CN106841272A - A kind of quantitative analysis method suitable for compound molecule group or blend component ratio - Google Patents
A kind of quantitative analysis method suitable for compound molecule group or blend component ratio Download PDFInfo
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Abstract
The invention provides a kind of quantitative analysis method, including：A the rCDPz spectrograms that cross-polarization contact time is respectively 0 and τ for the rCP spectrograms of τ and two times of contact) are gathered, respectively three spectrograms is carried out with Fourier transformation, phase place is corrected and Baseline wander, and to three spectrograms13C spectral peaks are integrated, and obtain IrCP(τ)、IrCDPzAnd I (0)rCDPz(τ)；B) according to formula rCDPz (τ)=IrCDPz(τ)/IrCDPz(0), rCP (τ)+rCDPz (τ)=1 and IrQCPz S=IrCP(τ)/rCP (τ), finally gives the quantitative integration value I of cross polarization spectral peakrQCPz S.The application provide method can with it is time saving accurately detect C H systems, C F systems, Si H systems or in Si F systems organic matter in the ratio or above-mentioned serial organic matter blend of group component proportionate relationship.
Description
Technical field
The present invention relates to the method for testing technical field of large-sized analytic instrument, more particularly to suitable for compound molecule group
Or the quantitative analysis method of blend component ratio.
Background technology
Hartmann and Hahn in 1962 is found that cross polarization phenomenon (CP), shown in pulse train such as Fig. 1 (a).With biography
The one-dimensional direct excitation experiment (DP) of system is compared, and the main advantage of one-dimensional CP technologies has at 2 points：1) it is greatly reduced needed for experiment
Time；2) under identical accumulative frequency, the signal to noise ratio highest of CP spectrograms can be promoted to four times.However, CP technologies and without fixed
Amount property, which greatly limits CP the fields such as chemistry, material, soil and mineral range of application.
At present, the quantitatively characterizing method of solid-state nuclear magnetic resonance is DP experiments.The quantitative result of the method is reliable, accurate, real
It is every time that the relaxation recovery time D before collection signal needs to meet D≤5T to test successful key1, wherein T1It is S in sample system
Atomic nucleus (13C、29Si etc.) longitudinal relaxation time.However, the S cores T of most sample systems1It is very long, usually a few minutes
Or even dozens of minutes.When an experiment need cumulative thousands of times it is even more many when, it is necessary to spend ten a few houres to several weeks when
Between, this greatly reduces the feasibility of DP quantitative tests.
In order to solve the problems, such as DP methods, time-consuming in quantitative test, and nuclear-magnetism workers propose various based on CP skills
The quantitative approach of art, it is desirable to the quantitatively characterizing of S cores during sample system can be completed in shorter experimental period.Such as 2005
The SD-CP-MAS methods that Zhang Lili et al. is proposed, Hou Guang in 2006 enters et al. the QUCP methods for proposing；Wherein, SD-CP-MAS methods are used for
The content of phase constituent in quantitative measurment heterogeneous system, and QUCP methods are primarily adapted for use in13The homogeneous system of C isotope enrichments is quantified
Characterize.Therefore, above two method as solid state nmr quantitatively characterizing technology and do not have universality., Shu Jie etc. in 2008
People proposes the QCP/QCP based on cross polarization reciprocal theoremRCMethod, experiment proves that the method can be realized to existing comprising mixture
Interior most sample systems13C and29The quantitatively characterizing of Si；Such as Fig. 1 (a), (b), respectively QCP/QCPRCUsed required for method
Test of pulse sequence C P and CDP sequence；Experiment need to gather the CP spectrograms that a cross-polarization contact time is τ and two contacts
Time is respectively the CDP spectrograms of 0 and τ, and obtains the quantitative information that spectral peak is integrated by simple mathematical computations.At present, QCP/
QCPRCThe weak point that method is present mainly has at 2 points：(1) the method is not suitable for the experiment condition of Fast Magic Angle Spinning；(2)CDP
In experiment, S atom core is constantly in spin locking state, the spin spin relaxation time T for I2 ISample more long, S from
Rotation locking time also needs corresponding extension, and this aspect makes S signals pass through T1ρThe loss of effect partial, reduces signal to noise ratio；It is another
Aspect improves experiment dutycycle, and easily the electronic component popped one's head in is caused to damage.
