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US5327086A Expired / Lapsed US ⏱️ 0.0 years remaining

Multiple-quantum NMR with frequency-modulated chirp pulses

Assignee: Bruker Biospin SAS
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Filing: 1990-07-11
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Granted: 1994-07-05
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Expires: 2010-07-11
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Abstract

Abstract Frequency-modulated "chirp" pulses for exciting multiple-quantum coherences over large bandwidths can be considered as an alternative to composite pulses to combat the effects of large offsets and tilted effective fields. Refocusing of the phase dispersion of double-quantum coherence can be combined with suitable detection sequences to yield pure absorption two-dimensional double-quantum spectra. The method of symmetrical excitation and detection by time-reversal may be applied to obtain t 1 -modulated longitudinal magnetization, which may then be converted into observable single-quantum coherence by a chirp echo sequence. Similar approaches can be used for many other NMR experiments involving coherence transfer.

Inventors

  • 👤 Geoffrey Bodenhausen
  • 👤 Jean-Marc Bohlen
  • 👤 Irene Burghardt

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-11-08 17:36
CPC Classifications
G; G01; G01R; G01R33/00; G01R33/20; G01R33/44; G01R33/446; G01R33/46; G01R33/4616

Claims Analysis

Total Claims: 30
Claim 1
Independent Claim 259 words
In a method which includes the step of exciting a multiple quantum coherence in an NMR pulse experiment, said exciting step including the steps of subjecting a nuclear spin system to a magnetic field and irradiating said nuclear spin system, while subjected to said magnetic field, with a first sequence of RF pulses which includes a basic sequence having a first π/ 2-pulse, a first π-pulse generated after a defocusing time interval τ following the first π/2-pulse, and a π/2-pulse generated after another time interval τ following the first π-pulse, said method further including the step of reconverting said excited multiple quantum coherence into a transverse magnetization for inducing a free induction decay, said reconverting step including the step of irradiating said nuclear spin system with a second sequence of RF pulses; the improvement comprising wherein said step of irradiating with said first sequence of RF pulses includes the step of generating each of the three RF pulses of said basic sequence as a chirp pulse having a duration t p by sweeping the frequency of the exciting RF field in a monotonic fashion with respect to time during said duration t p between a lower limit frequency ω RFmin and an upper limit frequency ω RFmax ; and wherein said step of irradiating with said second sequence of RF pulses includes the step of generating as one of the pulses of said second sequence a fourth chirp pulse with a duration t p /2 and an amplitude between 2 and 4 times the amplitude of said first π/2-pulse.
Claim 2
Dependent Claim 259 words
In a method which includes the step of exciting a multiple quantum coherence in an NMR pulse experiment, said exciting step including the steps of subjecting a nuclear spin system to a magnetic field and irradiating said nuclear spin system, while subjected to said magnetic field, with a first sequence of RF pulses which includes a basic sequence having a first π/ 2-pulse, a first π-pulse generated after a defocusing time interval τ following the first π/2-pulse, and a π/2-pulse generated after another time interval τ following the first π-pulse, said method further including the step of reconverting said excited multiple quantum coherence into a transverse magnetization for inducing a free induction decay, said reconverting step including the step of irradiating said nuclear spin system with a second sequence of RF pulses; the improvement comprising wherein said step of irradiating with said first sequence of RF pulses includes the step of generating each of the three RF pulses of said basic sequence as a chirp pulse having a duration t p by sweeping the frequency of the exciting RF field in a monotonic fashion with respect to time during said duration t p between a lower limit frequency ω RFmin and an upper limit frequency ω RFmax ; and wherein said step of irradiating with said second sequence of RF pulses includes the step of generating as one of the pulses of said second sequence a fourth chirp pulse with a duration t p /2 and an amplitude between 2 and 4 times the amplitude of said first π/2-pulse.
Claim 3
Dependent Claim 13 words
The method according to claim 1, applied to one of NMR-imaging and NMR-in-vivo-spectroscopy.
Claim 4
Dependent Claim 11 words
The method according to claim 1, applied to heteronuclear correlation spectroscopy.
Claim 5
Dependent Claim 222 words
