CN106841272B - 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 present invention provides a kind of quantitative analysis methods, include: A) acquire the rCP spectrogram that a cross-polarization contact time is τ and the rCDPz spectrogram that two times of contact are respectively 0 and τ, Fourier transformations, phase correction and Baseline wander carried out to three spectrograms respectively, and to three spectrograms13C spectral peak is integrated, and I is obtainedrCP(τ)、IrCDPz(0) and IrCDPz(τ)；B) according to formula rCDPz (τ)=IrCDPz(τ)/IrCDPz(0), rCP (τ)+rCDPz (τ)=1 and IrQCPz S=IrCP(τ)/rCP (τ) finally obtains the quantitative integration value I of cross polarization spectral peakrQCPz S.Method provided by the present application can be gone out with time saving accurate detection C-H system, C-F system, in Si-H system or Si-F system organic matter in the ratio of group or above-mentioned serial organic matter blend component proportionate relationship.
Description
Technical field
The present invention relates to the test method technical fields of large-sized analytic instrument, more particularly to are suitable for compound molecule group
Or the quantitative analysis method of blend component ratio.
Background technique
Hartmann and Hahn in 1962 has found 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 technology has two o'clock: 1) being greatly reduced needed for experiment
Time；2) under identical accumulative frequency, the signal-to-noise ratio highest of CP spectrogram can be promoted to four times.However, CP technology and do not have it is fixed
Amount property, the application range which greatly limits CP in fields such as chemistry, material, soil and mineral.
Currently, the quantitatively characterizing method of solid-state nuclear magnetic resonance is DP experiment.The quantitative result of this method is reliable, accurate, real
Testing successful key is that the relaxation recovery time D before each acquisition signal needs to meet D≤5T1, wherein T1For S in sample system
Atomic nucleus (13C、29Si etc.) longitudinal relaxation time.However, the S core T of most sample systems1It is very long, usually a few minutes
Even dozens of minutes.When an experiment needs to add up thousands of time even more, it is necessary to spend ten a few houres to several weeks when
Between, this greatly reduces the feasibility of DP quantitative test.
In order to solve the problems, such as DP method, time-consuming in quantitative test, and nuclear-magnetism workers propose a variety of based on CP skill
The quantitative approach of art, it is desirable to the quantitatively characterizing of S core in sample system can be completed in shorter experimental period.Such as 2005
Zhang Lili et al. propose SD-CP-MAS method, Hou Guang in 2006 into et al. propose QUCP method；Wherein, SD-CP-MAS method is used
The content of phase constituent in quantitative measurment heterogeneous system, and QUCP method is primarily adapted for use in13The homogeneous system of C isotope enrichment is determined
Scale sign.Therefore, above two method as solid state nmr quantitatively characterizing technology and do not have universality.2008, Shu Jie
Et al. propose the QCP/QCP based on cross polarization reciprocal theoremRCMethod, experiments have shown that this method may be implemented to comprising mixture
Most sample systems inside13C and29The quantitatively characterizing of Si；Such as Fig. 1 (a), (b), respectively QCP/QCPRCMake required for method
Test of pulse sequence C P and CDP sequence；Experiment need to acquire the CP spectrogram that a cross-polarization contact time is τ and two
Time of contact is respectively the CDP spectrogram of 0 and τ, and the quantitative information of spectral peak integral is obtained by simple mathematical computations.Currently,
QCP/QCPRCShortcoming existing for method mainly has two o'clock: (1) this method is not suitable for the experiment condition of Fast Magic Angle Spinning；
(2) in CDP experiment, S atom core is constantly in spin locking state, for the spin spin relaxation time T of I2 ILonger sample
Product, the spin locking time of S also need accordingly to extend, and this aspect makes S signal pass through T1ρThe loss of effect partial, reduces letter
It makes an uproar ratio；On the other hand experiment duty ratio is improved, is easy that the electronic component of probe is caused to damage.
