CN103885013B - Under a kind of non-uniform magnetic field, obtain the method that nuclear magnetic resonance two dimension J divides spectrum unscrambling - Google Patents
Under a kind of non-uniform magnetic field, obtain the method that nuclear magnetic resonance two dimension J divides spectrum unscrambling Download PDFInfo
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Abstract
Under non-uniform magnetic field, obtain the method that nuclear magnetic resonance two dimension J divides spectrum unscrambling, relate to nuclear magnetic resonance spectrometer. 1) by one dimension spectrum of conventional one dimension pulse train sampling, obtain the live width of spectral line, for the setting of spectrum width parameter provides foundation, line width values has reflected magnetic field environment uniformity situation simultaneously; 2) on nuclear magnetic resonance chemical analyser, import in advance compiled intermolecular single quantum coherent two dimension J and divide spectrum unscrambling pulse train; 3) opening intermolecular single quantum coherent two dimension J divides intermolecular single quantum coherent signal selection module of spectrum unscrambling pulse train, indirectly ties up evolution phase t1Module, indirectly tie up evolution phase t2Module, signal sampling phase t3Module, arranges the experiment parameter of this pulse train modules; 4) execution step 3) the two-dimentional J that arranges after experiment parameter divides spectrum unscrambling pulse train, carries out data sampling; 5) after data sampling completes, carry out relevant Data Post, the high resolution 2 d J that obtaining avoiding non-uniform magnetic field affects divides spectrum unscrambling.
Description
Technical field
The present invention relates to nuclear magnetic resonance (NMR, NuclearMagneticResonance) spectrometer, especially relate to a kind of unevenUnder even magnetic field, obtain the method that nuclear magnetic resonance two dimension J divides spectrum unscrambling.
Background technology
Two dimension J divide spectrum unscrambling (Two-dimensionalJ-resolvedspectroscopy, 2DJRES) be nuclear magnetic resonance field the earliestOne of two-dimentional spectrum method is proposed. Its pulse train can be expressed as (pi/2)-t1/2-(π/)-t1/2+t2, by a pi/2 pulse, oneIndividual π pulse, a quilt is divided the indirect dimension evolution phase t of two halves equally1An and sampling period t2Form. This conventional J divides Spectra Unfolding Methods(AueW.P., KarhanJ., andErnstR.R.Two-dimensional are proposed in 1976 by Ernst the earliestspectroscopyapplicationtonuclearmagneticresonance[J].J.Chem.Phys.,1976,64,2229-2246）。Divide in spectrum unscrambling at two-dimentional J, chemical shiftsum J coupling information lays respectively at two disalignments of spectrogram, i.e. F1 and F2 dimension. CauseThis, utilize this technology can realize the separation of NMR signal chemical shiftsum J coupling information completely, solved one dimension coreThe problem of traffic congestion in magnetic resonance spectrum, for biological tissue's metabolin and complicated chemical composition ownership and detection have important shouldWith. Because the sampling time of J decomposition technique is depended on indirect dimension J coupling size, therefore its sampling efficiency is better than that other are normal greatlyRule two-dimensional spectrum learns a skill, generally as long as divide spectrum unscrambling with the interior two-dimentional J of acquisition that just can sample in two minutes. Nowadays two-dimentional J dividesSpectrum stripping techniques in analysis has become a kind of important testing tool (LudwigC.andViantM.R. in metabolism group researchTwo-dimensionalJ-resolvedNMRspectroscopy:reviewofakeymethodologyinthemetabolomicsToolbox[J] .Phytochem.Anal., 2010,21,22-32.). For example, the people such as Foxall (FoxallP.J.D., ParkinsonJ.A.,SadlerI.H.,LindonJ.C.,andNicholsonJ.K..Analysisofbiological-fluidsusing600MHzprotonNMRspectroscopy:applicationofhomonuclear2-dimensionalJ-resolvedspectroscopytourineandblood-plasmaforspectralsimplificationandassignment[J].J.Pharmaceut.Biomed.Anal., 1993,11,21-31.) research that divides spectrum unscrambling to be applied to human urine and plasma metabolism composition two-dimentional J, for analyzing spyDetermine the feature metabolin of disease. The people such as Lutz (LutzN.W., MailletS., NicoliF., VioutP., andCozzoneP.J.Furtherassignmentofresonancesin1HNMRspectraofcerebrospinalfluid(CSF)[J].FebsLett.,1998,425,345-351.) utilize two-dimentional J divide the