Quality identification method of Yuling paste based on ultrafast gas phase electronic nose technology

Abstract

The invention relates to a method for distinguishing the quality of Yuling paste based on an ultra-fast gas phase electronic nose technology, comprising: step one, homogenizing the Yuling paste after being treated with different steaming times to obtain a plurality of Yuling paste test samples; step two, using the ultra-fast gas phase electronic nose technology to perform odor analysis and detection on each Yuling paste test sample to obtain electronic nose gas chromatography information of each Yuling paste test sample, and obtaining an odor fingerprint of the Yuling paste according to all the electronic nose gas chromatography information; step three, using a PCA multivariate statistical method to screen differential chromatographic peaks in the odor fingerprint, performing qualitative material analysis on the differential chromatographic peaks to obtain a plurality of main differential volatile odor substances, selecting several of the main differential volatile odor substances as target characteristic differential volatile odor substances according to preset screening conditions, and determining an optimal steaming time range; and step four, establishing a discriminant factor analysis model DFA according to the electronic nose gas chromatography information.

Description

Technical Field

[0001] The invention relates to the field of traditional healthy food with medicinal and edible properties, and in particular to a method for distinguishing the quality of Yuling paste based on ultra-fast gas phase electronic nose technology, and in particular to a method for distinguishing the quality of Yuling paste for improving nutritional anemia based on ultra-fast gas phase electronic nose technology. Background Art

[0002] With the development of society and the improvement of people's living standards, people's pace of life is getting faster and faster, and the pressure of life is getting greater and greater. Overeating, overdrinking, working overtime and staying up late, and overthinking have become the norm, which easily leads to symptoms of insufficient qi and blood, manifested as fatigue, weakness in the limbs, yellow complexion, insomnia, mental depression, cold hands and feet, irregular menstruation, etc. Traditional Chinese medicine attaches great importance to the role of food in disease prevention and treatment, so there is a traditional Chinese medicine diet therapy view that "people rely on food for nourishment, but improper diet may harm their health" and "you should know the taste of food".

[0003] Yuling Paste is an ancient Chinese medicine recipe for dietary therapy. It was first recorded in the "Suixiju Diet" by Wang Mengying, a famous Chinese medicine expert in the Qing Dynasty. "Yuling Paste, also known as Daishen Paste. Peel the longan and put it in a bamboo tube porcelain bowl. Add one liang of meat to each and one qian of white sugar. If the body is hot, add American ginseng slices, the same as the amount of sugar. Cover the bowl with a layer of silk cotton and steam it in a rice cooker every day for a hundred times. For those who are weak, old and weak, and have no phlegm and fire, and have loose stools, take one spoonful of it with boiling water every time. It greatly replenishes qi and blood. It is more effective than ginseng and astragalus. It is especially effective for women who are about to give birth. "Yuling Paste not only has the functions of replenishing qi and blood, invigorating qi, calming the mind, and improving sleep, but also has the function of regulating the spleen and stomach. It is suitable for people with symptoms such as weakness, fatigue, palpitations, loss of appetite, blood deficiency and qi weakness after illness, weakness in the limbs, dizziness, sallow complexion, weak women, listlessness, poor appetite, lack of energy, easy fatigue, thinness due to consumptive fatigue, insomnia and dreaminess, dizziness, fatigue, lack of body fluid and dry mouth.

[0004] Although the raw material ratio and steaming method of Yuling Paste are recorded in the ancient recipe, Wang Mengying recorded in "Suixiju Food Recipe" that it should be steamed on rice every day for 100 times, but there is no specific time and relevant basis. Therefore, the Yuling Paste currently sold on the market believes that the longer the steaming time, the better, and even claims that it is steamed for 120 hours. In the preparation method of Yuling Paste in the patent application number CN110771885A "A Yuling Paste for Replenishing Qi and Blood and Its Preparation Method", the steaming time of the mixed system is 40-56h; in the patent application number CN113491311A, "A Yuling Paste", the steaming method of Yuling Paste is to steam for 1 hour each time, and steam for 9 times in total, so the total steaming time is 9h. In the patent application number CN107822012A "Yuling Paste Preparation Method", the steaming method of Yuling Paste is to steam with rice soup steam for 40 hours. Whether it is the Yuling paste steamed for 120 hours on the market, or the above-mentioned patent steaming for 40-56 hours, 9 hours and 40 hours, the selection of the steaming time has no scientific basis. At the same time, whether it is the ancient recipe or the Yuling paste products currently sold on the market and the Yuling paste products with the published invention patent, there is no quality judgment method. Therefore, determining the optimal steaming time of Yuling paste and finding a quality judgment method for Yuling paste are of great significance to the quality control of Yuling paste. Summary of the invention

[0005] In order to solve one or more of the above-mentioned technical problems, the present invention provides a method for distinguishing the quality of Yuling paste based on ultra-fast gas phase electronic nose technology, utilizes the ultra-fast gas phase electronic nose technology, establishes the quality distinguishing method of Yuling paste based on ultra-fast gas phase electronic nose technology, and studies the steaming process of Yuling paste, thereby providing a scientific basis for the steaming process and quality control of Yuling paste.

