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    • 专利摘要:
    Application for Patent of RICHARD R. ERNST for TWO DIMENSIONAL GYROMAGNETIC RESONANCE SPECTROSCOPY The multiplet spectral structure produced by coupled gyromagnetic resonators, such as heteronuclear coupling, is resolved by inducing a train of transient free induction decay (RID) resonances of a first group of gyromagnetic bodies, such as carbon-13 nuclei coupled to a second group of gyromagnetic bodies, such as protons, and detecting the FID resonance. A decoupling r.f. magnetic field is applied to the second group during free induction decay resonance of the first group for decoupling the spins of the first and second groups during detection of resonance of the first group. The duration of the decoupling effect is changed from one successive free induction decay resonance to the next and the detected resonance data is stored as a function of the change in the decoupling effect. The detected resonance data which is a function of two time intervals is then double Fourier transformed into the frequency domain and displayed as a two dimensional plot for resolving the multiplet structure of the spectra of the first group of gyromagnetic bodies.
    公开号:SU980637A3
    申请号:SU762430851
    申请日:1976-12-14
    公开日:1982-12-07
    发明作者:Ричард Р. Эрнст
    申请人:Вариан Ассошиейтс,Инк,(Фирма)；
    IPC主号:
    专利说明:

    (5) METHOD OF TWO-DIMENSIONAL SPECTROSCOPY OF HYROMAGNETIC RESONANCE
    one
    The invention relates to spectroscopy. scopies of gyromagnetic resonance and can be used for two-dimensional spectrometry of the gyromagnetic resonance of the multiplet structure of coupled gyromagnetic resonators.
    The carbon 13 (C) nuclear magnetic resonance is used to study the structure of organic molecules in solution and in the solid state, and it is possible to obtain a spectrum with complete disruption of the bond with protons with one single resonance line for each carbon site (C). This simplifies the spectrum of large molecules. Although coupled spectra, for example coupled proton-carbon and proton-nitrogen (N) spectra. contain much more information, formations, and cannot be fully analyzed due to the significant overlap of various multiplets. The most famous example of bound nuclei are those associated with proton
    carbon 13, nitrogen 15) and deuterium. The spectra and deuterium are used to study complex molecules, such as biomolecules, enzymes, pentides, proteins, and generally complex organic Cl 3 molecules.
    Closest to the proposed method is gyromagnetic resonance spectroscopy, based on inducing a set of transient gyromagnetic resonances for the first group of gyromagnetic resonators that have an internal connection with the second group of gyromagnetic resonators of the test substance. At the same time, to simplify the spectrum of the test substance, the bonds of the protons (the first group of gyromagnetic resonators) with other dramas, for example C or N (the second group of g, 20 magnetic resonators), or the weak ones are completely disrupted. leads to the destruction of all information contained in the relations, and the exclusion of weak links allows us to interpret the multiplet structure of rare nuclei only for simple spectra, i.e. for small molecules 2. The purpose of the invention is to increase the resolution in the spectroscopy of complex substances. This goal is achieved by the fact that, according to the method of two-dimensional spectroscopy of gyromagnetic resonance, based on inducing a set of transitional gyromagnetic resonances for the first group of gyromagnetic resonators that have an internal connection with the second group of gyromagnetic resonators of the substance under investigation, the separation of the multiplet structures of the spectrum periodically during each transient gyromagnetic resonances violate the interaction of the resonances of both groups of resonators by imposing for the first group of resonators, determine the induced set of transition gyromagnetic resonances for the first group of resonators. In the function of changing the duration of the disturbed and associated periods of transition resonances for the first group of resonators, and get simplified spectral data of the gyromagnetic resonance. A resonant magnetic field is used as the driving high frequency magnetic field to excite the gyromagnetic resonances of the second group of resonators. The resonances of the second group of resonators are excited prior to the induction of each of the transition gyromagnetic resonances of the first group of resonators, and if there are two resonant frequencies for the resonances of the first group of resonators, the freely induced damped transition resonances of the first resonator frequency having the first resonant frequency are detected. FIG. Figure 1 shows the spectrum of gyromagnetic resonance associated with a proton for the C nucleus in the h-hexane molecule; in fig. 2 - the spectrum of gyromagnetic resonance associated with a proton for nuclei in the same molecule, reflecting multiplex structures associated with each of the two interacting nuclei of protons in FIG. 3 is a timing diagram showing the shielding of the proton-related field and the resonance signal of the free-induced damping (cc) for the nuclei in FIG. t two-dimensional image of the spectral data of gyromagnetic resonance; in fig. 5 is a block diagram of a two-dimensional spectrometer allowing the implementation of a two-dimensional spectroscopy method; in fig. 6 - a program for an electronic computing machine (computer) of the specified spectrometer. The method includes creating a transverse magnetization of gyromagnetic resonators, for example, nuclei with a pulse, for example, an EO pulse, at the time t О. Over a period of time О t t, the magnetization of the substance under study can precess under the influence of the total Hamiltonian, i.e. in linked mode. At the moment, a broadband link violation begins and the PPE signal is recorded as a function of t t-t (Fig. 3). This experiment is repeated for different t values, as a result, a two-dimensional signal function SS is created (t-7, 2 A three-dimensional two-dimensional Fourier transform gives a two-dimensional spectrum) J | cos (and; ω5 () (UJ ,. о о (.. Two-dimensional the resolved spectrum Cc for the h-hexane molecule is shown in Fig. (parallel to the axis and; the multiplet structure is retained, the spectrum of which is shown in Fig. 2, and along the W2 axis, the fully developed spectrum shown in Fig. 1 is obtained). 