The content of the invention
Present invention solves the technical problem that being to provide a kind of suitable for compound molecule group or blend component ratio
Quantitative analysis method, the quantitative analysis method that the application is provided is capable of detecting when the ratio of molecular radical in organic matter, moreover it is possible to
Detect the ratio of various organic matters in mixture.
This application provides a kind of quantitative analysis method suitable for compound molecule group or blend component ratio, bag
Include following steps：
A), sample is positioned in solid-state NMR spectroscopy instrument, during the cross-polarization contact of one sample S group of collection
Between the rCDPz spectrograms of 0 and τ are respectively for the rCP spectrograms of τ and two cross-polarization contact time, three spectrograms are entered respectively
Row Fourier transformation, phase place is corrected and Baseline wander, and S group spectral peaks to three spectrograms are integrated, and obtain S groups
IrCP(τ)、IrCDPzAnd I (0)rCDPz(τ)；The atomic nucleus of the solid-state NMR spectroscopy instrument detection includes29Si-1H、13C-1H、13C-19F or29Si-19F；
B), according to formula rCDPz (τ)=IrCDPz(τ)/IrCDPz(0) the intersection depolarising efficiency rCDPz of S groups, is obtained
(τ)；According to formula rCP (τ)+rCDPz (τ)=1, cross polarization efficiency rCP (τ) of S groups is obtained；
C), according to formula IrQCPz S=ICP(τ)/rCP (τ), obtains the quantitative integration value of the cross polarization spectral peak of S groups
IrQCPz S, obtain the ratio of molecular radical or blend component in compound；The S is13C or29Si。
Preferably, the cross polarization pulse of the rCP spectrograms is ramp shaped pulses, the pulse sequence of the rCDPz spectrograms
For two time intervals are t in channel S between the process of cross polarization twice of rowd90 degree of pulses, and cross polarization pulse is
Ramp shaped pulses.
Preferably, the compound is13C-1During the compound of H systems, the pulse train of the rCDPz spectrograms is twice
Between cross polarization process13For two time intervals are t on C-channeld90 ° of pulses, and cross polarization pulse be ramp shapes
Shape pulse.
Preferably, the compound is13C-1During the compound of H systems, the pulse sequence of the rCP spectrograms and rCDpz spectrograms
Row190 ° of pulse widths of H are 3.2 μ s, and power is 78kHz；1390 ° of pulse widths of C are 3.2 μ s, and power is 78kHz.
Preferably, the compound is13C-1During the compound of H systems, in the rCP spectrograms and the rCDPz spectrograms
In, the relaxation stand-by period before sampling is 3~5s every time.
Preferably, the t of the pulse train of the rCDPz spectrogramspIt is 200~3000 μ s, tdIt is 2~100ms, tcpIt is 100
~500 μ s.
