CN107941837A - The method that low-field nuclear magnetic resonance differentiates donkey-hide gelatin quality - Google Patents
The method that low-field nuclear magnetic resonance differentiates donkey-hide gelatin quality Download PDFInfo
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Abstract
The invention discloses a kind of method that low-field nuclear magnetic resonance differentiates donkey-hide gelatin quality, include the following steps:1) NMR signal collection is carried out under identical parameters for the donkey-hide gelatin sample of different qualities, known standard specimen is analyzed with diffusion coefficient correlation spectrum using lateral relaxation time spectrum and lateral relaxation time, the nuclear magnetic resonance test data difference of different quality donkey-hide gelatin class samples is found out, and reperformance test verification is carried out to same quality donkey-hide gelatin class sample;2) test data is carried out with the quality of donkey-hide gelatin class sample according to the result of analysis corresponding, determines the correlation of donkey-hide gelatin class sample quality and nuclear magnetic resonance data;3) the attribute test database of donkey-hide gelatin class sample is established according to the test data of different quality donkey-hide gelatin class samples, and forms analysis testing standard;4) NMR signal collection is carried out to donkey-hide gelatin class sample to be measured, quality identification is carried out to it by the test data in database.This method test speed is fast, accuracy is high, stability is good, does not destroy sample.
Description
Technical field
It is more particularly to a kind of to differentiate food using low-field nuclear magnetic resonance profile information the invention belongs to medicine Quality Detection field
The method of pseudo- amount is mixed with adulterant donkey-hide gelatin in donkey-hide gelatin and adulterant donkey-hide gelatin, and the edible donkey-hide gelatin of detection.
Technical background
Donkey hide is the drying skin of equine equus donkey Equus asinus L., is the important of manufacture traditional Chinese medicine donkey-hide gelatin
Raw material.《Compendium of Materia Medica》Donkey-hide gelatin is classified as " top grade ", is favored since ancient times as a kind of product of integration of drinking and medicinal herbs be subject to people.Ah
Glue is the medicinal material of typical most exquisite " genuineness " in Chinese medicine, and genuine donkey-hide gelatin must draw the water of Donga, obtain the marvellous of inheritance people
Skill refining forms.Because there is nourishing yin and supplementing blood, adjust immune and improve metabolic balance and other effects, it is classified as by country and supports to produce energetically
Industry.
The production scale of donkey-hide gelatin is larger, and the market sales volume is higher, and more than 30, donkey-hide gelatin industry is flourishing for national donkey-hide gelatin factory
Development.In recent years, with the improvement of living standards, donkey-hide gelatin dosage increases year by year, supply falls short of demand in market.At present, some illegal business
Dealer practises fraud, and adulterates, and pretends to be donkey hide to make fake and forged donkey-hide gelatin with leftover bits and pieces such as ox-hide, pigskins, is gone out with base price
Sell, therefrom reap staggering profits.Not only clinical efficacy is poor for the false glue,medicinal boiled using gelatine, miscellaneous skin etc., and quality can not ensure, and
And it is also possible that intoxicating phenomenon.Only a kind of qualification in 12 kinds of donkey-hide gelatin of CCTV sampling observation in 2014, these malfeasance very disruptives
Donkey-hide gelatin market.For adulterant donkey-hide gelatin existing in the market, discrimination method mainly has observation method of naked eye, near infrared spectroscopy, heat
Analytic approach and HPLC methods etc..The experience dependence of observation method of naked eye is stronger, the TuPu method of near infrared spectroscopy and thermal analysis system
Not strong, HPLC methods are more time-consuming and laborious.
The content of the invention
For above-mentioned technical problem existing in the prior art, the purpose of the invention is to provide a kind of low field nuclear-magnetism to be total to
Shake and differentiate the method for donkey-hide gelatin quality, this method is not only able to the quality measurement suitable for various animal gelatin crude drugs, and tests speed
Degree is fast, accuracy is high, stability is good, does not destroy sample, is that one kind can really apply to actual animal glue class medical material quanlity mirror
In not working, effective detection method.
