A new time-of-flight (TOF) mass spectrometer with a corkscrew ion trajectory was designed and constructed. The spiral trajectory was realized by using four toroidal electrostatic sectors. Each had fifteen-stories made of sixteen Matsuda plates piled up inside a cylindrical electrostatic sector. The ions passed the four toroidal electrostatic sectors sequentially and revolved along a figure-eight-shaped orbit on a certain projection plane. During the multiple revolutions, each ion trajectory was shifted by 50 mm per cycle on a direction perpendicular to the projection plane, thus generating a spiral trajectory. The flight path length of one cycle was 1.308 m so that the maximum flight path length became ϳ20 m. The mass resolution, mass accuracy, and ion transmission were tested by utilizing an orthogonally coupled electron ionization source. A mass resolution of 35,000 (FWHM) for m/z greater than 300 was achieved. Even in a lower mass region, mass resolutions of more than 20,000 (FWHM) were confirmed with a doublet of 12 C 5 1 H 5 14 N ϩ and 13 C 12 C 5 1 H 6 ϩ . The mass accuracy was also improved such that it was better than 1 ppm with only one internal standard peak. . With the advent of matrix-assisted laser desorption/ionization (MALDI) [3,4] and electrospray ionization (ESI) techniques [5], the TOF mass spectrometer has become a powerful analytical tool, especially in biochemistry and biotechnology. Its characteristic features are high sensitivity, theoretically infinite massrange, and rapid measurements. It also provides a simple and easy method to obtain exact mass measurements. These features give the TOF mass spectrometer a great advantage over other mass spectrometers, such as the quadrupole, ion trap, and magnetic sector-type mass spectrometers. However, a drawback of the TOF mass spectrometer is the intrinsic characteristic of poor mass resolving power for accurate mass analysis, especially for small molecules, compared with a Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometer. In an orthogonal acceleration (oa-) TOF mass spectrometer, the mass resolution and mass accuracy are limited to approximately 10,000 (FWHM) and 3 ppm, respectively. On the other hand, in the FT-ICR mass spectrometer, they have reached over 100,000 (FWHM) and 1 ppm, respectively.The mass resolution of the TOF mass spectrometer is expressed as R ϭ m/⌬m ϭ t/2⌬t, where t is the total time of flight, which is given by the flight path length divided by the ion velocity, and ⌬t is the peak width measured at FWHM. Thus, it is essential to extend the flight path length and minimize the peak width to improve the mass resolution. The peak width depends on the broadening of the ion packet at the detector, especially along the velocity axis and the response time of the detector. Various ion optical techniques have been reported to minimize the peak width: space focusing [6], time-lag focusing [6], orthogonal acceleration [7], and an ion mirror [8] or sector fields [9]. The mass accuracy can be steadily improved by increas...
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.
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.
Its recent adaptation to low-resolution mass spectra of polymers using fractional base units raises the question of the minimal resolution needed for a Kendrick mass defect (KMD) analysis. Intuiting an oligomeric resolution since the mass of a repeat unit is the sole value to be known, it is challenged by the relative failure of the KMD plots computed from an isotopically resolved matrix-assisted laser desorption ionization-time-of-flight (MALDI-TOF) mass spectrum to display clear alignments in the high mass range. Another procedure based on the remainders of Kendrick mass (RKMs) overcomes this pitfall with oligomers perfectly aligned in a new RKM plot. Despite a concomitant degradation of the resolving power and accuracy, with the example of MALDI-TOF/TOF mass spectra of a variety of homo- and copolymer ions, the RKM procedure still allows a rapid enumeration, assignment, and any further manipulation of all the product ion series in visual RKM plots. Successfully extended to the critical case of a MALDI mass spectrum recorded with a linear TOF analyzer allowing a bare oligomeric resolution, the RKM plot turns the distributions differing by their end-groups or adducted ion into clear horizontal lines. It eventually gives intuition its due by answering the original question: the minimal resolution required for a mass defect analysis can be as low as oligomeric with the appropriate formulas.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.