This application provides a kind of quantitative analysis method suitable for compound molecule group or blend component ratio, bag
Include following steps：A) the one cross-polarization contact time of collection is the rCP spectrograms of τ and two times of contact to be respectively 0 and τ's
Three spectrograms are carried out Fourier transformation, phase place is corrected and Baseline wander by rCDPz spectrograms respectively, and to three S groups of spectrogram
Spectral peak is integrated, and obtains IrCP(τ)、IrCDPzAnd I (0)rCDPz(τ)；B) according to formula rCDPz (τ)=IrCDPz(τ)/IrCDPz
(0), obtain intersecting depolarising efficiency rCDPz (τ)；According to formula rCP (τ)+rCDPz (τ)=1, cross polarization efficiency rCP is obtained
(τ)；C) according to formula IrQCPz S=IrCP(τ)/rCP (τ), obtains the quantitative integration value I of cross polarization spectral peakrQCPz S.The application is carried
The method of confession can accurately be detected with time saving13C-1H systems,13C-19F systems,29Si-1H systems or29Si-19In F systems organic matter13C bases
Group or29The ratio of Si groups and13C-1H systems,13C-19F systems,29Si-1H systems or29Si-19Each group in F systems organic matter blend
The proportionate relationship divided, is particularly suited for the experiment condition of Fast Magic Angle Spinning, and intersect the depolarisation test loss of signal reducing
While, it is adaptable to T2 ISample system more long.Therefore, the method that the application is provided is in kinds of experiments condition and sample system model
Versatility in enclosing is stronger.
Brief description of the drawings
Fig. 1 is that cross polarization (CP) test of pulse sequence diagram is illustrated with depolarising (CDP) test of pulse sequence is intersected
Figure；
Fig. 2 is cross polarization (rCP) the test of pulse sequence chart and rCDPz experiment arteries and veins suitable for Fast Magic Angle Spinning condition
Rush sequence diagram；
Fig. 3 is molecular structure of chemistry schematic diagram and alanine, the histidine and the two blend of alanine and histidine
's13C nuclear magnetic resoance spectrums, spectral peak is pointed out referring to the mark in chemical constitution schematic diagram；
Fig. 4 is rCP (t), the rCDPz (t) and sum (t) curve maps of alanine；
Fig. 5 is rCP (t), the rCDPz (t) and sum (t) curve maps of histidine.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, but
It should be appreciated that these descriptions are simply to further illustrate the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
The embodiment of the invention discloses a kind of quantitative analysis suitable for compound molecule group or blend component ratio
Method, comprises the following steps：
A), sample is positioned in solid-state NMR spectroscopy instrument, during the cross-polarization contact of one sample S group of collection
Between the rCDPz spectrograms of 0 and τ are respectively for the rCP spectrograms of τ and two cross-polarization contact time, three spectrograms are carried out respectively
Fourier transformation, phase place is corrected and Baseline wander, and S group spectral peaks to three spectrograms are integrated, and obtain the I of S groupsrCP
(τ)、IrCDPzAnd I (0)rCDPz(τ)；The atomic nucleus of the solid-state NMR spectroscopy instrument detection includes29Si-1H、13C-1H、13C-19F or29Si-19F；
B), according to formula rCDPz (τ)=IrCDPz(τ)/IrCDPz(0) the intersection depolarising efficiency rCDPz of S groups, is obtained
(τ)；According to formula rCP (τ)+rCDPz (τ)=1, cross polarization efficiency rCP (τ) of S groups is obtained；
C), according to formula IrQCPz S=IrCP(τ)/rCP (τ), obtains the quantitative integration value of the cross polarization spectral peak of S groups
IrQCPz S, obtain the ratio of molecular radical or blend component in compound；The S is13C or29Si。
The quantitative detecting method that the application is provided can be described as rQCPz methods, the method difference similar with QCP methods, main
When part is that spectrogram is gathered, the test of pulse sequence that rQCPz is used is rCP and rCDPz, and QCP/QCPRCThe experiment of use
Pulse train is CP and CDP, and the test of pulse sequence of the application is specifically as shown in Figure 2.The rCP technologies of the application are by former QCP side
The rectangular cross polarization pulse of S is replaced by ramp shaped pulses in the pulse train of the CP that method is used；The rCDPz skills of the application
Art there occurs change for the pulse train of existing CDP technologies, by between cross polarization process twice13C spin locking pulses
Two time intervals have been changed to for td90 degree of pulses, while by the rectangular cross polarization pulse of S in the pulse train of CDP spectrograms
Change is for ramp shaped pulses.
