CN108445094A - Gaseous ion migration spectrum quickly differentiates method for building up and the application of age of Chinese rice wine - Google Patents
Gaseous ion migration spectrum quickly differentiates method for building up and the application of age of Chinese rice wine Download PDFInfo
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- CN108445094A CN108445094A CN201810125131.0A CN201810125131A CN108445094A CN 108445094 A CN108445094 A CN 108445094A CN 201810125131 A CN201810125131 A CN 201810125131A CN 108445094 A CN108445094 A CN 108445094A
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- 235000019991 rice wine Nutrition 0.000 title claims abstract description 125
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000001228 spectrum Methods 0.000 title claims abstract description 14
- 230000005012 migration Effects 0.000 title claims abstract description 11
- 238000013508 migration Methods 0.000 title claims abstract description 11
- 235000014101 wine Nutrition 0.000 claims abstract description 97
- 238000003860 storage Methods 0.000 claims abstract description 74
- 238000001514 detection method Methods 0.000 claims abstract description 19
- 238000004458 analytical method Methods 0.000 claims abstract description 16
- 230000004069 differentiation Effects 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims description 68
- 239000007789 gas Substances 0.000 claims description 35
- 239000000463 material Substances 0.000 claims description 15
- 230000014759 maintenance of location Effects 0.000 claims description 12
- 238000000513 principal component analysis Methods 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000001871 ion mobility spectroscopy Methods 0.000 claims description 8
- 239000012159 carrier gas Substances 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 5
- 238000010926 purge Methods 0.000 claims description 5
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 claims description 4
- 238000009791 electrochemical migration reaction Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000005070 sampling Methods 0.000 claims description 4
- 229910052722 tritium Inorganic materials 0.000 claims description 4
- 238000010812 external standard method Methods 0.000 claims description 3
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- 230000009466 transformation Effects 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
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- 230000032683 aging Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 241001269238 Data Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000209094 Oryza Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N27/622—Ion mobility spectrometry
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/86—Signal analysis
- G01N30/8675—Evaluation, i.e. decoding of the signal into analytical information
- G01N30/8686—Fingerprinting, e.g. without prior knowledge of the sample components
Abstract
The invention discloses method for building up and applications that a kind of gaseous ion migration spectrum quickly differentiates age of Chinese rice wine.This method carries out gaseous ion migration spectrum detection to the volatile ingredient of yellow rice wine, principal component point analysis is carried out to chromatogram characteristic region, to carry out preliminary quick differentiation to yellow rice wine.It further chooses three kinds of volatile ingredients with significant difference and specific peak intensity analysis is carried out to yellow rice wine different labeled wine storage time, it was found that yellow rice wine different labeled wine storage time can be accurately distinguished, compared to traditional analysis, the method is simple and effective, it takes and greatly shortens, with high sensitivity, can be used for age of Chinese rice wine and whether adulterated live on-line checking.
Description
Technical field
The invention belongs to quickly analyze detection field, it is related to a kind of based on gas phase-ion mobility spectrometry（GC-IMS）Technology knot
Close the method that chemical analysis quickly differentiates age of Chinese rice wine.
Background technology
Yellow rice wine is the brewed wine of Chinese traditional, with beer, grape wine and be known as " three great Gu wine of the world ".Yellow rice wine is one
Grain wine caused by kind is made using rice as raw material, without distillation process, alcohol content is less than 20%, because its Alcohol degree is low, again
It is favored by consumers with very high nutritive value.The quality of yellow rice wine and yellow rice wine traditional aging process and wine storage time are closely related.Wine storage time
Refer to the time limit that the finished product former wine after fermentation is stored in the containers such as wine jar, wine tank.And the wine marked on market sale packaging label
Age is then with the wine storage time weighted average calculation of blended liquor.National standard GB/T 13662-2000 regulation wine storage time is 3 years (or 3 years or more)
Yellow rice wine, should be using top grade wine as base liquor, wherein the base liquor marked wine storage time is not less than 50 %.In general, the Huang newly brewed out
Wine taste is relatively rough, it is fragrant insufficient to hear, and relatively stimulates, and owes soft, and between alcohol molecule being effectively facilitated by " ageing ", wine
The esterification between association and alcohol and acid between smart molecule and hydrone keeps wine flavour strong fragrant, and taste is sweet suitable, soft.So
And the quality of yellow rice wine with the increase in ageing time nor be continuously increased, because the tax perfume (or spice) mechanism of yellow rice wine Chen Xiang is in alcohol
Substance constantly by oxidation reduce and Ester be continuously generated between exist a Best Point, i.e., the best ageing time, but Huang
The best ageing time of wine has not been reported.The phenomenon that advanced age wine is pretended to be with low wine storage time is commonly present in current commercially available yellow rice wine, it is empty
Report wine storage time has not only invaded consumers' rights and interests, has upset yellow rice wine market, has also seriously affected the reputation of yellow rice wine, therefore has urgently found
A method of quick and precisely detecting age of Chinese rice wine.