Summary 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, quantitative analysis method provided by the present application 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, packets
Include following steps:
A), sample is placed in solid-state NMR spectroscopy instrument, when acquiring the cross-polarization contact of a sample S group
Between for τ rCP spectrogram and two cross-polarization contact times be respectively 0 and τ rCDPz spectrogram, respectively to three spectrograms into
Row Fourier transformation, phase correction and Baseline wander, and the S group spectral peak of three spectrograms is integrated, obtain the I of S grouprCP(τ)、IrCDPz(0) and IrCDPz(τ)；The atomic nucleus of 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 group is obtained
(τ)；According to formula rCP (τ)+rCDPz (τ)=1, the cross polarization efficiency rCP (τ) of S group is obtained；
C), according to formula IrQCPz S=IrCP(τ)/rCP (τ) obtains determining for the cross polarization spectral peak of S group
Measure integrated value 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 spectrogram is ramp shaped pulse, the pulse sequence of the rCDPz spectrogram
It in channel S for two time intervals is t between the process of cross polarization twice of columnd90 degree of pulses, and cross polarization pulse is
Ramp shaped pulse.
Preferably, the compound is13C-1When the compound of H system, the pulse train of the rCDPz spectrogram is twice
Between cross polarization process13On C-channel for two time intervals be td90 ° of pulses, and cross polarization pulse be ramp shape
Shape pulse.
Preferably, the compound is13C-1When the compound of H system, the pulse of the rCP spectrogram and rCDpz spectrogram
Sequence190 ° of pulse widths of H are 3.2 μ s, power 78kHz；1390 ° of pulse widths of C are 3.2 μ s, power 78kHz.
Preferably, the compound is13C-1When the compound of H system, in the rCP spectrogram and the rCDPz spectrogram
In, the relaxation waiting time before sampling is 3~5s every time.
Preferably, the t of the pulse train of the rCDPz spectrogrampFor 200~3000 μ s, tdFor 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, packets
Including following steps: A) the one cross-polarization contact time of acquisition is the rCP spectrogram of τ and two times of contact are respectively 0 and τ
RCDPz spectrogram carries out Fourier transformation, phase correction and Baseline wander to three spectrograms respectively, and to the S group of three spectrograms
Spectral peak is integrated, and I is obtainedrCP(τ)、IrCDPz(0) and IrCDPz(τ)；B) according to formula rCDPz (τ)=IrCDPz(τ)/IrCDPz
(0), it obtains intersecting depolarising efficiency rCDPz (τ)；According to formula rCP (τ)+rCDPz (τ)=1, cross polarization efficiency is obtained
rCP(τ)；C) according to formula IrQCPz S=IrCP(τ)/rCP (τ) obtains the quantitative integration value I of cross polarization spectral peakrQCPz S.This Shen
The method that please be provided can be gone out with time saving accurate detection13C-1H system,13C-19F system,29Si-1H system or29Si-19In F system organic matter13C group or29The ratio of Si group and13C-1H system,13C-19F system,29Si-1H system or29Si-19In F system organic matter blend
Each component proportionate relationship, be particularly suitable for the experiment condition of Fast Magic Angle Spinning, and intersect depolarisation test letter reducing
Number loss while, be suitable for T2 ILonger sample system.Therefore, method provided by the present application is in various experimental conditions and sample
Versatility within the scope of system is stronger.
Detailed description of the invention
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) test of pulse sequence chart and rCDPz the experiment arteries and veins suitable for Fast Magic Angle Spinning condition
Rush sequence diagram；
Fig. 3 is the molecular structure of chemistry schematic diagram and alanine, histidine and the two blend of alanine and histidine
's13C nuclear magnetic resoance spectrum, spectral peak are pointed out referring to the mark in chemical structure schematic diagram；
Fig. 4 is rCP (t), the rCDPz (t) and sum (t) curve graph of alanine；
Fig. 5 is rCP (t), the rCDPz (t) and sum (t) curve graph of histidine.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are only further explanation 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 analyses suitable for compound molecule group or blend component ratio
Method, comprising the following steps:
A), sample is placed in solid-state NMR spectroscopy instrument, when acquiring the cross-polarization contact of a sample S group
Between for the rCP spectrogram of τ and two cross-polarization contact times be respectively 0 and τ rCDPz spectrogram, three spectrograms are carried out respectively
Fourier transformation, phase correction and Baseline wander, and the S group spectral peak of three spectrograms is integrated, obtain the I of S grouprCP
(τ)、 IrCDPz(0) and IrCDPz(τ)；The atomic nucleus of 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 group is obtained
(τ)；According to formula rCP (τ)+rCDPz (τ)=1, the cross polarization efficiency rCP (τ) of S group 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 group
IrQCPz S, obtain the ratio of molecular radical or blend component in compound；The S is13C or29Si。
Quantitative detecting method provided by the present application can be described as rQCPz method, and this method is similar with QCP method, main difference
When place is spectrogram acquisition, test of pulse sequence used by rQCPz 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 technology of the application is by the former side QCP
The rectangular cross polarization pulse of S is changed to ramp shaped pulse in the pulse train of CP used in method；The rCDPz of the application
Technology is changed for the pulse train of existing CDP technology, will be between cross polarization process twice13C spin locking arteries and veins
It is t that punching, which has been changed to two time intervals,d90 degree of pulses, while by the pulse train of CDP spectrogram S rectangular cross polarize arteries and veins
Punching change is for ramp shaped pulse.