The pulse train of the application rCP spectrograms has advantages below with the change of the pulse train of rCDPz spectrograms：First,
In original CDP technologies, B is locked in1When the S losses of signal on direction are mostly derived from the spin lattice relaxation under rotating coordinate system
Between, i.e. the T of S1ρEffect, generally several milliseconds are arrived hundreds of milliseconds, and in rCDPz technologies, S signals are locked in B0On direction, letter
Number loss be mostly derived from the T of longitudinal relaxation time, i.e. S1Effect, generally several seconds to hundreds of seconds, in addition it is longer.Cause
This, in certain tdIn time, the loss of signal that S signals are produced due to relaxation in rCDPz is smaller, the signal to noise ratio of spectrogram
Higher, measurement result is more accurate；In addition, transverse relaxation time (the T for I2 I) sample more long, TdTime need prolong
It is long, general >=5*T2 I, and for CDP technologies, T when longdB when meaning long1Field spin locking, this improves experiment duty
Than easily the element to instrument probe causes to damage；And in rCDPz technologies, TdExtension be simply waiting for the extension of time, it is right
The hardware of instrument does not influence；Finally, using the cross polarization process of ramp pulses, Fast Magic Angle Spinning speed pair can be reduced
The modulation of cross polarization Hartman-Hahn matching conditions.Therefore, with QCP/QCPRCMethod is compared, and uses the rQCPz of rCDPz technologies
On the one hand method goes for the experiment condition of Fast Magic Angle Spinning；On the other hand, intersection depolarising experimental signal is being reduced
While loss, it is adaptable to T2 ISample system more long.Therefore, rQCPz methods are in kinds of experiments condition and sample system scope
Interior versatility is stronger.
From the foregoing, just because of the change of pulse train, and rCP technologies and rCDPz technologies have been obtained, and then make this
Apply for that the method for providing can quantitative analysis detection13C-1H、29Si-1H、13C-19F or29Si-19Carbon-containing group in F organic matters, contain
The ratio of the organic matter in silicon group or mixture.
According to the present invention, sample is positioned in solid-state NMR spectroscopy instrument, sample with13C-1As a example by H systems organic matter,
The one cross-polarization contact time of collection is τ's13C rCP spectrograms and two cross-polarization contact times are respectively 0 and τ's13C
RCDPz spectrograms, and Fourier's change, phase place is corrected and Baseline wander are carried out to spectrogram, and in spectrogram13C spectral peaks are accumulated
Point, obtain IrCP(τ)、IrCDPzAnd I (0)rCDPz(τ).During collection, in the pulse train of the rCP and rCDPz1H's
90 ° of pulse widths are 3.2 μ s, and power is 78kHz；1390 ° of pulse widths of C are 3.2 μ s, and power is 78kHz；The rCDPz spectrums
The t of the pulse train of figurepIt is 200~3000 μ s, tdIt is 2~100ms, tcpIt is 100~500 μ s；Relaxation before sampling every time etc.
Treat that the time is 5s；The setting of above-mentioned parameter can be set according to mode well known to those skilled in the art, according to specific feelings
Shape is set, and in the embodiment of the present application, the parameter setting of pulse train is as described above.Specific collection sample is with alanine
As a example by, according to the method described above, in cross-polarization contact time (tcp) for τ when, gather one13C rCP (τ) spectrogram, and to spectrogram
In C=O, CH and CH3's13C spectral peaks are integrated, while when the cross-polarization contact time being 0 and τ, collection13C rCDPz
(0) spectrogram and13C rCDPz (τ) spectrogram, and respectively to C=O, CH and the CH in spectrogram3's13C spectral peaks are integrated.