In order to solve the above technical problems, the technical scheme is that:
A kind of method that low-field nuclear magnetic resonance differentiates donkey-hide gelatin quality, includes the following steps:
1) NMR signal collection is carried out under identical parameters for the donkey-hide gelatin sample of different qualities, utilizes transverse relaxation
Time spectrum and lateral relaxation time analyze known standard specimen with diffusion coefficient correlation spectrum, find out different quality donkey-hide gelatin class samples
The nuclear magnetic resonance test data difference of product, and reperformance test verification is carried out to same quality donkey-hide gelatin class sample;
2) test data is carried out with the quality of donkey-hide gelatin class sample according to the result of analysis corresponding, determines donkey-hide gelatin class sample product
Matter and the correlation of nuclear magnetic resonance data;
3) the attribute test database of donkey-hide gelatin class sample, and shape are established according to the test data of different quality donkey-hide gelatin class samples
Into analysis testing standard;
4) NMR signal collection is carried out to donkey-hide gelatin class sample to be measured, it is carried out by the test data in database
Quality identification.
Compared with traditional measuring method, nuclear magnetic resonance method can keep the integrality of sample, be a kind of nondestructive
Detection means;Operating method is simple and quick, and measurement is accurate, and repeatability is high;Sample need not add solvent, and measurement result is from material
The influence of sample size and appearance luster, and the technology of operator and judgement influence are smaller.
Nuclear magnetic resonance application technology is based primarily upon the measurement of 6 important parameters:δ (chemical shift), (dipole is indirectly mutual by J
Effect), DD (dipole-dipole direct interaction) and T1(longitudinal relaxation time), T2(lateral relaxation time), D (diffusion system
Number).First three parameter mainly reflects the structural information of molecule, is the object of NMR spectrum technical research, and field strength is higher, ginseng
Number is differentiated better;Latter three then mainly reflects the multidate information of molecule, is low-field nuclear magnetic resonance analysis and testing technology research field.
Low-field nuclear magnetic resonance analytical technology is compared to NMR spectrum technology with speed is fast, accuracy is high, one-shot measurement can obtain
Multiple parameters, on sample nondestructive consumption, sample preparation it is simple, on the health and environment of operating personnel without influencing many advantages, such as.
Preferably, in step 1), the preparation method of the lateral relaxation time spectrum is:By CPMG sequence to certified products donkey-hide gelatin
Transverse relaxation analysis is carried out with donkey-hide gelatin inferior, and is calculated using one-dimensional anti-Laplacian algorithm as lateral relaxation time spectrum inverting
Method, draws the relaxation time spectrum of certified products donkey-hide gelatin and donkey-hide gelatin inferior, if the relaxation time spectrum of the two is not exclusively overlapping, to them
Aggregate sample carry out transverse relaxation analysis, and draw relaxation time spectrum.
Still more preferably, if the relaxation time spectrum of the relaxation time spectrum of certified products donkey-hide gelatin and donkey-hide gelatin inferior is nonoverlapping
Part exists in aggregate sample, and proportional with the content of donkey-hide gelatin inferior in aggregate sample, then selects the part of relaxation time spectrum
As donkey-hide gelatin quartile length standard.
Still further preferably, the nonoverlapping part of relaxation time spectrum of the relaxation time spectrum of certified products donkey-hide gelatin and donkey-hide gelatin inferior
The ratio of the overall signal of signal and biased sample is Y, and the content of certified products donkey-hide gelatin or donkey-hide gelatin inferior in aggregate sample is X, is passed through
Change the value of X, analysis obtains corresponding Y value, carries out once linear and is fitted to obtain fitting a straight line Y=kX+b, obtains in aggregate sample
The content and the relation of relaxation time spectrum corresponding part signal of certified products donkey-hide gelatin or donkey-hide gelatin inferior.
