Ion/surface reactions and ion soft-landing.

Ion/surface collision phenomena in the hyperthermal collision energy regime (1-100 eV) are reviewed, with emphasis on chemical processes associated with the impact of small organic and biological ions at functionalized self-assembled monolayer surfaces. Inelastic collisions can lead to excitation of the projectile ion and can result in fragmentation, a process known as surface-induced dissociation which is useful in chemical analysis using tandem mass spectrometry. Changes in charge can accompany ion/surface collisions and those associated with a change in polarity (positive to negative ions or vice versa) are an attractive method for ion structural characterization and isomer differentiation.

Ion soft-landing into liquids: Protein identification, separation, and purification with retention of biological activity.

Protein ions, after mass spectrometric separation, can be soft-landed into liquid surfaces with preservation of their native structures. Retention of biological activity is strongly favored in glycerol-based surfaces but not in self-assembled monolayer solid surfaces. Soft-landing efficiency for multiply-charged hexokinase ions was found to be some four times higher for a glycerol/fructose liquid surface than for a fluorinated self-assembled monolayer surface.

Mass spectrometry sampling under ambient conditions with desorption electrospray ionization.

A new method of desorption ionization is described and applied to the ionization of various compounds, including peptides and proteins present on metal, polymer, and mineral surfaces. Desorption electrospray ionization (DESI) is carried out by directing electrosprayed charged droplets and ions of solvent onto the surface to be analyzed. The impact of the charged particles on the surface produces gaseous ions of material originally present on the surface.

Electrosonic spray ionization. A gentle technique for generating folded proteins and protein complexes in the gas phase and for studying ion-molecule reactions at atmospheric pressure.

Electrosonic spray ionization (ESSI), a variant on electrospray ionization (ESI), employs a traditional micro ESI source with supersonic nebulizing gas. The high linear velocity of the nebulizing gas provides efficient pneumatic spraying of the charged liquid sample. The variable electrostatic potential can be tuned to allow efficient and gentle ionization.

Preparing protein microarrays by soft-landing of mass-selected ions.

Intact, multiply protonated proteins of particular mass and charge were selected from ionized protein mixtures and gently landed at different positions on a surface to form a microarray. An array of cytochrome c, lysozyme, insulin, and apomyoglobin was generated, and the deposited proteins showed electrospray ionization mass spectra that matched those of the authentic compounds. Deposited lysozyme and trypsin retained their biological activity.