[0006] The technical solution of the present invention to solve the above technical problems is as follows: a method for distinguishing the quality of Yuling paste based on ultra-fast gas phase electronic nose technology, comprising the following steps:

[0007] Step 1, homogenizing the Yuling paste after being processed for different steaming times to obtain multiple Yuling paste test samples;

[0008] Step 2, using ultra-fast gas phase electronic nose technology to perform odor analysis on each Yuling paste test sample, obtain electronic nose gas chromatography information of each Yuling paste test sample, and obtain the odor fingerprint of Yuling paste based on all electronic nose gas chromatography information;

[0009] Step 3, using PCA multivariate statistical method to screen the differential chromatographic peaks in the odor fingerprint, performing qualitative material analysis on the differential chromatographic peaks to obtain a variety of main differential volatile odor substances, and selecting several of the main differential volatile odor substances as target signature differential volatile odor substances according to preset screening conditions;

[0010] Analyze the contents of multiple target characteristic volatile odor substances at different steaming times, determine the optimal steaming time range, and use the optimal steaming time range as a quality control indicator to control the quality of Yuling Paste;

[0011] Step 4, establishing a discriminant factor analysis model DFA according to the electronic nose gas chromatography information of each Yuling paste test sample with different steaming time;

[0012] The ultra-fast gas phase electronic nose technology was used to conduct odor analysis on the unknown Ling ointment test samples, and the electronic nose gas chromatography information of the unknown Yuling ointment samples was obtained;

[0013] The electronic nose gas chromatography information of the unknown Yuling paste sample is projected onto the discriminant factor analysis model DFA to obtain the steaming time of the unknown Yuling paste sample, and to determine whether the steaming time of the unknown Yuling paste sample falls within the optimal steaming time range. When determining whether the steaming time of the unknown Yuling paste sample falls within the optimal steaming time range, if yes, it indicates that the quality is reliable, and if no, the quality is unreliable.

[0014] The beneficial effect of the present invention is as follows: the present invention applies ultrafast gas phase electronic nose technology to the quality judgment of Yuling paste, analyzes the odor fingerprints of Yuling paste detection samples at different steaming times, determines the main differential volatile compounds in Yuling paste at different steaming times, determines the optimal steaming time of Yuling paste in combination with the efficacy test for improving nutritional anemia, takes several volatile odor substances with the highest content in Yuling paste within the optimal steaming time range of the main differential volatile compounds as target characteristic volatile odor substances, establishes a statistical analysis model, takes the optimal steaming time range as a quality control indicator, and realizes the quality control of Yuling paste.

[0015] Based on the above technical solution, the present invention can also be improved as follows.

[0016] Furthermore, the use of the PCA multivariate statistical method to screen the differential chromatographic peaks in the odor fingerprint spectrum includes: using the PCA multivariate statistical software corresponding to the PCA multivariate statistical method to screen out chromatographic peaks with a discrimination ability greater than 0.95 and a peak area greater than 1000 from the screened odor fingerprint spectrum as differential chromatographic peaks.

[0017] The beneficial effects of adopting the above further scheme are: these chromatographic peaks have good separation effect, are easy to identify, have high resolution accuracy, and are the main odor components of Yuling Paste.

[0018] Furthermore, the qualitative analysis of the differential chromatographic peaks is performed to obtain a variety of differential volatile odor substances, including: searching through the Arochembase database, combining the retention index corresponding to the differential chromatographic peaks, analyzing the odor differences of Yuling paste test samples with different steaming times, and screening to obtain a variety of main differential volatile odor substances, wherein the retention time of the differential chromatographic peaks is converted to obtain the retention index corresponding to the differential chromatographic peaks.

[0019] Furthermore, according to preset screening conditions, several major differential volatile odor substances are selected as target signature differential volatile odor substances, and the contents of multiple target signature differential volatile odor substances with different steaming times are analyzed to determine the optimal steaming time, including: conducting an efficacy test on improving nutritional anemia on Yuling paste test samples with different steaming times to screen out target Yuling paste test samples with significant efficacy in improving nutritional anemia, determining the optimal steaming time range based on the steaming time of the target Yuling paste test samples with significant efficacy in improving nutritional anemia, and then screening multiple major differential volatile odor substances in these target Yuling paste test samples relative to other steaming times, and screening the several major differential volatile odor substances with the highest content in the optimal steaming time range as target signature differential volatile odor substances.

[0020] Furthermore, the various differentially volatile odor substances include 2-methylbutanol, trans-2-pentenal, n-pentanol, cis-2-hexen-1-ol, n-octanal, methyl propionate, ethanol, 3-hexanol, γ-terpinene, monomethylfuranone, isobutyraldehyde, crotonaldehyde, 2,3-pentanedione, furfural, 5-methylfuranaldehyde, isovaleric acid, and sorbital.

[0021] Furthermore, the target characteristic differential volatile odor substances include isobutylaldehyde, crotonaldehyde, 2,3-pentanedione, furfural, and 5-methylfuranaldehyde.

[0022] Furthermore, it also includes:

[0023] According to the electronic nose gas chromatography information of each Yuling paste test sample with different steaming time, the discriminant factor analysis model DFA was established;

[0024] The ultra-fast gas phase electronic nose technology was used to conduct odor analysis on the unknown Ling ointment test samples, and the electronic nose gas chromatography information of the unknown Yuling ointment samples was obtained;

[0025] The electronic nose gas chromatography information of the unknown Yuling paste sample was projected onto the discriminant factor analysis model DFA to obtain the steaming time of the unknown Yuling paste sample.

[0026] Furthermore, by conducting an efficacy test on improving nutritional anemia on Yuling paste samples with different steaming times, it was determined that the Yuling paste samples obtained with the optimal steaming time had a significant effect in improving nutritional anemia.

[0027] Further, in step 2, the detection conditions for the odor analysis detection of Yuling paste detection samples with different steaming times using an ultra-fast gas phase electronic nose include: the Yuling paste detection sample loaded into the injection bottle is 1-5g, the sample injection volume is 500-5000mL, the sample shaking incubation temperature is 30-80°C, the sample shaking incubation time is 10-40min, the injection port temperature is 200-280°C, the injection duration is 20-50s, the initial temperature of the trap is 40-60°C, and the final temperature of the trap is 240-260°C;

[0028] The chromatographic column heating program of the ultra-fast gas phase electronic nose is as follows: the initial column temperature is 40-60°C, lasting for 10-30s, heating to 120-150°C at 0.5-1°C / s, and heating to 250°C at 1-3°C / s.

