CN105651803B - A kind of nuclear magnetic resonance two-dimensional diffusion sequence spectral method for any magnetic field environment - Google Patents
A kind of nuclear magnetic resonance two-dimensional diffusion sequence spectral method for any magnetic field environment Download PDFInfo
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N24/00—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects
- G01N24/08—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects by using nuclear magnetic resonance
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Abstract
A kind of nuclear magnetic resonance two-dimensional diffusion sequence spectral method for any magnetic field environment, is related to nuclear magnetic resonance spectroscopy detection method.1) the pi/2 non-selective radio frequency pulse width needed for measurement sample excitation, and (pi/2)ISolvent selectivity RF pulse width;2) nuclear magnetic resonance pulse sequence is imported on nuclear magnetic resonance chemical analyser;3) genetic module and diffusion order module, set the experiment parameter of each module when opening intermolecular zero quantum coherent signal selection module, the perseverance of nuclear magnetic resonance pulse sequence;4) data sampling is performed;5) Data Post is carried out, high resolution 2 d diffusion sequence spectrum is obtained.It is simple and easy to do without the operation of any shimming and sample pretreatment process, and without any special hardware device, it is adaptable to any conventional nuclear magnetic resonance chemical analyser.
Description
Technical field
The present invention relates to nuclear magnetic resonance (NMR, Nuclear Magnetic Resonance) Wave Spectrum detection method, especially
It is a kind of nuclear magnetic resonance for any magnetic field environment for being related to mix ingredients separation and composition analysis under any magnetic field environment
Two-dimensional diffusion sequence spectral method.
Background technology
Nuclear magnetic resonance (Nuclear Magnetic Resonance, NMR) as a kind of important detection and analysis means, by
In it is accurate, efficiently, Non-Destructive Testing many advantages, such as, have extensively in ambits such as physics, chemistry, biology and materials
Application.For the detection of complex mixture nuclear magnetic resonance, the spectral peak of various different materials is all presented in same spectrum, past
It is past to cause spectral peak crowded and be difficult to obtain correct composition ownership.Therefore, general require before testing to carry out blend sample
Separating-purifying, this not only wasting manpower and material resources, and separating-purifying process may destroy the original structure of sample.Utilize nuclear-magnetism
Resonance diffusion correlation technique, i.e. diffusion sequence spectrum (Diffusion Order SpectroscopY, DOSY), can be without right
In the case that sample carries out physics and chemistry separation, realize that each component is in sample cell in solution mixture using the difference of diffusion coefficient
" void " is separated, and the H NMR spectroscopy being associated by resulting diffusion coefficient and other spectroscopy information directly to mixture into
It is grouped into and is analyzed.This method has not only saved the time of physics and chemistry separation but also has avoided the damage of the sample caused by separation
It is bad.
However, existing diffusion sequence spectral method still suffers from significant limitation in actual mix application.Diffusion sequence
Spectrum can just fit correct diffusion dimension information only in the case where spectral peak is differentiated completely.In the case of Magnetic field inhomogeneity, spectrum
The uneven broadening effect of line can cause spectral peak not differentiate, and cause diffusion sequence spectral method not apply.Under normal circumstances, spread
Sequence spectrum experiment has very high requirement to magnetic field homogeneity.But under many circumstances, magnetic field homogeneity is often can not be exhausted
To guarantee, magnetic various samples and environmental factor caused by even can not be also completely eliminated in experimentation using shimming technique
Field is uneven.For example, in the research of some biological medicine blend samples, the bar that sample molecule often only coexists in tissue
Just there is given activity and function under part, and this organization internal magnetic susceptibility can cause the uneven of magnetic field, therefore existing expansion
Sequence spectral method is dissipated to be generally difficult to be applied to this kind of mixture system.If existing diffusion sequence spectral method can be breached not
Uniform magnetic field application limitation, design one kind can be applied to any magnetic field environment under (including field homogeneity situation and
Magnetic field inhomogeneity situation caused by various samples and environmental factor) mix ingredients separation and component analysis high resolution 2 d
Diffusion sequence spectral method will be significant, further expands the application of diffusion sequence spectrum.
The content of the invention
Separated it is an object of the invention to provide the composition that can be suitably used for blend sample and one kind of component analysis is used for
The nuclear magnetic resonance two-dimensional diffusion sequence spectral method of any magnetic field environment.
