Method for enriching and extracting empty-cup aroma-remaining flavor components of white spirit and application of empty-cup aroma-remaining flavor components

Abstract

The invention relates to the technical field of detection of flavor components of liquor, in particular to a method for enriching and extracting flavor components of empty-cup fragrance of liquor and application. The method comprises the following steps: pouring a to-be-detected wine sample into a tulip-shaped headspace bottle, standing, and pouring out the wine sample; the headspace bottle is air-dried and heated in a water bath, and flavor components are extracted through headspace solid-phase microextraction; repeating the steps for at least two times, and continuously extracting to obtain a white spirit empty cup fragrance retention sample to be detected. According to the method for enriching and extracting the flavor components of the empty-cup aroma retention of the white spirit, more flavor components can be extracted, the requirement for detecting the flavor components of the empty-cup aroma retention of the white spirit is well met by combining GC-MS, the flavor components of the empty-cup aroma retention of the white spirit are extracted and enriched to a greater extent, and the composition of the empty-cup aroma retention of the white spirit is convenient to analyze so as to evaluate the aroma contribution of each component.

Description

Technical Field

[0001] This invention relates to the field of baijiu flavor component detection technology, and in particular to a method and application for enriching and extracting baijiu aroma components remaining in an empty glass. Background Technology

[0002] The lingering aroma of baijiu in an empty glass refers to the phenomenon where, after baijiu has been poured out, the aroma remains on the glass for a period of time. This phenomenon is an important criterion for evaluating the quality of baijiu and is directly related to the types of flavor components it contains. Therefore, analyzing the flavor components of this lingering aroma in an empty glass is of great significance for the scientific evaluation of baijiu quality.

[0003] In the prior art, patent application CN115792050 A discloses a method for detecting the lingering aroma of baijiu in an empty glass, which utilizes solid-phase microextraction to detect semi-volatile or non-volatile flavor components, and the detection stability is good. Although the existing patent application can detect semi-volatile or non-volatile flavor components in the lingering aroma of baijiu in an empty glass, the types of flavor components extracted and enriched are relatively small, which is not conducive to systematically exploring the aroma characteristics of baijiu in an empty glass. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides a method for enriching and extracting flavor components from the empty glass of baijiu (Chinese liquor) and its application. This invention solves the problem of low flavor component content and poor enrichment in an empty glass, making it difficult to systematically explore the aroma characteristics of baijiu in an empty glass. This method can extract more flavor components from the empty glass of baijiu, and combined with GC-MS, it well meets the requirements for detecting flavor components in the empty glass of baijiu. It can extract and enrich flavor components from the empty glass of baijiu to a greater extent, facilitating the analysis of the composition of the empty glass aroma and evaluating the aroma contribution of each component.

[0005] In a first aspect, the present invention provides a method for enriching and extracting flavor components remaining in an empty glass of baijiu (Chinese liquor), comprising the following steps: 1) Pour the wine sample to be tested into a tulip-shaped headspace bottle, let it stand, and then pour out the wine sample.

[0006] 2) The headspace vial is air-dried and heated in a water bath, and flavor components are extracted using headspace solid-phase microextraction.

[0007] 3) Repeat steps 1) and 2) at least twice to continuously extract the baijiu aroma sample from the empty glass.

[0008] This invention utilizes tulip-shaped glass headspace vials and employs HS-SPME continuous multiple extraction combined with GC-MS to analyze the aroma components remaining in the empty glass of baijiu. This method for enriching and extracting the aroma components remaining in the empty glass of baijiu utilizes continuous multiple headspace solid-phase microextraction, enabling the extraction of more flavor components. Combined with GC-MS, it meets the requirements for detecting the aroma components remaining in the empty glass of baijiu. This invention extracts and enriches the aroma components remaining in the empty glass of baijiu to a greater extent, facilitating the analysis of the composition of the aroma and evaluating the aroma contribution of each component.

[0009] Preferably, the repetition is performed 2-5 times; more preferably, it is performed 3 times. This allows for a greater enrichment and extraction of the flavor components that contribute to the lingering aroma in the empty glass of the liquor.

[0010] Preferably, 12-18 mL of wine sample is poured into the headspace bottle, gently shaken 3-8 times, and allowed to stand for 4-6 minutes. The wine sample is then poured out and allowed to air dry naturally for 1-2 minutes.