[0029] Further, in step 1, the Yuling paste sample is steamed, including:

[0030] Step 1, prepare Yuling ointment sample for use;

[0031] Step 2, evenly spread the washed and soaked rice on the steamer, and form rice steam during steaming;

[0032] Step 3, placing the container containing the Yuling paste sample on a steamer evenly spread with rice, and spreading gauze on the container, starting steaming, and starting timing after the steamer is steamed;

[0033] Step 4, stop steaming every 10 hours, wait for the steamed Yuling paste sample to cool down, replace the rice according to step 2, and repeat step 3 for steaming. The total steaming time is 10-120 hours. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 Fingerprints of multiple Yuling paste test samples on a MXT-5 chromatographic column of the present invention;

[0035] Figure 2 Fingerprints of multiple Yuling paste test samples on the MXT-1701 chromatographic column of the present invention;

[0036] Figure 3 The PCA analysis diagram of multiple Yuling paste test samples of the present invention;

[0037] Figure 4 DFA analysis diagram of multiple Yuling paste test samples of the present invention;

[0038] Figure 5 This is the DFA projection discriminant diagram of the unknown Yuling paste sample. DETAILED DESCRIPTION

[0039] The principles and features of the present invention are described below in conjunction with the accompanying drawings. The examples given are only used to explain the present invention and are not used to limit the scope of the present invention.

[0040] Example 1

[0041] According to the quality identification method of Yuling paste based on ultra-fast gas phase electronic nose technology, the flavor risk of Yuling paste was studied and its quality control model was established. The specific implementation steps are as follows:

[0042] Materials and instruments: Yuling paste samples steamed for 0, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, and 120 h, nC6-nC16 normal alkane mixed standard, RESTEK, USA; ultrapure water.

[0043] Heracles NEO 300-G ultra-fast gas phase electronic nose is equipped with Arochembase database and AlphaSoftVersion 2021 data processing software, Alpha Mos, France; CPA225D electronic balance, Sartorius, Germany.

[0044] Preparation of Yuling paste test samples: Yuling paste is steamed according to the Yuling paste steaming process. After the Yuling paste samples steamed for different times are homogenized, they are set aside as Yuling paste test samples.

[0045] Heraclese parameter settings and experimental conditions: The Heracles ultrafast gas chromatography electronic nose system uses MXT-5 weak polarity chromatographic column and MXT-1701 medium polarity chromatographic column for simultaneous analysis, and the spectrum simultaneously presents the separation results of the two chromatographic columns. In order to make the sample have a good analysis effect and obtain better chromatographic information, the specific analysis parameters of the sample are: the sample loaded into the injection bottle is 2g, the sample injection volume is 3000mL, the sample shaking incubation temperature is 60℃, the sample shaking incubation time is 20min, the injection port temperature is 240℃, the injection duration is 50s, the initial temperature of the trap is 50℃, and the final temperature of the trap is 240℃; the heating program is: the initial column temperature is 40℃, lasts for 20s, 1℃ / s, and the temperature rises to 180℃; 2℃ / s rises to 250℃.

[0046] Determination and analysis of Yuling paste test samples: Yuling paste test samples were determined and analyzed on the ultra-fast gas chromatography electronic nose Heracles. Three parallel samples were made for each sample. 2.0g of Yuling paste sample was accurately drawn into a 20mL headspace bottle dedicated to the electronic nose, sealed with a PTFE septum, and the prepared sample was placed on the automatic sampler device for analysis. The AlphaSoft V2021 data processing software that comes with the Heracles electronic nose was used for principal component analysis model (PCA) and discriminant factor analysis model (DFA). The normal alkane standard solution (nC6~nC16) was used for calibration, and the retention time was converted into retention index (RI). Then, the compounds were qualitatively analyzed through the AroChemBase database.

[0047] Data processing: The principal component analysis model (PCA) and the discriminant factor analysis model (DFA) were analyzed using the multivariate statistics module in the AlphaSoftVersion 2021 data processing software, and the main differential odor compounds were qualitatively analyzed in combination with the retention index and AroChemBase database; the fingerprint spectrum was analyzed and mapped using Origin statistical software.

[0048] Analysis of the results of the Yuling paste odor fingerprint: The Yuling paste samples steamed for 0, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, and 120 hours were analyzed to obtain the odor chromatographic information of the Yuling paste samples at different steaming times. The information was imported into the Origin2021 statistical software to create a waterfall chart of the chromatographic information, and the odor fingerprint of the Yuling paste was obtained. The odor fingerprint image can be used to distinguish the odor differences of the Yuling paste at different steaming times. Figure 1 , Figure 2 The waterfall fingerprints of the chromatographic information of Yuling paste samples with different steaming times were obtained on two different polarity chromatographic columns, MXT-5 and MXT-1701. Figure 1 , Figure 2 From the fingerprint of Yuling paste, we can see that the chromatographic information of Yuling paste samples steamed at different times is obviously different. In order to quickly screen out the components with large content differences and great contribution to the flavor in the samples, PCA statistics are used to find out the differences in odor between sample groups, determine the differential chromatographic peaks, and then use the Arochembase database to perform qualitative analysis of the substances to find out the differential volatile odor substances.

[0049] PCA analysis model establishment: PCA is a commonly used multivariate statistical method that can convert and reduce the collected multiple indicators, and linearly classify the reduced eigenvectors to capture the maximum difference between the entire data set and present a two-dimensional or three-dimensional graph. PCA analysis can quickly browse all data without any sample information, find the correlation between them, and establish a reasonable model. After the chromatographic peak area and peak number of Yuling paste samples with different steaming times are obtained through ultra-fast gas phase electronic nose detection, the chromatographic peaks with a distinguishing ability of ≥0.950 and a peak area of ​​≥1000 are screened as sensors, that is, the main components, and PCA analysis is performed. If the volatile components and content of the samples are more similar, they will be in a closer position on PCA, and the size of the difference can be measured from the distance between different samples.