The present invention comprises the following steps:
1) the pi/2 non-selective radio frequency pulse width needed for measurement sample excitation, and (pi/2)ISolvent selectivity radio frequency
Pulse width;
2) nuclear magnetic resonance pulse sequence is imported on nuclear magnetic resonance chemical analyser;
3) genetic module and expansion when opening intermolecular zero quantum coherent signal selection module, the perseverance of nuclear magnetic resonance pulse sequence
Order module is dissipated, the experiment parameter of each module is set;
4) data sampling is performed;
5) Data Post is carried out, high resolution 2 d diffusion sequence spectrum is obtained.
In step 1) in, the pi/2 non-selective radio frequency pulse width needed for the measurement sample excitation is to utilize conventional one
Tie up pulse train to complete, by setting a series of pulse operating times sampling corresponding signals, when obtaining 90 degree of upsets of magnetization vector
The corresponding burst length is pi/2 non-selective radio frequency pulse width, while this measurement also obtain field homogeneity disposition
Condition, foundation, (pi/2) are provided for spectrum width parameter settingIThe measurement of solvent selectivity RF pulse width is by conventional one
Tie up soft pulse sequence to complete, obtain selective pulse action time corresponding during the 90 degree of upsets of solvent magnetization vector.
In step 2) in, the nuclear magnetic resonance pulse sequence has used intermolecular zero quantum coherent signal selection module, perseverance
When genetic module and diffusion order module;
The intermolecular zero quantum coherent signal selection module is by a pi/2 non-selective radio frequency pulse, (a pi/2
)ISolvent selectivity radio-frequency pulse and a phase dry separation gradient G are constituted;Pass through intermolecular zero quantum coherent signal selection module
Its resonant frequency of selected signal is the difference for the resonant frequency that solvent and solute spin;In the case of Magnetic field inhomogeneity, solvent
The difference of resonant frequency between solute can eliminate the influence of Magnetic field inhomogeneity and obtain high-resolution spectroscopy information.In field homogeneity
In the case of, it can also equally obtain high-resolution spectroscopy information;
Genetic module (t when described permanent1CTModule) it is by t1/2—π—(τ-t1/ 2) constitute, t1For when dimension develops indirectly
Between, τ is the Time constant constant of setting, usually a few tens of milliseconds;Genetic module can eliminate spectral line caused by J couplings when permanent
Split a point effect so that signal is in t1Only acted on indirectly in the dimension evolution time by chemical shift, simplify spectrogram information.
The diffusion order module is by two diffusion gradient GDConstituted with a π non-selective radio frequencies pulse;Two expansions
The interval time for dissipating gradient is △, i.e. diffusion time;To ensure that signal is met again completely, the two diffusion gradients must be
Exactly the same.In the module, the signal width caused by molecule spreads is obtained by one group of descending diffusion gradient value
Degree change, signaling molecule diffusion coefficient can be fitted according to the change of the signal amplitude of gained;The change of usual this group of diffusion gradient value
Change number n and be set to 15~20, and ensure that minimum signal amplitude is the 10% of maximum signal amplitudes, to improve data fitting
Accuracy.
In step 3) in, the experiment parameter of each module includes directly dimension spectrum width SW, indirectly dimension spectrum width SW1, one group of expansion
Dissipate gradient intensity value GDAnd its action time, diffusion time △, phase dry separation gradient intensity value G and action time, pi/2 and
π non-selective radio frequencies pulse width, (pi/2)ISolvent selectivity RF pulse width, indirectly Time constant constant tau, dimension evolution phase
t1Points ni, directly tie up sampling time t2。
In step 4) in, the detailed process of the execution data sampling is:Often perform pulsatile once sequence, modules according to
It is secondary that signal evolution effect is carried out to sample, finally directly tieing up sampling period t2Carry out data sampling;Above-mentioned sequence implementation procedure is only
It is to once tieing up t indirectly1The data of points and a specific diffusion gradient value are sampled, for a complete data sampling
Need to repeat ni × n time, wherein n is diffusion gradient change number.
In step 5) in, the Data Post includes extraction, the signal that high-resolution One-Dimensional Pure chemical shift information is tieed up
Diffusion coefficient fitting and its error calculation, the extraction of diffusion dimension information, finally obtain diffusion coefficient-purifying displacement study related
Two-dimensional diffusion sequence spectrogram.