Donkey-hide gelatin inferior can be divided into new donkey-hide gelatin, oxhide gelatin, pseudo- donkey-hide gelatin etc., between the relaxation time spectrum of different donkey-hide gelatin inferior
Have nonoverlapping place, by analyzing different donkey-hide gelatin samples inferior and certified products donkey-hide gelatin sample, can find out certified products donkey-hide gelatin and
The corresponding spectrogram of difference poor quality donkey-hide gelatin, when the donkey-hide gelatin inferior that different content is filled in certified products donkey-hide gelatin, or addition are different types of
During donkey-hide gelatin inferior, appropriate section the changing of pests occurrence rule of relaxation time spectrum can be caused, can using the regular change of this kind
Judge the quality of donkey-hide gelatin.
Still further preferably, the certified products donkey-hide gelatin in sample is calculated using the Y value obtained in calibration line and sample analysis
Or donkey-hide gelatin content X inferior, so as to find out the difference of different quality donkey-hide gelatin class samples and establish donkey-hide gelatin class attribute test data with this
Storehouse.
Calibration line is the linear equation of certified products donkey-hide gelatin content in unknown sample.
Still more preferably, if the relaxation time spectrum of the relaxation time spectrum of certified products donkey-hide gelatin and donkey-hide gelatin inferior is nonoverlapping
Partly exist in aggregate sample but disproportionate with the content of donkey-hide gelatin inferior in aggregate sample, then aligned by PGSE-CPMG sequences
Product donkey-hide gelatin, donkey-hide gelatin inferior and their aggregate sample carry out lateral relaxation time and diffusion coefficient correlation analysis, and using two dimension
Anti- Laplacian algorithm as lateral relaxation time and diffusion coefficient correlation spectrum inversion algorithm, draw certified products donkey-hide gelatin, inferior Ah
The correlation of the lateral relaxation time of glue and aggregate sample and diffusion coefficient is composed, find in the spectrum completely self-contained certified products donkey-hide gelatin with it is bad
Matter donkey-hide gelatin component is as donkey-hide gelatin class quality identification standard.
Preferably, in step 1), the reperformance test is the donkey-hide gelatin class using the method in step 1) to same quality
Sample carries out the test analysis of more than six times.
To understand the error of multiple test data, reflect so as to understand low-field nuclear magnetic resonance method in animal glue class medical material quanlity
False Rate in fixed.
Preferably, in step 1), while alternating temperature is carried out to certified products donkey-hide gelatin sample, donkey-hide gelatin sample inferior and both aggregate samples
Test.Temperature variation testing refers to be heated up in donkey-hide gelatin class sample or cooling test, to draw temperature to different donkey-hide gelatin class sample product
The influence of matter, and correlation is found out, so that it is determined that donkey-hide gelatin class sample quality and the correlation of temperature.
Application of the above method in donkey-hide gelatin quality is differentiated.
CPMG sequence involved in the method for the present invention is the conventional nuclear-magnetism pulse train for transverse relaxation analysis;And
PGSE-CPMG sequences are then the conventional nuclear-magnetism pulse train for transverse relaxation and diffusion correlation analysis;At the same time in the present invention
The one-dimensional anti-Laplacian algorithm being related to is the conventional algorithm for relaxation time spectruminversion;And the anti-Laplce's algorithm of two dimension
It is the conventional algorithm for lateral relaxation time and the spectrum inverting of diffusion coefficient correlation.
It is an advantage of the invention that:
1st, the method for the present invention can guarantee that fast and accurately carries out nuclear magnetic resonance spectroscopy test to animal glue class sample, so as to
Understand the quality of animal glue class sample, be the edible offer quality assurance of people so as to fast and accurately differentiate glue inferior.
2nd, compared with traditional method, the method for the present invention not only increases detection speed, and the accuracy that detects and steady
It is qualitative also to greatly improve.
3rd, without adding other chemical reagent and complicated pre-treatment to sample, sample does not produce pollution with destroying, sample preparation side
Just, the integrality of sample is ensured.
4th, the method for the present invention is fast for the detection speed of animal glue class sample quality, time-consuming short, and whole test substantially can be 5
Completed within minute, favorable reproducibility.
5th, measurement result from sample of material size and appearance luster influence.
6th, it is easily achieved the scene discriminating of animal glue class quality.