[0050] After PCA analysis of Yuling paste samples with different steaming times, Figure 3 As shown in the figure, the sum of the contribution rates of principal component 1 and principal component 2 reaches 90.735%, so principal component 1 and principal component 2 can well represent the actual situation of the product. At the same time, the discrimination index (DI) is a judgment method used to characterize the degree of distinction between samples. The effective range of the DI value is 80 to 100, and the larger the value, the better the data effect. In this study, the recognition index is 95, so the flavor distinction of Yuling paste at different steaming times is effective, and the distinction effect is good.

[0051] Analysis of main odor compounds in Yuling paste: Based on PCA analysis, chromatographic peaks with a discrimination ability greater than 0.95 and a peak area greater than 1000 were selected, and their retention times were converted into retention indices. The odor differences of Yuling paste samples with different steaming times were analyzed by searching the Arochembase database. A total of 17 main different volatile odor substances such as ethanol, isobutanol, methyl propionate, crotonaldehyde, furfural, etc. were screened out. The specific information is shown in Tables 1 and 2.

[0052] Table 1 Main differences in volatile odor substances 1

[0053]

[0054] Table 2 Main differences in volatile odor substances 2

[0055]

[0056] From the analysis in Table 1, we can see that the six compounds, 2-methylbutanol, trans-2-pentenal, n-pentanol, cis-2-hexen-1-ol, n-octanal, and methyl propionate, are the highest at 0 hours, that is, the highest content in the raw materials of the unsteamed Yuling paste sample, and the content of ethanol is also relatively high in the unsteamed raw materials; while 3-hexanol, γ-terpinene, and monomethyl furanone are the highest in the Yuling paste products steamed for 10 hours, and these alcohols, aldehydes, and esters may be the main volatile compounds of the dryness of longan and American ginseng. As the steaming time is delayed, their content decreases, thereby reducing the dryness of longan and American ginseng. The content of isovaleric acid and sorbital is the lowest when it is not steamed, and its content reaches the highest after steaming for 10 hours, and then tends to be stable.

[0057] From the analysis of Table 2, it can be seen that the contents of the five main compounds, namely, isobutyraldehyde, crotonaldehyde, 2,3-pentanedione, furfural, and 5-methylfuranaldehyde, are the lowest in the unsteamed Yuling paste raw materials. Therefore, the changes in the contents of these five main compounds during the steaming process were analyzed. Among them, the contents of the five main compounds, namely, isobutyraldehyde, crotonaldehyde, 2,3-pentanedione, furfural, and 5-methylfuranaldehyde, reached the highest levels when steaming for 40-60 hours, and then decreased or tended to be stable as the steaming time increased.

[0058] Therefore, through the analysis of 17 main differential compounds of Yuling paste with different steaming times, it was found that 2-methylbutanol, trans-2-pentenal, n-pentanol, cis-2-hexen-1-ol, n-octanal, and methyl propionate were the highest at 0 hours, and the content of ethanol in the unsteamed raw materials was also relatively high; while 3-hexanol, γ-terpinene, and monomethyl furanone were the highest in the Yuling paste product steamed for 10 hours. Therefore, as the steaming time was delayed, these 10 substances all decreased significantly. Therefore, these 10 main compounds may be the main odor compounds with dryness in the raw materials of longan, American ginseng, and white sugar. The contents of the seven main compounds, namely, isobutyraldehyde, crotonaldehyde, 2,3-pentanedione, furfural, 5-methylfuranaldehyde, isovaleric acid and sorbitaldehyde, were the lowest in the unsteamed Yuling paste raw materials. As the steaming time was delayed, the contents of the five main compounds, namely, isobutyraldehyde, crotonaldehyde, 2,3-pentanedione, furfural and 5-methylfuranaldehyde, reached the highest in the Yuling paste samples steamed for 40-60 hours, and then tended to be stable. Aldehyde compounds such as furfural are the intermediate products of the Maillard reaction of traditional Chinese medicine and the main substances for the efficacy of traditional Chinese medicine. Combined with the experiment on the efficacy of Yuling paste in improving nutritional anemia with different steaming times, it was found that the Yuling paste samples steamed for 40-60 hours had the best effect in improving nutritional anemia. Therefore, it was determined that isobutyraldehyde, crotonaldehyde, 2,3-pentanedione, furfural and 5-methylfuranaldehyde were the main flavor compounds in Yuling paste products, the main functional substances of Yuling paste in improving nutritional anemia, and the main characteristic compounds in Yuling paste samples. In order to further quickly identify Yuling paste samples with different steaming times, it is necessary to further establish its DFA analysis model.

[0059] DFA model establishment: DFA is a statistical method to determine the category to which an individual belongs. Based on PCA, it maximizes the differences between data of different groups and minimizes the differences between data of the same group, thereby establishing a better identification data model and better reflecting the differences of samples. Based on the PCA and main differential compounds of Yuling paste at different steaming times, the DFA model was established according to the chromatographic information of the main differential compounds screened.

[0060] Analysis of discriminant factors of Yuling paste products with different steaming times Figure 4 As shown in the figure, the sum of discriminant factors 1 and 2 is 77.578%, indicating that DFA can effectively distinguish Yuling paste products with different steaming times. Using DFA analysis in AlphaSoftVersion 2021 multivariate statistics, the chromatographic information of unknown samples is projected, and the projection results are used to determine the attribution of the unknown samples. In this study, the electronic nose gas chromatography information of unknown samples 1 (Yuling paste steamed for 10 hours), unknown sample 2 (Yuling paste steamed for 50 hours), unknown sample 3 (Yuling paste steamed for 60 hours), unknown sample 4 (Yuling paste steamed for 70 hours), unknown sample 5 (Yuling paste steamed for 100 hours), and unknown sample 6 (Yuling paste steamed for 110 hours) was projected onto the established DFA model. The projection results are shown in the figure. Figure 5 As shown in the figure, the projection results are judged, and the unknown samples 1-6 belong to groups 10, 50, 60, 70, 100, and 110 respectively, with identification values ​​of 100%, 100%, 100%, 85.6%, 100%, and 100%, respectively, indicating that DFA has a high ability to distinguish unknown samples. Therefore, the established DFA model can be used to quickly identify Yuling paste with different steaming times.