metabolin composition that Spectrum stripping techniques in analysis analyzes human body cerebrospinal fluid and change accordinglyProcess. From these application, we find that these now conventional two-dimentional J divide the main application of Spectra Unfolding Methods to concentrate on chemical solutionLiquid or biological fluid. For semi-solid biological tissue, as brain tissue, cartilaginous tissue, even musculature, conventional two-dimentional JPoint Spectra Unfolding Methods often cannot be for detection of analysis. Wherein chief reason is that conventional magnetic resonance detection is for magnetic field homogeneityHave high requirement, though fluid sample relatively uniformly, often before experiment, still need to do very careful shimming process withEnsure the acquisition of high-resolution spectroscopy information. And for biological tissue, the factors such as its sample interior magnetic susceptibility can be introduced magnetic field notUniformity, thus cause conventional two-dimentional J to divide the signal peak of spectrum unscrambling, along chemical shift dimension (F1 dimension), inhomogeneous broadening, nothing occurMethod belongs to metabolite signals. Although conventional two-dimentional J divides the J coupling dimension (F2 dimension) of spectrum unscrambling can not be subject to Magnetic field inhomogeneityThe impact of effect, but because signal causes the overlapping of each signal peak in the broadening meeting of chemical shift dimension, finally also cannot be to metabolismThing J coupling constant is measured accurately. The Magnetic field inhomogeneity visible, sample interior magnetic susceptibility and actual measurement environment causeOften cause conventional two-dimentional J to divide Spectra Unfolding Methods cannot obtain correct detection information, seriously hindered the application of J decomposition technique, spyIt not the application aspect biological tissue.
Occurred at present a series of methods of improving and operate to improve magnetic field homogeneity by shimming hardware aspect, and this needsExpend considerable effort, comprise careful shimming, rotary sample, strictly remove paramagnetism or the graininess impurity in sample, withAnd the container that mates with magnetic sample rate of employing etc. Also develop at present the method for utilizing radiofrequency field compensation B0 field inhomogeneities,And obtain High Resolution Spectrum for non-uniform magnetic field. For example,, for the outer nuclear magnetic resonance of magnet, the design of Bl ü mich research groupMonolateral movably magnetic resonance detection means (PerloJ., CasanovaF., andBlumichB.Ex under a kind of downfield are gone outsituNMRinhighlyhomogeneousfields:H-1spectroscopy[J].Science.,2007,315(5815),1110-1112); Pines research group utilizes " ex situ pulse " and " shimming pulse " technology to eliminate the impact of non-uniform field（MerilesC.A.,SakellariouD.,HeiseH.,MouleA.J.,andPinesA.Approachtohigh-resolutionexSituNMRspectroscopy[J] .Science., 2001,293 (5527), 82-85); In addition, also there is researcher to carry from software aspectHaving gone out some compensates by data post processing method or magnetic field for correcting inhomogeneous broadening effect. For example, the people such as Sersa (SersaI.,MacuraS.Improvementofspectralresolutionbyspectroscopicimaging[J].ApplMagn.Reson.,2004,27,259-266.) propose the post-processing approach that a kind of imaging deconvolutes and carried out compensating field inhomogeneous broadening effect. Existing theseThe method (comprising from hardware and software) that improves magnetic field homogeneity has many restrictions in application, as needs obtain magnetic in advanceField distribution etc.
Although had the method for shimming of some row hardware or software to improve magnetic field homogeneity, due to the limitation order of himselfThe two-dimentional J of front routine divides Spectra Unfolding Methods still cannot be applied in undesirable magnetic field environment, particularly in the detection of biological tissue application.If can resolve this problem, do not need complicated hardware shimming operation not need to know in advance Distribution of Magnetic Field situation yet, andOnly, from pulse train design angle, designing one can be in the lower acquisition of non-uniform magnetic field environment (particularly biological tissue)The method that high-resolution two dimension J divides spectrum unscrambling, just can improve two-dimentional J decomposition technique range of application greatly.