[0011] Further preferred method: Pour 15 mL of wine sample into the tulip-shaped glass headspace bottle, gently shake 5 times and let stand for 5 minutes, then pour out the wine sample; air dry naturally for 1.5 minutes; heat the headspace bottle in a water bath and insert an extraction head to adsorb the aroma and flavor components remaining in the empty glass of the baijiu.

[0012] In this invention, the repetition refers to the entire process of repeatedly pouring in the wine sample, letting it stand, pouring out the wine sample, air-drying, and inserting the extraction head for adsorption. Preferably, the volume of wine sample poured in is the same, the standing time is the same, and the air-drying time is the same, without changing the extraction head. The headspace solid-phase microextraction is performed by using the same extraction head for repeated and continuous extraction. More preferably, the same extraction head is used for repeated and continuous extraction to obtain the extraction head with the aroma components of baijiu left in the empty glass, and the extraction temperature and extraction time are the same for each repetition.

[0013] Further optimization is made by selecting a liquor sample to be tested, preferably a sauce-flavored liquor.

[0014] Further preferably, the water bath heating and / or the extraction temperature is 50-70℃, and the extraction time for a single extraction is 8-15 min.

[0015] Further preferably, the headspace bottle is tulip-shaped. The tulip-shaped glass headspace bottle of the present invention can better simulate a standard tasting glass for baijiu (Chinese liquor) while improving the enrichment and extraction effect of aroma components remaining in the empty glass of baijiu.

[0016] Further optimized, the tulip-shaped glass headspace bottle includes a stemless base with bottom support, a tulip-shaped body, a rounded neck, and a threaded cap that matches the headspace bottle cap. The tulip-shaped glass headspace bottle is an integrated device; the stemless base ensures bottle stability and connects to the headspace bottle body, facilitating heating of the device. The tulip-shaped bottle body mimics the standard baijiu tasting glass, connecting seamlessly with the neck below. The connection between the neck and body is a rounded corner, closely resembling the shape of a standard baijiu tasting glass, with the body and neck forming a convex shape. The neck depth ensures the extraction head is 2±0.5 cm from the bottom after fixing, maintaining optimal extraction and adsorption distance. The outer side of the neck features a spiral pattern for use with a standard headspace bottle cap and gasket.

[0017] Secondly, the present invention provides a method for detecting the flavor components of baijiu (Chinese liquor) left in an empty glass. The method described above is used to obtain a baijiu sample to be tested for its lingering aroma in an empty glass, and gas chromatography is used to detect the flavor components of the baijiu sample to be tested for its lingering aroma in an empty glass. Preferably, the extraction head is inserted into the inlet of a gas chromatograph-mass spectrometer, and the flavor components in the baijiu sample to be tested for its lingering aroma in an empty glass are detected by gas chromatography-mass spectrometry.

[0018] Preferably, the gas chromatographic temperature program includes: increasing the temperature from 35-42℃ to 45-60℃ at 9-12℃ / min and holding for 3-7 min; increasing the temperature to 70-90℃ at 2-5℃ / min and holding for 3-7 min; and increasing the temperature to 200-250℃ at 4-6℃ / min and holding for 3-7 min. Using the preferred gas chromatographic conditions, especially the temperature program, can better address the challenge of the limited variety of flavor components in the lingering aroma of baijiu samples in an empty glass.

[0019] Further optimization involves setting the heating program as follows: increasing the temperature from 40°C to 50°C at a rate of 10°C / min and holding for 5 minutes; increasing the temperature to 80°C at a rate of 3°C / min and holding for 5 minutes; and finally increasing the temperature to 230°C at a rate of 5°C / min and holding for 5 minutes.

[0020] Preferably, the gas chromatography uses a DB-WAX column with dimensions of 30-50m × 0.25mm × 0.25µm, high-purity helium as the carrier gas, and a constant flow rate of 1-1.5mL / min.

[0021] Further optimization included the following mass spectrometry parameters: an electron impact source, an ion source temperature of 220-230℃, an electron energy of 60-80 eV, a quadrupole temperature of 140-160℃, and a full scan mode.

[0022] Thirdly, the present invention provides the application of the above-described method or the above-described detection method in analyzing the aroma characteristics of baijiu left in an empty glass; preferably, the number of flavor components detected in the baijiu left in an empty glass is ≥50.