[0061] To summarize the above results, this experimental study used ultrafast gas phase electron microscopy to screen out 17 major different compounds such as ethanol, isobutanol, methyl propionate, crotonaldehyde, furfural, etc. from Yuling paste products with different steaming times. Among them, 2-methylbutanol, trans-2-pentenal, n-pentanol, cis-2-hexen-1-ol, n-octanal, and methyl propionate were the highest at 0 hour, and the content of ethanol in the unsteamed raw materials was also relatively high; while 3-hexanol, γ-terpinene, and monomethylfuranone were the highest in the Yuling paste products steamed for 10 hours. The contents of seven major compounds, including isobutyraldehyde, crotonaldehyde, 2,3-pentanedione, furfural, 5-methylfuranaldehyde, isovaleric acid and sorbitaldehyde, were the lowest in the unsteamed Yuling paste raw materials. As the steaming time was delayed, the contents of these five major compounds, including isobutyraldehyde, crotonaldehyde, 2,3-pentanedione, furfural and 5-methylfuranaldehyde, reached the highest in the Yuling paste samples steamed for 40-60 hours, and then tended to be stable. Therefore, combined with the experimental results of the efficacy of Yuling paste in improving nutritional anemia with different steaming times and the fact that the intermediate products of Maillard reaction are the main effective substances of traditional Chinese medicine, it was determined that isobutyraldehyde, crotonaldehyde, 2,3-pentanedione, furfural and 5-methylfuranaldehyde were the main effective substances for improving nutritional anemia and were the main characteristic compounds in Yuling paste samples. By screening the main chromatographic information with chromatographic discrimination ability greater than 0.95 and chromatographic peak area greater than 1000, the gas phase fingerprint of Yuling paste samples with different steaming times was established, and its PCA analysis model was established with a recognition index of 95. Therefore, the flavor of Yuling paste with different steaming times was effectively distinguished, and the distinction effect was good. Its DFA model was established, and the sum of the discriminant factor 1 and the discriminant factor 2 was 77.578%, indicating that DFA can effectively distinguish Yuling paste products with different steaming times. The chromatographic information of unknown sample 1, unknown sample 2, unknown sample 3, unknown sample 4, unknown sample 5, and unknown sample 6 was projected to the established DFA model, and the recognition values ​​were 100%, 100%, 100%, 85.6%, 100%, and 100%, respectively, indicating that the DFA model can quickly identify unknown steamed Yuling paste samples. Therefore, the established PCA, DFA, can effectively distinguish the flavor of Yuling paste with different steaming times and can be used as a quality discrimination method for Yuling paste.

[0062] Therefore, the present invention can be used for odor analysis of different steamed Yuling paste samples based on ultra-fast gas phase electronic nose technology, and the contents of five compounds, namely, isobutylaldehyde, crotonaldehyde, 2,3-pentanedione, furfural, and 5-methyl furanaldehyde, are relatively high in Yuling paste samples steamed for 40-60 hours, and these five compounds are determined to be target differential compounds of Yuling paste. The established PCA and DFA models can effectively distinguish Yuling pastes with different steaming times, so it is feasible to apply ultra-fast gas phase electronic nose technology to improve the quality discrimination of Yuling paste for nutritional anemia, thereby realizing the control of the quality of Yuling paste.

[0063] Example 2

[0064] Different from Example 1, this example adopts Heraclese parameter settings and experimental conditions: the Heracles ultrafast gas chromatography electronic nose system uses MXT-5 weak polarity chromatographic column and MXT-1701 medium polarity chromatographic column for simultaneous analysis, and the spectrum simultaneously presents the separation results of the two chromatographic columns. In order to make the sample have a good analysis effect and obtain better chromatographic information, the specific analysis parameters of the sample are: the sample loaded into the injection bottle is 3g, the sample injection volume is 2000mL, the sample shaking incubation temperature is 50℃, the sample shaking incubation time is 30min, the injection port temperature is 250℃, the injection duration is 40s, the initial temperature of the trap is 40℃, and the final temperature of the trap is 250℃; the heating program is: the initial column temperature is 40℃, lasts for 20s, 1℃ / s, and the temperature is raised to 150℃; 2℃ / s is raised to 250℃.

[0065] Example 3

[0066] Different from Example 1, this example adopts Heraclese parameter settings and experimental conditions: the Heracles ultrafast gas chromatography electronic nose system uses MXT-5 weak polarity chromatographic column and MXT-1701 medium polarity chromatographic column for simultaneous analysis, and the spectrum simultaneously presents the separation results of the two chromatographic columns. In order to make the sample have a good analysis effect and obtain better chromatographic information, the specific analysis parameters of the sample are: the sample loaded into the injection bottle is 4g, the sample injection volume is 1000mL, the sample shaking incubation temperature is 40℃, the sample shaking incubation time is 10min, the injection port temperature is 260℃, the injection duration is 40s, the initial temperature of the trap is 60℃, and the final temperature of the trap is 260℃; the heating program is: the initial column temperature is 40℃, lasts for 20s, 1℃ / s, and the temperature is raised to 150℃; 2℃ / s is raised to 250℃.