The present invention proposes a kind of high-resolution that can be applied to mix ingredients separation and composition analysis under any magnetic field environment
Rate nuclear magnetic resonance two-dimensional diffusion sequence spectral method, in the magnetic resonance detection of mixture, the spectral peak of various different materials is whole
It is presented in same spectrum, often leads to spectral peak crowded and be difficult to obtain correct composition ownership.Particularly in Magnetic field inhomogeneity feelings
Under condition, the uneven broadening effect of spectral line can further cover spectroscopy information, composition ownership is become impossible.The present invention is by combining
Diffusion sequence, it is permanent when develop and intermolecular zero quantum coherent technology realizes under any magnetic field environment (including field homogeneity feelings
Magnetic field inhomogeneity situation caused by condition and various samples and environmental factor) high resolution 2 d diffusion sequence spectrum is obtained, it can use
In the separation of complex mixture composition and composition analysis.First, realized and mixed using the difference of coefficient of molecular diffusion in diffusion sequence
The separation of thing each component.Secondly, spectral line is eliminated using during perseverance developing to split point effect and obtain pure chemistry displacement information, simplify spectrum
Figure, realizes the associated two-dimensional diffusion sequence spectrum of diffusion coefficient-chemical shift.Finally, intermolecular zero quantum coherent signal is utilized
The characteristic for resisting non-uniform magnetic field realizes that high-resolution is obtained under any magnetic field environment spreads sequence spectrum, breaches existing diffusion
The limitation that sequence spectral method is applied in non-uniform magnetic field.This method is without the operation of any shimming and sample pretreatment process, letter
Easy row, and without any special hardware device, it is adaptable to any conventional nuclear magnetic resonance chemical analyser.
The present invention is by nuclear magnetic resonance pulse sequence design and corresponding data processing procedure, using spreading order module and perseverance
When genetic module be implemented in combination with the associated two-dimensional diffusion sequence spectrum of diffusion coefficient-purifying displacement study, effectively simplify and differentiate
Spectral peak information, is easy to the separation of mixture each component.Simultaneously non-uniform magnetic field is resisted using intermolecular zero quantum coherent module
Characteristic realizes that under any magnetic field environment (including magnetic field caused by field homogeneity situation and various samples and environmental factor is uneven
Even situation) high-resolution diffusion sequence spectrum is obtained, breach the limitation that existing diffusion sequence spectral method is applied in non-uniform magnetic field
Property.The present invention is easy to operation to be total to without the operation of any shimming and sample pretreatment process, and suitable for any conventional nuclear-magnetism
Vibration wave spectrometer, without any special hardware device, is that the separation of complex mixture composition and component analysis provide a kind of effective hand
Section.
Brief description of the drawings
Fig. 1 is the high resolution 2 d diffusion sequence spectral method institute applied to the separation of blend sample composition and component analysis
Pulse train, wherein rectangular strip are pi/2 and π non-selective radio frequency pulses, and the bar shaped of gaussian shape is (pi/2)ISolvent is selected
Selecting property radio-frequency pulse, I represents solvent, the rectangular block of oblique line filling be along the linear phase dry separation gradient G of Z-direction, horizontal line filling
Rectangular block is along Z-direction diffusion gradient GD, Δ is diffusion time, t1CTGenetic module during for perseverance, t2During for directly dimension sampling
Between.
Fig. 2 is method proposed by the invention applied to pyridine under non-uniform magnetic field and two obtained by propyl alcohol mixed solution
Frequency spectrum is tieed up, wherein dimension is covering Magnetic field inhomogeneity degree 250Hz indirectly, directly dimension is high-resolution purifying displacement study dimension.Along
Directly dimension, which carries out one-dimensional accumulation projection, can just extract high-resolution One-Dimensional Pure chemical shift information dimension.
Fig. 3 be experimental data by high-resolution One-Dimensional Pure chemical shift information dimension extract after, diffusion order module in one
The lower one-dimensional chemical shift dimensional signal changes in amplitude figure of the descending diffusion gradient value effect of group.With the increasing of diffusion gradient value
By force, signal is constantly decayed.Diffusion dimension can be obtained by being diffused Coefficient Fitting and its error calculation to this series of signal
Information.