Traditional wine storage time and provenance is generally carried out by sensory evaluation, the method have to by training and have through
That tests comments wine Shi Caineng reliably to evaluate, and is vulnerable to the influence of extraneous subjective factor.It is more accurate as a result, at present in order to obtain
Frequently with high performance liquid chromatography, gaseous mass spectrum and the analytical technologies knot such as chromatograph joint used, capillary and inductive coupling plasma mass spectrometry
Chemometrics method is closed come the analysis that carries out qualitative and quantitative analysis, experimental results are accurate, but instrumentation process is complicated,
Analysis time is long, is unfavorable for the quick analysis of sample.Also have in the prior art and attempts traditional gas sensor array type electronics
Nose identifies wine storage time, but there are the interference of second alcohol and water, the precision and discriminating accuracy of detection are poor；In addition also have using new
The gas-chromatography type electronic nose of type obtains smell fingerprint image, and utilize master by opposed polarity chromatographic column and double hydrogen flame detectors
Constituent analysis quickly to differentiate age of Chinese rice wine, but its modeling sampling quantity is big, and ingredient is difficult to qualitative.Therefore, a kind of quick letter is explored
Just age of Chinese rice wine detection method is necessary.
Invention content
For overcome the deficiencies in the prior art, the purpose of the present invention is to provide a kind of gaseous ion migration spectrums quickly to differentiate
The method for building up of age of Chinese rice wine and application.
A kind of gaseous ion migration spectrum quickly differentiates the method for building up of age of Chinese rice wine, and steps are as follows：
Step 1 prepares yellow rice wine sample：Prepare different brands yellow rice wine N kind different labeled wine storage time, N is just whole between 1-20
Number, wine sample are within 3 months date of production, and it is the same sample number of repetition that N × M yellow rice wine sample, which is respectively taken 1mL, M, is 3-
Positive integer between 20 is respectively placed in the headspace sampling bottle of 20 mL and seals, and stands 10-30 minutes at room temperature, makes yellow rice wine
Escaping gas be diffused into the headspace of sample injection bottle, to obtain headspace gas；
Step 2, gas phase-ionic migration spectrum detection process：The chromatographic column of gas phase-ion mobility spectrometry combined instrument is integrated capillary
Column MCC-OV-5, ionization source are tritium（3H）, carrier gas and purge gas are 99.999 % high pure nitrogens, set the carrier gas stream of instrument
Speed is 2.0-10.0 mL/min, and drift tube temperature is 40 DEG C, and injector temperature is 80 DEG C, and the analysis time of each sample is
10 min, to obtain the three-dimensional finger print information spectrogram of detection sample；
Step 3, chromatogram characteristic region are chosen：The characteristic value on finger print information collection of illustrative plates obtained using comparison method extraction step two
Region, the comparison method are the change of divergence of color or peak intensity signal, selection in finger print information spectrogram according to property material
Material color changes the chromatogram characteristic region of apparent or peak intensity difference greatly between different yellow rice wine；
Step 4, principal component analysis：Using 19.0 data processing softwares of SPSS to the object of whole characteristic areas selected by step 3
Mass peak intensity data carries out orthogonal transformation and dimensionality reduction, realizes and carries out Fast Classification to N × M yellow rice wine sample wine storage time；
Step 5, age of Chinese rice wine property material are chosen：According to the difference of substance peak intensity signal and the corresponding retention time of substance
And transit time, the 3 kinds of substances that can significantly distinguish different labeled wine storage time yellow rice wine are chosen from the characteristic area of step 3 to yellow rice wine
Wine storage time carries out careful differentiation：
Wherein the gas phase retention time of substance one is 7.80 min, and the ion drift time is 1.078 ms, for further confirming that
5 years or less and 8 years or more mark wine storage time yellow rice wine in principal component analysis, when the substance peak intensity is mark wine less than 0.678 V
5 years ages yellow rice wine below is the yellow rice wine for marking 8 years wine storage time or more higher than 0.850 V；