[0067] Example 4

[0068] The steaming process of the Yuling paste sample is specifically as follows: steaming the Yuling paste sample includes:

[0069] Step 1, prepare Yuling paste sample for later use; prepare Yuling paste raw materials, according to the ratio of longan pulp: white sugar: American ginseng = 10:1:1, weigh 250g of longan pulp, 25g of white sugar, and 25g of American ginseng in a porcelain bowl for later use;

[0070] Step 2, evenly spread the washed and soaked rice on a steamer, and form rice steam when steaming; prepare 100g of rice, wash it once, add appropriate amount of water to soak it for 2-4 hours, drain the water, and evenly spread the soaked rice on a wooden steamer, and form rice steam when steaming;

[0071] Step 3, placing the ceramic bowl containing the raw materials of Yuling paste on the wooden steamer evenly spread with soaked rice, and spreading gauze on the ceramic bowl, starting steaming, and starting timing after the steamer is steamed;

[0072] Step 4, stop steaming every 10 hours, wait for the steamed Yuling paste sample to cool down, replace the rice according to step 2, repeat step 3, and the total steaming time is 40 hours. After steaming, transfer the steamed Yuling paste to a sterilized glass bottle for consumption, thus forming a Yuling paste sample.

[0073] Example 5

[0074] The difference from Example 4 is that the total steaming time in step 4 is 50 hours.

[0075] Example 6

[0076] The difference from Example 4 is that the total steaming time in step 4 is 60 hours.

[0077] Test example

[0078] Human food trial of Yuling paste in improving nutritional anemia

[0079] 1 Experimental Purpose

[0080] The purpose of this experiment is to evaluate the improvement effect of Yuling paste samples with different steaming times on nutritional anemia, so as to determine the optimal steaming time of Yuling paste.

[0081] 2 Materials and methods

[0082] 2.1 Samples and method of consumption: Steam Yuling paste samples for 0, 20, 40, 60, 80, 100, and 120 hours, and consume 10 g directly or with warm water before going to bed daily for a total of 60 days.

[0083] 2.2 Subjects

[0084] 2.2.1 Inclusion criteria: Adult females, hemoglobin level <120 g / L.

[0085] 2.2.2 Exclusion criteria:

[0086] 1) Patients with serious primary diseases of the heart, liver, kidney and hematopoietic system, and mental illness.

[0087] 2) Those with allergic constitution or allergic to the sample.

[0088] 3) Patients with severe anemia.

[0089] 4) Taking items related to the function being tested in the short term may affect the judgement of the results.

[0090] 5) The test substance is not consumed as specified, and the efficacy cannot be determined or the incomplete data affects the judgment of efficacy or safety.

[0091] 2.3 Experimental method: Voluntary subjects who meet the inclusion criteria and guarantee cooperation with the experiment are randomly divided into 7 groups, with 15 people in each group. The main factors affecting the results, such as age and economic status, are considered as much as possible, and a balance test is conducted to ensure the comparability between groups. The subjects began to take samples every day on March 25, 2022, for 60 consecutive days. The food tasting test was conducted in a blind manner. During the trial, the original eating habits were not changed and the diet was normal.

[0092] 3 Observation indicators:

[0093] Each observation index was measured once at the beginning and end of the feeding trial.

[0094] 3.1 Safety indicators

[0095] 3.1.1 General physical examination: Before the test, the subject's mental state, sleep, diet, urination and defecation, etc. were asked in detail and the changes in weight, blood pressure and heart rate before and after the test were measured.

[0096] 3.1.2 Routine blood test: red blood cell count, white blood cell count, etc.

[0097] 3.1.3 Urinalysis: pH value, white blood cells, urine sugar, etc.

[0098] 3.1.4 Routine stool examination.

[0099] 3.1.5 Biochemical tests: serum total protein (TP), albumin (ALB), alanine aminotransferase (ALT), aspartate aminotransferase (AST), cholesterol (CHOL), triglyceride (TG), urea nitrogen (BUN), creatinine (Cr), uric acid (UA), and blood glucose (GLU) determination.

[0100] 3.1.6 Electrocardiogram, abdominal B-ultrasound, chest X-ray and other examinations (only once before the start of the test).

[0101] 3.1.7 Observation of adverse reactions.

[0102] 3.2 Dietary survey.

[0103] 3.3 Efficacy Observation:

[0104] 3.3.1 Hemoglobin determination.

[0105] 3.3.2 Free protoporphyrin in erythrocytes: Detected using RF-540 Rongguang photometer.

[0106] 3.3.3 Serum ferritin determination: ACS180 fully automatic chemiluminescence immunoassay was used for detection.

[0107] 4 Experimental data processing: INSTAT software was used for processing.

[0108] 5 Results

[0109] 5.1 General situation: The initial test population control group consumed the raw material of Yuling paste, and the control group had 15 people; the test subjects who consumed the steamed Yuling paste samples for 20, 40, 60, 80, 100, and 120 hours had 15 people per person. Before and after the test, the subjects' mental sleep, diet, and urination and defecation conditions were normal. The test population in the test group and the control group were all 26-38 years old.

[0110] 5.2 Safety Observation

[0111] There was no significant difference in red blood cell count before consuming the Yuling paste samples (P>0.05). After the test, there was no significant difference in red blood cell count between the experimental group and itself before the tasting and between the control group and after the tasting (P>0.05); no obvious abnormal changes were found in body weight, blood pressure, heart rate, urine routine, stool routine, white blood cell and biochemical indexes before and after the tasting and between the tasting group and the control group; electrocardiogram, abdominal B-ultrasound and chest X-ray were all within the normal range; no obvious adverse reactions were observed during the tasting period.

[0112] 5.3 Main nutrient intake

[0113] There was no significant change in energy intake, dietary protein intake, and dietary iron intake of anemic people in the trial group and the control group before and after the trial.