The change of the pulse train of the pulse train and rCDPz spectrogram of the application rCP spectrogram have the advantage that firstly,
In original CDP technology, it is locked in B1When the S loss of signal on direction is 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 technology, S signal is locked in B0On direction, letter
Number loss be mostly derived from longitudinal relaxation time, the i.e. T of S1Effect, generally several seconds to hundreds of seconds or even longer.Cause
This, in certain tdIn time, the loss of signal that S signal is generated due to relaxation in rCDPz is smaller, the signal-to-noise ratio of spectrogram
Higher, measurement result is more acurrate；In addition, for the transverse relaxation time (T of I2 I) longer sample, TdTime need prolong
It is long, general >=5*T2 I, and the T for CDP technology, when longdB when meaning long1Field spin locking, this improves experiment and accounts for
Empty ratio is easy to cause to damage to the element of instrument probe；And in rCDPz technology, TdExtension be simply waiting the extension of time,
The hardware of instrument is not influenced；Finally, can reduce Fast Magic Angle Spinning rate using the cross polarization process of ramp pulse
Modulation to cross polarization Hartman-Hahn matching condition.Therefore, with QCP/QCPRCMethod is compared, and rCDPz technology is used
On the one hand rQCPz method can be adapted for the experiment condition of Fast Magic Angle Spinning；On the other hand, intersection depolarising experiment is being reduced
While the loss of signal, it is suitable for T2 ILonger sample system.Therefore, rQCPz method is in various experimental conditions and sample system
Versatility in range is stronger.
It can be seen from the above, just because of the change of pulse train, and rCP technology and rCDPz technology have been obtained, and then make
Method provided by the present application can quantitative analysis detection13C-1H、29Si-1H、13C-19F or29Si-19Carbon-containing group in F organic matter,
The ratio of organic matter in silicon-containing group or mixture.
According to the present invention, sample is placed in solid-state NMR spectroscopy instrument, sample with13C-1For H system organic matter,
Acquiring a cross-polarization contact time is τ's13C rCP spectrogram and two cross-polarization contact times are respectively 0 and τ13C
RCDPz spectrogram, and Fourier's variation, phase correction and Baseline wander are carried out to spectrogram, and in spectrogram13C spectral peak is accumulated
Point, obtain IrCP(τ)、IrCDPz(0) and IrCDPz(τ).During acquisition, in the pulse train of the rCP and rCDPz1H's
90 ° of pulse widths are 3.2 μ s, power 78kHz；1390 ° of pulse widths of C are 3.2 μ s, power 78kHz；The rCDPz spectrum
The t of the pulse train of figurepFor 200~3000 μ s, tdFor 2~100ms, tcpFor 100~500 μ s；Relaxation etc. before sampling every time
It is 5s to the time；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 acquisition sample is with alanine
For, according to the method described above, in cross-polarization contact time (tcp) be τ when, acquire one13C rCP (τ) spectrogram, and to spectrogram
In C=O, CH and CH3's13C spectral peak is integrated, while when the cross-polarization contact time is 0 and τ, acquisition13C rCDPz
(0) spectrogram and13C rCDPz (τ) spectrogram, and respectively to C=O, CH and CH in spectrogram3's13C spectral peak is integrated.
