CN102645502A - Method for detecting age of yellow rice wine by using high-speed gas chromatography type electronic nose fingerprint analysis system - Google Patents

Abstract

The invention discloses a method for identifying the age of yellow rice wine by using a fast gas chromatography type electronic nose analysis system, that is, firstly, after establishing a yellow rice wine age identification model, then shaking the yellow rice wine sample to be tested, taking 5mL and placing it in a fast gas chromatography type electronic nose analysis system. In the 20mL airtight sample bottle of the nasal analysis system, the olfactory fingerprint information of the rice wine sample to be tested was collected by the fast gas chromatography electronic nose analysis system, and the chromatographic olfactory fingerprint of the rice wine sample to be tested was obtained, and the chromatographic olfactory fingerprint of the rice wine sample to be tested was obtained. The principal component analysis was carried out to form the characteristic olfactory fingerprint vector, which was then transferred to the established rice wine age identification model to obtain the wine age of the yellow rice wine sample to be tested. A method for identifying the age of yellow rice wine using a fast gas chromatography-type electronic nose analysis system of the present invention has high identification accuracy and simple operation. new method.

Description

A method for identifying the age of rice wine using a fast gas chromatography-type electronic nose fingerprint analysis system

technical field

The invention belongs to the field of food analysis, in particular to a method for identifying the age of rice wine by using a fast gas chromatography type electronic nose fingerprint analysis system.

Background technique

Yellow rice wine is famous for its mildness, mellowness, low alcohol content, nutrition and health care, and has gradually been recognized, accepted and liked by more and more consumers. The newly brewed rice wine has a strong spicy taste, rough taste and insufficient aroma; after aging, the association, esterification reaction, redox reaction, condensation reaction, etc. of the internal components occur, and the taste becomes more mellow and soft. , plump, fresh, and comfortable aroma. Yet, there is the phenomenon of posing as high-aged wine with low-aged wine in commercially available yellow rice wine. Falsely reporting the age of wine not only violates the rights of consumers, but also disrupts the rice wine market. Therefore, there is an urgent need for a detection method to quickly identify the age of yellow rice wine.

Aroma is an important sensory evaluation index of rice wine, and traditionally, sensory evaluation can be used to identify the age of wine. However, sensory evaluation has subjective factors, which will produce different results depending on factors such as the evaluator's physical condition, emotional changes, and discrimination ability. Since the 1990s, electronic nose has been gradually introduced into the sensory evaluation of drinking wine. An electronic nose is an electronic system that uses the response curve of an array of gas sensors to identify odors. Different from conventional analytical instruments, the electronic nose does not obtain the qualitative and quantitative results of the various components of the tested sample, but the overall information about the flavor of the sample, that is, "fingerprint data". They can not only conduct simple comparative analysis of the aroma information of different samples, but also establish a database by collecting standard sample information, and use chemometrics to identify and analyze unknown samples.

The traditional electronic nose is a gas sensor array type, and the mass spectrometry electronic nose and fast gas chromatography electronic nose are new electronic noses. Due to the interference of water and alcohol in drinking wine, the response signal of the gas sensor array electronic nose is unstable. The fast gas chromatographic electronic nose uses an ultra-fast chromatographic olfactory fingerprint analyzer instead of a gas sensor array, which can be better used for the olfactory flavor analysis of beverage wine.

At present, the identification of rice wine age is mostly carried out by high-performance liquid chromatography, gas chromatography-mass spectrometry or capillary electrophoresis combined with chemometrics. These methods have the disadvantages of complicated operation, cumbersome pretreatment and unsuitable for rapid analysis. ;Near-infrared spectroscopy analysis technology is also applied in the field of rice wine wine age identification, which is a rapid non-destructive detection method, but near-infrared spectroscopy has a low response to volatile aroma substances in rice wine that are closely related to the wine age but have a low content. .

Contents of the invention

The purpose of the present invention is to provide a method for identifying the age of yellow rice wine using a fast gas chromatography-type electronic nose fingerprint analysis system in order to solve the above technical problems. The method has the advantages of high identification accuracy, simple operation, fast identification, and low detection cost. features.