Summary of the invention
The object of the present invention is to provide a kind of high resolution nuclear magnetic resonance two dimension that obtains under non-uniform magnetic field on nuclear magnetic resonance spectrometerJ divides the method for spectrum unscrambling, and the method can be applicable to biological tissue's detection application.
The present invention includes following steps:
1) by one dimension spectrum of conventional one dimension pulse train sampling, obtain the live width of spectral line, for the setting of spectrum width parameter provides foundation,Line width values has reflected magnetic field environment uniformity situation simultaneously;
2) on nuclear magnetic resonance chemical analyser, import in advance compiled intermolecular single quantum coherent two dimension J and divide spectrum unscrambling pulse train;
3) open intermolecular single quantum coherent signal selection module that intermolecular single quantum coherent two dimension J divides spectrum unscrambling pulse train,Meet dimension evolution phase t1Module, indirectly tie up evolution phase t2Module, signal sampling phase t3Module, arranges this pulse train modulesExperiment parameter;
4) execution step 3) the two-dimentional J that arranges after experiment parameter divides spectrum unscrambling pulse train, carries out data sampling;
5) after data sampling completes, carry out relevant Data Post, obtain avoiding the high resolution 2 d of non-uniform magnetic field impactJ divides spectrum unscrambling.
In step 1), described conventional one dimension pulse train is the one dimension pulse train that nuclear magnetic resonance spectrometer carries, non-by oneSelective pi/2 radio-frequency pulse and sampling period, form, i.e. after non-selective pi/2 radio-frequency pulse effect followed by signal sampling, objectBe in order to check without any shimming in the situation that, magnetic field homogeneity situation in experiment, simultaneously for the setting of spectrum width parameter provides foundation.
In step 2) in, described intermolecular single quantum coherent two dimension J divides spectrum unscrambling pulse train to use intermolecular single quantum coherent letterNumber select module, indirectly tie up evolution phase t1Module, indirectly tie up evolution phase t2Module, directly tie up sampling period t3Module;
Described intermolecular single quantum coherent signal selection module is by the pulse of a non-selective rectangle pi/2, a non-selective rectangleπ pulse, two solvent selectivity gaussian shapes (pi/2)IPulse, and three linear magnetic field gradients formations in the z-direction, pass throughIntermolecular single quantum coherent signal selection module can be selected desired intermolecular single quantum coherent signal; Due to intermolecular single quantumCoherent signal comes from long-range dipolar interaction, and the coverage of this dipolar interaction is 10～100 μ m, under normal circumstancesThis scope is far smaller than the yardstick of sample, and under this small yardstick magnetic field uniformity all very high energy meet High Resolution SpectrumRequirement, therefore the selected signal out of intermolecular single quantum coherent signal selection module has immune spy to non-uniform magnetic fieldProperty;
Described indirect dimension evolution phase t1Module is a supper-fast space encoding process, by the adiabatic π pulse of a pair of sinc shape withAnd corresponding encode gradient field forms; Selected go out intermolecular single quantum coherent signal after this module develops, justCan encode to magnetic field bump, form information (the F1 dimension corresponding indirectly dimension evolution phase of three-dimensional sampled signal along F1 dimensiont1）。
Indirectly tie up evolution phase t with routine1Different, this module space encoding process is once sampled just can realize signal evolution,Without carrying out signal evolution according to specific incremental time, greatly improve sampling efficiency.
Described indirect dimension evolution phase t2Module is two parts t being equated by front and back2/ 2 formations, and two t2In the middle of/2, insert oneThe signal of non-selective π pulse shaping spin echo develops.