1, 2, and 4 show resonances 1–3 from the corresponding nuclei in the h-hexane molecule. Each peak is on a two-dimensional axis. The image corresponds to a single spectral multiplex line (shown along the axis) shifted in the tu direction by a chemical shift of the corresponding core. The associated spectrum can be considered as a projection of a two-dimensional spectrum onto the axis and. With the full resolution of the developed spectrum, each multiplet is divided into a two-dimensional image ( Fig. k. There are several variants of the proposed method. In the first modification, the sensitivity of the method and its resolving power are increased by applying a test substance to the sample. high-frequency magnetic pop, which is resonant for the second group of resonators, such as protons, for a period of time About t t followed by observation of the signal of the PPE resonance in the time interval t yt (Fig. k) under the influence of a complete Hamil tonian, i.e. in a full interaction mode. The number of required experiments for resolving all resonances 0b-C is determined from the expression H-kF / u (where and is the minimum separation of lines in the developed spectrum; F is the total overlapping spectral range). o In another embodiment, the second group of resonators, for example, protons, are excited before each of the transitional gyromagnetic resonances of the first group of resonators is induced, for example, prior to applying an initial 3Q ° pulse for G C (Fig. The proposed method can be implemented using a two-dimensional a spectrometer that contains a container k with a test substance consisting of two groups of gyromagnetic resonators having an internal bond between them. Such substances include relatively complex molecules, such as bi Omolecules, pentide enzymes, prostains, or generally complex organic molecules. The transceiver coil 5 of a two-dimensional spectrometer is located coaxially and around container 4, winds around with the axis. Model SPX -100 by Bruker. Container k with the analyte is placed in a relatively intense polarizing magnetic field HO, created between the poles 7 and 8 of the electromagnet. A one-dimensional spectrometer 6 is connected to a digital computer 9, for example, a model 620 / L-100 manufactured by Variant with a memory capacity of at least 12 Kbps through an analog-to-digital converter (ADC) 10 One of the outputs of the computer 9 is connected to a display 11, on the screen of which 9 76, two-dimensional spectral imaging of the resonance spectra of the analyte is obtained. On line 12 of synchronization and control, signals from computer 9 are fed to a one-dimensional spectrometer 6. A spin separation device 13 is connected to computer 9 via a second synchronization and control line 1. Spin-release device 13 supplies high-frequency energy to the analyte using a second transmitting coil 15 located orthogonally to the transmitting / receiving coil 5 and to the direction of the magnetic field Nd. In the case of analysis of the location of the nuclei in the sample, the device of spins uncoupling delivers extra high frequency energy to the analyte in a sufficiently wide frequency band to cover the resonant spectrum of the resonators being opened. When using protons, this frequency band is several thousand Hertz. The HO magnetic field source usually includes a field frequency capture device or a magnetic flux stabilizer (not shown), which serves to link the HO value to the line frequency of a predetermined magnetic resonance of the analyte. A two-dimensional spectrometer operates as follows. The one-dimensional spectrometer 6 feeds a burst of pulses of high-frequency magnetic field to a transmitter and receiver coil 5 for the analyte in container 4. The frequency of the applied high-frequency magnetic field is chosen equal to the resonant frequency of the hydromagnetic resonance of the first group of gyro resonators, for example, the resonance frequency for nuclei -hexane (Fig. 1). The intensity of the applied high-frequency magnetic field is chosen so that during the duration of each high-frequency pulse the magnetic magnetic moments of the observed gyromagnetic resonators (for example, the magnetic moments of the nuclei) deviate relative to the direction of the magnetic H roll, i.e. The magnetic moments of the observed resonators should have a projection on the XY plane of the reduced Cartesian coordinate axis. After the termination of a high-frequency pulse, for example, a 90-pulse, at time t, the gyromagnetic resonators of the first group (core) enter the range of the resonance signal of the PPE (Fig. 3). During time t; The magnetic moments of the first group of resonators (cores) perform free induced damping upon the interaction of their magnetic moments with the magnetic moments of the nuclei of the second group of resonators (protons). During this period, the multiplet structures of the nuclei overlap (Fig.). In order to increase the resolution of the device, i.e., to separate the multiplet structure of the cores (Fig. 2) and identify with each respective place of the cores or with developed resonant lines 1, 2 and 3 (Fig. After the time t turn on the device 13 of the spins and sampling the PPE signal using the ADC 10, carried out at regular intervals of time, for example, 0.5 ms, and the number of samples is N during time t (Fig. 3). The device 13 of the spin separation applies to the analyte relative to wide energy band and to excite the resonance of the proton spectral lines, thereby spinning the protons from the analyzed nucleus C. The experiment yields m different, but equally spaced t values, and N values are sampled for each case during the t interval. corresponding to different values of t. are accumulated in successive columns of the matrix shown in the table.