After obtaining above-mentioned integrated value, according to formula rCDPz (τ)=IrCDPz(τ)/IrCDPz(0), it obtains 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 obtaining cross polarization efficiency rCP (τ), finally according to formula IrQCPz S=IrCP(τ)/rCP (τ), obtains cross polarization
The quantitative integration value of spectral peak, thus obtains13C-1The quantitative detection of H system content of organics.In a particular embodiment, to examine respectively
Containing in survey alanine, histidine13For the content and alanine/histidine blending ratio of C group, in detection alanine13In the embodiment of C group, C=O, CH and CH in alanine can detecte3Proportionate relationship, detection histidine in C group
Embodiment in, can detecte C in histidinea、Cf、Cd、Ce、CbAnd CcIt is (each13The mark in the site C is tied referring to the chemistry of Fig. 3
Structure schematic diagram) proportionate relationship, detection alanine and histidine blend proportionate relationship embodiment in, with alanine
The CH of CO spectral peak and histidine3Spectral peak is Integrating, finally obtains respective IrQCPz S, carry out ratio to it finally to get arriving
The molar ratio of alanine and histidine.
For a further understanding of the present invention, below with reference to embodiment to provided by the invention13C-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 verifying of 1 reciprocal relation of embodiment
The quantitative principle of rQCPz method based on cross polarization efficiency rCP (t) with intersect depolarising efficiency rCDPz (t)
Reciprocal relation.Therefore, the successful key of rQCPz method is to investigate whether meet reciprocal relation between rCP (t) and rCDPz (t).
Based on this, the present embodiment uses rCP and rCDPz sequence by changing t firstcpAcquire a series of alanine13C spectrum, then
Respectively to three of alanine13The integrated value of C spectral peak integral is normalized, and the specific method is as follows:
(1) by tcp=0 μ s's13C rCDPz spectral peak integrated value is set to 1, thus to a series of difference tcp's13C rCDPz spectrum
Peak integrated value is normalized, and the integrated value after normalized namely tests measured rCDPz (t), wherein t=tcp；
(2) t is setcpWhen=100 μ s, rCP (100)+rCDPz (100)=1, i.e. rCP (100)=1-rCDPz (100), with rCP
(100) numerical value is reference, to remaining13The spectral peak integrated value of C rCP spectrum 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) curve is symmetrical along the straight line of y=0.5, and sum (t)=rCP (t)+rCDPz (t) is substantially straight with y=1
Line coincide, i.e. rCP (t) and rCDPz (t) meet reciprocal relation.Wherein the rCDPz spectrum noise of C=O carbon is relatively low, thus
RCDPz (t) curve shakes, and causes sum (t) and the y=1 goodness of fit not high.In addition, the sum (t) of CH is with time of contact
Increase have the tendency that reduction, this is mainly due to the T of hydrogen nuclei near CH1ρCaused by relaxation.Therefore, guaranteeing to compose
Under the premise of figure good signal-to noise ratio.As far as possible by tcpI.e. above-mentioned τ is arranged shorter, generally between 100us to 500us.
The more complex histidine system of chemical structure is also investigated simultaneously, if Fig. 5 is six kinds in histidine samples13C spectral peak
RCP (t) and rCDPz (t) experimental data and sum (t)=rCP (t)+rCDPz (t).Equally, six kinds13The nuclear rCP of C
(t) and rCDPz (t) curve is along the symmetrical of y=0.5, and sum (t) coincide with the straight line of y=1 substantially.Due to histidine system
The T of middle hydrogen nuclei1ρRelaxation time is longer, and therefore, the goodness of fit of sum (t) and y=1 straight line is higher.Of particular note is that
The rCDPz spectrum noise of COOH carbon is relatively low, thus rCDPz (t) curve shakes, and leads to sum (t) and the y=1 goodness of fit not
It is high.
By above-mentioned experimental work as it can be seen that the reciprocal relation between rCP (t) and rCDPz (t) is set up, rQCPz theoretical method
It is upper feasible.