In a method which includes the step of exciting a multiple quantum coherence in an NMR pulse experiment, said exciting step including the steps of subjecting a nuclear spin system to a magnetic field of high field strength and irradiating said nuclear spin system, while subjected to said magnetic field of high field strength, with a first sequence of RF pulses which includes a basic sequence having a first π/2-pulse, a first π-pulse generated after a time interval τ following the first π/2-pulse, and a second π/2-pulse generated after another time interval τ following the first π-pulse, said method further including the step of reconverting said excited multiple quantum coherence into a transverse magnetization for inducing a spin echo, said reconverting step including the step of irradiating said nuclear spin system with a second sequence of RF pulses; the improvement comprising wherein said step of irradiating with said second sequence of RF pulses includes the steps of generating, a dephasing time interval τ 1 following the spin echo, a chirp refocusing π-pulse having a duration t p /2 by sweeping the frequency of the RF field monotonically with respect to time during said duration t p /2 between a lower limit frequency ω RFmin and an upper limit frequency ω RFmax and generating a subsequent chirp π/2-pulse of furation t p .
Claim 6
Dependent Claim 222 words
In a method which includes the step of exciting a multiple quantum coherence in an NMR pulse experiment, said exciting step including the steps of subjecting a nuclear spin system to a magnetic field of high field strength and irradiating said nuclear spin system, while subjected to said magnetic field of high field strength, with a first sequence of RF pulses which includes a basic sequence having a first π/2-pulse, a first π-pulse generated after a time interval τ following the first π/2-pulse, and a second π/2-pulse generated after another time interval τ following the first π-pulse, said method further including the step of reconverting said excited multiple quantum coherence into a transverse magnetization for inducing a spin echo, said reconverting step including the step of irradiating said nuclear spin system with a second sequence of RF pulses; the improvement comprising wherein said step of irradiating with said second sequence of RF pulses includes the steps of generating, a dephasing time interval τ 1 following the spin echo, a chirp refocusing π-pulse having a duration t p /2 by sweeping the frequency of the RF field monotonically with respect to time during said duration t p /2 between a lower limit frequency ω RFmin and an upper limit frequency ω RFmax and generating a subsequent chirp π/2-pulse of furation t p .
Claim 7
Dependent Claim 79 words
The method according to claim 4, wherein said step of irradiating with said second sequence of RF pulses includes the step of generating as one of the pulses of said second sequence of RF pulses a further chirp π-pulse of duration τ.sub.π =t p /2 a time delay τ 2 following said subsequent chirp π/2-pulse, and the step of detecting a spin echo resulting from said further chirp π-pulse a final delay τ 3 following said further chirp π-pulse.
Claim 8
Dependent Claim 33 words
The method according to claim 5, including the steps of selecting said time delay τ 2 so that τ 2 ≈0, and selecting said final delay τ 3 so that τ 3 ≈τ.sub.π.
Claim 9
Dependent Claim 59 words
The method according to claim 5, including the steps of selecting said time delay τ 2 so that τ 2 ≈(2J AM ) -1 , and selecting said final delay τ 3 so that τ 2 +τ.sub.π +τ 3 ≈J AM -1 , where J AM designates a scalar coupling constant for coupling between spin A and spin M.
Claim 10
Dependent Claim 60 words
The method according to claim 5, including the steps of selecting said time delay τ 2 so that τ 2 ≈(4J AM ) -1 , and selecting said final delay τ 3 so that τ 2 +τ.sub.π +τ 3 ≈(2J AM ) -1 , where J AM designates a scalar coupling constant for coupling between spin A and spin M.
Claim 11
Dependent Claim 239 words
In a method which includes the steps of exciting a multiple quantum coherence in an NMR pulse experiment, said exciting step including the steps of subjecting a nuclear spin system to a magnetic field of high field strength and irradiating said nuclear spin system, while subjected to said magnetic field of high field strength, with a first sequence of RF pulses which includes a basic sequence having a first π/2-pulse, a first π-pulse generated after a defocusing time interval τ following the first π/2-pulse, and a second π/2-pulse generated after another time interval τ following the first π-pulse, said method further including the step of reconverting said excited multiple quantum coherence into a transverse magnetization for inducing a free induction decay, said reconverting step including the step of irradiating said nuclear spin system with a second sequence of RF pulses; the improvement comprising wherein said step of irradiating with said first sequence of RF pulses includes the steps of generating each of the three RF pulses of said basic sequence as a chirp pulse having a duration t p by sweeping the frequency of the exciting RF field in a monotonic fashion with respect to time during said duration t p between a lower limit frequency ω RFmin and an upper limit frequency ω RFmax and then generating, after an evolution interval t 1 , an additional sequence which is an exact time reversed version of said basic sequence.
Claim 12
Dependent Claim 239 words