[0114] 5.4 Observation of efficacy indicators

[0115] 5.4.1 Effect of Yuling Paste on Hemoglobin

[0116] After the subjects were given the test substance for 60 days, the changes in hemoglobin content are shown in Table 3. There was no significant difference in the hemoglobin content of the groups before the test (P>0.05), and the hemoglobin content of the test groups increased after the test, and the difference between the before and after test and the control group was significant (P<0.05). Among them, the hemoglobin content of the subjects who tried the Yuling paste sample steamed for 40 hours and 60 hours increased significantly (P<0.01), and the average hemoglobin content increased by 13.79g / L and 13.47g / L.

[0117] Table 3 Changes of hemoglobin before and after the experiment (g / L, )

[0118]

[0119] a: Compared with the control group, the difference is significant, P<0.05; b: Compared with itself, the difference is significant, P<0.05; *: Compared with itself, the difference is extremely significant, P<0.01.

[0120] 5.4.2 Effect of Yuling Paste on Free Protoporphyrin Concentration in Erythrocytes

[0121] As shown in Table 4, before consuming the Yuling paste samples, there was no significant difference in the free protoporphyrin concentration in the red blood cells of the test groups (P>0.05). After the test, the free protoporphyrin concentration in the red blood cells of the test group decreased, and there was a significant difference between itself and the control group (P<0.05). Among them, the free protoporphyrin concentration in the red blood cells of the test group who ate the steamed Yuling paste samples for 40 hours and 60 hours decreased extremely significantly (P<0.01), and the free protoporphyrin concentration in the red blood cells decreased by 94.73ug / L and 90.53ug / L respectively.

[0122] Table 4 Changes of hemoglobin before and after the experiment (g / L, )

[0123]

[0124] a: Compared with the control group, the difference is significant, P<0.05; b: Compared with itself, the difference is significant, P<0.05;

[0125] *: The difference is extremely significant compared with itself, P<0.01.

[0126] 5.4.3 Effect of Yuling Paste Samples on Serum Ferritin

[0127] There was no significant difference in serum ferritin before consuming the Yuling paste samples (P>0.05), and no significant change was found in serum ferritin after the trial consumption (P>0.05).

[0128] 6. Summary

[0129] The results showed that after consuming Yuling paste samples with different steaming times, the hemoglobin content of the experimental group was significantly different from that of the control group and before the experiment (P<0.05). The hemoglobin content of the subjects who ate Yuling paste samples steamed for 40 hours and 60 hours increased significantly (P<0.01), and the average hemoglobin increased by 13.79g / L and 13.47g / L. The free protoporphyrin concentration in the erythrocytes of the experimental group decreased, and there was a significant difference compared with the control group and before the experiment (P<0.05). The free protoporphyrin concentration in the erythrocytes of the subjects who ate Yuling paste samples steamed for 40 hours and 60 hours decreased significantly (P<0.01), and the free protoporphyrin concentration in the erythrocytes decreased by 94.73μg / L and 90.53μg / L, respectively. According to the evaluation criteria stipulated in the Technical Specifications for Inspection and Evaluation of Health Food, it is suggested that Yuling Paste steamed for different times has the function of improving nutritional anemia, among which Yuling Paste steamed for 40 and 60 hours has more significant function in improving nutritional anemia.

[0130] The above test example of Yuling paste sample improving nutritional anemia shows that Yuling paste sample steamed for 40-60 hours has significant effect on improving nutritional anemia, while as the steaming time increases, its effect on improving nutritional anemia decreases. Therefore, the optimal steaming time of Yuling paste is determined to be 40-60 hours. In Example 1, an ultra-fast gas-phase electronic nose was used to analyze the odor substances of Yuling paste at different steaming times, and it was determined that the contents of the five main compounds, namely, isobutyraldehyde, crotonaldehyde, 2,3-pentanedione, furfural, and 5-methylfuranaldehyde, reached the highest level when the Yuling paste was steamed for 40-60 hours. According to the experiment on the efficacy of Yuling paste samples in improving nutritional anemia, the Yuling paste samples steamed for 40-60 hours had the most significant effect on improving nutritional anemia. In addition, aldehydes such as furfural are intermediate products of the Maillard reaction of traditional Chinese medicine and are the main effective substances of traditional Chinese medicine. Therefore, it was determined that the five compounds, namely, isobutyraldehyde, crotonaldehyde, 2,3-pentanedione, furfural, and 5-methylfuranaldehyde, were the target characteristic volatile compounds of Yuling paste, and their gas chromatographic fingerprints, PCA, and DFA models were established, which could be used to distinguish the quality of Yuling paste, thereby achieving quality control of Yuling paste.

[0131] The present invention not only uses ultra-fast gas phase electronic nose technology to analyze the flavor of Yuling paste, establishes its PCA and DFA quality discrimination models, determines that five compounds, namely, isobutylaldehyde, crotonaldehyde, 2,3-pentanedione, furfural, and 5-methyl furanaldehyde, are target characteristic volatile compounds of Yuling paste, and achieves quality discrimination of Yuling paste, but also determines that the optimal steaming time of Yuling paste is 40-60 hours according to the nutritional anemia efficacy test, so that the quality of Yuling paste can be controlled according to the established PCA and DFA quality discrimination models. Compared with the prior art, the present invention has significant technical advantages, and the technical progress obtained by the present invention in its field is groundbreaking.

[0132] The above embodiments are only used to illustrate the present invention, but not to limit the present invention. Although the present invention is described in detail with reference to the embodiments, it should be understood by those skilled in the art that various combinations, modifications or equivalent substitutions of the technical solutions of the present invention do not depart from the spirit and scope of the technical solutions of the present invention, and should be included in the scope of the claims of the present invention.

[0133] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations of the present invention. A person skilled in the art may change, modify, replace and vary the above embodiments within the scope of the present invention.