This is a conventional indirect dimension evolutionary process, need carry out signal evolution according to specific incremental time; Selected go out scoreBetween son, single quantum coherent signal is being tieed up evolution phase t indirectly2After interior evolution, eliminate chemical shift completely and only retained J coupling information,Form information (the F2 dimension corresponding indirectly dimension evolution phase t of three-dimensional sampled signal along F2 dimension2), two-dimentional J divides the J coupling of spectrum unscramblingInformation Dimension. Dimension evolution phase t indirectly2Only comprise J coupling information and develop, in three dimensional signal sampling process, F2 dimension spectrum width size only needsCover J coupling constant and without covering chemical shift width, therefore greatly improve three-dimensional sampling efficiency.
Described direct dimension sampling period t3Module is that a space decoding forms, with indirect dimension evolution phase t1The cataloged procedure of module is relativeShould, this module is to be made up of a pair of decoding gradient fields, finally realizes the sampling of three dimensional signal. Meanwhile, it has also formed three-dimensionalSignal is at information (the corresponding directly dimension of the F3 dimension sampling period t of F3 dimension3）。
Due to the characteristic of intermolecular single quantum coherent signal, Magnetic field inhomogeneity effect is to be associated along F1 and F3 dimension, therefore passes throughSpecific data rotation processing can make the Magnetic field inhomogeneity effect of F1 peacekeeping F3 dimension mutually compensate, finally along F3 dimension magneticField inhomogeneous broadening effect is eliminated and has formed two-dimentional J divides the chemical shift information of spectrum unscrambling to tie up.
In step 3), described experiment parameter comprises direct dimension spectrum width SW, first dimension spectrum width SW1, second dimension indirectly indirectlySpectrum width SW2, sampling time at, indirectly tie up evolution phase t2The ni2 that counts, sequence delays time RD, constant time lag 2 Δs, pi/2The time of non-selective rectangular pulse, the time of the non-selective rectangular pulse of π, (pi/2)ITime, the sinc of selective Gaussian pulseThe time of the adiabatic π pulse of shape, linear coherent gradient field intensity and action time thereof, space encoding gradient fields intensity and effect thereofTime, space decoding gradient strength degree and action time thereof; The setting range of described constant time lag 2 Δs can be 40～120ms.
In step 4), described in carry out data sampling concrete grammar can be: sequence implementation each time, first, sequenceThe time that postpones one section of RD, object is in order to allow magnetization vector relaxation recover; Then, the modules of pulse train is complied withInferior sample effect is developed, select corresponding intermolecular single quantum coherent signal, at indirect dimension evolution phase t1EncodedCheng Jinhang signal develops, and is indirectly tieing up evolution phase t2Carry out signal evolution according to specific incremental time; Finally, directly tieing up and adoptingSample phase t3Carry out space decoding collection signal; Above-mentioned sequence implementation is just to indirect dimension t once2The sampling of counting, forA whole three-dimensional data need to repeat ni2 time above-mentioned sequence implementation.
In step 5), described in carry out relevant Data Post, first, obtained three-dimensional data is carried out once three-dimensionalFourier transformation, obtains an initial graphics; Then, initial graphics is implemented to a three-dimensional rotation processing, three-dimensional is revolvedTurning processing is along being rotated counterclockwise 45 ° on F1-F3 in-plane, processes the graphics obtaining and eliminates completely along F2 peacekeeping F3The impact of Magnetic field inhomogeneity effect, and formed along this bidimensional the information that two-dimentional J divides spectrum unscrambling; Finally, to handled threeDimension figure carries out the once two-dimentional accumulation projection along F2 and F3 dimension.