In a method which includes the steps of exciting a multiple quantum coherence in an NMR pulse experiment, said exciting step including the steps of subjecting a nuclear spin system to a magnetic field of high field strength and irradiating said nuclear spin system, while subjected to said magnetic field of high field strength, with a first sequence of RF pulses which includes a basic sequence having a first π/2-pulse, a first π-pulse generated after a defocusing time interval τ following the first π/2-pulse, and a second π/2-pulse generated after another time interval τ following the first π-pulse, said method further including the step of reconverting said excited multiple quantum coherence into a transverse magnetization for inducing a free induction decay, said reconverting step including the step of irradiating said nuclear spin system with a second sequence of RF pulses; the improvement comprising wherein said step of irradiating with said first sequence of RF pulses includes the steps of generating each of the three RF pulses of said basic sequence as a chirp pulse having a duration t p by sweeping the frequency of the exciting RF field in a monotonic fashion with respect to time during said duration t p between a lower limit frequency ω RFmin and an upper limit frequency ω RFmax and then generating, after an evolution interval t 1 , an additional sequence which is an exact time reversed version of said basic sequence.
Claim 13
Dependent Claim 21 words
The method according to claim 9, including the step of selecting said evolution time t 1 so that t 1 ≈0.
Claim 14
Dependent Claim 38 words
The method according to claim 10, including the step of generating immediately after said basic sequence a fourth chirp pulse having an amplitude which is about 3.3 times the amplitude of said first π/2-pulse in said basic sequence.
Claim 15
Dependent Claim 63 words
The method according to claim 9, wherein said step of irradiating with said second sequence of RF pulses includes the step of generating as two of the pulses of said second sequence of RF pulses a chirp π/2-pulse followed by a chirp π-pulse having half the duration and between 2 and 4 times the amplitude of the chirp π/2-pulse of said second sequence.
Claim 16
Dependent Claim 196 words
In a method for exciting, by means of a first sequence of RF pulses, at least one of a multiple quantum coherence and a double quantum coherence in an NMR pulse experiment by irradiating a nuclear spin system, subjected to a magnetic field, with the first pulse sequence which includes a first π/2-pulse, a first π-pulse generated after a defocusing time interval τ following the first π/2-pulse, and a second π/2-pulse generated after another time interval τ following the first π-pulse, and for reconverting, by irradiating the nuclear spin system with a second sequence of RF-pulses, the excited multiple quantum coherence into a transverse magnetization for inducing a free induction decay, the improvement comprising wherein the three RF pulses of the first pulse sequence are chirp pulses each having a duration t p during which the frequency of the exciting RF field is swept in a monotonic fashion with respect to time between a lower frequency ω RFmin and an upper frequency ω RFmax and the second sequence of RF pulses includes a fourth chirp pulse with a duration t p /2 and an amplitude between 2 and 4 times the amplitude of the first π/2-pulse.
Claim 17
Dependent Claim 196 words
In a method for exciting, by means of a first sequence of RF pulses, at least one of a multiple quantum coherence and a double quantum coherence in an NMR pulse experiment by irradiating a nuclear spin system, subjected to a magnetic field, with the first pulse sequence which includes a first π/2-pulse, a first π-pulse generated after a defocusing time interval τ following the first π/2-pulse, and a second π/2-pulse generated after another time interval τ following the first π-pulse, and for reconverting, by irradiating the nuclear spin system with a second sequence of RF-pulses, the excited multiple quantum coherence into a transverse magnetization for inducing a free induction decay, the improvement comprising wherein the three RF pulses of the first pulse sequence are chirp pulses each having a duration t p during which the frequency of the exciting RF field is swept in a monotonic fashion with respect to time between a lower frequency ω RFmin and an upper frequency ω RFmax and the second sequence of RF pulses includes a fourth chirp pulse with a duration t p /2 and an amplitude between 2 and 4 times the amplitude of the first π/2-pulse.
Claim 18
Dependent Claim 10 words
The method of claim 13, applied to heteronuclear correlation spectroscopy.
Claim 19
Dependent Claim 14 words
The method of claim 13, applied to at least one of NMR-imaging and NMR-in-vivo-spectroscopy.
Claim 20
Dependent Claim 182 words
In a method for exciting, by means of a first sequence of RF-pulses, at least one of a multiple quantum coherence and a double quantum coherence in an NMR pulse experiment by irradiating a nuclear spin system, subjected to a magnetic field of high field strength, with the first pulse sequence which includes a first π/2-pulse, a first π-pulse generated after a time interval τ following the first π/2-pulse, and a second π/2-pulse generated after another time interval τ following the first π-pulse, and for reconverting, by irradiating the nuclear spin system with a second sequence of RF-pulses, the excited multiple quantum coherence into a transverse magnetization for inducing a spin echo, the improvement wherein the second sequence of RF pulses further includes, after a dephasing time interval τ 1 following the spin echo, a chirp refocusing π-pulse having a duration t p /2 during which the frequency of the RF field is monotonically swept with respect to time between a lower frequency ω RFmin and an upper frequency ω RFmax , and a subsequent chirp π/2-pulse of duration t p .
