Increased Sensitivity in Proton Transfer Reaction Mass Spectrometry by Using a Novel Focusing Quadrupole Ion Funnel.

Sensitivity enhancement in proton transfer reaction mass spectrometry (PTR-MS) is an important development direction. We developed a novel drift tube called a focusing quadrupole ion funnel (FQ-IF) for use in PTR-MS to improve the sensitivity. The FQ-IF consists of 20 layers of stainless steel electrodes, and each layer has 4 quarter rings. The first 6 layers have a constant inner hole diameter of 22 mm; the latter 14 layers taper the inner diameter down to 8 mm. The FQ-IF drift tube can also operate in the direct current (DC) mode (similar to a conventional drift tube) and ion funnel (IF) mode (similar to a conventional ion funnel drift tube) by changing the voltage loading method. The simulation results show that the transmission efficiency of the FQ-IF is significantly improved compared to that of the other two modes. Further experiments show that the product ions of limonene tend to convert into smaller / fragment ions at higher voltages for the DC and IF modes. However, unlike the DC and IF modes, the distribution of product ions is stable at higher voltages for the FQ-IF. In other words, a higher RF voltage for the FQ-IF will not increase the collision energy of ions. In addition, the improvements in sensitivity for the FQ-IF range from 13.8 to 87.9 times compared to the DC mode and from 1.7 to 4.8 times compared to the IF mode for the 12 test compounds. The improvements in the limit of detection (LOD) for the FQ-IF range from 2.7 to 35.7 times compared to the DC mode. The FQ-IF provides a valuable reference for improving the sensitivity of PTR-MS and other mass spectrometers.