Claims

1. A method for distinguishing the quality of Yuling Paste based on ultrafast gas phase electronic nose technology, characterized in that: The following steps are involved: Step 1, homogenizing the Yuling paste after being processed for different steaming times to obtain multiple Yuling paste test samples; Step 2, using ultra-fast gas phase electronic nose technology to perform odor analysis on each Yuling paste test sample, obtain electronic nose gas chromatography information of each Yuling paste test sample, and obtain the odor fingerprint of Yuling paste based on all electronic nose gas chromatography information; Step 3, using PCA multivariate statistical method to screen the differential chromatographic peaks in the odor fingerprint, performing qualitative material analysis on the differential chromatographic peaks to obtain a variety of main differential volatile odor substances, and selecting several of the main differential volatile odor substances as target signature differential volatile odor substances according to preset screening conditions; Analyze the contents of multiple target characteristic volatile odor substances at different steaming times, determine the optimal steaming time range, and use the optimal steaming time range as a quality control indicator to control the quality of Yuling Paste; Step 4, establishing a discriminant factor analysis model DFA according to the electronic nose gas chromatography information of each Yuling paste test sample with different steaming time; The ultra-fast gas phase electronic nose technology was used to conduct odor analysis on the unknown Ling ointment test samples, and the electronic nose gas chromatography information of the unknown Yuling ointment samples was obtained; Projecting the electronic nose gas chromatography information of the unknown Yuling paste sample to the discriminant factor analysis model DFA, obtaining the steaming time of the unknown Yuling paste sample, and judging whether the steaming time of the unknown Yuling paste sample falls within the optimal steaming time range; The main differential volatile odor substances included 2-methylbutanol, trans-2-pentenal, n-pentanol, cis-2-hexen-1-ol, n-octanal, methyl propionate, ethanol, 3-hexanol, γ-terpinene, monomethylfuranone, isobutylaldehyde, crotonaldehyde, 2,3-pentanedione, furfural, 5-methylfuranaldehyde, isovaleric acid, and sorbital; The target characteristic differential volatile odor substances include isobutyraldehyde, crotonaldehyde, 2,3-pentanedione, furfural, and 5-methylfuranaldehyde.

2. The method for distinguishing the quality of Yuling Paste based on ultrafast gas phase electronic nose technology according to claim 1, characterized in that: The method of using the PCA multivariate statistical method to screen the differential chromatographic peaks in the odor fingerprint spectrum includes: using the PCA multivariate statistical software corresponding to the PCA multivariate statistical method to screen out chromatographic peaks with a discrimination ability greater than 0.95 and a peak area greater than 1000 from the odor fingerprint spectrum as differential chromatographic peaks.

3. The method for distinguishing the quality of Yuling Paste based on ultrafast gas phase electronic nose technology according to claim 2 is characterized in that: The method of performing qualitative material analysis on the differential chromatographic peaks to obtain a plurality of main differential volatile odor substances comprises: analyzing the odor differences of Yuling paste test samples with different steaming times by searching the Arochembase database, combining the retention index corresponding to the differential chromatographic peaks, and screening to obtain a plurality of differential volatile odor substances, wherein the retention time of the differential chromatographic peaks is converted to obtain the retention index corresponding to the differential chromatographic peaks.

4. The method for distinguishing the quality of Yuling Paste based on ultrafast gas phase electronic nose technology according to claim 1, characterized in that: According to the preset screening conditions, several major differential volatile odor substances are selected as target signature differential volatile odor substances, and the contents of multiple target signature differential volatile odor substances with different steaming times are analyzed to determine the optimal steaming time, including: conducting an efficacy test on improving nutritional anemia on Yuling paste test samples with different steaming times to screen out target Yuling paste test samples with significant efficacy in improving nutritional anemia, determining the optimal steaming time range based on the steaming time of the target Yuling paste test samples with significant efficacy in improving nutritional anemia, and then screening multiple major differential volatile odor substances in these target Yuling paste test samples relative to other steaming times, and screening the several major differential volatile odor substances with the highest content within the optimal steaming time range as target signature differential volatile odor substances.

5. The method for distinguishing the quality of Yuling Paste based on ultrafast gas phase electronic nose technology according to claim 1, characterized in that: By testing the efficacy of Yuling paste samples with different steaming times in improving nutritional anemia, it was determined that the Yuling paste samples obtained with the optimal steaming time have significant efficacy in improving nutritional anemia.

6. The method for distinguishing the quality of Yuling Paste based on ultrafast gas phase electronic nose technology according to claim 1, characterized in that: In step 2, the detection conditions for the odor analysis detection of Yuling paste detection samples with different steaming times using an ultra-fast gas phase electronic nose include: the Yuling paste detection sample loaded into the injection bottle is 1-5g, the sample injection volume is 500-5000mL, the sample shaking incubation temperature is 30-80°C, the sample shaking incubation time is 10-40min, the injection port temperature is 200-280°C, the injection duration is 20-50s, the initial temperature of the trap is 40-60°C, and the final temperature of the trap is 240-260°C; The chromatographic column heating program of the ultra-fast gas phase electronic nose is as follows: the initial column temperature is 40-60°C, lasting for 10-30s, heating to 120-150°C at 0.5-1°C / s, and heating to 250°C at 1-3°C / s.

7. The method for distinguishing the quality of Yuling Paste based on ultrafast gas phase electronic nose technology according to claim 1, characterized in that: In step 1, the Yuling paste sample is steamed, including: Step 1, prepare Yuling ointment sample for use; Step 2, evenly spread the washed and soaked rice on the steamer, and form rice steam during steaming; Step 3, placing the container containing the Yuling paste sample on a steamer evenly spread with rice, and spreading gauze on the container, starting steaming, and starting timing after the steamer is steamed; Step 4, stop steaming every 10 hours, wait for the steamed Yuling paste sample to cool down, replace the rice according to step 2, and repeat step 3 for steaming. The total steaming time is 10-120 hours.

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