Abstract: The invention relates to a method and apparatus for the fragmentation of large molecules, especially biopolymers. The invention consists in reacting analyte ions with excited or radical neutral particles, whereby, at least in the case of bombardment of analyte ions with helium atoms from an FAB generator, a new type of fragmentation occurs which strongly resembles fragmentation by electron capture (ECD). The reactions may be performed in magnetic ion traps (ion cyclotron resonance cells, ICR), in RF ion traps according to Wolfgang Paul, in RF ion guides, or in free beams of analyte ions or neutral particles.

Abstract: Methods and apparatus are provided to obtain efficient Electron capture dissociation (ECD) of positive ions, particularly useful in the mass spectrometric analysis of complex samples such as of complex mixtures and large biomolecules of peptides and proteins. Due to the low efficiency of ECD as previously used, the technique has so far only been employed with Penning cell ion cyclotron resonance mass spectrometers, where the ions are confined by a combination of magnetic and electrostatic fields. To substantially increase the efficiency of electron capture, the invention makes use of a high-intensity electron source producing a high-flux low-energy electron beam of a diameter comparable to that of the confinement volume of ions. Such a beam possesses trapping properties for positive ions. The ions confined by electron beam effectively capture electrons, which leads much shorter analysis time.

Abstract: Multiply charged ions are trapped and accumulated in a spatially limited region before being injected into an ion trap mass spectrometer such as a Fourier transform ion cyclotron resonance mass spectrometer (FTICR MS). In the ion trap electron capture dissociation (ECD) and vibrational excitation dissociation are sequentially applied on ions of the same ion ensemble. The first dissociation process does not fragment all primary ions. Following the detection of the dissociation products, the primary ions that remain undissociated undergo the vibrational excitation and again, a part of them dissociate, and the fragments are detected. Thus, the same ion ensemble is used for two fragmentation processes. During these processes, further ions generated in the external ion source are accumulated in the spatially limited region for subsequent analyses.

Abstract: The present invention relates to ion fragmentation techniques by electron-ion reactions in multipolar radiofrequency fields like those in quadrupole ion traps or in ion guides, and devices to perform ion fragmentation by such techniques. The fragmentation techniques are useful for tandem mass spectrometry. The invention consists of the application of a magnetic field essentially parallel to the axis of the radiofrequency field to confine the electrons in the direction perpendicular to the magnetic field.

Abstract: Methods and apparatus are provided to obtain efficient Electron capture dissociation (ECD) of positive ions, particularyly useful in the mass spectrometric analysis of complex samples such as of complex mixtures and large biomolecules of peptides and proteins. Due to the low efficiency of ECD as previously used, the technique has so far only been employed with Penning cell ion cyclotron resonance mass spectrometers, where the ions are confined by a combination of magnetic and electrostatic fields. To substantially increase the efficiency of electron capture, the invention makes use of a high-intensity electron source producing a high-flux low-energy electron beam of a diameter comparable to that of the confinement volume of ions. Such a beam possesses trapping properties for positive ions. The ions confined by electron beam effectively capture electrons, which leads much shorter analysis time.