The present invention utilizes intermolecular single quantum coherent signal selection module and three-dimensional sampling indirectly to tie up and develop by the design of pulse trainPhase t1And t2Module, carries out signal evolution and samples and do corresponding Data Post, finally obtains avoiding Magnetic field inhomogeneity impactHigh-resolution two dimension J divide spectrum unscrambling. Although need to carrying out three-dimensional sampling, described pulse train obtains required signal, due toF1 and F3 dimension has been utilized respectively ultrafast Code And Decode process to realize signal to develop, the whole three-dimensional sampling time only with F2 dimension inJ coupling size is relevant, and it is identical that the sampling time of this pulse train is divided the sampling time of spectrum unscrambling with conventional two-dimentional J, generally twoMinute divide spectrum unscrambling with interior high-resolution two dimension J that can obtain. High-resolution two-dimensional correlation spectrum is for biological tissue's metabolin and multipleAssorted chemical example attribution analysis has important application, but often magnetic field bump has affected spectrum analysis, and therefore each experiment allWill be by regulating shim coil electric current to carry out shimming to sample, the requirement in operating experience, some sample is (for example rawFabric texture) uniformity be difficult to realize by this shimming mode. The present invention can overcome various magnetic field on nuclear magnetic resonance chemical analyserInhomogeneous impact and obtain high-resolution two dimension J and divide spectrum unscrambling, without shimming operation, is biological tissue's metabolin and complicated chemicalSample analysis provides a kind of simple and effective method. The present invention makes any change without the hardware to nuclear magnetic resonance chemical analyser, onlyNeed on spectrometer, import compiled pulse train and corresponding Data Post code with text formatting, therefore the method can be fittedFor the nuclear magnetic resonance chemical analyser of all routines.
Brief description of the drawings
Fig. 1 is applied under non-uniform magnetic field to obtain the pulse train that high-resolution two dimension J divides spectrum unscrambling, and wherein rectangular strip is non-selectionProperty pi/2 and π radio-frequency pulse, the bar shaped of gaussian shape is solvent selectivity (pi/2)IAnd solvent selectivity (pi/2)SRadio-frequency pulse,Sinc shape bar is adiabatic π pulse, and the rectangular block that oblique line is filled is that space rectangles piece is along the linear relevant gradient of selecting of Gz directionSpace encoding and decoding gradient, I represents solvent, S represents solute, NEDimension space coding number of times, NDFor space decoding number of times.
Fig. 2 is the conventional one dimension spectrum of pig brain tissue, and line width is 120Hz. Wherein, 0.7～4.2ppm part in one dimension spectrogramComprise pig brain tissue's metabolite signals, its intensity is amplified to 400 times and be presented at the top of one dimension spectrum corresponding part.
Fig. 3 knot that intermolecular single quantum coherent two dimension J divides Spectra Unfolding Methods to obtain for pig brain tissue utilizes in the situation of same magnetic fieldReally.
Detailed description of the invention
Intermolecular single quantum two dimension J proposed by the invention divides Spectra Unfolding Methods can overcome Magnetic field inhomogeneity on nuclear magnetic resonance chemical analyserAnd the impact of tissue sample inner magnet rate inhomogeneous broadening effect and obtain high resolution 2 d J and divide spectrum unscrambling, save artificial shimmingOperation, for biological tissue's metabolin and complicated chemical sample analysis provide a kind of simple and effective method. The present invention specifically implementsEach step in process is as follows:
Step 1, the sampling of conventional one dimension spectrum
First the conventional one dimension pulse train carrying with nuclear magnetic resonance spectrometer is (i.e. after non-selective pi/2 radio-frequency pulse effectFollowed by signal sampling) sampling obtains an one dimension spectrum, is obtained the live width of spectral line by one dimension spectrum, and line width values has reflected that magnetic field is evenImplementations, this line width values is also for the setting of spectrum width parameter provides foundation simultaneously.
Step 2, the importing of pulse train
On nuclear magnetic resonance spectrometer operating desk, open the corresponding function software of spectrometer, import compiled intermolecular single quantum in advanceTwo dimension J divide spectrum unscrambling pulse train (as shown in Figure 1), selects specific test block, then calls in above-mentioned pulse train, is nextStep operation is prepared.
