CN108445094B - Establishment method and application for quickly identifying wine age of yellow wine by gas-phase ion mobility spectrometry - Google Patents
Establishment method and application for quickly identifying wine age of yellow wine by gas-phase ion mobility spectrometry Download PDFInfo
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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
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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
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
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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
- G01N30/86—Signal analysis
- G01N30/8675—Evaluation, i.e. decoding of the signal into analytical information
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Abstract
The invention discloses an establishing method and application for quickly identifying the age of yellow wine by gas phase ion mobility spectrometry. The method carries out gas phase-ion mobility spectrometry detection on volatile components of the yellow wine, and carries out principal component analysis on a spectrogram characteristic region, thereby carrying out preliminary and rapid differentiation on the yellow wine. And further selecting three volatile components with significant differences to perform specific peak intensity analysis on the yellow rice wine with different marked wine ages, and finding out that the yellow rice wine with different marked wine ages can be accurately distinguished.
Description
Technical Field
The invention belongs to the field of rapid analysis and detection, and relates to a method for rapidly identifying the age of yellow wine based on a gas phase-ion mobility spectrometry (GC-IMS) technology combined with a chemical analysis method.
Background
Yellow wine is the traditional brewed wine of Chinese nation, and is called as 'three ancient wines in the world' together with beer and wine. The yellow wine is grain wine brewed by using rice as a raw material, does not undergo a distillation process, has the alcohol content lower than 20 percent, has high nutritional value due to low alcohol content, and is highly popular with consumers. The quality of the yellow wine is closely related to the aging process and the wine age of the yellow wine. The wine age refers to the age of the fermented finished wine in a container such as a wine jar, a wine jar and the like. And the wine age marked on the marketing package label is calculated according to the wine age weighted average of blended wine. The yellow wine with the wine age of 3 years (or more than 3 years) specified by the national standard GB/T13662-2000 should take super wine as base wine, wherein the base wine with the marked wine age is not less than 50%. Generally speaking, the newly brewed yellow wine has rough taste, insufficient smell, stimulation and softness, and the aging can effectively promote the association among alcohol molecules, the association between the alcohol molecules and water molecules and the esterification between alcohol and acid, so that the wine has strong fragrance and sweet, smooth and soft taste. However, the quality of the yellow wine is not increased along with the increase of the aging year, because the aroma endowing mechanism of the yellow wine is that an optimal point exists between the continuous oxidation reduction of alcohol substances and the continuous generation of ester substances, namely the optimal aging year, but the optimal aging year of the yellow wine is not reported yet. The phenomenon that the old wine is impersonated by the low wine age often exists in the current commercially available yellow wine, the false wine age not only infringes the rights of consumers and disturbs the market of the yellow wine, but also seriously influences the reputation of the yellow wine, so that a method for quickly and accurately detecting the wine age of the yellow wine is urgently needed to be found.
Traditional wine age and origin analysis is generally performed through sensory evaluation, and the method can be reliably evaluated by trained and experienced wine evaluators and is easily influenced by external subjective factors. In order to obtain a more accurate result, qualitative and quantitative analysis is usually performed by combining analysis technologies such as high performance liquid chromatography, gas mass spectrometry and chromatography, capillary and inductively coupled plasma mass spectrometry and the like with a chemometric method at present, the obtained experimental result is accurate, but the operation process of an instrument is complex, the analysis time is long, and the rapid analysis of a sample is not facilitated. In the prior art, the traditional gas sensor array type electronic nose is tried to identify the wine age, but the interference of ethanol and water exists, and the detection precision and the identification accuracy are poor; in addition, a novel gas chromatography type electronic nose is used, an olfactory fingerprint image is obtained through chromatographic columns with different polarities and a double-hydrogen flame detector, and the age of the yellow wine is rapidly identified by utilizing principal component analysis, but the modeling sampling quantity is large, and the components are difficult to determine. Therefore, it is necessary to find a rapid and simple method for detecting the age of yellow wine.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide an establishing method and application for rapidly identifying the wine age of yellow wine by using gas-phase ion mobility spectrometry.