Brief description of the drawings
The accompanying drawings which form a part of this application are used for providing further understanding of the present application, and the application's shows
Meaning property embodiment and its explanation are used to explain the application, do not form the improper restriction to the application.
Fig. 1 is pure donkey-hide gelatin, new donkey-hide gelatin, oxhide gelatin, the relaxation time spectrum of donkey-hide gelatin sample inferior;
Fig. 2 is the multicomponent relaxation time spectrum for mixing new donkey-hide gelatin (0%-100%) known to puppet;
Fig. 3 is the T for mixing new donkey-hide gelatin (0%-100%) sample known to puppet21Peak initial time and the situation of change for mixing pseudo- amount;
Fig. 4 is the S for mixing new donkey-hide gelatin (0%-100%) sample known to puppet21Peak area percent and the situation of change for mixing pseudo- amount;
Fig. 5 is the multicomponent relaxation time spectrum for mixing oxhide gelatin known to puppet (0%-100%);
Fig. 6 is the T for mixing oxhide gelatin known to puppet (0%-100%) sample23Peak initial time and the situation of change for mixing pseudo- amount;
Fig. 7 is the S for mixing oxhide gelatin known to puppet (0%-100%) sample23Peak area percent and the situation of change for mixing pseudo- amount;
Fig. 8 is the multicomponent relaxation time spectrum for mixing glue (0%-100%) inferior known to puppet;
Fig. 9 is the T for mixing glue (0%-100%) sample inferior known to puppet23Peak initial time and the situation of change for mixing pseudo- amount;
Figure 10 is the S for mixing glue (0%-100%) sample inferior known to puppet23Peak area percent and the change feelings for mixing pseudo- amount
Condition.
Embodiment
It is noted that described further below is all illustrative, it is intended to provides further instruction to the application.It is unless another
Indicate, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singulative
It is also intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " bag
Include " when, it indicates existing characteristics, step, operation, device, component and/or combinations thereof.
Embodiment:The invention discloses a kind of method that low-field nuclear magnetic resonance differentiates donkey-hide gelatin quality, its specific implementation step
It is as follows:
Test objective:
1st, the NMR signal difference of different quality glue is tested;
2nd, different amounts of pseudo- glue is added in certified products donkey-hide gelatin, detects signal difference, and finds out and pseudo- glue is added in certified products donkey-hide gelatin
The test method of content;
3rd, the test model of nuclear-magnetism and donkey-hide gelatin quality is established.
Fig. 1 is pure donkey-hide gelatin, new donkey-hide gelatin, oxhide gelatin, the relaxation time spectrum of donkey-hide gelatin sample inferior, it is seen then that these four donkey-hide gelatin samples
There are three peaks in the relaxation time spectrum of product, be from left to right followed successively by T21、T22、T23。
Embodiment 1
6 colloid samples altogether, including pure donkey-hide gelatin sample, in addition 5 samples are to be separately added into certified products donkey-hide gelatin sample
20%th, the new donkey-hide gelatin of 40%, 60%, 80%, 100% mass fraction is made.The quality all same of all colloid samples is simultaneously put into
In same type of nuclear magnetic resonance test tube.
After the T2 relaxation times that 6 samples are measured using CPMG sequence, then using one-dimensional anti-Laplacian algorithm as horizontal
To relaxation time spectruminversion algorithm, draw the relaxation time spectrum of each sample, see Fig. 2~Fig. 4;It can be seen from the figure that pure donkey-hide gelatin
Sample is with new donkey-hide gelatin sample main difference is that T21The difference of peak initial time and peak-to-peak signal amount, when different toward addition in pure donkey-hide gelatin
During the new donkey-hide gelatin of content, with the increase of addition, T21Peak initial time and peak area are also gradually increasing.
The relaxation data combination Principal Component Analysis of certified products donkey-hide gelatin and adulterated donkey-hide gelatin and new donkey-hide gelatin is analyzed, is established
Regression analysis curve, so as to establish donkey-hide gelatin attribute test database.Finally using the database established to unknown donkey-hide gelatin sample
Carry out Quality Detection.
