded complex.

The light-induced response of a neutral Photoactive Yellow Protein chromophore in a hydrogen-bonded complex with a proton acceptor has been studied by dual-detection action absorption spectroscopy and density functional theory. We show that the chromophore is a 'photoacid' and that ultrafast excited-state proton transfer might be operative in an isolated complex.

How far can a single hydrogen bond tune the spectral properties of the GFP chromophore?

Photoabsorption of the hydrogen-bonded complex of a neutral and an anionic Green Fluorescent Protein chromophore has been studied using a new dual-detection approach to action-absorption spectroscopy. Following absorption of one photon, dissociation through a single channel ensures that the full absorption spectrum is measured. Our theoretical account of the spectral shape reveals that the anionic 0-0 transition (464 nm) is blue-shifted compared to that of the wild-type protein (478 nm) due to the stronger H-bond in the dimer, and represents an upper bound for that of the isolated anion. At the same time, the apparent effect of the H-bond for the neutral chromophore is as large as 0.5 eV, red-shifting the absorption maximum of the isolated neutral (340 nm) to that measured in the dimer (393 nm) and various proteins (∼395 nm). This shift results from changes in the topography of potential-energy surfaces in the Franck-Condon region of the H-bonded systems.

Computational analysis of an electrostatic separator design for removal of volatile organic compounds from indoor air.

Concentrations of volatile organic compounds (VOCs) in air can be reduced in electrostatic separators where VOCs are ionized using ion-molecule reactions, extracted using electric fields, and eliminated in a waste flow. Embodiments for such separator technology have been explored in only a few studies, despite the possible advantage of purification without adsorbent filters. In one design, based on ionization of VOCs in positive polarity with hydrated protons as reactant ions, efficiencies for removal were measured as 30-40% . The results were fitted to a one-dimensional convective diffusion model requiring an unexpectedly high production rate of reactant ions to match both the model and data. A realistic rate of reactant ion production was used in finite element method simulations (COMSOL) and demonstrated that low removal efficiency could be attributed to non-uniform patterns of sample flow and to incomplete mixing of VOCs with reactant ions. In analysis of complex systems, such as this model, even limited computational modeling can outperform a pure analytical approach and bring insights into limiting factors or system bottlenecks.Implications: In this work, we applied modern computational methods to understand the performance of an air purifier based on electrostatics and ionized volatile organic compounds (VOCs). These were described in the publication early 2000s. The model presented was one-dimensional and did not account for the effects of flow. In our multiphysics finite element models, the efficiency and operation of the filter is better explained by the patterns of flow and flow influences on ion distributions in electric fields. In general, this work helps using and applying computational modelling to understand and improve the performance bottlenecks in air purification system designs.

Quantitative Distributions of Product Ions and Reaction Times with a Binary Mixture of VOCs in Ambient Pressure Chemical Ionization.

A model to quantitatively predict ion abundances from atmospheric pressure chemical ionization (APCI) between hydrated protons and a volatile organic compound (VOC) was extended to binary mixtures of VOCs. The model includes differences in vapor concentrations, rate coefficients, and reaction times and is enhanced with cross reactions between neutral vapors and protonated monomers. In this model, two specific VOCs were considered, a ketone, 6-methyl-5-hepten-2-one (M, and an amine, 2,6-di-tert-butyl-pyridine (N), with measured "conditional rate coefficients" (in cm3·s-1) of kM = 1.11 × 10-9 and kN = 9.17 × 10-10, respectively. The cross reaction of MH+(H2O)x to NH+(H2O)y was measured as kcr = 1.31 × 10-12 at 60 °C. Cross reactions showed an impact on ion abundances at t > 30 ms for equal vapor concentrations of 100 ppb for M and N. In contrast, this impact was negligible for vapor concentrations of 1 ppb and did not exceed 5% change in product ion abundance up to 1000 ms reaction times. The model was validated with laboratory measurements to within ∼10% using an ion mobility spectrometer and effective reaction time obtained from computational fitting of experimental findings. This was necessitated by complex flow patterns in the ion source volume and was determined as ∼10.5 ms. The model has interpretative and predictive value for quantitative analysis of responses with ambient pressure ion sources for mass spectrometry and ion mobility spectrometry.

A multicoincidence study of fragmentation dynamics in collision of γ-aminobutyric acid with low-energy ions.

Fragmentation of the γ-aminobutyric acid molecule (GABA, NH(2)(CH(2))(3)COOH) following collisions with slow O(6+) ions (v≈0.3 a.u.) was studied in the gas phase by a combined experimental and theoretical approach. In the experiments, a multicoincidence detection method was used to deduce the charge state of the GABA molecule before fragmentation. This is essential to unambiguously unravel the different fragmentation pathways. It was found that the molecular cations resulting from the collisions hardly survive the interaction and that the main dissociation channels correspond to formation of NH(2)CH(2)(+), HCNH(+), CH(2)CH(2)(+), and COOH(+) fragments. State-of-the-art quantum chemistry calculations allow different fragmentation mechanisms to be proposed from analysis of the relevant minima and transition states on the computed potential-energy surface. For example, the weak contribution at [M-18](+), where M is the mass of the parent ion, can be interpreted as resulting from H(2)O loss that follows molecular folding of the long carbon chain of the amino acid.

