An electrostatic linear ion trap (ELIT) has been configured to allow for the simultaneous acquisition of mass spectra via Fourier transform (FT) techniques (frequency measurement) and via time-of-flight (TOF; time measurement). In the former case, the time-domain image charge derived from a pick-up electrode in the field-free region of the ELIT is converted to frequency-domain data via Fourier transformation (i.e., FT-ELIT MS). In the latter case, the time difference between ion injection into the ELIT and ion detection after release from the ELIT using a microchannel plate (MCP) enables the acquisition of multireflection time-of-flight mass spectra (MR-TOF MS). The ELIT geometry facilitates the acquisition of both types of data simultaneously because the detection schemes are independent and do not preclude one another. The two MS approaches exhibit a degree of complementarity. Resolution increases much faster with time with the MR-TOF approach, for example, but the closed-path nature of executing MR-TOF in an ELIT limits both the m/z range and the peak capacity. For this reason, the FT-ELIT MS approach is most appropriate for wide m/z range applications, whereas MR-TOF MS can provide advantages in a "zoom-in" mode in which moderate resolution (M/ΔM ≈ 10000) at short analysis times (10 ms) is desirable.
Collision cross sections (CCSs) were determined from the frequency-domain linewidths in a Fourier transform electrostatic linear ion trap. With use of an ultrahigh-vacuum precision leak valve and nitrogen gas, transients were recorded as the background pressure in the mass analyzer chamber was varied between 4× 10 and 7 × 10 Torr. The energetic hard-sphere ion-neutral collision model, described by Xu and coworkers, was used to relate the recorded image charge to the CCS of the molecule. In lieu of our monoisotopically isolating the mass of interest, the known relative isotopic abundances were programmed into the Lorentzian fitting algorithm such that the linewidth was extracted from a sum of Lorentzians. Although this works only if the isotopic distribution is known a priori, it prevents ion loss, preserves the high signal-to-noise ratio, and minimizes the experimental error on our homebuilt instrument. Six tetraalkylammonium cations were used to correlate the CCS measured in the electrostatic linear ion trap with that measured by drift-tube ion mobility spectrometry, for which there was an excellent correlation (R ≈ 0.9999). Although the absolute CCSs derived with our method differ from those reported, the extracted linear correlation can be used to correct the raw CCS. With use of [angiotensin II] and reserpine, the corrected CCSs (334.9 ± 2.1 and 250.1 ± 0.5, respectively) were in good agreement with the reported ion mobility spectrometry CCSs (335 and 254.3, respectively). With sufficient signal-to-noise ratio, the CCSs determined are reproducible to within a fraction of a percent, comparable to the uncertainties reported on dedicated ion mobility instruments. Graphical Abstract ᅟ.
This paper summarizes the results of research, funded by the Canadian Energy Pipeline Association (CEPA), to determine whether the initiation of near-neutral pH stress corrosion cracking (SCC) could be correlated with pipe metallurgical factors. The factors considered included residual stress, surface roughness, chemical composition, cyclic stress-strain behavior, inclusion properties (number, area, and composition), microhardness, and local galvanic behavior. The project focused on pipes installed from the 1950s through 1970s that exhibit near-neutral-pH SCC. Fourteen pipe samples were examined, ranging in diameter from 8 to 42 inches and grades from X52 to X70.
Ion isolation was achieved via selective pulsing of the entrance and exit ion mirrors in an electrostatic linear ion trap mass spectrometer (ELIT). Mirror switching has been described previously as a method for capturing injected ions in ELIT devices. After ion trapping, mirror switching can be used as a method for ion isolation of successively narrower ranges of mass-to-charge (m/z) ratio. By taking advantage of the spatial separation of ions in an ELIT device, pulsing of the entrance and/or exit mirrors can release unwanted ions while continuing to store ions of interest. Furthermore, mirror switching can be repeated multiple times to isolate ions of very similar m/z values with minimal loss of the stored ions, as is demonstrated by the isolation of protonated L-glutamine and L-lysine (Δ m/z = 0.0364) from a mixture of the two amino acid ions and the isobaric mixture of [PC P-18:0/22:6] and [PC 19:0/19:0] (Δ m/z = 0.0575). As isolation is accomplished due to the spatial/temporal separation of ion packets within the ELIT, multiple reflection-time-of-flight (MR-TOF) mass spectra are shown to demonstrate separation in the ELIT at the time of isolation. An isolation resolution of greater than 35 000 fwhm is demonstrated here using a 5.25 in. ELIT. This resolution corresponds to the fwhm resolution necessary to reduce contaminant overlap of an equally abundant adjacent ion to 1% or less of the isolated ion intensity.
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