The gas phase retention time of substance two be 7.25 min, the ion drift time be 1.350 ms, principal component analysis distinguish and
Substance one is distinguished on the basis of 5 years following and 8 years or more mark wine storage time yellow rice wine, and substance two marks wine storage time for confirming 3 years and 5 years
Yellow rice wine, peak intensity be 0.280 V or less be mark wine storage time be 3 years yellow rice wine, peak intensity be 0.416V or more be mark wine storage time 5
The yellow rice wine in year, substance two are also used for confirming that 20 years 8 years, 10 years mark wine storage time yellow rice wine and differentiation mark wine storage time yellow rice wine, peak intensity are
It is mark 8 years wine storage time yellow rice wine when 0.125 V or less, peak intensity is mark 10 years wine storage time yellow rice wine, peak when being 0.148 V-0.226 V
Intensity is 0.246 V or more, to mark 20 years wine storage time yellow rice wine；
The gas phase retention time of substance three is 7.72 min, and the ion drift time is 1.410 ms, in principal component analysis, substance one
On the basis of being distinguished with substance two, for further confirming that mark wine storage time is 10 years and 20 years yellow rice wine, when the substance peak intensity is
0.213 V-0.219 V are to mark the yellow rice wine that wine storage time is 10 years, and peak intensity is that 0.238 V or more is to mark the Huang that wine storage time is 20 years
It is 8 that wine, and mark 8 years wine storage time yellow rice wine for supplementary globe, which is mark wine storage time when the substance peak intensity is 0.200 V or less,
The yellow rice wine in year.
It is to utilize face of the qualitative method by comparing each substance in picture library that the chromatogram characteristic region of the step 3, which is chosen,
Aberration exclusive or peak intensity signal difference, to which the apparent Physical Zone of selection differences is as chromatogram characteristic region；Or it utilizes quantitative
Method is used external standard method, standard curve is established using ethyl acetate as standard substance to determine the absolute of each volatile materials
Content further chooses chromatogram characteristic region according to the absolute content of each substance.
A kind of application of the method for building up, using gaseous ion migration spectrum obtain yellow rice wine sample to be measured substance one,
Substance two, substance three, to differentiate age of Chinese rice wine.
Beneficial effects of the present invention：
Using a kind of simple and quick gas phase-Ion mobility spectrometry combination chemical analysis to yellow rice wine sample different labeled wine storage time
Directly carry out nondestructive analysis so that pass through retention time and Ion transfer time in the case of without knowing specific volatile materials
It determines sample characteristic information area, and combines three kinds of changing from peak intensity for specific substance to carry out substep mirror by principal component analysis
It is fixed, to quickly accurately predict the commercially available wine storage time of different yellow rice wine.This method is easy to operate, sample detection time is short and does not need
Complicated sample pre-treatments have higher application value.
Description of the drawings
Fig. 1 is yellow rice wine sample initial three-dimensional spectrogram；
Fig. 2 is different yellow rice wine sample volatile materials different characteristic area view libraries；
Fig. 3 is sample first principal component and Second principal component, distribution map.
Specific implementation mode
The invention will be further described with example below in conjunction with the accompanying drawings.
A kind of gaseous ion migration spectrum quickly differentiates the method for building up of age of Chinese rice wine：
Step 1, the acquisition of three-dimensional fingerprint chromatogram.It is detection object, totally 15 samples, using Germany with the yellow rice wine different wine storage time
Model FlavourSpec gas phases-ionic migration spectrometer of GAS companies is detection device, obtains the yellow rice wine volatile materials
A series of spectral datas as sample classification information, as shown in Figure 1.
Step 2, the selection in chromatogram characteristic region：The three-dimensional fingerprint chromatogram information of acquisition is visualized by color system
Characteristic component of the apparent region of the different multiple color changes of sample for characterizing the sample is selected afterwards, by forming each region
Spectrogram library determines that a characteristic area for distinguishing different yellow rice wine types, the characteristic area of gained are as shown in Figure 2.