After above-mentioned integrated value is obtained, according to formula rCDPz (τ)=IrCDPz(τ)/IrCDPz(0), obtain intersecting depolarising
Efficiency rCDPz (τ)；Also according to formula rCP (τ)+rCDPz (τ)=1, cross polarization efficiency rCP (τ)=1-rCDPz is obtained
(τ).After cross polarization efficiency rCP (τ) is obtained, finally according to formula IrQCPz S=IrCP(τ)/rCP (τ), obtains cross polarization
The quantitative integration value of spectral peak, thus obtains13C-1The quantitative determination of H systems content of organics.In a particular embodiment, examining respectively
Survey containing in alanine, histidine13As a example by the content and alanine/histidine blending ratio of C groups, in alanine is detected13In the embodiment of C groups, C=O, CH and CH in alanine can be detected3Proportionate relationship, detect histidine in C groups
Embodiment in, C in histidine can be detecteda、Cf、Cd、Ce、CbAnd Cc(each13The mark in C sites is tied referring to the chemistry of Fig. 3
Structure schematic diagram) proportionate relationship, in the embodiment of the proportionate relationship of detection alanine and histidine blend, with alanine
The CH of CO spectral peaks and histidine3Spectral peak is Integrating, finally gives respective IrQCPz S, ratio finally is carried out to it, that is, obtain
The mol ratio of alanine and histidine.
For a further understanding of the present invention, the present invention is provided with reference to embodiment13C-1H system content of organics
Quantitative detecting method be described in detail, protection scope of the present invention is not limited by the following examples.
The checking of the reciprocal relation of embodiment 1
The quantitative principle of rQCPz methods based on cross polarization efficiency rCP (t) with intersect depolarising efficiency rCDPz (t)
Reciprocal relation.Therefore, whether the successful key of rQCPz methods is to investigate meet reciprocal relation between rCP (t) and rCDPz (t).
Based on this, the present embodiment is first by rCP and rCDPz sequences by changing tcpAcquire a series of alanine13C is composed, Ran Houfen
Other three to alanine13The integrated value of C spectral peaks integration is normalized, and specific method is as follows：
(1) by tcp=0 μ s'13C rCDPz spectral peak integrated values are set to 1, so as to a series of different tcp's13C rCDPz are composed
Peak integrated value is normalized, and the integrated value after normalized namely tests measured rCDPz (t), wherein t=tcp；
(2) t is setcpDuring=100 μ s, rCP (100)+rCDPz (100)=1, i.e. rCP (100)=1-rCDPz (100), with rCP (100)
Numerical value be reference, to remaining13The spectral peak integrated value of C rCP spectrums is normalized, and obtains rCP (t).
By rCP (t) and rCDPz (t) to tcpMapping, as shown in figure 4, as seen from Figure 4, three kinds13The nuclear rCP of C
T () and rCDPz (t) curves are symmetrical along the straight line of y=0.5, and sum (t)=rCP (t)+rCDPz (t) substantially with the straight line of y=1
It coincide, i.e. rCP (t) and rCDPz (t) meet reciprocal relation.The rCDPz spectrum signal to noise ratios of wherein C=O carbon are relatively low, thus rCDPz
T there is concussion in () curve, and cause sum (t) and the y=1 goodnesses of fit not high.Additionally, increases of the sum (t) of CH with time of contact
There is the trend of reduction, this T mainly due to hydrogen nuclei near CH1ρWhat relaxation caused.Therefore, ensureing that spectrogram is good
On the premise of signal to noise ratio.As far as possible by tcpIt is shorter that i.e. above-mentioned τ is set, typically between 100us to 500us.
The more complicated histidine system of chemical constitution has also been investigated simultaneously, and such as Fig. 5 is six kinds in histidine samples13C spectral peaks
RCP (t) and rCDPz (t) experimental datas and sum (t)=rCP (t)+rCDPz (t).Equally, six kinds13The nuclear rCP (t) of C
It is coincide with the straight line of y=1 substantially along the symmetrical of y=0.5, and sum (t) with rCDPz (t) curves.Due to hydrogen in histidine system
Nuclear T1ρRelaxation time is more long, therefore, the goodness of fit of sum (t) and y=1 straight lines is higher.Of particular note is that COOH
The rCDPz spectrum signal to noise ratios of carbon are relatively low, thus concussion occur in rCDPz (t) curves, and cause sum (t) and the y=1 goodnesses of fit not high.