Ion density of positive and negative ions at ambient pressure in air at 12-136 mm from 4.9 kV soft x-ray source.

The abundance of ions is an essential parameter for ion mobility and mass spectrometry instrument design and for the control or optimization of chemical reactions with reactant ions. This information also advances the study of atmospheric pressure ion kinetics under continuous ionization, which has a role in developing trace level chemical analyzers. In this study, an ionization chamber is described to measure the abundance of ions produced by a 4.9 keV, model L12535, soft x-ray source from Hamamatsu Corporation. Ions of positive and negative polarity were measured independently in an 8 × 30 mm2 cross section at distances of 12-136 mm at ambient air from an uncollimated beam. Ions were collected using electric fields and 16 sets of plates. The ion current decreased exponentially with distance from the source, and the calculated ion concentration varied between 1.0 × 108 and 3.8 × 105 ions cm-3 on plates. A 2D-COMSOL model including losses by recombination and diffusion was favorably matched to changes in ion current intensity in the ionization chamber. Although the ionization chamber was built to characterize a commercial ion source, the design may be considered generally applicable to other x-ray sources.

Parametric Sensitivity in a Generalized Model for Atmospheric Pressure Chemical Ionization Reactions.

Gas phase reactions between hydrated protons H+(H2O)n and a substance M, as seen in atmospheric pressure chemical ionization (APCI) with mass spectrometry (MS) and ion mobility spectrometry (IMS), were modeled computationally using initial amounts of [M] and [H+(H2O)n], rate constants k1 to form protonated monomer (MH+(H2O)x) and k2 to form proton bound dimer (M2H+(H2O)z), and diffusion constants. At 1 × 1010 cm-3 (0.4 ppb) for [H+(H2O)n] and vapor concentrations for M from 10 ppb to 10 ppm, a maximum signal was reached at 4.5 µs to 4.6 ms for MH+(H2O)x and 7.8 µs to 46 ms for M2H+(H2O)z. Maximum yield for protonated monomer for a reaction time of 1 ms was ∼40% for k1 from 10-11 to 10-8 cm3·s-1, for k2/k1 = 0.8, and specific values of [M]. This model demonstrates that ion distributions could be shifted from [M2H+(H2O)z] to [MH+(H2O)x] using excessive levels of [H+(H2O)n], even for [M] > 10 ppb, as commonly found in APCI MS and IMS measurements. Ion losses by collisions on surfaces were insignificant with losses of <0.5% for protonated monomer and <0.1% for proton bound dimer of dimethyl methylphosphonate (DMMP) at 5 ms. In this model, ion production in an APCI environment is treated over ranges of parameters important in mass spectrometric measurements. The models establish a foundation for detailed computations on response with mixtures of neutral substances.

High resolution AFM studies of irradiated mica-following the traces of swift heavy ions under grazing incidence.

High resolution AFM imaging of swift heavy ion irradiated muscovite mica under grazing incidence provides detailed insight into the created nanostructure features. Swift heavy ions under grazing incidence form a complex track structure along the surface, which consists of a double track of nanohillocks at the impact site accompanied by a single, several 100 nm long protrusion. Detailed track studies by varying the irradiation parameters, i.e. the angle of incidence (0.2°-2°) and the kinetic energy of the impinging ions (23, 55, 75, 95 MeV) are presented. Moreover, the track formation in dependence of the sample temperature (between room temperature and 600 °C) and of the chemical composition (muscovite mica and fluorphlogopite mica) is studied.

Swift heavy ion irradiation of CaF2 - from grooves to hillocks in a single ion track.

A novel form of ion-tracks, namely nanogrooves and hillocks, are observed on CaF2 after irradiation with xenon and lead ions of about 100 MeV kinetic energy. The irradiation is performed under grazing incidence (0.3°-3°) which forces the track to a region in close vicinity to the surface. Atomic force microscopy imaging of the impact sites with high spatial resolution reveals that the surface track consists in fact of three distinct parts: each swift heavy ion impacting on the CaF2 surface first opens a several 100 nm long groove bordered by a series of nanohillocks on both sides. The end of the groove is marked by a huge single hillock and the further penetration of the swift projectile into deeper layers of the target is accompanied by a single protrusion of several 100 nm in length slowly fading until the track vanishes. By comparing experimental data for various impact angles with results of a simulation, based on a three-dimensional version of the two-temperature-model (TTM), we are able to link the crater and hillock formation to sublimation and melting processes of CaF2 due to the local energy deposition by swift heavy ions.