2 Alanine Molecule group rQCPz quantitative experiment of embodiment and data processing detailed process are as follows:
(a) alanine structural formula is as shown in Figure 3, is first fitted into alanine solid powder in solid state nmr sample cell simultaneously
It being placed in probe, transfers rCP pulse sequence program file, the pulse train of the present embodiment has shape as shown in Figure 2, if
Set tcpFor 100 μ s, Magic angle spinning rate is 10kHz, then to Alanine Molecule group13C signal is acquired, and chooses tcp
=100 μ s acquire one13C rCP (100) spectrogram, and to C=O, CH and CH in spectrogram3's13C spectral peak is integrated, phase
To integrated value ICPIt (100) is respectively 0.162,1 and 0.644；
(b) rCDPz pulse sequence program file is transferred, the pulse train of the present embodiment has shape as shown in Figure 2, if
Determine tpFor 1000 μ s, tdFor 10ms, t is selectedcp=0 and 100 μ s, acquisition13C rCDPz (0) and13C rCDPz (100) spectrogram, and
To C=O, CH and CH in spectrogram3's13C spectral peak is integrated,13The integrated value I of three spectral peaks in C rCDP (0) spectrumrCDPz
It (0) is respectively 0.696,0.760 and 1；13The integrated value I of three spectral peaks in C rCDPz (100) spectrumrCDPz(100) it is respectively
0.631,0.324 and 0.645；
(c) according to formula rCDPz (100)=IrCDPz(100)/IrCDPz(0), the wherein μ s of τ=100, can obtain C=O, CH and
CH3's13The rCDPz (100) of C spectral peak is 0.907,0.426 and 0.645；
(d) according to cross polarization reciprocal theorem it is found that rCP (100)=1-rCDPz (100), i.e. C=O, CH and CH3's13The rCP (100) of C spectral peak is 0.093,0.574 and 0.355.
(e) according to formula IrQCPz S=IrCP(100) integrated value of rCP (100) is corrected 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
Integral ratio 1:1:1 compares, and error is only ± 0.027.
1 embodiment of the present invention 2 of table carries out the related data and experimental period data of quantitatively characterizing to Alanine Molecule group
Table
| Quantitative approach | CO | CH | CH3 | 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 | -- | -- |
3 histidine molecular radical rQCPz quantitative experiment of embodiment and data processing detailed process are as follows:
(a) as shown in histidine structure formula in Fig. 3, illustrate according to rQCPz method, be first packed into histidine solid powder
It in solid state nmr sample cell and is placed in probe, transfers rCP pulse sequence program file, the pulse train tool of the present embodiment
Just like shape shown in Fig. 2, t is setcp=360 μ s, Magic angle spinning rate are 10kHz, acquire one13C rCP (360) spectrogram,
By low field to High-Field successively to the C in spectrograma、Cf、Cd、Ce、CbAnd Cc's13C spectral peak is integrated, relative integral value IrCP(360)
Respectively 0.428,0.637,0.705,0.761,0.913 and 1；
(b) rCDPz pulse sequence program file is transferred, the pulse train of the present embodiment has shape as shown in Figure 2, if
Set tpFor 1000 μ s, tdFor 10ms, t is chosencp=0 and 360 μ s, acquisition13C rCDPz (0) and13C rCDPz (360) spectrogram, and
To the C in spectrograma、Cf、 Cd、Ce、CbAnd CcSpectral peak is integrated,13The integrated value I of six spectral peaks in C rCDP (0) spectrumrCDPz
It (0) is respectively 0.700,0.891,0.748,0.767,1 and 0.914；13The integrated value of six spectral peaks in C rCDPz (360) spectrum
IrCDPzIt (360) is respectively 0.471,0.494,0.338,0.320,0.328 and 0.190；
(c) according to formula rCDPz (360)=IrCDPz(360)/IrCDPz(0), the wherein μ s of τ=360, can obtain Ca、Cf、Cd、Ce、
CbAnd Cc's13The rCDPz (360) of C spectral peak is respectively 0.673,0.554,0.452,0.417,0.328 and 0.208；
(d) according to cross polarization reciprocal theorem it is found that rCP (360)=1-rCDPz (360), therefore Ca、Cf、Cd、Ce、CbWith
Cc's13The rCP (360) of C spectral peak is respectively 0.327,0.446,0.548,0.583,0.672 and 0.792；
(e) according to formula IrQCPz S=IrCP(360) integrated value of rCP (360) is corrected C by/rCP (360)a、Cf、
Cd、Ce、CbAnd CcIrQCPz SRespectively 1.309,1.428,1.286,1.305,1.359 and 1.263 are after normalized
0.989,1.078,0.971,0.985,1.026 and 0.953.Compared with theory integral ratio, error is ± 0.078.