From above-mentioned experimental work, the reciprocal relation between rCP (t) and rCDPz (t) is set up, on rQCPz theoretical methods
It is feasible.
The Alanine Molecule group rQCPz quantitative experiments of embodiment 2 and data processing idiographic flow are as follows：
A as shown in Figure 3, be fitted into solid state nmr sample cell alanine solid powder simultaneously first by () alanine structural formula
It is positioned in probe, transfers rCP pulse sequence program files, the pulse train of the present embodiment has shape as shown in Figure 2, if
Put tcpIt is 100 μ s, Magic angle spinning speed is 10kHz, then to Alanine Molecule group13C signal is acquired, and chooses tcp
=100 μ s, gather one13C rCP (100) spectrogram, and to C=O, CH and the CH in spectrogram3's13C spectral peaks are integrated, relatively
Integrated value ICP(100) it is respectively 0.162,1 and 0.644；
B () transfers rCDPz pulse sequence program files, the pulse train of the present embodiment has shape as shown in Figure 2, if
Determine tpIt is 1000 μ s, tdIt is 10ms, selectes tcp=0 and 100 μ s, collection13C rCDPz (0) and13C rCDPz (100) spectrogram, and
To C=O, CH and CH in spectrogram3's13C spectral peaks are integrated,13Three integrated value I of spectral peak in C rCDP (0) spectrumsrCDPz(0)
Respectively 0.696,0.760 and 1；13Three integrated value I of spectral peak in C rCDPz (100) spectrumsrCDPz(100) be respectively 0.631,
0.324 and 0.645；
C () is according to formula rCDPz (100)=IrCDPz(100)/IrCDPz(0), wherein τ=100 μ s, can obtain C=O, CH and
CH3's13The rCDPz (100) of C spectral peaks is 0.907,0.426 and 0.645；
D () understands according to cross polarization reciprocal theorem, rCP (100)=1-rCDPz (100), i.e. C=O, CH and CH3's13C
The rCP (100) of spectral peak is 0.093,0.574 and 0.355.
E () is according to formula IrQCPz S=IrCP(100) be corrected for the integrated value of rCP (100) by/rCP (100), C=O, CH
And CH3IrQCPz SRespectively 1.742,1.742 and 1.814, are 0.986,0.986 and 1.027 after normalized；With theory
Integration ratio 1:1:1 compares, and error is only ± 0.027.