Claim 21
Dependent Claim 182 words
In a method for exciting, by means of a first sequence of RF-pulses, at least one of a multiple quantum coherence and a double quantum coherence in an NMR pulse experiment by irradiating a nuclear spin system, subjected to a magnetic field of high field strength, with the first pulse sequence which includes a first π/2-pulse, a first π-pulse generated after a time interval τ following the first π/2-pulse, and a second π/2-pulse generated after another time interval τ following the first π-pulse, and for reconverting, by irradiating the nuclear spin system with a second sequence of RF-pulses, the excited multiple quantum coherence into a transverse magnetization for inducing a spin echo, the improvement wherein the second sequence of RF pulses further includes, after a dephasing time interval τ 1 following the spin echo, a chirp refocusing π-pulse having a duration t p /2 during which the frequency of the RF field is monotonically swept with respect to time between a lower frequency ω RFmin and an upper frequency ω RFmax , and a subsequent chirp π/2-pulse of duration t p .
Claim 22
Dependent Claim 54 words
The method of claim 16, wherein the second sequence of RF pulses further includes a subsequent chirp π-pulse of duration τ.sub.τ =t p /2 irradiated after a time delay τ 2 following the subsequent chirp π/2-pulse to generate a spin echo for detection after a final delay τ 3 following the subsequent chirp π-pulse.
Claim 23
Dependent Claim 19 words
The method of claim 17, wherein the time delay τ 2 ≈0 and the final delay τ 3 ≈τ.sub.π.
Claim 24
Dependent Claim 50 words
The method of claim 17, wherein the time delay τ 2 ≈(2J AM ) -1 and the final delay τ 3 is chosen such that τ 2 +τ.sub.π +τ 3 ≈J AM -1 , where J AM designates a scalar coupling constant for coupling between spin A and spin M.
Claim 25
Dependent Claim 51 words
The method of claim 17, wherein the time delay τ 2 ≈(4J AM ) -1 and the final delay τ 3 is chosen such that τ 2 +τ.sub.π +τ 3 ≈(2J AM ) -1 , where J AM designates a scalar coupling constant for coupling between spin A and spin M.
Claim 26
Dependent Claim 197 words
In a method for exciting, by means of a first pulse sequence of RF pulses, at least one of a multiple and a double quantum coherence in an NMR pulse experiment by irradiating a nuclear spin system, subjected to a magnetic field of high field strength, with the first pulse sequence which includes a first π/2-pulse, a first π-pulse generated after a defocusing time interval τ following the first π/2-pulse, and a second π/2-pulse generated after another time interval τ following the first π-pulse, and for reconverting, by irradiating the nuclear spin system with a second sequence of RF pulses, the excited multiple quantum coherence into a transverse magnetization for inducing a free induction decay, the improvement wherein the three RF pulses of said first pulse sequence are chirp pulses each having a duration t p during which the frequency of the exciting RF field is swept in a monotonic fashion with respect to time between a lower frequency ω RFmin and an upper frequency ω RFmax and the first pulse sequence is followed, after an evolution interval t 1 , by an additional pulse sequence which is a time reversed version of said first pulse sequence.
Claim 27
Dependent Claim 197 words
In a method for exciting, by means of a first pulse sequence of RF pulses, at least one of a multiple and a double quantum coherence in an NMR pulse experiment by irradiating a nuclear spin system, subjected to a magnetic field of high field strength, with the first pulse sequence which includes a first π/2-pulse, a first π-pulse generated after a defocusing time interval τ following the first π/2-pulse, and a second π/2-pulse generated after another time interval τ following the first π-pulse, and for reconverting, by irradiating the nuclear spin system with a second sequence of RF pulses, the excited multiple quantum coherence into a transverse magnetization for inducing a free induction decay, the improvement wherein the three RF pulses of said first pulse sequence are chirp pulses each having a duration t p during which the frequency of the exciting RF field is swept in a monotonic fashion with respect to time between a lower frequency ω RFmin and an upper frequency ω RFmax and the first pulse sequence is followed, after an evolution interval t 1 , by an additional pulse sequence which is a time reversed version of said first pulse sequence.
Claim 28
Dependent Claim 9 words
The method of claim 21, wherein t 1 ≈0.
Claim 29
Dependent Claim 35 words
The method of claim 21, wherein the first pulse sequence is immediately followed by a fourth chirp pulse having an amplitude about 3.3 times the amplitude of the first π/2-pulse in the first pulse sequence.
Claim 30
Dependent Claim 40 words
The method of claim 21, wherein the additional sequence of RF pulses includes an additional chirp π/2-pulse followed by an additional chirp π-pulse having half the duration and between 2 and 4 times the amplitude of the additional chirp π/2-pulse.

References Cited (Backward Citations)

US3725773A Cited
US4238735A Cited
US4703270A Cited
US5045790A Cited
US5166616A Cited
US5168229A Cited

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