Technical scheme of the present invention

A method for identifying the age of yellow rice wine using a fast gas chromatography-type electronic nose fingerprint analysis system, characterized in that it comprises the following steps:

(1) The establishment of the rice wine age identification model includes the following steps:

①. Collect yellow rice wine with definite wine age as the standard sample set for building the model;

②. Shake each standard sample well, take 5mL and place it in a 20mL airtight sample bottle of the fast gas chromatography electronic nose analysis system;

③. Collect the olfactory fingerprint information of the yellow rice wine standard sample set with a fast gas chromatography type electronic nose fingerprint analysis system, and obtain the chromatographic olfactory fingerprint of the yellow rice wine standard sample set;

④. Perform principal component analysis on the chromatographic olfactory fingerprint of the yellow rice wine standard sample set to obtain the characteristic olfactory fingerprint vector;

5. Adopt the discriminant analysis method to establish the yellow rice wine age identification model based on the characteristic olfactory fingerprint vector of step ④ of the yellow rice wine standard sample set;

(2) Shake the rice wine sample to be tested, take 5mL and place it in a 20mL airtight sample bottle of the fast gas chromatography electronic nose fingerprint analysis system;

(3) Using the fast gas chromatography electronic nose fingerprint analysis system to collect the olfactory fingerprint information of the rice wine sample to be tested, and obtain the chromatographic olfactory fingerprint of the rice wine sample to be tested;

(4) Perform principal component analysis on the chromatographic olfactory fingerprint of the rice wine sample to be tested to form a characteristic olfactory fingerprint vector;

(5) Transfer the characteristic olfactory fingerprint vector of the rice wine sample to be tested obtained in step (4) into the rice wine age identification model established in step (1), and predict the wine age of the rice wine sample to be tested.

Beneficial effects of the present invention

A method for identifying the age of yellow rice wine by using a fast gas chromatography-type electronic nose fingerprint analysis system of the present invention, because the gas chromatography-type electronic nose fingerprint analysis system is used, compared with the traditional sensory evaluation method, the detection time spent is shorter; Compared with traditional gas chromatography-mass spectrometry and other methods, the detection efficiency is improved and the detection cost is reduced; compared with the traditional gas sensor array electronic nose, the anti-interference ability to alcohol and water has been greatly improved. And improved detection precision and identification accuracy.

In addition, the method for identifying the age of rice wine by using a fast gas chromatography-type electronic nose fingerprint analysis system of the present invention has the characteristics of high identification accuracy, simple operation, and high identification efficiency.

Description of drawings

Figure 1. The chromatographic olfactory fingerprint of the 1-year-old yellow rice wine standard sample, the left picture is the spectrum of DB 5 gas chromatographic column, and the right picture is the spectrum of DB 1701;

Figure 2. The chromatographic olfactory fingerprint of the standard sample of 3-year-old rice wine. The left picture is the spectrum of DB 5 gas chromatography column, and the right picture is the spectrum of DB 1701;

Figure 3. The chromatographic olfactory fingerprint of the 5-year-old rice wine standard sample. The left picture is the spectrum of DB 5 gas chromatography column, and the right picture is the spectrum of DB 1701;

Figure 4. Principal component diagrams of standard sample sets of 1-year-old, 3-year-old and 5-year-old rice wine, in which PC1 represents principal component 1, and PC2 represents principal component 2;

Fig. 5, the discriminant analysis classification diagram of 1 year old and 3 year old yellow rice wine standard sample set;

Fig. 6, the discriminant analysis classification diagram of 1 year old and 5 year old yellow rice wine standard sample set;

Figure 7. Discriminant analysis classification diagrams of standard sample sets of 3-year-old and 5-year-old rice wine.

Detailed ways

The present invention will be further described below through specific embodiments in conjunction with the accompanying drawings, but the present invention is not limited.

The yellow rice wine standard samples used in the present invention are different batches of yellow rice wine of the same variety with definite wine age produced by Shanghai Jinfeng Wine Industry Co., Ltd. Among them, 13 bottles of 1-year-old rice wine samples, 12 bottles of 3-year-old rice wine samples and 7 bottles of 5-year-old rice wine samples.

The rice wine sample to be tested in the present invention is the 5-year-old rice wine produced by Shanghai Jinfeng Wine Co., Ltd.

The electronic nose fingerprint analysis system used in the present invention is the Heracles electronic nose fingerprint analysis system of French Alpha M.O.S company; The Heracles electronic nose fingerprint analysis system is composed of a Heracles ultra-fast chromatographic olfactory fingerprint analyzer host, capillary columns with different polarities ( DB 5 and DB 1701, DB5 is polar and DB1701 is non-polar), dihydrogen flame detector, ultra-fast temperature ramp, thermal desorption setup, heated inlet, autosampler and chemometric software and so on.