Embodiment 2
6 colloid samples altogether, including pure donkey-hide gelatin sample, in addition 5 samples are to be separately added into certified products donkey-hide gelatin sample
20%th, the oxhide gelatin of 40%, 60%, 80%, 100% mass fraction is made.The quality all same of all colloid samples is simultaneously put into
In same type of nuclear magnetic resonance test tube.
After the T2 relaxation times that 6 samples are measured using CPMG sequence, then using one-dimensional anti-Laplacian algorithm as horizontal
To relaxation time spectruminversion algorithm, draw the relaxation time spectrum of each sample, see Fig. 5~Fig. 7;It can be seen from the figure that pure donkey-hide gelatin
Sample is with oxhide gelatin sample main difference is that T23The difference of peak initial time and peak-to-peak signal amount, when different toward addition in pure donkey-hide gelatin
During the oxhide gelatin of content, T23Peak initial time reach, with the increase of addition, T23Peak initial time changes little but peak face
Product gradually increase.
The relaxation data combination Principal Component Analysis of certified products donkey-hide gelatin and adulterated donkey-hide gelatin and oxhide gelatin is analyzed, is established
Regression analysis curve, so as to establish donkey-hide gelatin attribute test database.Finally using the database established to unknown donkey-hide gelatin sample
Carry out Quality Detection.
Embodiment 3
6 colloid samples altogether, including pure donkey-hide gelatin sample, in addition 5 samples are to be separately added into certified products donkey-hide gelatin sample
10%th, the glue inferior of 30%, 50%, 70%, 100% mass fraction is made.The quality all same of all colloid samples is simultaneously put into
In same type of nuclear magnetic resonance test tube.
After the T2 relaxation times that 6 samples are measured using CPMG sequence, then using one-dimensional anti-Laplacian algorithm as horizontal
To relaxation time spectruminversion algorithm, draw the relaxation time spectrum of each sample, see Fig. 8~Figure 10;It can be seen from the figure that pure donkey-hide gelatin
Sample is with glue sample inferior main difference is that T23The difference of peak initial time and peak-to-peak signal amount, when different toward addition in pure donkey-hide gelatin
During the glue inferior of content, T23Peak initial time reach, with the increase of addition, T23Peak initial time is gradually successively decreased, when for
During 100% glue inferior, initial time is most short, T23Peak peak area gradually increases.
The relaxation data combination Principal Component Analysis of certified products donkey-hide gelatin and adulterated donkey-hide gelatin and glue inferior is analyzed, is established
Regression analysis curve, so as to establish donkey-hide gelatin attribute test database.Finally using the database established to unknown donkey-hide gelatin sample
Carry out Quality Detection.
Above-mentioned experiment can prove that low field nuclear-magnetism test method can be measured and adulterant and bad is added in certified products donkey-hide gelatin
Quartile length after matter donkey-hide gelatin, and adulterant and the content of donkey-hide gelatin inferior can be added in accurate test sample.From test data with
From the point of view of test result, low-field nuclear magnetic resonance differentiates that the method for donkey-hide gelatin quality is a kind of very quickly and easily test method, and energy
Accurate test data is obtained, a kind of detection method of quick nondestructive is provided for donkey-hide gelatin attributional analysis and Quality Detection.
The foregoing is merely the preferred embodiment of the application, the application is not limited to, for the skill of this area
For art personnel, the application can have various modifications and variations.It is all within spirit herein and principle, made any repair
Change, equivalent substitution, improvement etc., should be included within the protection domain of the application.
Claims (9)
1. a kind of method that low-field nuclear magnetic resonance differentiates donkey-hide gelatin quality, it is characterised in that:Include the following steps:
1) NMR signal collection is carried out under identical parameters for the donkey-hide gelatin sample of different qualities, utilizes lateral relaxation time
Spectrum and lateral relaxation time analyze known standard specimen with diffusion coefficient correlation spectrum, find out different quality donkey-hide gelatin class samples
Nuclear magnetic resonance test data is distinguished, and carries out reperformance test verification to same quality donkey-hide gelatin class sample;
2) test data is carried out with the quality of donkey-hide gelatin class sample according to the result of analysis it is corresponding, determine donkey-hide gelatin class sample quality with
The correlation of nuclear magnetic resonance data;
3) the attribute test database of donkey-hide gelatin class sample is established according to the test data of different quality donkey-hide gelatin class samples, and is formed and divided
Analyse testing standard;
4) NMR signal collection is carried out to donkey-hide gelatin class sample to be measured, quality is carried out to it by the test data in database
Identification.