2 embodiment of the present invention 3 of table 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 experiment and data processing detailed process are as follows:
(a) illustrate according to rQCPz method, alanine/histidine solid powder is fitted into solid state nmr sample cell first
And be placed in probe, rCP pulse sequence program file is transferred, the pulse train of the present embodiment has shape as shown in Figure 2,
T is setcp=400 μ s, Magic angle spinning rate are 10kHz, then acquire one13C rCP (400) spectrogram, to the CO of alanine
The CH of spectral peak and histidine3Spectral peak is integrated, integrated value ICPIt (400) is respectively 0.484 and 0.974；
(b) rCDPz pulse sequence program file is transferred, the pulse train of the present embodiment has shape as shown in Figure 2, if
Set tpFor 1000 μ s, tdFor 10ms, t is chosencp=0 and 400 μ s, acquisition13C rCDPz (0) and13C rCDPz (400) spectrogram, and
To the CO spectral peak of alanine in spectrogram and the CH of histidine3Spectral peak is integrated,13The product of two component spectral peaks in C rCDP (0) spectrum
Score value IrCDPzIt (0) is respectively 0.590 and 0.934；13The integrated value I of two component spectral peaks in C rCDPz (400) spectrumrCDPz(400) divide
It Wei 0.405 and 0.180；
(c) according to formula rCDPz (400)=IrCDPz(400)/IrCDPz(0), the wherein μ s of τ=400, 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) according to cross polarization reciprocal theorem it is found that rCP (400)=1-rCDPz (400), therefore the CO spectral peak of alanine
With the CH of histidine3The rCP (400) of spectral peak is respectively 0.314 and 0.807；
(e) according to formula IrQCPz S=IrCP(400) integrated value of rCP (400) is corrected by/rCP (400), alanine
CO spectral peak and histidine CH3The I of spectral peakrQCPz SRespectively 1.541 and 1.207；Therefore alanine and histidine in mixture
Molar ratio be 1.541 ÷ 1.207=1.277, compared with the result 1.245 that DP quantitative approach measures, measurement error is
2.57%.
The related data for the component ratio quantitative detection that 3 embodiment of the present invention 4 of table carries out alanine/histidine blend
And experimental period tables of data
| Quantitative approach | CO (third)/CH3(group) | Percent error | Experimental period/h |
| CP | 0.497 | 40.4% | 0.5 |
| DP | 1.245 | -- | 336 |
| rQCPz | 1.277 | 2.6% | 1.5 |
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to 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, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (5)
1. a kind of quantitative analysis method suitable for compound molecule group or blend component ratio, comprising the following steps:
A), sample is placed in solid-state NMR spectroscopy instrument, the cross-polarization contact time for acquiring a sample S group is
The rCP spectrogram of τ and two cross-polarization contact times are respectively the rCDPz spectrogram of 0 and τ, carry out Fu to three spectrograms respectively
In leaf transformation, phase correction and Baseline wander, and the S group spectral peak of three spectrograms is integrated, obtains the I of S grouprCP
(τ)、IrCDPz(0) and IrCDPz(τ)；The atomic nucleus of 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 depolarising efficiency rCDPz (τ) of S group is obtained；Root
According to formula rCP (τ)+rCDPz (τ)=1, the cross polarization efficiency rCP (τ) of S group is obtained；
C), according to formula IrQCPz S=IrCP(τ)/rCP (τ) obtains the quantitative integration value I of the cross polarization spectral peak of S grouprQCPz S,
Obtain the ratio of molecular radical or blend component in compound；The S group is13C or29Si；
The cross polarization pulse of the rCP spectrogram is ramp shaped pulse, the intersection twice of the pulse train of the rCDPz spectrogram
Between polarization process in channel S for two time intervals be td90 degree of pulses, and cross polarization pulse be ramp shaped pulse.
2. quantitative analysis method according to claim 1, which is characterized in that the compound is13C-1The chemical combination of H system
When object, between the process of cross polarization twice of the pulse train of the rCDPz spectrogram13It is for two time intervals on C-channel
td90 ° of pulses, and cross polarization pulse be ramp shaped pulse.
3. quantitative analysis method according to claim 1, which is characterized in that the compound is13C-1The chemical combination of H system
When object, the pulse train of the rCP spectrogram and rCDPz spectrogram190 ° of pulse widths of H are 3.2 μ s, power 78kHz；13C
90 ° of pulse widths be 3.2 μ s, power 78kHz.
4. quantitative analysis method according to claim 1, which is characterized in that the compound is13C-1The chemical combination of H system
When object, in the rCP spectrogram and the rCDPz spectrogram, the relaxation waiting time before sampling is 3~5s every time.
5. quantitative analysis method according to claim 1, which is characterized in that the t of the pulse train of the rCDPz spectrogrampFor
200~3000 μ s, tdFor 2~100ms, tcpFor 100~500 μ s.
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