Hideya Koizumi

Trapping of intact, singly-charged, bovine serum albumin ions injected from the atmosphere with a 10-cm diameter, frequency-adjusted linear quadrupole ion trap.

High-resolution real-time particle mass measurements have not been achievable because the enormous amount of kinetic energy imparted to the particles upon expansion into vacuum competes with and overwhelms the forces applied to the charged particles within the mass spectrometer. It is possible to reduce the kinetic energy of a collimated particulate ion beam through collisions with a buffer gas while radially constraining their motion using a quadrupole guide or trap over a limited mass range. Controlling the pressure drop of the final expansion into a quadrupole trap permits a much broader mass range at the cost of sacrificing collimation. To achieve high-resolution mass analysis of massive particulate ions, an efficient trap with a large tolerance for radial divergence of the injected ions was developed that permits trapping a large range of ions for on-demand injection into an awaiting mass analyzer. The design specifications required that frequency of the trapping potential be adjustable to cover a large mass range and the trap radius be increased to increase the tolerance to divergent ion injection. The large-radius linear quadrupole ion trap was demonstrated by trapping singly-charged bovine serum albumin ions for on-demand injection into a mass analyzer. Additionally, this work demonstrates the ability to measure an electrophoretic mobility cross section (or ion mobility) of singly-charged intact proteins in the low-pressure regime. This work represents a large step toward the goal of high-resolution analysis of intact proteins, RNA, DNA, and viruses.

Controlling the Expansion into Vacuum—the Enabling Technology for Trapping Atmosphere-Sampled Particulate Ions

A new inlet has been designed to control the kinetic energy distributions of ions into a large-radius, frequency-adjusted, linear quadrupole ion trap. The work presented here demonstrates trapping singly-charged, intact proteins in the 10 to 200 kDa range injected from the atmosphere. The trapped ions were held while collisions with a buffer gas removed the remaining amounts of expansion-induced kinetic energy. The ions were then ejected from the trap on-demand into an awaiting detector. There is no low mass limit for ion injection and trapping. The upper limit presented in this study was defined by the limit of the conversion dynode-based detector at ∼1.5 MDa. Trapping larger masses should be achievable. The transmission and capture efficiency across the entire mass range should be very high because the entire flow from the inlet empties directly into the trap. The kinetic energy distribution of massive ions is the primary reason for the working range limitation of mass spectrometers. Trapping ions with collisional cooling before mass analysis permits the motion of the ions to be completely defined by the applied fields. For this reason, this new inlet and trapping system represents a large step toward sensitive, high-resolution mass spectrometry into the megadalton range and beyond.

ESI-QIMS Investigation of Sr, Rb, and Crown Ether Mixture Solutions

The isotope distribution of Sr, alternatively 87Sr/86Sr ratio frequently reported in geologic investigations, is obtained by direct electrospray ionization of aqueous samples containing Sr(II), Rb(I) with added 18-crown-6 (18c6) [1,4,7,10,13,16-Hexaoxacyclooctadecane C12H24O6 m/z 264.3]. At relatively high concentrations of Sr and Rb, we observed favorable formation of Sr2+(18c6)2 and Rb+(18c6) rather than Sr2+(18c6) complexes. Significant Sr2+(18c6)2 suppression observed in post column addition of samples into water solvent disappeared when formic acid was present in the carrier solvent. Electrospray ionization-quadrupole-ion trap mass spectrometry (ESI-QITMS) successfully obtained the expected isotope distribution of Sr showing no interference from Rb without chromatographic separation of 87Sr and 87Rb necessary in ICP-MS studies.