A novel MALDI-TOF mass spectrometer that utilizes a spiral ion trajectory was developed. In this mass spectrometer, the ions sequentially passed through four toroidal electrostatic sectors and revolved along a figure-eight-shaped orbit on a particular projection plane. Each toroidal electrostatic sector had eight stories, and during multiple revolutions, the ion trajectory shifted perpendicular to the projection plane in every cycle, thereby generating a spiral trajectory. The flight path length of one cycle was 2.1 m; therefore, when the ions completed eight cycles, the total flight path length was 17 m. By adopting an ion optical system that had a flight path length five times longer than that in the commonly used reflectron ion optical system, the mass dependence on the mass resolving power was reduced, while improving the mass accuracy of the mass measurements. The basic performance of the system was tested by using standard peptides or the tryptic digest of bovine serum albumin. A mass resolving power of 80,000 (full width at half maximum) was achieved at m/z = 2564 (ACTH18-39). An improved mass accuracy less than 2 ppm was realized over a wide m/z range of 500 to 3000 by correction using one or two internal standard substances.

Accurate mass measurements were obtained for a number of compounds with masses In the 500-16 000 u range analyzed with a double-focusing magnetic-sector mass spectrometer equipped with an electrospray Ionization (ESI) source. Mass accuracies In the low-ppm range were obtained for positive and negative Ions by using either magnetic field scans or acderating voltage scan methods. These mass measurements were sufficiently accurate to permit the determination of elemental compositions for smaler molecules, and they provide confidence In the mass assignments for larger biomolecules such as hen egg-white lysozyme and equine myoglobin. The utility of poly(ethylene oxide) and polypropylene oxide) as posltlve-km reference standards and poly(ethylene oxide), poly(propylene oxide), and poly (propylene oxide) sulfates as negative-ton reference standards Is demonstrated, and factors affecting accurate mass measurements for large molecules are discussed. The ESI mass spectrum of the lysozyme [M + 9Hf+ species measured at a resolution of 10 000 permits the determination of the masses of Individual Isotopes to within 0.15 u (12 ppm) of the theoretical value, and a peak assigned to water toss Is observed.

A new MALDI-TOF/TOF system with monoisotopic precursor selection was applied to the analysis of triacylglycerols in an olive oil sample. Monoisotopic precursor selection made it possible to obtain product-ion mass spectra without interference from species that differed by a single double bond. Complete structure determination of all triacylglycerols, including structural isomers, was made possible by interpreting the charge-remote fragmentation resulting from high-energy collision-induced dissociation (CID) of the sodiated triacylglycerols.

In this study, we have developed a tandem time-of-flight mass spectrometry (TOF/TOF) technique involving the use of a matrix-assisted laser desorption/ionization ion source that exhibits high precursor ion selectivity. An ion optical system with a 17 m spiral ion trajectory was used in the first time-of-flight mass spectrometer. High precursor ion selectivity was achieved by realizing a 15 m flight path, which is considerably longer than that of the conventional MALDI-TOF/TOF before the precursor ion selection by an ion gate; monoisotopic ions could be selected properly up to m/z 2500. Furthermore, the first time-of-flight mass spectrometer was composed of electrostatic sectors and could eliminate post-source decay (PSD) ions. Precursor ions with 20 keV kinetic energy were selected and injected into a collision cell, leading to the generation of fragment ions by high-energy collision-induced dissociation (HE-CID). The optimized second time-of-flight mass spectrometer included a post-acceleration region and an offset parabolic reflectron to record product ion spectra in the entire mass range. Our system could generate a simple HE-CID product ion spectrum because each fragment pathway could be observed as a single peak by the selection of monoisotopic ions of all precursor ions and HE-CID fragment pathways could be predominantly observed by the PSD ion elimination.

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