An establishment method for rapidly identifying the age of yellow wine by gas phase ion mobility spectrometry comprises the following steps:
step one, preparing a yellow wine sample: preparing N types of yellow wine with different brands and different marked wine ages, wherein N is a positive integer between 1 and 20, wine samples are all within 3 months of the factory date, taking 1mL of each of NxM yellow wine samples, M is the repetition frequency of the same sample and is a positive integer between 3 and 20, respectively placing the N xM yellow wine samples into 20 mL headspace sample bottles for sealing, and standing for 10 to 30 minutes at room temperature to enable volatile gas of the yellow wine to diffuse into headspace of the sample bottles, thereby obtaining headspace gas;
step two, the gas phase-ion mobility spectrometry detection process: the gas-ion mobility spectrometry combined instrument has integrated capillary column MCC-OV-5 as chromatographic column and tritium (tritium)3H) Carrier gas and purge gas are both high-purity nitrogen with the purity of 99.999 percent, the flow rate of the carrier gas of the instrument is set to be 2.0-10.0 mL/min, the temperature of a drift tube is 40 ℃, the temperature of a sample injector is 80 ℃, and the analysis time of each sample is 10min, so that a three-dimensional fingerprint information spectrogram of a detected sample is obtained;
step three, selecting a spectrogram characteristic region: extracting a characteristic value area on the fingerprint information spectrogram obtained in the second step by adopting a comparison method, wherein the comparison method is to select a spectrogram characteristic area with obvious substance color change or large peak intensity difference among different yellow rice wines according to the color difference change or peak intensity signal of the characteristic substance in the fingerprint information spectrogram;
step four, analyzing main components: performing orthogonal transformation and dimensionality reduction on the material peak intensity data of all the characteristic regions selected in the step three by using SPSS 19.0 data processing software to realize rapid classification of the wine ages of the NxM yellow wine samples;
step five, selecting yellow wine age characteristic substances: and (3) selecting 3 substances capable of obviously distinguishing yellow wine with different labeled wine ages from the characteristic region in the third step according to the difference of the substance peak intensity signals and the retention time and migration time corresponding to the substances to carefully distinguish the wine ages of the yellow wine:
wherein the gas phase retention time of the first substance is 7.80 min, the ion drift time is 1.078 ms, and the first substance is used for further confirming that yellow wine with the marked wine age of less than 5 years and more than 8 years is marked in the main component analysis, and yellow wine with the marked wine age of less than 5 years is marked when the peak intensity of the first substance is lower than 0.678V, and yellow wine with the marked wine age of more than 8 years is marked when the peak intensity of the first substance is higher than 0.850V;
the gas phase retention time of a second substance is 7.25 min, the ion drift time is 1.350 ms, on the basis of analyzing and distinguishing yellow rice wine labeled with the wine age below 5 years and above 8 years from a first substance, the second substance is used for confirming yellow rice wine labeled with the wine age above 3 years and 5 years, the yellow rice wine labeled with the wine age below 0.280V is the yellow rice wine labeled with the wine age below 3 years, the yellow rice wine labeled with the wine age above 0.416V is the yellow rice wine labeled with the wine age above 5 years, the second substance is also used for confirming yellow rice wine labeled with the wine age above 8 years and 10 years and distinguishing yellow rice wine labeled with the wine age above 20 years, the yellow rice wine labeled with the wine age below 0.125V is the yellow rice wine labeled with the wine age below 8, the yellow rice wine labeled with the wine age above 10 is the peak intensity between 0.148V and 0.226V, and the yellow rice wine;
and the gas phase retention time of the third substance is 7.72 min, the ion drift time is 1.410 ms, and the method is used for further confirming yellow wine with the wine age of 10 years and 20 years on the basis of main component analysis and distinguishing of the first substance and the second substance, wherein the yellow wine with the wine age of 10 years is marked when the substance has the peak intensity of 0.213V-0.219V, the yellow wine with the wine age of 20 years is marked when the substance has the peak intensity of more than 0.238V, the yellow wine with the wine age of 8 years is marked for auxiliary distinguishing, and the yellow wine with the wine age of 8 years is marked when the substance has the peak intensity of less than 0.200V.
Selecting a spectrogram characteristic region in the third step by comparing the color difference or the peak intensity signal difference of each substance in a picture library by using a qualitative method so as to select a substance region with obvious difference as the spectrogram characteristic region; or determining the absolute content of each volatile substance by using a quantitative method, namely an external standard method and establishing a standard curve by using ethyl acetate as a standard substance, and further selecting a spectrogram characteristic region according to the absolute content of each substance.
The application of the establishing method is to obtain the first substance, the second substance and the third substance of a yellow wine sample to be detected by adopting gas phase ion mobility spectrometry so as to identify the age of the yellow wine.
The invention has the beneficial effects that:
the method is characterized in that a simple and rapid gas phase-ion migration spectrum technology is combined with chemical analysis to directly perform nondestructive analysis on yellow wine samples with different marked wine ages, so that a sample characteristic information area is determined through retention time and ion migration time under the condition that specific volatile substances are not needed, and the main component analysis is combined with the peak separation intensity change of three specific substances to perform step-by-step identification, so that the commercial wine ages of different yellow wines can be rapidly and accurately predicted. The method is simple to operate, short in sample detection time, free of complex sample pretreatment and high in application value.