The embodiment of the present invention 2 of table 1 carries out the related data and experimental period data of quantitatively characterizing to Alanine Molecule group
Table
| Quantitative approach | CO | CH | Percent error | Experimental period/h | |
| CP | 0.27 | 1.66 | 1.07 | ± 73% | 0.08 |
| DP | 0.99 | 0.96 | 1.05 | ± 5% | 10.67 |
| rQCPz | 0.99 | 0.99 | 1.03 | ± 3% | 0.25 |
| Theoretical value | 1 | 1 | 1 | -- | -- |
The histidine molecular radical rQCPz quantitative experiments of embodiment 3 and data processing idiographic flow are as follows：
A (), according to the explanation of rQCPz methods, first loads histidine solid powder as shown in histidine structure formula in Fig. 3
In solid state nmr sample cell and be positioned over probe in, transfer rCP pulse sequence program files, the pulse train of the present embodiment has
Shape as shown in Figure 2, sets tcp=360 μ s, Magic angle spinning speed is 10kHz, gathers one13C rCP (360) spectrogram, by
Low field is to High-Field successively to the C in spectrograma、Cf、Cd、Ce、CbAnd Cc's13C spectral peaks are integrated, relative integral value IrCP(360) divide
Wei 0.428,0.637,0.705,0.761,0.913 and 1；
B () transfers rCDPz pulse sequence program files, the pulse train of the present embodiment has shape as shown in Figure 2, if
Put tpIt is 1000 μ s, tdIt is 10ms, chooses tcp=0 and 360 μ s, collection13C rCDPz (0) and13C rCDPz (360) spectrogram, and
To the C in spectrograma、Cf、Cd、Ce、CbAnd CcSpectral peak is integrated,13Six integrated value I of spectral peak in C rCDP (0) spectrumsrCDPz(0)
Respectively 0.700,0.891,0.748,0.767,1 and 0.914；13Six integrated value I of spectral peak in C rCDPz (360) spectrumsrCDPz
(360) it is respectively 0.471,0.494,0.338,0.320,0.328 and 0.190；
C () is according to formula rCDPz (360)=IrCDPz(360)/IrCDPz(0), wherein τ=360 μ s, can obtain Ca、Cf、Cd、Ce、
CbAnd Cc's13The rCDPz (360) of C spectral peaks is respectively 0.673,0.554,0.452,0.417,0.328 and 0.208；
D () understands according to cross polarization reciprocal theorem, rCP (360)=1-rCDPz (360), therefore Ca、Cf、Cd、Ce、CbWith
Cc's13The rCP (360) of C spectral peaks is respectively 0.327,0.446,0.548,0.583,0.672 and 0.792；
E () is according to formula IrQCPz S=IrCP(360)/rCP (360), C is corrected by the integrated value of rCP (360)a、Cf、
Cd、Ce、CbAnd CcIrQCPz SRespectively 1.309,1.428,1.286,1.305,1.359 and 1.263, be after normalized
0.989th, 1.078,0.971,0.985,1.026 and 0.953.Compared with theory integration ratio, error is ± 0.078.
The embodiment of the present invention 3 of table 2 carries out the related data and experimental period data of quantitatively characterizing to histidine molecular radical
Table
4 alanine of embodiment/histidine blend rQCPz quantitative experiments and data processing idiographic flow are as follows：
A be fitted into alanine/histidine solid powder in solid state nmr sample cell first according to the explanation of rQCPz methods by ()
And be positioned in probe, rCP pulse sequence program files are transferred, the pulse train of the present embodiment has shape as shown in Figure 2,
T is setcp=400 μ s, Magic angle spinning speed is 10kHz, then gathers one13C rCP (400) spectrogram, to the CO spectrums of alanine
The CH at peak and histidine3Spectral peak is integrated, integrated value ICP(400) it is respectively 0.484 and 0.974；
B () transfers rCDPz pulse sequence program files, the pulse train of the present embodiment has shape as shown in Figure 2, if
Put tpIt is 1000 μ s, tdIt is 10ms, chooses tcp=0 and 400 μ s, collection13C rCDPz (0) and13C rCDPz (400) spectrogram, and
To the CO spectral peaks and the CH of histidine of alanine in spectrogram3Spectral peak is integrated,13The product of two component spectral peaks in C rCDP (0) spectrums
Score value IrCDPz(0) it is respectively 0.590 and 0.934；13The integrated value I of two component spectral peaks in C rCDPz (400) spectrumsrCDPz(400) divide
Wei 0.405 and 0.180；
C () is according to formula rCDPz (400)=IrCDPz(400)/IrCDPz(0), wherein τ=400 μ s, can obtain the CO of alanine
The CH of spectral peak and histidine3The rCDPz (400) of spectral peak is respectively 0.686 and 0.193；
D () understands according to cross polarization reciprocal theorem, rCP (400)=1-rCDPz (400), thus alanine CO spectral peaks
With the CH of histidine3The rCP (400) of spectral peak is respectively 0.314 and 0.807；
E () is according to formula IrQCPz S=IrCP(400) be corrected for the integrated value of rCP (400) by/rCP (400), alanine
CO spectral peaks and histidine CH3The I of spectral peakrQCPz SRespectively 1.541 and 1.207；Therefore alanine and histidine in mixture
Mol ratio be 1.541 ÷ 1.207=1.277, compared with the result 1.245 that DP quantitative approach is measured, measurement error is
2.57%.