Step 3, principal component analysis：The characteristic area data volume acquired is larger, wherein including some inessential letters
Breath, needs to carry out dimension-reduction treatment to it, to reduce data operation quantity.Using principal component analytical method, pass through the tribute of score matrix
The rate of offering selects best principal component number.The data of gained are analyzed to realize the quick differentiation to yellow rice wine sample, gained
Principal component analysis it is as shown in Figure 3.
Step 4, age of Chinese rice wine otherness detection method are established：It is selected from the region changed with obvious characteristic chosen
It takes three kinds that can distinguish different age of Chinese rice wine and represents sex differernce substance, different age of Chinese rice wine are carried out with careful differentiation, to
Realize the accurate quick differentiation of age of Chinese rice wine.
Embodiment
The present embodiment is detection object to mark the Guyue Longshan yellow rice wine that wine storage time is 3 years, 5 years, 8 years, 10 years and 20 years, is adopted
Amount to the three-dimensional fingerprint chromatogram of 15 yellow rice wine samples under the same conditions to 5 kinds of yellow rice wine with gas phase-ion mobility spectrometry instrument
Information is measured and analyzes, and the chromatographic column of Instrumental is integrated capillary column MCC-OV-5, and ionization source is tritium（3H）, carrier gas
It is high pure nitrogen (99.999 %) with purge gas.Specifically location parameter is：Drift tube temperature is 40 DEG C, injector temperature
It it is 80 DEG C, flow rate of carrier gas is 2.0 mL/min, and the analysis time of each sample is 10 min.
A kind of gaseous ion migration spectrum quickly differentiates the method for building up of age of Chinese rice wine, the specific steps are：
（1）Prepare yellow rice wine sample：Prepare 5 kinds of different wine storage time of the Guyue Longshan yellow rice wine, wine sample is within 3 months date of production
Product, every group of sample detection is in triplicate.15 yellow rice wine samples are respectively taken into 1mL, are respectively placed in close in the headspace sampling bottle of 20 mL
Envelope, and 10-30 minutes are stood at room temperature, so that the escaping gas of yellow rice wine is diffused into the headspace of sample injection bottle, to obtain
Headspace gas, while it is control to set up air.
（2）Gas phase-ionic migration spectrum detection process：The chromatographic column of gas phase-ion mobility spectrometry combined instrument is integrated capillary
Column MCC-OV-5, ionization source are tritium（3H）, carrier gas and purge gas are high pure nitrogen (99.999 %).Before detection starts,
Set the purging cleaning that gas phase-ion mobility spectrometry combined instrument carries out 3 hours, remaining material composition when removing last time detection；
After the completion of cleaning, the 100 μ L of gas that gas phase-ion mobility spectrometry combined instrument extracts in ml headspace bottle are detected, and set the load of instrument
Gas velocity is 2.0 mL/min, and drift tube temperature is 40 DEG C, and injector temperature is 80 DEG C, and the analysis time of each sample is 10
Min, to obtain the three-dimensional finger print information spectrogram of detection sample.
（3）It chooses in chromatogram characteristic region：The characteristic value on finger print information collection of illustrative plates obtained using comparison method extraction step two
Region, the comparison method are the change of divergence of color or peak intensity signal, selection in finger print information spectrogram according to property material
Material color changes the chromatogram characteristic region of apparent or peak intensity difference greatly between different yellow rice wine.
（4）Principal component analysis：Using 19.0 data processing softwares of SPSS to the object of whole characteristic areas selected by step 3
Mass peak intensity data carries out orthogonal transformation and dimensionality reduction, realizes and carries out Fast Classification to 15 yellow rice wine sample wine storage time.
（5）Age of Chinese rice wine otherness detection method is established：According to the difference of substance peak intensity signal and the corresponding guarantor of substance
Stay time and transit time, chosen from the characteristic area of step 3 can significantly distinguish 3 kinds of different labeled wine storage time yellow rice wine it is aobvious
It writes otherness substance and careful differentiation is carried out to age of Chinese rice wine, in conjunction with step 4 to realize the accurate quick differentiation of age of Chinese rice wine.