Drawings
FIG. 1 is an original three-dimensional spectrogram of a yellow wine sample;
FIG. 2 is a library of different characteristics of volatile substances in different yellow wine samples;
FIG. 3 is a graph showing the distribution of the first principal component and the second principal component of a sample.
Detailed Description
The invention is further illustrated with reference to the following figures and examples.
An establishment method for rapidly identifying the age of yellow wine by gas phase ion mobility spectrometry comprises the following steps:
step one, collecting a three-dimensional fingerprint spectrogram. Yellow rice wine with different wine ages is taken as a detection object, 15 samples are totally adopted, a FlavourSpec GAS phase-ion mobility spectrometer of the Germany GAS company is taken as detection equipment, and a series of spectrogram data of the volatile substances of the yellow rice wine are obtained as sample classification information, as shown in figure 1.
Selecting a spectrogram characteristic region: the obtained three-dimensional fingerprint spectrogram information is visualized through a color system, then a plurality of color change obvious areas of different samples are selected to represent the characteristic components of the samples, a spectrogram library of each area is formed to determine a characteristic area for distinguishing different yellow wine types, and the obtained characteristic area is shown in figure 2.
Step three, principal component analysis: the obtained feature region has a large data volume, which contains some unimportant information, and needs to be subjected to dimension reduction processing to reduce the data operation amount. And selecting the optimal number of the principal components by the contribution rate of the scoring matrix by adopting a principal component analysis method. The data obtained were analyzed to achieve rapid differentiation of yellow wine samples, and the principal component analysis obtained is shown in fig. 3.
Step four, establishing a method for detecting the difference of the wine ages of the yellow rice wine: three representative difference substances capable of distinguishing different yellow wine ages are selected from the selected areas with obvious characteristic changes, and the different yellow wine ages are carefully distinguished, so that the yellow wine ages are accurately and quickly distinguished.
Examples
In this embodiment, the guyue longshan yellow wine labeled with the wine ages of 3 years, 5 years, 8 years, 10 years and 20 years is used as a detection object, a gas phase-ion mobility spectrometry instrument is adopted to measure and analyze three-dimensional fingerprint spectrogram information of 5 types of yellow wine and 15 types of yellow wine samples in total under the same condition, wherein a chromatographic column of the instrument is an integrated capillary column MCC-OV-5, and an ionization source is tritium (tritium: (tritium) ((ii) ((iii))3H) Both the carrier gas and purge gas were high purity nitrogen (99.999%). The specific measurement parameters are as follows: the drift tube temperature was 40 deg.C, the injector temperature was 80 deg.C, the carrier gas flow rate was 2.0 mL/min, and the analysis time for each sample was 10 min.
An establishment method for rapidly identifying the age of yellow wine by gas phase ion mobility spectrometry comprises the following specific steps:
(1) preparing a yellow wine sample: preparing 5 kinds of Guyue Longshan yellow wine with different wine ages, wherein wine samples are all products with the date of leaving factory within 3 months, and detecting each group of samples is repeated for three times. Taking 1mL of each 15 yellow wine samples, respectively placing the samples in 20 mL headspace sample bottles, sealing, standing at room temperature for 10-30 minutes to enable volatile gas of the yellow wine to diffuse into headspace of the sample bottles so as to obtain headspace gas, and setting air as a reference.
(2) Gas phase-ion mobility spectrometry detection process: the gas-ion mobility spectrometry combined instrument has integrated capillary column MCC-OV-5 as chromatographic column and tritium (tritium)3H) Both the carrier gas and purge gas were high purity nitrogen (99.999%). Before the detection is started, a gas phase-ion mobility spectrometry instrument is set to perform purging and cleaning for 3 hours so as to remove the residual substance components in the last detection; after the cleaning is finished, a gas phase-ion mobility spectrometry instrument is used for extracting 100 mu of gas in the headspace bottleAnd L, detecting, wherein the flow rate of carrier gas of the instrument is set to be 2.0 mL/min, the temperature of the drift tube is set to be 40 ℃, the temperature of the sample injector is set to be 80 ℃, and the analysis time of each sample is set to be 10min, so that the three-dimensional fingerprint information spectrogram of the detected sample is obtained.