2. according to the method described in claim 1, it is characterized in that:In step 1), the acquisition side of the lateral relaxation time spectrum
Method is:Transverse relaxation analysis is carried out to certified products donkey-hide gelatin and donkey-hide gelatin inferior by CPMG sequence, and is calculated using one-dimensional anti-Laplce
Method composes inversion algorithm as lateral relaxation time, the relaxation time spectrum of certified products donkey-hide gelatin and donkey-hide gelatin inferior is drawn, if the relaxation of the two
Henan time spectrum is not exclusively overlapping, then carries out transverse relaxation analysis to their aggregate sample, and draw relaxation time spectrum.
3. according to the method described in claim 2, it is characterized in that:If the relaxation time spectrum of certified products donkey-hide gelatin and donkey-hide gelatin inferior
The nonoverlapping part of relaxation time spectrum exists in aggregate sample, and proportional with the content of donkey-hide gelatin inferior in aggregate sample, then selects
The part of relaxation time spectrum is as donkey-hide gelatin quartile length standard.
4. according to the method described in claim 3, it is characterized in that:The relaxation of the relaxation time spectrum of certified products donkey-hide gelatin and donkey-hide gelatin inferior
The ratio of the overall signal of the nonoverlapping part signal of time spectrum and biased sample is Y, certified products donkey-hide gelatin or poor quality in aggregate sample
The content of donkey-hide gelatin is X, and by varying the value of X, analysis obtains corresponding Y value, carries out once linear and is fitted to obtain fitting a straight line Y=
KX+b, obtains the content and the relation of relaxation time spectrum corresponding part signal of certified products donkey-hide gelatin or donkey-hide gelatin inferior in aggregate sample.
5. according to the method described in claim 4, it is characterized in that:Utilize the Y value meter obtained in calibration line and sample analysis
The certified products donkey-hide gelatin in sample or donkey-hide gelatin content X inferior are calculated, so as to find out the difference of different quality donkey-hide gelatin class samples and be established with this
Donkey-hide gelatin class attribute test database.
6. according to the method described in claim 2, it is characterized in that:If the relaxation time spectrum of certified products donkey-hide gelatin and donkey-hide gelatin inferior
The nonoverlapping part of relaxation time spectrum exists but disproportionate with the content of donkey-hide gelatin inferior in aggregate sample in aggregate sample, then passes through
It is related to diffusion coefficient that PGSE-CPMG sequence pair certified products donkey-hide gelatin, donkey-hide gelatin inferior and their aggregate sample carry out lateral relaxation time
Property analysis, and obtained using the anti-Laplacian algorithm of two dimension as lateral relaxation time and diffusion coefficient correlation spectrum inversion algorithm
The correlation of the lateral relaxation time and diffusion coefficient that go out certified products donkey-hide gelatin, donkey-hide gelatin inferior and aggregate sample is composed, and is found in the spectrum completely
Independent certified products donkey-hide gelatin is with donkey-hide gelatin component inferior as donkey-hide gelatin class quality identification standard.
7. according to the method described in claim 1, it is characterized in that:In step 1), the reperformance test is using step 1)
In method the test analysis of more than six times is carried out to the donkey-hide gelatin class sample of same quality.
8. according to the method described in claim 1, it is characterized in that:In step 1), while to certified products donkey-hide gelatin sample, donkey-hide gelatin inferior
Sample and both aggregate samples carry out temperature variation testing.
9. application of any the methods of claim 1-8 in donkey-hide gelatin quality is differentiated.
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CN101975788A (en) * | 2010-09-01 | 2011-02-16 | 苏州纽迈电子科技有限公司 | Method for identifying quality of edible oil with low-field NMR (Nuclear Magnetic Resonance) |
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