The related data of the component ratio quantitative determination that the embodiment of the present invention 4 of table 3 is carried out to alanine/histidine blend
And experimental period tables of data
| Quantitative approach | Percent error | Experimental period/h | |
| CP | 0.497 | 40.4% | 0.5 |
| DP | 1.245 | -- | 336 |
| rQCPz | 1.277 | 2.6% | 1.5 |
The explanation of above example is only intended to help and understands the method for the present invention and its core concept.It should be pointed out that right
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or uses the present invention.
Various modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, the present invention
The embodiments shown herein is not intended to be limited to, and is to fit to and principles disclosed herein and features of novelty phase one
The scope most wide for causing.
Claims (6)
1. a kind of quantitative analysis method suitable for compound molecule group or blend component ratio, comprises the following steps：
A), sample is positioned in solid-state NMR spectroscopy instrument, gather a sample S group the cross-polarization contact time be
The rCP spectrograms of τ and two cross-polarization contact time are respectively the rCDPz spectrograms of 0 and τ, carry out Fu to three spectrograms respectively
In leaf transformation, phase place is corrected and Baseline wander, and S group spectral peaks to three spectrograms are integrated, and obtain the I of S groupsrCP
(τ)、IrCDPzAnd I (0)rCDPz(τ)；The atomic nucleus of the solid-state NMR spectroscopy instrument detection includes29Si-1H、13C-1H、13C-19F or29Si-19F；
B), according to formula rCDPz (τ)=IrCDPz(τ)/IrCDPz(0) intersection for, obtaining S groups depolarizes efficiency rCDPz (τ)；Root
According to formula rCP (τ)+rCDPz (τ)=1, cross polarization efficiency rCP (τ) of S groups is obtained；
C), according to formula IrQCPz S=ICP(τ)/rCP (τ), obtains the quantitative integration value I of the cross polarization spectral peak of S groupsrQCPz S,
Obtain the ratio of molecular radical or blend component in compound；The S is13C or29Si。
2. quantitative analysis method according to claim 1, it is characterised in that the cross polarization pulse of the rCP spectrograms is
Ramp shaped pulses, between two times in channel S between the process of cross polarization twice of the pulse train of the rCDPz spectrograms
It is divided into td90 degree of pulses, and cross polarization pulse be ramp shaped pulses.
3. quantitative analysis method according to claim 1, it is characterised in that the compound is13C-1The chemical combination of H systems
During thing, between the process of cross polarization twice of the pulse train of the rCDPz spectrograms13For two time intervals are on C-channel
td90 ° of pulses, and cross polarization pulse be ramp shaped pulses.
4. quantitative analysis method according to claim 1, it is characterised in that the compound is13C-1The chemical combination of H systems
During thing, the pulse train of the rCP spectrograms and rCDpz spectrograms190 ° of pulse widths of H are 3.2 μ s, and power is 78kHz；13C
90 ° of pulse widths be 3.2 μ s, power is 78kHz.
5. quantitative analysis method according to claim 1, it is characterised in that the compound is13C-1The chemical combination of H systems
During thing, in the rCP spectrograms with the rCDPz spectrograms, the relaxation stand-by period before sampling is 3~5s every time.
6. the quantitative analysis method according to any one of claim 1~2, it is characterised in that the pulse of the rCDPz spectrograms
The t of sequencepIt is 200~3000 μ s, tdIt is 2~100ms, tcpIt is 100~500 μ s.
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