Concrete analysis is as follows：
The gas phase retention time of substance one is 7.80 min, and the ion drift time is 1.078 ms.It is in 3 year wine storage time of the yellow rice wine
Minimum 0.599 V of peak intensity, and the substance has risen to 0.651V, but difference unobvious in 5 year wine storage time of the yellow rice wine.Thereafter,
Peak intensity of the substance one in 8 years, 10 years, 20 year wine storage time yellow rice wine is respectively 0.927 V, 0.589 V and 0.967 V, peak intensity
54.76 %, 43.41 % and 61.44% are changed respectively.Illustrate using substance one can clearly distinguish 5 years or less with 8 years with
On yellow rice wine, and substance peak intensity in the yellow rice wine 20 years wine storage time of mark is maximum, content highest.It is specifically shown in Tables 1 and 2.
The gas phase retention time of substance two is 7.25 min, and the ion drift time is 1.350 ms.It is in 3 year wine storage time of the yellow rice wine
Peak intensity is 0.278 V, and the substance peak intensity pole occurs and significantly rises in 5 year wine storage time of the yellow rice wine（P<0.01）, rise to
0.42 V, change rate are 51.08 %.And then there is conspicuousness decline in 8 years mark wine storage time of the yellow rice wine peak intensity（0.117
V, P< 0.01）, have dropped 57.92 %.And the substance peak intensity occurs significantly in yellow rice wine mark 10 years wine storage time and 20 years
The rising of property（P< 0.01）, 0.187 V and 0.254 V are risen to respectively.Illustrate substance two in the yellow rice wine 5 years wine storage time of mark
Peak intensity is maximum, content highest, and it can clearly divide into yellow rice wine different labeled wine storage time 3 years, 5 years, 8 years and 10 years or more
Four classes, are specifically shown in Tables 1 and 2.
The gas phase retention time of substance three is 7.72 min, and the ion drift time is 1.410 ms.The substance is in mark wine
Peak intensity is 0.192 V in the yellow rice wine that age is 3 years, and the substance peak intensity is in the yellow rice wine that mark wine storage time is 5 years thereafter
0.221V, peak intensity rise 15.10 %, significant difference occur（P<0.05）.In the yellow rice wine that then mark wine storage time is 8 years
The substance peak intensity declines 0.195 V, compared with mark wine storage time is 3 years yellow rice wine substance peak intensities, significance difference does not occur
It is different.Then, substance peak intensity in the yellow rice wine that mark wine storage time is 10 years and 20 years rises to 0.216 V and 0.24 V respectively,
12.5 % and 25.00 % are risen respectively.Illustrate that the peak intensity in the yellow rice wine that mark wine storage time is 20 years of substance three is maximum, content
Highest.And yellow rice wine different labeled wine storage time can clearly be divided into 3 years and 8 years, 5 years and 10 years, 20 years three classes by No. 10 substances, tool
Body is shown in Tables 1 and 2.
The step（3）Chromatogram characteristic region choose be utilize face of the qualitative method by comparing each substance in picture library
Aberration exclusive or peak intensity signal difference, to which the apparent Physical Zone of selection differences is as chromatogram characteristic region；Or it utilizes quantitative
Method is used external standard method, standard curve is established using ethyl acetate as standard substance to determine the absolute of each volatile materials
Content further chooses chromatogram characteristic region according to the absolute content of each substance.
Above-mentioned embodiment is merely to illustrate the present invention, and wherein this method is also applied for the discriminating of other age of Chinese rice wine.Respectively
The implementation steps etc. of method may be changed, and every equivalents carried out on the basis of the method for the present invention and change
Into should not exclude except protection scope of the present invention.
