Multigenerational Collision-Induced Dissociation for Characterization of Organic Compounds

Abstract

There are many cases in which limited information is obtained from a single stage of tandem mass spectrometry (MS or MS/MS). For example, isomeric cathinones give similar product ion MS spectra, but they can be differentiated by their unique MS fragments. Other drugs such as oxycodone and noroxycodone lose water in a single-stage tandem mass spectrometry experiment but give rich structural information in subsequent stages, as do many peptides. Here we utilize multigenerational collision-induced dissociation (CID) on a miniature mass spectrometer and emphasize useful applications. Unique fragmentation patterns consisting of several generations of fragment ions are obtained in these multigenerational spectra, allowing discrimination of cathinone isomers and structural characterization of small molecules, including drugs and peptides, all using a single sequence of ion injection, isolation, and mass scanning.

Rapid Screening of Ellagitannins in Natural Sources via Targeted Reporter Ion Triggered Tandem Mass Spectrometry

“…Although grandinin and acutissimin A have different major first-generation product ions, 487 and 457 respectively, the most abundant second and third-generation product ions are the same 249/275/301 reporter ions. These reporter ions are multi-generational and their intensities would no longer accurately be associated with specific product ion generations if spectral libraries were comprised of pseudo-CID spectra from even mild HCD conditions 63 . Standard normalized collision energies for CID (Tables S1 and S2 ) ranged from 15–25 and 30 was chosen to ensure complete fragmentation while minimizing the possibility that smaller species would be ejected from the LIT.…”

Open Port Probe Sampling Interface for the Direct Coupling of Biocompatible Solid-Phase Microextraction to Atmospheric Pressure Ionization Mass Spectrometry

“…Thus, aware of the extra challenges provided by the lack of a separation step, MRM 3 (m/z 277→259→168) was employed to overcome the lack of specificity encountered when exclusively performing MS/MS. [39][40][41] As shown in Figure 3, we demonstrated that Bio-SPME-OPP-MRM 3 can reach a LOQ value of 100 pg mL -1 upon performance of a 5 min extraction from 300 µL of urine spiked with clenbuterol (only the lower range of the calibration curve is shown in Figure 3 as to evidence the linearity of the method in this range of concentrations). Furthermore, exceptional linearity in the range of 100 pg mL −1 up to 100 ng mL −1 (see Figure S4, for full-calibration range), and good accuracy (i.e.…”

Ion isolation and multigenerational collision-induced dissociation using the inverse Mathieu q scan

“…generations of product ions and is hence a multigenerational CID technique. [46,47] This characteristic is clear in the product ion spectrum of noroxycodone, which in a typical MS 2 experiment loses only water to produce a highly abundant ion at m/z 284. Due to the multigenerational capabilities of the inverse Mathieu q scan, the water loss product also fragments during the CID step, generating, for example, the MS 3 -like product ions at m/z 229 and 187.…”

“…(c)), which produced abundant product ions with three bursts of a 4 ms frequency sweep. Because the frequency sweep is such that ions are fragmented from high to low m/z , the inverse Mathieu q scan produces several generations of product ions and is hence a multigenerational CID technique . This characteristic is clear in the product ion spectrum of noroxycodone, which in a typical MS 2 experiment loses only water to produce a highly abundant ion at m/z 284.…”