Step 3, intermolecular single quantum two dimension J divides the setting of spectrum unscrambling pulse train parameter
First open each correlation module of this pulse train, comprise intermolecular single quantum coherent signal selection module, indirectly tie up and drillChange phase t1Module, indirectly tie up evolution phase t2Module, directly tie up sampling period t3Module. Then according to detecting the setting of sample actual conditionsCorresponding experiment parameter, comprises direct dimension spectrum width SW, and first ties up spectrum width SW1 indirectly, and second ties up spectrum width SW2, sampling indirectlyTime at, ties up evolution phase t indirectly2The ni2 that counts, constant time lag 2 Δs, non-selective rectangular pulse time of pi/2 and π, (pi/2)IThe selective Gaussian pulse time, the time of the adiabatic π pulse of sinc shape, linear coherent gradient field intensity and action time thereof, skyBetween encode gradient field intensity and action time thereof, space decoding gradient strength degree and action time thereof. Wherein, space encoding decodingThe setting of the adiabatic π pulse of gradient and sinc shape can the conventional one dimension spectrum of refer step 1 line width values that obtains.
Step 4, intermolecular single quantum two dimension J divides spectrum unscrambling pulse train data sampling
Be different from conventional two-dimentional J and divide Spectra Unfolding Methods or other spectroscopy sequences, the present invention can skip the shimming process of sample, directly holdsThe pulse train that row sets, carries out data sampling. Each time in sequence implementation, first one section of RD of sequence delays timeBetween, object is in order to allow magnetization vector relaxation recover; Then, the modules of pulse train is successively to sample effectDevelop, select corresponding intermolecular single quantum coherent signal, indirectly tieing up evolution phase t1Cataloged procedure carries out signal evolution,Indirectly tieing up evolution phase t2Carry out signal evolution according to specific incremental time, finally directly tieing up sampling period t3Carry out space decodingCollection signal; Above-mentioned sequence implementation is just to indirect dimension t once2The sampling of counting, needs for a whole three-dimensional dataTo repeat ni2 time above-mentioned sequence implementation. After data sampling completes, carry out next step, otherwise continue sampling until adoptSample completes.
Step 5, Data Post
After data sampling completes, carrying out relevant Data Post, is first that obtained three-dimensional data is carried out once to three-dimensional FuIn leaf transformation, obtain an initial graphics, and then this graphics implemented to a three-dimensional rotation processing, this processAlong being rotated counterclockwise 45 ° on F1-F3 in-plane, last, carry out once along F2 and F3 dimension to handled graphicsTwo dimension accumulation projection, obtains high-resolution two dimension J and decomposes Correlated Spectroscopy.
Below provide specific embodiment:
This new method is scanned to a kind of biological tissue as an embodiment, verified this by this specific embodimentThe bright feasibility of particularly applying in biological tissue under non-uniform magnetic field environment. The sample that experiment adopts is pig brain tissue,Experiment test is to carry out under a Varian500MHzNMR spectrum view (Varian, PaloAlto, CA), and whole experimentation does not haveHave and carry out artificial shimming operation. The operating process of dividing Spectra Unfolding Methods according to above-mentioned intermolecular single quantum two dimension J, first uses routineSimple one dimension pulse train sampling obtains an one dimension spectrum, and the sampling time is 2s, and result as shown in Figure 2, is composed from this one dimensionCan obtain line width is 120Hz. Owing to directly sample being sampled and do not carried out shimming operation, magnetic field homogeneity is lower. RightThe part that one dimension spectrum 0.7～4.2ppm comprises brain tissue metabolism thing is carried out the amplification of 400 times of signal strength signal intensities, can find out metabolin letterNumber peak still cannot be differentiated. In addition, powerful water peak-to-peak signal has also further hindered the analysis of spectrogram. Then, import compiledIntermolecular single quantum two dimension J as shown in Figure 1 divide spectrum unscrambling pulse train, open each correlation module of pulse train, comprise pointSingle quantum coherent signal selection module between son, indirectly tie up evolution phase t1Module, indirectly tie up evolution phase t2Module, directly tie up sampling periodt3Module, arranges experiment parameter, the sample specifically adopting for the present embodiment, and its experiment parameter arranges as follows: directly dimension spectrumWide SW is 3000Hz, and the first indirect dimension spectrum width SW1 is 200Hz, and the second indirect dimension spectrum width SW2 is 60Hz, when samplingBetween at be 0.4s, indirectly tie up evolution phase t2The ni2 that counts be 40, pulse delay time, RD was 2s, pi/2 and π non-selectionThe property rectangular pulse time is 10s and 20s, (pi/2)ISelective Gaussian Pulse Width is 6ms, the adiabatic π pulse of sinc shapeTime is 10ms, and 2 Δs are 60ms, and linear coherent gradient field intensity and time are respectively 0.1T/m and 1.2ms, space encodingGradient fields intensity and time are respectively 0.039T/m and 10ms, and space decoding gradient strength degree and time are respectively 0.042T/mAnd 0.13ms. Skip shimming process and directly click beginning, carry out the sequence setting, sequence implementation, just can each timeTo obtain indirect dimension t once2Institute's respective signal of counting, will repeat 40 times the whole sampling time to this sample signal samplingFor 80s.