    The maximum number of samples representing a two-dimensional display of spectral data is limited by the amount of computer memory 9. These tables are converted using two
    权利要求:
    Claims (3)
    [1]
    1. A two-dimensional gyromagnetic resonance spectroscopy method based on a 7-dimensional Fourier transform to obtain a two-dimensional spectral display with m / 2 X N / 2 samples. In order to use the fast Fourier transform computer program on the computer 9, A1 and N are selected by the powers of 2. In the example shown in FIG. +, m tends to N. The method, which requires all N (N + 2) memory cells, but creates a two-dimensional mapping, is as follows. N SIZ signals consisting of N samples are accumulated in computer memory 9. To perform the first Fourier transform, N samples representing the free induced attenuation K-jtSj o, SK SKlN-fjl are transferred to a separate memory block and are replenished with N zero S) K (N-1) 0 (Q Fourier Transform then consists of N complex values, retaining only the real parts Rf, ...,) j, which are stored in the cells of the original PPE signal. After converting all the signals, the PPID matrix is transported, each table-filled with zero values, is transformed Fourier a second time. The absolute values of the N complex Fourier coefficients are further used to construct the two-dimensional spectrogram shown in FIG. A. Dropping the imaginary part after the first Fourier transform does not cause loss of information and does not degrade the sensitivity of the method. In the above example, the number of samples N is taken equal to 6. This gives the total number of sample values 409b. FIG. 6 shows a program for a computer 9 for controlling a one-dimensional spectrometer 6 and for collecting and processing resonant spectral data with display in the form of a two-dimensional spectrogram shown in FIG. t. The proposed method allows two-dimensional spectroscopy of complex molecules to be obtained with an increased resolution, which makes it possible to obtain consistent spectroscopic data. on inducing a multitude of transient gyromagnetic ozonances for the first group of gyromagnetic resonators having an internal connection with the second group of gyromagnetic resonators of the test substance, which is different from the fact that, in order to increase the resolving power in spectroscopy of complex substances, when separating the multiplet structures of the spectrum, periodically during part of each of the transitional gyromagnetic resonances, the interaction of the resonances of both groups of resonators is disturbed by imposing a high-frequency for the first group of resonators, determine the induced set of transition gyromagnetic resonances for the first group of resonators as a function of changing the duration of the disturbed and associated periods of the transition resonances for the first group of resonators and get simplified spectral data of the gyromagnetic reason for this. 2. A method according to Claim 1, characterized in that resonantly used as an unleashing high-frequency magnetic field; magnetic field for exciting gyromagnetic resonances of the second group of resonators, 3. Method according to claims. 1st 2, characterized in that the resonances of the second group of resonators are excited before each of the transitional gyromagnetic resonances of the first group of resonators is induced, and if there are two resonant frequencies for the resonances of the first group of resonators, the freely induced damped transition resonances of the first resonator are detected having a first resonant frequency. Sources of information taken into account in the examination 1.Ernst R. R. Nuclear Magnetic Double Resonance with an incoherent Radio-Frequeney Field. - J. Chemical Physics, 1966, V. k, W 10, p. 38 453861.
    [2]
    2. Farrar T. C ,, Becker E. D. Pulse and Fourier Transform NMR Jntroduction to Theory and Methods. N.
    [3]
    3. Academic Press 1971, ch. 3 (prototype).
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