Image Currents

Figure Bl.7.18. (a) Schematic diagram of the trapping cell in an ion cyclotron resonance mass spectrometer excitation plates (E) detector plates (D) trapping plates (T). (b) The magnetron motion due to tire crossing of the magnetic and electric trapping fields is superimposed on the circular cyclotron motion aj taken up by the ions in the magnetic field. Excitation of the cyclotron frequency results in an image current being detected by the detector electrodes which can be Fourier transfonned into a secular frequency related to the m/z ratio of the trapped ion(s).

Figure 4. Ions undergoing coherent cyclotron motion induce image currents in the plates of the FTMS analyzer cell. Reproduced with permission from Ref. 18. Copyright 1985, North-Holland Physics Publishing.

Figure 6. The sequence of events in a laser desorption FTMS experiment, (a) The laser beam enters the cell and strikes the crystal, (b) Some of the desorbed molecules are ionized by an electron beam, (c) Ions are trapped in the analyzer cell by the magnetic and electric fields, (d) Ions are accelerated by an RF pulse and the resulting coherent image current signal is detected. Reproduced with permission from Ref. 18. Copyright 1935, North-Holland Physics Publishing.

Solid/liquid probe Field desorption (FD) Radio frequency (RF) Image currents... 

Split outer electrode, also used for detection of image current... 

Figure 2.18. Schematic of an orbitrap analyzer. The z-direction oscillary motion of the ions induces an image current that is detected by the electrodes.

Ion detection is carried out using image current detection with subsequent Fourier transform of the time-domain signal in the same way as for the Fourier transform ion cyclotron resonance (FTICR) analyzer (see Section 2.2.6). Because frequency can be measured very precisely, high m/z separation can be attained. Here, the axial frequency is measured, since it is independent to the first order on energy and spatial spread of the ions. Since the orbitrap, contrary to the other mass analyzers described, is a recent invention, not many variations of the instrument exist. Apart from Thermo Fischer Scientific s commercial instrument, there is the earlier setup described in References 245 to 247. 

Examples are given in References 249 and 250 of about 100 ions detected in a single scan. This is about the practical detection limit for image current detection due to thermal noise in the detection system. Bradykinin has been detected from a sample concentration of 3 nM [249] and detection of sub-femtomole levels on a column is readily obtained [251]. 

Since a minimum of about 100 ions is needed to generate a detectable signal under normal circumstances (ion counting is inherently more sensitive than image current detection) and space-charge effects become influential with more than 106 to 107 ions, the dynamic range is relatively poor, about 104. The same applies to the FTICR as to the QIT and orbitrap. The signal depends on other species present in the trap at the same time, which limits quantification quality. 

Image current detection is (currently) the only nondestructive detection method in MS. The two mass analyzers that employ image current detection are the FTICR and the orbi-trap. In the FTICR ions are trapped in a magnetic field and move in a circular motion with a frequency that depends on their m/z. Correspondingly, in the orbitrap ions move in harmonic oscillations in the z-direction with a frequency that is m/z dependent but independent of the energy and spatial spread of the ions. For detection ions are made... 

FT-ICR detection is accomplished by monitoring the image current induced by the orbiting ion packet as it cycles between the two receiver plates of the ceU. After formation by an ionization event, all trapped ions of a given mIz have the same cyclotron frequency but have random positions in the FT-ICR cell. The net motion of the ions under these conditions does not generate a signal on the receiver plates of the FT-ICR cell because of the random locations of ions. To detect cyclotron motion, an excitation pulse must be applied to the FT-ICR cell so that the ions bunch... 

As a result of this excitation step, the net coherent ion motion produces a time-dependent signal on the receiver plates, termed the image current , which represents aU ions in the FT-ICR cell. The image current is converted to a voltage, ampMed, digitized, and Fourier transformed to yield a frequency spectrum that contains complete information about frequencies and abundances of all ions trapped in the cell. A mass spectrum can then be determined by converting frequency into mass because frequency can be measured precisely, the mass of an ion can be determined to one part in 10 or better. 

For FT-ICR-MS, the ICR cell itself must not necessarily differ from one used in scanning ICR-MS (Fig. 4.51). Two of the four side walls (jc-axis) of the ICR cell are connected to the RF power supply during the period of excitation. Then, the image current induced in the detector plates (y-axis) is recorded as transient signal for some period of time (0.5-30 s). The excitation of the ions within the ICR cell has to stop at a level low enough to avoid wall collisions of the lightest ions to be measured. [191,200,201]... 

Note In ICR cells, the ions circulate like separate swarms of birds rather than like matter in the rings of Saturn. If ions of the same m/z non-coherently circulated at the same frequency and radius, but occupied the total orbit rather than a small sector of it, there would be no image current induced upon their passage at the detector plates. 

Luker GD, Luker KE (2008) Optical imaging current applications and future directions. JNuclMed 49 1-4... 

P.J. Frinking, A. Bouakaz, J. Kirkhom, F.J. Ten Cate and N. de Jong, Ultrasound contrast imaging current and new potential methods, Ultrasound Med. Biol. 26 (2000) 965-975. 

Figure 1. Schematic representation of a cubic trapped ion cell commonly used in FTMS. Coherent motion of ions in the cell induces an image current in the receiver plates. The time domain signal is subjected to a Fourier transform algorithm to yield a mass spectrum.

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