After data sampling completes, according to the processing procedure of above-mentioned steps 5, obtained data are carried out to post processing, first do one time threeDimension Fourier transformation, obtains an initial graphics, and this graphics is implemented to a three-dimensional rotation processing, obtains processingGraphics. In the graphics of processing at this, F2 peacekeeping F3 dimension has jointly formed two-dimentional J and has decomposed spectrum information, and inhomogeneous magneticThe impact of broadening is eliminated, and carries out two-dimentional accumulation projection and just can obtain the high-resolution two of the present embodiment along F1 peacekeeping F3 dimensionDimension J divide spectrum unscrambling, and final result as shown in Figure 3, therefrom can find out, though organization internal magnetic susceptibility is inhomogeneous and magnetic field notUnder ideal situation, the present invention can make two-dimentional J divide spectrum unscrambling to be reduced to 20Hz along the live width of chemical shift dimension by 120Hz, and this hasBe beneficial to metabolite signals ownership; Live width along J coupling dimension drops to 3Hz by 120Hz, and this is conducive to metabolin J coupling informationDetect. As can be seen here, utilize method of the present invention can in pig brain tissue, recover high resolution 2 d J and divide spectrum unscrambling letterBreath, various metabolin ownership and J coupling information can obtain, and solvent peak is also effectively suppressed.
Claims (3)
1. under non-uniform magnetic field, obtain the method that nuclear magnetic resonance two dimension J divides spectrum unscrambling, it is characterized in that comprising the steps:
1) by one dimension spectrum of conventional one dimension pulse train sampling, obtain the live width of spectral line, for the setting of spectrum width parameter provides foundation,Line width values has reflected magnetic field environment uniformity situation simultaneously;
2) on nuclear magnetic resonance chemical analyser, import in advance compiled intermolecular single quantum coherent two dimension J and divide spectrum unscrambling pulse train; InstituteStating intermolecular single quantum coherent two dimension J divides spectrum unscrambling pulse train to use intermolecular single quantum coherent signal selection module, indirectly tie up and drillChange phase t1Module, indirectly tie up evolution phase t2Module, directly tie up sampling period t3Module;
Described intermolecular single quantum coherent signal selection module is by the pulse of a non-selective rectangle pi/2, a non-selective rectangleπ pulse, two solvent selectivity gaussian shapes (pi/2)IPulse, and three linear magnetic field gradients formations in the z-direction, pass throughIntermolecular single quantum coherent signal selection module can be selected desired intermolecular single quantum coherent signal; Due to intermolecular single quantumCoherent signal comes from long-range dipolar interaction, and the coverage of this dipolar interaction is 10～100 μ m;
Described indirect dimension evolution phase t1Module is a supper-fast space encoding process, by the adiabatic π pulse of a pair of sinc shape withAnd corresponding encode gradient field forms; Selected go out intermolecular single quantum coherent signal after this module develops, justCan encode to magnetic field bump, form the information of three-dimensional sampled signal along F1 dimension, the corresponding dimension evolution phase indirectly of F1 dimensiont1；
Described indirect dimension evolution phase t2Module is two parts t being equated by front and back2/ 2 formations, and two t2In the middle of/2, insert oneThe signal of non-selective π pulse shaping spin echo develops; Described evolution is conventional indirect dimension evolutionary process, need be according to specificIncremental time carry out signal evolution; Selected go out intermolecular single quantum coherent signal at indirect dimension evolution phase t2After interior evolution,Eliminated chemical shift completely and only retained J coupling information, formed the information of three-dimensional sampled signal along F2 dimension, two-dimentional J decomposesThe J coupling Information Dimension of spectrum, the corresponding dimension indirectly of F2 dimension evolution phase t2; Dimension evolution phase t indirectly2Only comprising J coupling information develops;
