EP0294683B1 - Verfahren zur Aufnahme von ICR-Massenspektren und zur Durchführung des Verfahrens ausgebildetes ICR-Massenspektrometer - Google Patents

Verfahren zur Aufnahme von ICR-Massenspektren und zur Durchführung des Verfahrens ausgebildetes ICR-Massenspektrometer Download PDF

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Publication number
EP0294683B1
EP0294683B1 EP88108648A EP88108648A EP0294683B1 EP 0294683 B1 EP0294683 B1 EP 0294683B1 EP 88108648 A EP88108648 A EP 88108648A EP 88108648 A EP88108648 A EP 88108648A EP 0294683 B1 EP0294683 B1 EP 0294683B1
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Prior art keywords
frequency
signals
time
dependent
pulse
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Expired - Lifetime
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EP88108648A
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German (de)
English (en)
French (fr)
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EP0294683A2 (de
EP0294683A3 (de
Inventor
Geoffrey Bodenhausen
Peter Pfändler
Jacques Rapin
Tino Gäumann
Raymond Hourriet
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Spectrospin AG
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Spectrospin AG
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/26—Mass spectrometers or separator tubes
    • H01J49/34—Dynamic spectrometers
    • H01J49/36—Radio frequency spectrometers, e.g. Bennett-type spectrometers, Redhead-type spectrometers
    • H01J49/38—Omegatrons ; using ion cyclotron resonance

