Ambient surface mass spectrometry using plasma-assisted desorption ionization: effects and optimization of analytical parameters for signal intensities of molecules and polymers.

Results are presented on the optimization and characterization of a plasma-assisted desorption ionization (PADI) source for ambient mass spectrometry. It is found that by optimizing the geometry we can increase ion intensities for valine and by tuning the plasma power we can also select a more fragmented or less fragmented spectrum. The temperature of the surface rises linearly with plasma power: at 19 W it is 71 °C and at 28 W it is 126 °C. To understand if the changes in signal intensity are related to thermal desorption, experiments using a temperature-controlled sample stage and low plasma power settings were conducted. These show markedly different signal intensities to experiments of equivalent surface temperature but higher plasma power, proving that the mechanisms of ionization and desorption are more complicated than just thermal processes. Four different polymers, poly(methyl methacrylate) (PMMA), poly(ethylene terephthalate) (PET), poly(lactic acid) (PLA), and poly(tetrafluoroethylene) (PTFE), are analyzed using PADI. Mass spectra are obtained from all the polymers in the negative ion mode and from PMMA and PLA in the positive ion mode. For each polymer, characteristic ions are identified showing the ability to identify materials. The ions are formed from bond cleavage with O and CH(2) as common adducts. Ions were detected up to m/z 1200 for PTFE.

Surface analysis using a new plasma assisted desorption/ionisation source for mass spectrometry in ambient air.

The authors report on a modified micro-plasma assisted desorption/ionisation (PADI) device which creates plasma through the breakdown of ambient air rather than utilising an independent noble gas flow. This new micro-PADI device is used as an ion source for ambient mass spectrometry to analyse species released from the surfaces of polytetrafluoroethylene, and generic ibuprofen and paracetamol tablets through remote activation of the surface by the plasma. The mass spectra from these surfaces compare favourably to those produced by a PADI device constructed using an earlier design and confirm that the new ion source is an effective device which can be used to achieve ambient mass spectrometry with improved spatial resolution.

Prevention of surface reconstruction at the Au(110)/electrolyte interface by the adsorption of cytosine.

It is shown that the adsorption of cytosine at the Au(110)/liquid interface at a potential of 0.0 V "freezes" the Au(110) surface in the (1x1) structure and that the molecule does not change its orientation on the surface as the potential is varied. In contrast the adsorption of adenine does not freeze the Au(110) surface even though both molecules adopt a base stacking structure with individual molecules oriented in a plane vertical to the Au(110) surface with their long axes along [110] rows. It is suggested that cytosine bonds to three Au atoms through the NH(2) group, the N(3) and O(8) sites, and that this arrangement stabilizes the Au(110) surface and prevents its reconstruction to the more open (1x2) and (1x3) structures as the applied voltage is varied. The weaker bonding of the adenine molecule with the gold surface is unable to prevent the voltage induced reconstruction of the Au(110) surface.

Spectral signatures of the surface reconstructions of Au(110)/electrolyte interfaces.

It is demonstrated that the (1 × 1) structure and the (1 × 2) and (1 × 3) surface reconstructions that occur at Au(110)/electrolyte interfaces have unique optical fingerprints. The optical fingerprints are potential, pH and anion dependent and have potential for use in monitoring dynamic changes at this interface. We also observe a specific reflection anisotropy spectroscopy signature that may arise from anions adsorbed on the (1 × 1) structure of Au(110).

Determination of the structure of adenine monolayers adsorbed at Au(110)/electrolyte interfaces using reflection anisotropy spectroscopy.

Reflection anisotropy spectroscopy (RAS) has been used to show that at saturation coverage adenine adsorbs on the Au(110)/electrolyte interface in a base-stacking configuration with the plane of the bases orientated vertically on the surface and with the long axis of the molecules parallel to the [110] direction. Changes in the RAS observed from adsorbed adenine as a result of changes in the potential applied to the Au(110) electrode could arise from slight changes in the orientation of the molecules in the vertical plane.