Fig. 4 is applied to the height that pyridine and propyl alcohol mixed solution are obtained under non-uniform magnetic field by method proposed by the invention
Differentiate two-dimensional diffusion sequence spectrum.Wherein vertical pivot is diffusion dimension information, and transverse axis is chemical shift information.
Embodiment
Method proposed by the invention can under any magnetic field environment (including field homogeneity situation and various samples and
Magnetic field inhomogeneity situation caused by environmental factor) obtain mix ingredients separation and the high resolution 2 d expansion needed for component analysis
Dissipate sequence spectrum.This method is easy to operation without the operation of any shimming and sample pretreatment process, and suitable for any conventional
Nuclear magnetic resonance chemical analyser, without any special hardware device, is that the separation of complex mixture composition and component analysis provide one kind and had
Effect means.Each step in specific implementation process of the present invention is as follows:
Step 1, the measurement of RF pulse width
Measurement including non-selective pulse and solvent selectivity pulse.It is using conventional one-dimensional pulse sequence and setting one
Row pulse operating time sampling corresponding signal, obtains the burst length corresponding to magnetization vector flip angle, while being also correlation
Spectrum width parameter setting provides foundation.
Step 2, the importing of pulse train used
On nuclear magnetic resonance spectrometer operating desk, open spectrometer and operate software accordingly, import pulse sequence compiled in advance
Arrange (as shown in Figure 1), select specific test block, then call in above-mentioned pulse train.
Step 3, experiment parameter used in pulse train is set
Open each correlation module for importing pulse train, including intermolecular zero quantum coherent signal selection module, perseverance
When genetic module and diffusion order module.Then according to the corresponding experiment parameter of detection sample actual conditions setting, including including
Directly dimension spectrum width SW, indirectly dimension spectrum width SW1, one group of diffusion gradient intensity level GDAnd its action time, diffusion time △, phase
Dry separation gradient intensity value G and action time, pi/2 and π non-selective radio frequencies pulse width, (pi/2)ISolvent selectivity RF pulse-to-pulse
Rush width, indirectly Time constant constant tau, dimension evolution phase t1Points ni, directly tie up sampling time t2.Wherein indirectly dimension spectrum width SW1
Set and refer to the line width values that the conventional one-dimensional spectrum of step 1 obtains spectral line.
Step 4, data sampling
The detailed process of data sampling is:Pulsatile once sequence is often performed, modules carry out signal to sample successively and drilled
Change is acted on, and is finally directly tieing up sampling period t2Carry out data sampling.Above-mentioned sequence implementation procedure simply to once tieing up t indirectly1Points
Sampled with the data of a specific diffusion gradient value, need to repeat ni × n times for a complete data sampling, wherein
N is that diffusion gradient changes number.Complete after a sampled data, perform next step, otherwise continue to sample until sampling is completed.
Step 5, Data Post
The extraction of high-resolution One-Dimensional Pure chemical shift information dimension, the diffusion coefficient fitting of signal and its error calculation, expansion
The extraction of dimension information is dissipated, the related two-dimensional diffusion sequence spectrogram of diffusion coefficient-purifying displacement study is finally obtained.
Below in conjunction with drawings and examples, the present invention will be further described:
Sample used in the present embodiment is the mixed solution of a kind of pyridine and propyl alcohol, and instrument used is a Varian
500MHz NMR spectrums are discussed.Main field remains uneven in whole experiment process.Proposed according to the invention described above
The operating process of method, the RF pulse width used in measurement pulse train, and measure Magnetic field inhomogeneity degree in this experiment and be about
250Hz.Then, compiled pulse train as shown in Figure 1 is imported, each correlation module of pulse train, including molecule is opened
Between zero quantum coherent signal selection module, it is permanent when genetic module and diffusion order module, corresponding experiment parameter is set.Particularly for
The sample that the present embodiment is used, it is as follows that it tests parameter setting:Directly dimension spectrum width SW is 5000Hz;Dimension spectrum width SW1 is indirectly
320Hz;One group of diffusion gradient intensity level GD, wherein minimum value 2.0G/cm, maximum 40G/cm, totally 20 step, gradient effect time
For 1.0ms;Diffusion time △ is 60ms;Phase dry separation gradient intensity value G1For 10.0G/cm and action time 1.2ms, π/
2 and π non-selective radio frequency pulse widths are respectively 11 μ s and 22 μ s;(π/2)ISolvent selectivity RF pulse width is 8.3ms;
Time constant constant tau is 50ms;Evolution phase t is tieed up indirectly1Points ni be 30;Directly tie up sampling time t2For 15ms.Whole experiment
Sampling time is 20min.