Definitions

  • the invention relates to a method and a device for recording ICR mass spectra in each case according to the preambles of patent claims 1 and 4. Such a method is known from US Pat. No. 3,937,955.
  • Ion cyclotron resonance is an excellent method for mass spectroscopy because of its versatility, sensitivity and high resolution. Ions of different types contained in a gas sample can be excited simultaneously by a corresponding broadband pulse, so that a frequency mixture is present in the high-frequency signal induced by the excited ions after the end of the pulse. The components contained in the induction signal can then be resolved by a Fourier transform according to frequency and intensity.
  • ICR mass spectroscopy allows not only the analysis of substances and mixtures of substances, but also the observation of dynamic processes, such as the observation of the products of ion-molecule collisions and unimolecular fragmentations, through double resonance.
  • this double resonance also known as an MS / MS experiment, all ions except the one type of ion that is to be investigated are first eliminated by the ions of the substance to be investigated, which are trapped in the measuring cell of an ICR mass spectrometer, by irradiation of appropriate cyclotron resonance frequencies. If necessary, a collision gas is then let into the measuring cell. The selected ion type is then excited to such an extent that there are collisions with one another or with the molecules of the collision gas and secondary fragments are formed by collision dissociation.
  • the secondary ions formed are then analyzed by the usual ICR measurement cycle. If the original mass spectrum contains a number of N lines, a number N of such experiments is required for a complete analysis. This creates a number of new spectral lines for each line of the original spectrum, see above that a two-dimensional array of spectral lines is obtained if the original spectral lines are plotted along a coordinate direction and the secondary spectral lines assigned to these spectral lines are plotted along a second coordinate direction. Even if such an MS / MS experiment is carried out automatically, carrying out such an experiment requires a very long time and a considerable outlay on equipment. The automatic also fails if the spectra are very complex and have overlapping lines or if they contain weak lines lying on the detection line.
  • the invention has for its object to further develop the generic method for recording ICR mass spectra so that it can be used with short measuring time even in complicated cases in which peaks lying close together must be resolved. Furthermore, it is an object of the invention to provide a device which is suitable for carrying out the method. This object is achieved by the features characterized in claims 1 and 4.
  • the dependent claims 2, 3 and 5 characterize advantageous developments thereof.
  • the method according to the invention is accordingly comparable in some respects to the method of 2D exchange spectroscopy (NOESY) known from nuclear magnetic resonance, which serves to process dynamic processes such as chemical reactions, isomerization and the like.
  • NOESY 2D exchange spectroscopy
  • nuclear magnetic resonance which serves to process dynamic processes such as chemical reactions, isomerization and the like.
  • To be examined see, for example, BH Meier and RR Ernst in J. Am. Chem. Soc. 101 (1979) 6441 and J. Jeener et al in J. Chem. Phys. 71 (1979) 4546). Nevertheless, it was not obvious to use an analog method in ICR spectroscopy, because there are fundamental differences between the transverse magnetization of the spins observed in NMR and the coherent resonance of the ions excited in ICR spectroscopy.
  • the resonance frequencies that occur in NMR spectroscopy are very closely adjacent, so that they differ from each other by a few percent at most, whereas the resonance frequencies in cyclotron ion resonance are in a ratio of up to about 1 because of the greatly different charge / mass ratios : 50 can stand.
  • the resonance frequencies of substances of interest can vary from about 50 kHz to 2.6 MHz.
  • the difficulties resulting therefrom can in an embodiment of the method according to the invention either are overcome in that the second RF pulse P 3 has a different frequency than the two partial pulses P 1 and P 2, or characterized also in that the high-frequency pulses broadband pulses given with a Range of varied frequency.
  • Such broadband pulses are also referred to as "chirp pulses" (MB Comisarow and AG Marshall in Chem. Phys. Lett. 26 (1974) 489).
  • the second sub-pulse P 2 has the same frequency and phase as the first sub-pulse P 1 . If, at the end of the variable preparation time t 1, the ions have a phase that is opposite to the phase of the second partial pulse P 2 , the second partial pulse P 2 partially cancels the effect of the first partial pulse P 1 .
  • the effect of the second partial pulse therefore depends on the instantaneous phase of the movement of the individual ions after the first time t 1 , which was therefore referred to as the preparation time. Therefore, the number of incoherent ions that are present after the end of the second partial pulse P 2 and thus at the beginning of the reaction time ⁇ m is a function of the preparation time t 1 .
  • the preparation time t 1 is varied systematically.
  • the signals converted into the frequency domain with respect to the time axis t 2 are converted into frequency-dependent signals with respect to the time axis t 1 , so that a two-dimensional representation of the secondary effects which are conceivable for the primary ions is obtained.
  • these substances can enter into the following reactions, namely a hydrogen transfer from neutral particles to the ion: A + ⁇ + A or B ⁇ AH + + neutral products, and proton transfer from ion to neutral particles, namely A + ⁇ or B + ⁇ + A ⁇ AH + + neutral products.
  • the Br-pyridine was ionized at a pressure of 6.10 -8 mbar with a 20 ms pulse of 70 eV electrons.
  • the duration of the excitation pulses was 20 ⁇ s and their amplitude 35 V pp .
  • the resulting spectral window was large enough to capture the signals from A + ⁇ and AH + , however the signals from BH + are folded published.
  • the second sub-pulse P 2 in the above-mentioned sequence has the effect of "de-excitation" of the ions which were originally excited by the first excitation pulse P 1 so that they have an almost vanishing kinetic energy in the reaction interval ⁇ m and can be brought back into the cyclotron orbits in which they are observed by the second high-frequency pulse P 3 .
  • FIG. 1b then shows the Fourier transform of the ICR signal according to FIG. 1a, in which even-numbered and odd-numbered sidebands with positive and negative amplitudes appear.
  • Fig. 2 shows the complete two-dimensional spectrum.
  • the ⁇ 2 frequency axis corresponds to the Fourier transform with respect to the observation time t 2 .
  • the vertical ⁇ 1 range which is determined by a real cosine transformation with respect to the Preparation time t 1 was obtained shows sideband families that are connected by arcs for clarity.
  • the first sidebands in all families lie on one of the diagonals shown by dashed lines in Fig. 2, apart from the resonance at ⁇ BH , which appears to be folded.
  • the frequency origin at the intersection of the dashed diagonals corresponds to the RF carrier frequency f 0 .
  • These signals provide direct evidence of the above-mentioned reaction A + ⁇ ⁇ AH + ⁇ Because of their alternating signs, these lines can be identified unambiguously.
  • the spectral width was 3000 Hz in both areas.
  • the number of observed points was 240 x 2048 in the two time ranges t 1 and t 2 , which were filled up to zero with 256 x 2048 points before the Fourier transformation. There was a line broadening of 20 Hz in the ⁇ 2 range and 40 Hz in the ⁇ 1 range.
  • the spectral width of the full matrix was 500 x 500 Hz, of which only 40% are shown. 56 x 4048 data points, filled up to 128 x 4048 data points with zeros, were processed. The line broadening was 30 Hz in the ⁇ 1 range and 20 Hz in the ⁇ 2 range.
  • broadband pulses in the form of so-called chirp pulses. whose frequency is varied over a certain range, which includes the resonance frequencies of the starting materials and the expected reaction products. The use of such broadband pulses does not change the basic sequence of the method according to the invention.
  • the method according to the invention delivers essentially the same results as can also be obtained with an MS / MS experiment. Nevertheless, the method according to the invention has many advantages, which are particularly useful when complex networks are to be examined, in which a multiplicity of exchange processes take place simultaneously, all of which are recorded simultaneously using the method according to the invention, whereas in an MS / MS experiment all possible exchange processes have to be recorded by individual measurements to be carried out one after the other.
  • the method according to the invention also allows the kinetics of reactions to be examined by observing the amplitude of the signals obtained as a function of the duration of the reaction interval ⁇ m or as a function of various manipulations to which the system under test is exposed during the reaction time ⁇ m , such as laser pulses, electron beam pulses or neutral gases introduced in the form of a pulse, the molecules of which give rise to collision reactions.