(3) Selecting a spectrogram characteristic region: and D, extracting the characteristic value area on the fingerprint information spectrogram obtained in the step two by adopting a comparison method, wherein the comparison method is to select a spectrogram characteristic area with obvious substance color change or large peak intensity difference among different yellow rice wines according to the color difference change or peak intensity signal of the characteristic substance in the fingerprint information spectrogram.
(4) And (3) main component analysis: and D, performing orthogonal transformation and dimensionality reduction on the material peak intensity data of all the characteristic regions selected in the step three by using SPSS 19.0 data processing software to realize rapid classification of the wine ages of the 15 yellow wine samples.
(5) The establishment of the method for detecting the difference of the wine ages of the yellow rice wine comprises the following steps: and (3) selecting 3 remarkably different substances capable of remarkably distinguishing yellow wine with different labeled wine ages from the characteristic region in the third step according to the difference of the substance peak intensity signals and the retention time and migration time corresponding to the substances to finely distinguish the wine ages of the yellow wine, and combining the fourth step to realize the precise and rapid distinguishing of the wine ages of the yellow wine. The specific analysis is as follows:
the gas phase retention time of substance one was 7.80 min and the ion drift time was 1.078 ms. The peak intensity of the compound in yellow wine with the age of 3 years is 0.599V at least, while the peak intensity of the compound in yellow wine with the age of 5 years is increased to 0.651V, but the difference is not obvious. Thereafter, the peak intensities of substance one in 8-year, 10-year and 20-year old yellow wine were 0.927V, 0.589V and 0.967V, respectively, and the peak intensities were changed by 54.76%, 43.41% and 61.44%, respectively. The yellow wine with the age of less than 5 years and the yellow wine with the age of more than 8 years can be clearly distinguished by using the first substance, and the substance has the highest peak intensity and the highest content in the yellow wine marked with the age of 20 years. See in particular tables 1 and 2.
The gas phase retention time of substance two was 7.25 min, and the ion drift time was 1.350 ms. The peak intensity of the substance in yellow wine aged 3 years is 0.278V, while the peak intensity of the substance in yellow wine aged 5 years is remarkably increased (P < 0.01), the peak intensity is increased to 0.42V, and the change rate is 51.08%. The peak intensity of yellow wine marked with wine age at the next 8 years is remarkably reduced (0.117V, P < 0.01), and is reduced by 57.92%. The peak intensity of the substance is obviously increased in yellow wine marked for 10 years and 20 years (P < 0.01), and is respectively increased to 0.187V and 0.254V. The second substance has the highest peak intensity and the highest content in yellow wine labeled for 5 years, and can clearly distinguish yellow wine labeled for different wine ages into four types of 3 years, 5 years, 8 years and more than ten years, which are shown in tables 1 and 2.
The gas phase retention time of substance three was 7.72 min, and the ion drift time was 1.410 ms. The peak intensity of the substance in yellow wine marked with the wine age of 3 years is 0.192V, and the peak intensity of the substance in yellow wine marked with the wine age of 5 years is 0.221V, the peak intensity is increased by 15.10%, and a significant difference (P < 0.05) appears. The peak intensity of the substance in yellow wine labeled as 8 years old was then reduced by 0.195V, and no significant difference was observed compared to the peak intensity of the substance in yellow wine labeled as 3 years old. Subsequently, the peak intensity of the material rose to 0.216V and 0.24V, respectively, 12.5% and 25.00% in yellow wine labeled as 10 years old and 20 years old, respectively. The third substance has the highest peak intensity and the highest content in yellow wine marked with the wine age of 20 years. And the substance No. 10 can clearly distinguish yellow rice wine with different marked wine ages into three types of 3 years, 8 years, 5 years, 10 years and 20 years, which are shown in tables 1 and 2.
Selecting the spectrogram feature region in the step (3) by comparing the color difference or the peak intensity signal difference of each substance in a picture library by using a qualitative method so as to select a substance region with obvious difference as the spectrogram feature region; or determining the absolute content of each volatile substance by using a quantitative method, namely an external standard method and establishing a standard curve by using ethyl acetate as a standard substance, and further selecting a spectrogram characteristic region according to the absolute content of each substance.
The above examples are only used to illustrate the present invention, wherein the method is also suitable for the identification of the wine age of other yellow wine. The implementation steps of each method and the like can be changed, and the equivalent change and the improvement on the basis of the method of the invention are not excluded from the protection scope of the invention.