The working parameters used by the Heracles electronic nose fingerprint analysis system to collect the olfactory fingerprint information of standard samples of rice wine with different ages are: injection volume is 1500 μL, injection speed is 270 μL/s, sample retention time is 8 s, and the temperature of the injection port is 180 °C. The sampling temperature was 43 °C, the purge was 15 s, the injection time was 40 s, the injection duration was 2 s, the heating rate was 2 °C/s, the final time was 200 s, and the final retention time was 10 s.

For the discriminant analysis method used in the present invention, see Liang Yizeng, Yu Ruqin. Analytical Chemistry Handbook (Tenth Volume) Chemometrics. Beijing: Chemical Industry Press, 2000 (Second Edition), 332~333.

Example 1

A method for identifying the age of yellow rice wine using a fast gas chromatography-type electronic nose fingerprint analysis system, characterized in that it comprises the following steps:

(1) The establishment of the rice wine age identification model includes the following steps:

①. Collect 13 bottles of 1-year-old rice wine samples, 12 bottles of 3-year-old rice wine samples and 7 bottles of 5-year-old rice wine samples as the standard sample set for building the model;

②. Shake each standard sample in step ①, take 5mL and place it in a 20mL airtight sample bottle of the fast gas chromatography electronic nose analysis system;

③. Collect the olfactory fingerprint information of the rice wine standard sample set in the 20mL airtight sample bottle in step ② with the fast gas chromatography type electronic nose fingerprint analysis system, and obtain the chromatographic olfactory fingerprint of the yellow rice wine standard sample set, wherein Fig. 1 and Fig. 2 Figure 3 and Figure 3 are the chromatographic olfactory fingerprints of standard samples of 1-year-old, 3-year-old and 5-year-old rice wine respectively. The left picture in each figure is the spectrum of DB 5 gas chromatographic column, and the right picture is the spectrum of DB 1701 ;

It can be seen from Fig. 1, Fig. 2 and Fig. 3 that the two chromatographic columns with different polarities, DB 5 and DB 1701, have different peak peak times and peak numbers; However, the peak areas are different, and the number of peaks collected by the DB 5 chromatographic column of the 5-year-old sample is less than that of the 1-year-old and 3-year-old samples;

The working parameters used by the Heracles electronic nose fingerprint analysis system to collect the olfactory fingerprint information of standard samples of rice wine of different ages are: injection volume 1500 μL, injection speed 270 μL/s, sample retention time 8 s, inlet temperature 180 °C, sampling The temperature is 43°C, the purge is 15s, the injection time is 40s, the injection duration is 2s, the heating rate is 2°C/s, the final time is 200s, and the final retention time is 10s;

4. Carry out principal component analysis to the chromatographic olfactory fingerprint of the yellow rice wine standard sample set obtained in step ③, and obtain the characteristic olfactory fingerprint vector. The principal component diagrams of the 1-year-old, 3-year-old and 5-year-old yellow rice wine standard sample sets are shown in Figure 4 shown;

It can be seen from Figure 4 that: principal component 1 explained 77.898% of the difference between samples, and principal component 2 explained 12.594% of the difference; 1-year-old, 3-year-old and 5-year-old rice wine samples were well distinguished;

⑤. Using the discriminant analysis method to establish the yellow rice wine age identification model based on the characteristic olfactory fingerprint vector of the yellow rice wine standard sample set, Figure 5, Figure 6, and Figure 7 are respectively 1 year old and 3 year old, 1 year old and 5 year old, Discriminant analysis classification diagram of 3-year-old and 5-year-old rice wine standard sample sets;

It can be seen from Figure 5 and Figure 6 that: 1-year old and 3-year-old, 1-year-old and 5-year-old can be distinguished in pairs. It can be seen from Figure 7 that a 3-year-old sample is identified as 5 aged samples;

Among them, 13, 11 and 7 samples from the 1-year-old, 3-year-old and 5-year-old samples were identified correctly, and the correct identification rates were 100%, 91.67% and 100%, respectively. The performance of the alcohol age identification model is robust;

(2) Shake the 5-year-old rice wine sample produced by Shanghai Jinfeng Wine Co., Ltd. to be tested, and take 5mL into a 20mL airtight sample bottle of the fast gas chromatography-type electronic nose fingerprint analysis system;