Claims (3)
1. a kind of gaseous ion migration spectrum quickly differentiates the method for building up of age of Chinese rice wine, which is characterized in that steps are as follows：
Step 1 prepares yellow rice wine sample：Prepare different brands yellow rice wine N kind different labeled wine storage time, N is just whole between 1-20
Number, wine sample are within 3 months date of production, and it is the same sample number of repetition that N × M yellow rice wine sample, which is respectively taken 1mL, M, is 3-
Positive integer between 20 is respectively placed in the headspace sampling bottle of 20 mL and seals, and stands 10-30 minutes at room temperature, makes yellow rice wine
Escaping gas be diffused into the headspace of sample injection bottle, to obtain headspace gas；
Step 2, gas phase-ionic migration spectrum detection process：The chromatographic column of gas phase-ion mobility spectrometry combined instrument is integrated capillary
Column MCC-OV-5, ionization source are tritium（3H）, carrier gas and purge gas are 99.999 % high pure nitrogens, set the carrier gas stream of instrument
Speed is 2.0-10.0 mL/min, and drift tube temperature is 40 DEG C, and injector temperature is 80 DEG C, and the analysis time of each sample is
10 min, to obtain the three-dimensional finger print information spectrogram of detection sample；
Step 3, chromatogram characteristic region are chosen：The characteristic value on finger print information collection of illustrative plates obtained using comparison method extraction step two
Region, the comparison method are the change of divergence of color or peak intensity signal, selection in finger print information spectrogram according to property material
Material color changes the chromatogram characteristic region of apparent or peak intensity difference greatly between different yellow rice wine；
Step 4, principal component analysis：Using 19.0 data processing softwares of SPSS to the object of whole characteristic areas selected by step 3
Mass peak intensity data carries out orthogonal transformation and dimensionality reduction, realizes and carries out Fast Classification to N × M yellow rice wine sample wine storage time；
Step 5, age of Chinese rice wine property material are chosen：According to the difference of substance peak intensity signal and the corresponding retention time of substance
And transit time, the 3 kinds of substances that can significantly distinguish different labeled wine storage time yellow rice wine are chosen from the characteristic area of step 3 to yellow rice wine
Wine storage time carries out careful differentiation：
Wherein the gas phase retention time of substance one is 7.80 min, and the ion drift time is 1.078 ms, for further confirming that
5 years or less and 8 years or more mark wine storage time yellow rice wine in principal component analysis, when the substance peak intensity is mark wine less than 0.678 V
5 years ages yellow rice wine below is the yellow rice wine for marking 8 years wine storage time or more higher than 0.850 V；
The gas phase retention time of substance two be 7.25 min, the ion drift time be 1.350 ms, principal component analysis distinguish and
Substance one is distinguished on the basis of 5 years following and 8 years or more mark wine storage time yellow rice wine, and substance two marks wine storage time for confirming 3 years and 5 years
Yellow rice wine, peak intensity be 0.280 V or less be mark wine storage time be 3 years yellow rice wine, peak intensity be 0.416V or more be mark wine storage time 5
The yellow rice wine in year, substance two are also used for confirming that 20 years 8 years, 10 years mark wine storage time yellow rice wine and differentiation mark wine storage time yellow rice wine, peak intensity are
It is mark 8 years wine storage time yellow rice wine when 0.125 V or less, peak intensity is mark 10 years wine storage time yellow rice wine, peak when being 0.148 V-0.226 V
Intensity is 0.246 V or more, to mark 20 years wine storage time yellow rice wine；
The gas phase retention time of substance three is 7.72 min, and the ion drift time is 1.410 ms, in principal component analysis, substance one
On the basis of being distinguished with substance two, for further confirming that mark wine storage time is 10 years and 20 years yellow rice wine, when the substance peak intensity is
0.213 V-0.219 V are to mark the yellow rice wine that wine storage time is 10 years, and peak intensity is that 0.238 V or more is to mark the Huang that wine storage time is 20 years
It is 8 that wine, and mark 8 years wine storage time yellow rice wine for supplementary globe, which is mark wine storage time when the substance peak intensity is 0.200 V or less,
The yellow rice wine in year.
2. method for building up according to claim 1, it is characterised in that：It is profit that the chromatogram characteristic region of the step 3, which is chosen,
Colour-difference exclusive or peak intensity signal difference with qualitative method by comparing each substance in picture library, to which selection differences are apparent
Physical Zone is as chromatogram characteristic region；Or utilize sizing technique, that is, external standard method is used, is established using ethyl acetate as standard substance
Standard curve determines the absolute content of each volatile materials, further chooses spectrogram spy according to the absolute content of each substance
Levy region.
3. a kind of application of method for building up according to claim 1, it is characterised in that：It is obtained using gaseous ion migration spectrum
Substance one, substance two, the substance three of yellow rice wine sample to be measured, to differentiate age of Chinese rice wine.
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