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
  • Electron Tubes For Measurement (AREA)
EP88108648A 1987-06-06 1988-05-31 Verfahren zur Aufnahme von ICR-Massenspektren und zur Durchführung des Verfahrens ausgebildetes ICR-Massenspektrometer Expired - Lifetime EP0294683B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3719018 1987-06-06
DE19873719018 DE3719018A1 (de) 1987-06-06 1987-06-06 Verfahren zur aufnahme von icr-massenspektren und zur durchfuehrung des verfahrens ausgebildetes icr-massenspektrometer

Publications (3)

Publication Number Publication Date
EP0294683A2 EP0294683A2 (de) 1988-12-14
EP0294683A3 EP0294683A3 (de) 1990-12-27
EP0294683B1 true EP0294683B1 (de) 1996-10-23

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EP88108648A Expired - Lifetime EP0294683B1 (de) 1987-06-06 1988-05-31 Verfahren zur Aufnahme von ICR-Massenspektren und zur Durchführung des Verfahrens ausgebildetes ICR-Massenspektrometer

Country Status (4)

Country Link
US (1) US4855593A (enrdf_load_stackoverflow)
EP (1) EP0294683B1 (enrdf_load_stackoverflow)
JP (1) JP2666147B2 (enrdf_load_stackoverflow)
DE (1) DE3719018A1 (enrdf_load_stackoverflow)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4990775A (en) * 1988-06-06 1991-02-05 University Of Delaware Resolution improvement in an ion cyclotron resonance mass spectrometer
US4945234A (en) * 1989-05-19 1990-07-31 Extrel Ftms, Inc. Method and apparatus for producing an arbitrary excitation spectrum for Fourier transform mass spectrometry
US5013912A (en) * 1989-07-14 1991-05-07 University Of The Pacific General phase modulation method for stored waveform inverse fourier transform excitation for fourier transform ion cyclotron resonance mass spectrometry
US5015848A (en) * 1989-10-13 1991-05-14 Southwest Sciences, Incorporated Mass spectroscopic apparatus and method
US5047636A (en) * 1990-01-08 1991-09-10 Wisconsin Alumni Research Foundation Linear prediction ion cyclotron resonance spectrometry apparatus and method
AUPR474801A0 (en) * 2001-05-03 2001-05-31 University Of Sydney, The Mass spectrometer
JP5103628B2 (ja) * 2006-01-16 2012-12-19 国立大学法人神戸大学 気体核磁気共鳴装置
GB201504934D0 (en) 2015-03-24 2015-05-06 Micromass Ltd Improved method of FT-IMS
GB201616017D0 (en) 2016-09-20 2016-11-02 Micromass Ltd Improved method ion mobility spectrometry

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3535512A (en) * 1966-07-21 1970-10-20 Varian Associates Double resonance ion cyclotron mass spectrometer for studying ion-molecule reactions
US3742212A (en) * 1971-02-16 1973-06-26 Univ Leland Stanford Junior Method and apparatus for pulsed ion cyclotron resonance spectroscopy
US3937955A (en) * 1974-10-15 1976-02-10 Nicolet Technology Corporation Fourier transform ion cyclotron resonance spectroscopy method and apparatus
DE3124465C2 (de) * 1981-06-22 1985-02-14 Spectrospin AG, Fällanden, Zürich Verfahren zur Ionen-Zyklotron-Resonanz-Spektroskopie
US4686365A (en) * 1984-12-24 1987-08-11 American Cyanamid Company Fourier transform ion cyclothon resonance mass spectrometer with spatially separated sources and detector
US4682027A (en) * 1986-04-25 1987-07-21 Varian Associates, Inc. Method and apparatus for sample confirmation in gas chromatography
US4761545A (en) * 1986-05-23 1988-08-02 The Ohio State University Research Foundation Tailored excitation for trapped ion mass spectrometry

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
J.D. Baldeschwieler und S.S.Woodgate Acc.Chem.Res. 4 (1971) S.114-120. *
The Journal of Chemical Physics, band 71, no 11, 1 dec.1979. S. 4546-4553, J.Jeener et al.: "Investigation of exchange processes by two-dimensional NMR spectroscopy". *

Also Published As

Publication number Publication date
EP0294683A2 (de) 1988-12-14
EP0294683A3 (de) 1990-12-27
JPH02118441A (ja) 1990-05-02
JP2666147B2 (ja) 1997-10-22
DE3719018A1 (de) 1988-12-22
US4855593A (en) 1989-08-08
DE3719018C2 (enrdf_load_stackoverflow) 1992-04-16

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