(3) Using the fast gas chromatography electronic nose fingerprint analysis system to collect the olfactory fingerprint information of the rice wine sample to be tested, and obtain the chromatographic olfactory fingerprint of the rice wine sample to be tested;

The working parameters used by the Heracles electronic nose fingerprint analysis system to collect the olfactory fingerprint information of the rice wine sample to be tested are as follows: the injection volume is 1500 μL, the injection speed is 270 μL/s, the sample retention time is 8 s, the inlet temperature is 180 °C, and the sampling temperature is 43°C, purge for 15s, injection time 40s, injection duration 2s, heating rate 2°C/s, final time 200s, final retention time 10s;

(4) Perform principal component analysis on the chromatographic olfactory fingerprint of the rice wine sample to be tested to form a characteristic olfactory fingerprint vector;

(5) Transfer the characteristic olfactory fingerprint vector of the yellow rice wine sample obtained in step (4) into the yellow rice wine age identification model established in step (1), and obtain the wine age of the yellow rice wine sample to be tested as 5 years.

However, the sensory evaluation method (GB/T 13662-2000) was used to judge that the wine age of the yellow rice wine sample to be tested was 5 years.

In summary, the fast gas chromatography-type electronic nose of the present invention can be better used to identify the age of yellow rice wine, and the method of using the fast gas chromatography electronic nose of the present invention to identify the age of yellow rice wine is different from traditional sensory evaluation methods, etc. Compared with the method, the method has the advantages of simple operation, short detection time and high identification accuracy, and is a new method for identifying the age of yellow rice wine.

The above content is only a basic description of the concept of the present invention, and any equivalent transformation made according to the technical solution of the present invention shall belong to the protection scope of the present invention.

Claims (3)

1. a method utilizing fast gas chromatography type electronic nose fingerprint analysis system to identify yellow rice wine wine age, it is characterized in that comprising the steps: (1) The establishment of the rice wine age identification model includes the following steps: ①. Collect yellow rice wine with definite wine age as the standard sample set for building the model; ②. Shake each standard sample well, take 5mL and place it in a 20mL airtight sample bottle of the fast gas chromatography electronic nose fingerprint analysis system; ③. Collect the olfactory fingerprint information of the yellow rice wine standard sample set with a fast gas chromatography type electronic nose fingerprint analysis system, and obtain the chromatographic olfactory fingerprint of the yellow rice wine standard sample set; ④. Perform principal component analysis on the chromatographic olfactory fingerprint of the yellow rice wine standard sample set to obtain the characteristic olfactory fingerprint vector; 5. Adopt the discriminant analysis method to establish the yellow rice wine age identification model based on the characteristic olfactory fingerprint vector of step ④ of the yellow rice wine standard sample set; (2) Shake the rice wine sample to be tested, take 5mL and place it in a 20mL airtight sample bottle of the fast gas chromatography electronic nose fingerprint analysis system; (3) Using the fast gas chromatography electronic nose fingerprint analysis system to collect the olfactory fingerprint information of the rice wine sample to be tested, and obtain the chromatographic olfactory fingerprint of the rice wine sample to be tested; (4) Perform principal component analysis on the chromatographic olfactory fingerprint of the rice wine sample to be tested to form a characteristic olfactory fingerprint vector; (5) Transfer the characteristic olfactory fingerprint vector of the rice wine sample to be tested obtained in step (4) into the rice wine age identification model established in step (1) to obtain the wine age of the rice wine sample to be tested. 2. A method for identifying the age of yellow rice wine using a fast gas chromatography-type electronic nose fingerprint analysis system as claimed in claim 1, characterized in that ③ in step (1) and the fast gas chromatography described in step (3) The type electronic nose analysis system is the Heracles electronic nose fingerprint analysis system of the French company Alpha M.O.S. 3. A method for identifying the age of rice wine using a fast gas chromatography-type electronic nose fingerprint analysis system as claimed in claim 2, characterized in that ③ in step (1) and the method described in step (3) use fast gas chromatography When the chromatographic electronic nose fingerprint analysis system collects the olfactory fingerprint information of the rice wine standard sample set, the working parameters used by the Heracles electronic nose fingerprint analysis system are: injection volume 1500μL, injection speed 270μL/s, sample retention time 8s, injection port The temperature is 180°C, the sampling temperature is 43°C, the purge is 15s, the injection time is 40s, the injection duration is 2s, the heating rate is 2°C/s, the final time is 200s, and the final retention time is 10s.

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