After the completion of data sampling, according to the Data Post process of above-mentioned steps 5 at the sampled data that is obtained
Reason.Be first high-resolution One-Dimensional Pure chemical shift information dimension extraction process, by the direct peacekeeping to data tie up indirectly into
Row two-dimensional Fourier transform and rotation transformation can obtain two-dimensional spectrum as shown in Figure 2.In the two-dimensional spectrum, dimension is covering magnetic field indirectly
Unevenness 250Hz, directly dimension are the high-resolution pure chemistry displacement information for eliminating Magnetic field inhomogeneity influence.Along directly dimension
High-resolution One-Dimensional Pure chemical shift information dimension can just be extracted by carrying out one-dimensional accumulation projection.Secondly, the diffusion coefficient of signal is intended
Close and its error calculation, the extraction of diffusion dimension information.It is resulting after high-resolution One-Dimensional Pure chemical shift information dimension is extracted
Data eliminate the influence of Magnetic field inhomogeneity.But data are by one group of descending diffusion gradient value in diffusion order module
The diffusion of generation, its show as One-Dimensional Pure chemical shift information dimension on signal amplitude with diffusion gradient value increase without
Disconnected decay (as shown in Figure 3).It can be spread by being diffused Coefficient Fitting and its error calculation to this series of signal
Information is tieed up.Finally, the height of pyridine and propyl alcohol mixed solution can be reconstructed with reference to pure chemistry displacement information peacekeeping diffusion information dimension
Resolution ratio two-dimensional diffusion sequence spectrum, as shown in Figure 4.Can intuitively it find out, this two-dimensional diffusion sequence spectrum has been completely free of magnetic field
The interference of inhomogeneities, wherein vertical pivot are diffusion information dimension, and transverse axis is tieed up for chemical shift.Pyridine and alcohol component correspond to difference
Molecule diffusion property, different diffusion coefficients are shown as on vertical pivot, both compositions can be realized along in plotted
Separation.As shown in figure 4, green dotted line is the propyl alcohol signal isolated, red dotted line is the pyridine signal isolated.Pyrrole in sample
The content of pyridine and alcohol component also has difference, and the difference of this content chemically displacement can tie up acquisition, pass through and measure chemistry
Both components can be carried out related content analysis by the upper corresponding spectral strength of displacement dimension.
Claims (5)
- The spectral method 1. a kind of nuclear magnetic resonance two-dimensional diffusion for any magnetic field environment sorts, it is characterised in that including following step Suddenly:1) the pi/2 non-selective radio frequency pulse width needed for measurement sample excitation, and (pi/2)ISolvent selectivity radio-frequency pulse is wide Degree;2) nuclear magnetic resonance pulse sequence is imported on nuclear magnetic resonance chemical analyser;3) genetic module and diffusion row when opening intermolecular zero quantum coherent signal selection module, the perseverance of nuclear magnetic resonance pulse sequence Sequence module, sets the experiment parameter of each module;The intermolecular zero quantum coherent signal selection module is by a pi/2 non-selective radio frequency pulse, one (pi/2)ISolvent Selective radio-frequency pulse and a phase dry separation gradient G are constituted;By selected by intermolecular zero quantum coherent signal selection module Signal its resonant frequency be the resonant frequency that solvent and solute spin difference;In the case of Magnetic field inhomogeneity, solvent and solute Between the difference of resonant frequency can eliminate the influence of Magnetic field inhomogeneity and obtain high-resolution spectroscopy information;In field homogeneity situation Under, it is same to obtain high-resolution spectroscopy information;Genetic module is by t when described permanent1/2—π—(τ-t1/ 2) constitute, t1For the dimension evolution time indirectly, τ is the constant of setting Time constant, is a few tens of milliseconds;When permanent genetic module can eliminate J coupling caused by spectral line split a point effect so that signal exists t1Only acted on indirectly in the dimension evolution time by chemical shift, simplify spectrogram information;The diffusion order module is by two diffusion gradient GDConstituted with a π non-selective radio frequencies pulse;Two diffusion gradients Interval time be △, i.e. diffusion time;To ensure that signal is met again completely, the two diffusion gradients must be identical 's;In the module, the signal amplitude caused by molecule spreads is obtained by one group of descending diffusion gradient value and is changed, Signaling molecule diffusion coefficient is fitted according to the change of the signal amplitude of gained;The change number n of this group of diffusion gradient value is set to 15~20, and ensure that minimum signal amplitude is the 10% of maximum signal amplitudes, to improve the accuracy of data fitting;4) data sampling is performed;5) Data Post is carried out, high resolution 2 d diffusion sequence spectrum is obtained;The Data Post includes high-resolution one The extraction of pure chemistry displacement information dimension, the diffusion coefficient fitting of signal and its error calculation, the extraction of diffusion dimension information are tieed up, finally Obtain the related two-dimensional diffusion sequence spectrogram of diffusion coefficient-purifying displacement study.