Described direct dimension sampling period t3Module is that a space decoding forms, with indirect dimension evolution phase t1The cataloged procedure of module is relativeShould, this module is to be made up of a pair of decoding gradient fields, finally realizes the sampling of three dimensional signal; Meanwhile, it also forms three-dimensional letterNumber at the information of F3 dimension, the corresponding sampling period t that directly ties up of F3 dimension3；
3) open intermolecular single quantum coherent signal selection module that intermolecular single quantum coherent two dimension J divides spectrum unscrambling pulse train,Meet dimension evolution phase t1Module, indirectly tie up evolution phase t2Module, directly tie up sampling period t3Module, arranges this pulse train modulesExperiment parameter;
4) execution step 3) the two-dimentional J that arranges after experiment parameter divides spectrum unscrambling pulse train, carries out data sampling; Described numberAccording to sampling concrete grammar be: sequence implementation each time, first, the time of one section of RD of sequence delays, object be forAllow magnetization vector relaxation recover; Then, the modules of pulse train develops to sample effect successively, selectsCorresponding intermolecular single quantum coherent signal, is tieing up evolution phase t indirectly1Cataloged procedure carries out signal evolution, is indirectly tieing up the evolution phaset2Carry out signal evolution according to specific incremental time; Finally, directly tieing up sampling period t3Carry out space decoding collection signal; OnState sequence implementation just to indirect dimension t once2The sampling of counting, need to be to above-mentioned sequence for a whole three-dimensional dataImplementation repeats ni2 time;
5) after data sampling completes, carry out relevant Data Post, obtain avoiding the high resolution 2 d of non-uniform magnetic field impactJ divides spectrum unscrambling; Describedly carry out relevant Data Post, first, obtained three-dimensional data is carried out once to three-dimensional Fourier and becomeChange, obtain an initial graphics; Then, initial graphics is implemented to a three-dimensional rotation processing, three-dimensional rotation processing isAlong being rotated counterclockwise 45 ° on F1-F3 in-plane, process the graphics obtaining and eliminated magnetic field completely not along F2 and F3 dimensionThe evenly impact of effect, and formed along this bidimensional the information that two-dimentional J divides spectrum unscrambling; Finally, handled graphics is carried outOnce along the two-dimentional accumulation projection of F2 and F3 dimension.
2. under a kind of non-uniform magnetic field, obtain the method that nuclear magnetic resonance two dimension J divides spectrum unscrambling as claimed in claim 1, it is characterized in thatIn step 1) in, described conventional one dimension pulse train is the one dimension pulse train that nuclear magnetic resonance spectrometer carries, by a non-selectionProperty forms pi/2 radio-frequency pulse and sampling period, i.e. after non-selective pi/2 radio-frequency pulse effect followed by signal sampling.
3. under a kind of non-uniform magnetic field, obtain the method that nuclear magnetic resonance two dimension J divides spectrum unscrambling as claimed in claim 1, it is characterized in thatIn step 3) in, when described experiment parameter comprises direct dimension spectrum width SW, F1 dimension spectrum width SW1, F2 dimension spectrum width SW2, samplingBetween at, indirectly tie up evolution phase t2The ni2 that counts, sequence delays time RD, constant time lag 2 Δs, non-selective rectangle pi/2 arteries and veinsThe time of punching, the time of non-selective rectangle π pulse, selective Gauss's (pi/2)IThe time of pulse, the adiabatic π arteries and veins of sinc shapeThe time of punching, linear coherent gradient field intensity and action time thereof, space encoding gradient fields intensity and action time thereof, Space SolutionsCode gradient fields intensity and action time thereof; The setting range of described constant time lag 2 Δs is 40～120ms.
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