Secondary ion mass spectrometry of organic compounds

Sputtering is a very effective means to ionize large organic molecules, even those which are involatile and thermally labile. It can be applied to organic trace detection, identification and structural elucidation, to the analysis of body fluids, and as a detector in HPLC and TLC.     

Secondary ion mass spectrometry of nucleic acid components: Pyrimidines,purines, nucleosides and nucleotides

Biologically important involatile organic compounds including nucleotides, nucleosides, purines and pyrimidines have been analysed by secondary ion mass spectrometry. For the emission of molecule-like secondary ions small amounts of the substances were deposited as thin layers on silver foils and bombarded with 3 keV [AR]⁺ ions. All the compounds investigated yielded intense molecular ions of the general composition [M±H]^± and [M + Ag]⁺, but only a few characteristic fragment ions due to simple bond cleavages. Similarities and differences as compared with spectra obtained by other mass spectrometric ionization techniques are illustrated and discussed.     

Secondary ion mass spectrometry and alpha-spectrometry of electrodeposited thorium films

The main aim of this work was the preparation of samples with thorium content on the steel discs by electrodeposition for determination of natural thorium isotope by alpha spectrometry and secondary ion mass spectrometry and finding out their possible linear correlation between these methods. The analysis of the composition of surface was other aim of study. Discs were measured by alpha spectrometer. After that, alpha spectrometry discs were analyzed by TOF-SIMS IV, which is installed in the International Laser Centre in Bratislava. The integral and normalized intensities of isotope of ²³²Th and intensities of ions of ThO⁺, ThOH⁺, ThO₂H⁺, Th₂O₄H⁺, ThO₂ ^?, ThO₃H^?, ThH₃O₃ ^? a ThN₂O₅H^? were measured. The linear correlation is between surface’s weights of Th and intensities of ions of Th⁺ from identified in SIMS spectra. We found out the chemical binding between thorium and oxygen and hydrogen on the surface of samples by SIMS method. Obtained intensities of ions ²³²ThO⁺, ²³²ThOH⁺, ²³²ThO₂H⁺ prove the presence of oxidized forms of thorium in the upper layers of surface. The oxidized ions predominate in univalent form of thorium up to deep about 3,000 nm.     

Secondary ion mass spectrometry in the characterisation of boron-based ceramics

A secondary ion mass spectrometry (SIMS) study of Zr- and Ti-based borides is reported: ZrB2 ceramic samples (with and without nickel addition) and a TiB2-Ni-B4C/Cu joint were investigated. For Zr-based samples, SIMS measurements show evidence for induced effects by the presence of nickel with regard to oxygen and hydrogen absorption and zirconia formation. In the case of the TiB2-Ni-B4C/Cu joint, the ceramic-metal interface region was analysed and the extent of Cu diffusion into the ceramic material was established. SIMS results were in agreement with previously obtained SEM-EDS data.     

Identification of butyryl derivatives of cyclic nucleotides by positive ion fast atom bombardment mass spectrometry and mass-analysed ion kinetic energy spectrometry

The syntheses of the dibutyryl derivatives of the 3′,5′-cyclic monophosphates of adenosine, guanosine and cytidine are described. The fast atom bombardment mass spectra of these compounds are discussed, together with the mass-analysed ion kinetic energy spectra of their protonated molecular ions and of diagnostic fragments. A protocol for the identification of the derivatives is reported which includes criteria for confirming retention of the cyclic phosphodiester moiety, substitution of both heterocyclic base and ribose ring, and butyrylation of the 2′-O-position. The origins of significant fragments in the spectra are discussed.     

Ion-induced CO adsorption on polycrystalline nickel. Secondary ion mass spectrometry study

In the process of ion-induced CO adsorption (Ar⁺, 4 keV, 4 A/cm²) on polycrystalline Ni at room temperature and P=(1–40)×10^–6 Pa the emission of Ni⁺, NiCO⁺, CO⁺, NiO⁺ and C⁺ ions is observed. The emission of the last three ions is due to the ion-stimulated dissociation of weakly bound CO state and NiO formation. The weakly bound state is formed owing to surface defects produced by ion bombardment. The cross sections of the ion-induced desorption are 1.8 and 0.8×10^–14 cm², respectively, for weakly bound and strongly bound states.     

Secondary ion formation of low molecular weight organic dyes in time-of-flight static secondary ion mass spectrometry

Time-of-flight static secondary ion mass spectrometry (TOF-S-SIMS) was used to characterize thin layers of oxy- and thiocarbocyanine dyes on Ag and Si. Apart from adduct ions a variety of structural fragment ions were detected for which a fragmentation pattern is proposed. Peak assignments were confirmed by comparing spectra of dyes with very similar structures. All secondary ions were assigned with a mass accuracy better than 50 ppm. The intensity of molecular ions as well as fragment ions has been studied as a function of the type of organic dye, the substrate, the layer thickness and the type of primary ion. A large yield difference of two orders of magnitude was observed between the precursor ions of cationic carbocyanine dyes and the protonated molecules of the anionic dyes. Fragment ions, on the other hand, yielded similar intensities for both types of dye. As the dye layers deposited on an Ag substrate yielded higher secondary ion intensities than those deposited on a Si substrate, the Ag metal clearly acts as a promoting agent for secondary ion formation. The effect was more pronounced for precursor signals than for fragment ions. The promoting effect decreased as the deposited layer thickness of the organic dye layer was increased.     

Secondary ion mass spectrometry of some promazines and photochemistry of chlorpromazine in glycerol

SIMS using 6 keV Cs⁺ ions has been performed on glycerol solutions of various promazines. Fragmentation patterns are compared to those obtained by other ionization methods. The photochemical degradation of chlorpromazine has been observed directly in the glycerol droplet, showing the potentiality of SIMS for the direct study of photochemical reactions in solution.     

Secondary ion mass spectrometry of organic materials with the use of a glycerol matrix

Changes in the concentration of solute molecules in a glycerol matrix were studied using mass spectrometry of secondary ions that appeared under the bombardment of a sample-solution by primary ions. The objects of study were several organic dyes and glucose oxidase. The concentration of solute molecules in the surface layer of the matrix was determined by the competition between the destruction of analyte molecules by primary ions and the replenishment of the number of undamaged molecules as a result of diffusion from the bulk.     

High-pressure ion trap mass spectrometry

The effects of buffer gas pressure on ion trap stability, mass resolution/calibration, and choice of mass scanning are described. Pressure effects were treated phenomenologically by adding a drag term to the ion equations of motion. The resulting collisional damping enlarges the mass-dependent stability region but reduces the region in which mass-selective resonance ejection can be performed. The pressure effects can be reduced by increasing the frequency of the alternating quadrupole field.     

Secondary ion mass spectra of oligosaccharides

The mass spectra of oligosaccharides such as glucose, sucrose, lactose and raffinose obtained by static secondary ion mass spectrometry operated at 10^?6 Torr are presented. Cationized molecular ions are observed in high intensity. Fragment ions are compared with daughter ions produced by collision induced dissociation of field desorbed cationized molecular ions.     

Secondary ion mass spectra of oligopeptides

Secondary ion mass spectrometry for oligopeptides, such as tri-tetra-, penta- and hexapeptides, and bioactive peptides, are presented. Quasimolecular ions and cationized molecules were observed, together with many kinds of fragments, which were helpful in structural assignments. Secondary ion mass spectrometry did not prove to be dependent on temperature. Thermal migration of samples on a surface was observed at high temperature. Secondary ion mass spectra obtained with a silver substrate and an aluminium substrate are compared.