- Spectral method, its feature 2. a kind of nuclear magnetic resonance two-dimensional diffusion for any magnetic field environment as claimed in claim 1 sorts It is in step 1) in, the pi/2 non-selective radio frequency pulse width needed for the measurement sample excitation is to utilize conventional one-dimensional arteries and veins Sequence completion is rushed, by setting a series of pulse operating times sampling corresponding signals, institute is right when obtaining 90 degree of upsets of magnetization vector The burst length answered is pi/2 non-selective radio frequency pulse width, while this measurement also obtain field homogeneity implementations, is Spectrum width parameter setting provides foundation, (pi/2)IThe measurement of solvent selectivity RF pulse width is by conventional one-dimensional soft arteries and veins Sequence completion is rushed, selective pulse action time corresponding during the 90 degree of upsets of solvent magnetization vector is obtained.
- Spectral method, its feature 3. a kind of nuclear magnetic resonance two-dimensional diffusion for any magnetic field environment as claimed in claim 1 sorts It is in step 2) in, drilled when the nuclear magnetic resonance pulse sequence is using intermolecular zero quantum coherent signal selection module, perseverance Change module and diffusion order module.
- Spectral method, its feature 4. a kind of nuclear magnetic resonance two-dimensional diffusion for any magnetic field environment as claimed in claim 1 sorts It is in step 3) in, the experiment parameter of each module includes directly dimension spectrum width SW, indirectly dimension spectrum width SW1, one group of diffusion ladder Spend intensity level GDAnd its action time, diffusion time △, phase dry separation gradient intensity value G and action time, pi/2 and π are non- Selective RF pulse width, (pi/2)ISolvent selectivity RF pulse width, indirectly Time constant constant tau, dimension evolution phase t1's Count ni, directly dimension sampling time t2。
- Spectral method, its feature 5. a kind of nuclear magnetic resonance two-dimensional diffusion for any magnetic field environment as claimed in claim 1 sorts It is in step 4) in, the detailed process of the execution data sampling is:Pulsatile once sequence is often performed, modules are right successively Sample carries out signal evolution effect, is finally directly tieing up sampling period t2Carry out data sampling;Above-mentioned sequence implementation procedure is pair T is once tieed up indirectly1The data of points and a specific diffusion gradient value are sampled, and are needed for a complete data sampling Repetition ni × n times, wherein n are that diffusion gradient changes number.
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CN107328804B (en) * | 2017-07-21 | 2019-02-05 | 中国科学院山西煤炭化学研究所 | A kind of magnetic resonance detection method of glycerine hydrogenation reaction mixture |
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CN107894436B (en) * | 2017-10-30 | 2019-11-05 | 厦门大学 | A kind of fast two-dimensional J spectral method applied to non-uniform magnetic field |
CN108303439B (en) * | 2018-03-16 | 2020-05-19 | 浙江大学 | Method for testing fluoride diffusion sequencing spectrum based on nuclear magnetic resonance technology |
CN109636725B (en) * | 2018-12-13 | 2022-05-17 | 厦门大学 | High-resolution reconstruction method of magnetic resonance diffusion sequencing spectrum |
CN110044944A (en) * | 2019-04-22 | 2019-07-23 | 中国科学院山西煤炭化学研究所 | A kind of magnetic resonance detection method for F- T synthesis waste water component analysis |
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