Claims (3)
1. An establishment method for rapidly identifying the age of yellow wine by gas phase ion mobility spectrometry is characterized by comprising the following steps:
step one, preparing a yellow wine sample: preparing N types of yellow wine with different brands and different marked wine ages, wherein N is a positive integer between 1 and 20, wine samples are all within 3 months of the factory date, taking 1mL of each of NxM yellow wine samples, M is the repetition frequency of the same sample and is a positive integer between 3 and 20, respectively placing the N xM yellow wine samples into 20 mL headspace sample bottles for sealing, and standing for 10 to 30 minutes at room temperature to enable volatile gas of the yellow wine to diffuse into headspace of the sample bottles, thereby obtaining headspace gas;
step two, the gas phase-ion mobility spectrometry detection process: the gas-ion mobility spectrometry combined instrument has integrated capillary column MCC-OV-5 as chromatographic column and tritium (tritium)3H) Carrier gas and purge gas are both high-purity nitrogen with the purity of 99.999 percent, the flow rate of the carrier gas of the instrument is set to be 2.0-10.0 mL/min, the temperature of a drift tube is 40 ℃, the temperature of a sample injector is 80 ℃, and the analysis time of each sample is 10min, so that a three-dimensional fingerprint information spectrogram of a detected sample is obtained;
step three, selecting a spectrogram characteristic region: extracting a characteristic value area on the fingerprint information spectrogram obtained in the second step by adopting a comparison method, wherein the comparison method is to select a spectrogram characteristic area with obvious substance color change or large peak intensity difference among different yellow rice wines according to the color difference change or peak intensity signal of the characteristic substance in the fingerprint information spectrogram;
step four, analyzing main components: performing orthogonal transformation and dimensionality reduction on the material peak intensity data of all the characteristic regions selected in the step three by using SPSS 19.0 data processing software to realize rapid classification of the wine ages of the NxM yellow wine samples;
step five, selecting yellow wine age characteristic substances: and (3) selecting 3 substances capable of obviously distinguishing yellow wine with different labeled wine ages from the characteristic region in the third step according to the difference of the substance peak intensity signals and the retention time and migration time corresponding to the substances to carefully distinguish the wine ages of the yellow wine:
wherein the gas phase retention time of the first substance is 7.80 min, the ion drift time is 1.078 ms, and the first substance is used for further confirming that yellow wine with the marked wine age of less than 5 years and more than 8 years is marked in the main component analysis, and yellow wine with the marked wine age of less than 5 years is marked when the peak intensity of the first substance is lower than 0.678V, and yellow wine with the marked wine age of more than 8 years is marked when the peak intensity of the first substance is higher than 0.850V;
the gas phase retention time of a second substance is 7.25 min, the ion drift time is 1.350 ms, on the basis of analyzing and distinguishing yellow rice wine labeled with the wine age below 5 years and above 8 years from a first substance, the second substance is used for confirming yellow rice wine labeled with the wine age above 3 years and 5 years, the yellow rice wine labeled with the wine age below 0.280V is the yellow rice wine labeled with the wine age below 3 years, the yellow rice wine labeled with the wine age above 0.416V is the yellow rice wine labeled with the wine age above 5 years, the second substance is also used for confirming yellow rice wine labeled with the wine age above 8 years and 10 years and distinguishing yellow rice wine labeled with the wine age above 20 years, the yellow rice wine labeled with the wine age below 0.125V is the yellow rice wine labeled with the wine age below 8, the yellow rice wine labeled with the wine age above 10 is the peak intensity between 0.148V and 0.226V, and the yellow rice wine;
and the gas phase retention time of the third substance is 7.72 min, the ion drift time is 1.410 ms, and the method is used for further confirming yellow wine with the wine age of 10 years and 20 years on the basis of main component analysis and distinguishing of the first substance and the second substance, wherein the yellow wine with the wine age of 10 years is marked when the substance has the peak intensity of 0.213V-0.219V, the yellow wine with the wine age of 20 years is marked when the substance has the peak intensity of more than 0.238V, the yellow wine with the wine age of 8 years is marked for auxiliary distinguishing, and the yellow wine with the wine age of 8 years is marked when the substance has the peak intensity of less than 0.200V.
2. The method of establishing according to claim 1, wherein: selecting a spectrogram characteristic region in the third step by comparing the color difference or the peak intensity signal difference of each substance in a picture library by using a qualitative method so as to select a substance region with obvious difference as the spectrogram characteristic region; or determining the absolute content of each volatile substance by using a quantitative method, namely an external standard method and establishing a standard curve by using ethyl acetate as a standard substance, and further selecting a spectrogram characteristic region according to the absolute content of each substance.
3. Use of the set-up method according to claim 1, characterized in that: and (3) obtaining a substance I, a substance II and a substance III of the yellow wine sample to be detected by adopting gas phase ion mobility spectrometry so as to identify the age of the yellow wine.
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