[0023] In this embodiment of the invention, 61 flavor components were detected that contribute to the lingering aroma of baijiu in an empty glass (ethyl acetate, dimethyl ether, pentanol, ethyl hexanoate, furfuryl ethyl ether, 2,6-dimethyl-pyrazine, ethyl heptaate, ethyl lactate, 4-methylpentanol, 2-ethyl-6-methylpyrazine, 2,3,5-trimethylpyrazine, ethyl octanoate, acetic acid, 2,3-dimethyl-5-ethylpyrazine, furfural, 2,3,5,6-tetramethylpyrazine, benzaldehyde, ethyl nonanoate, DL-2-hydroxy-4-methylpentanoate, octanol, alkanol lactate, isobutyric acid, 5-methylfurfural, 2-propionyl furan, 2-decanoyl ketone, hexyl hexanoate, ethyl levulinate, 5-methyl-2-acetylfuran, ... The amount of ethyl 2-furfurylate, butyric acid, ethyl decanoate, phenylacetaldehyde, nonanol, acetophenone, isovaleric acid, ethyl benzoate, diethyl succinate, o-phenylenediamine, ethyl phenylacetate, 2-trialkylone, ethyl acetate, ethyl laurate, valeric acid, ethyl isobutyrate, ethyl phenylpropionate, (Z)-8-dodecen-1-ol, phenethyl alcohol, 3-tolylisocyanate, 5-methyl-1-phenylhexane-1-one, phenylacetic acid, ethyl isovalerate, ethyl tetradecanoate, ethyl 2-pentadecanone, ethyl pentadecanoate, phytone, ethyl hexadecanoate, ethyl 9-hexadecenoate, N-benzyl-2-phenylethylamine, ethyl heptadecanate, ethyl oleate, and ethyl linoleate far exceeds the amount detected in existing baijiu (Chinese liquor) empty glass aroma lingering.

[0024] The beneficial effects of this invention are at least as follows: This invention uses a tulip-shaped glass-topped empty bottle, allowing the liquor to air dry naturally after pouring, thus reflecting the distribution of flavor components in the empty glass of baijiu. By enriching relevant flavor components through multiple consecutive extractions, and then combining this with gas chromatography-mass spectrometry, a wider range of flavor components can be detected, increasing the effective quantity of detection and enabling a more comprehensive analysis of the aroma lingering in the empty glass of baijiu. Attached Figure Description

[0025] To more clearly illustrate the technical solutions in this invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of this invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0026] Figure 1 This is a diagram of the apparatus for enriching and extracting the aroma components of baijiu (Chinese liquor) in an empty glass, as provided in an embodiment of the present invention.

[0027] Figure 2 This is a schematic diagram of the structure of a tulip-shaped glass top-empty bottle provided in an embodiment of the present invention.

[0028] In the picture, 1-bottom base; 2-bottle body; 3-neck of bottle; 4-mouth of bottle. Detailed Implementation

[0029] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this invention, not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0030] The endpoints and any values ​​of the ranges disclosed in this invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this invention.

[0031] Unless otherwise specified, the techniques or conditions described in the literature of this invention shall apply, or the product instructions shall be followed. Devices, instruments, reagents, etc., without a specified manufacturer, are all conventional products that can be purchased from legitimate channels. All experimental reagents and raw materials involved are commercially available, and all reagents are chromatographically pure products.

[0032] According to embodiments of the present invention, the study of the flavor components remaining in an empty glass of baijiu provides a material basis for scientifically understanding its sensory characteristics. However, the operational difficulty of this process is that, compared to solution systems, the flavor components in the empty glass aroma system are difficult to enrich and extract for subsequent detection and analysis. Existing solid-phase microextraction methods can enrich and extract relatively few flavor components, while adsorption pen methods are costly and have limited application. Based on this, embodiments of the present invention provide a method for enriching and extracting flavor components remaining in an empty glass of baijiu and its application, which can effectively solve the above-mentioned technical problems.

[0033] In this embodiment of the invention, the soy sauce-flavored baijiu used is produced in Guizhou, China. This invention does not limit the specific baijiu selection, such as soy sauce-flavored baijiu.

[0034] In this embodiment of the invention, the tulip-shaped glass headspace bottle used, such as Figure 1-2 As shown, the device includes a stemless, cup-shaped base 1 with bottom support, a tulip-shaped bottle body 2, a rounded neck 3, and a bottle neck 4 that matches the threaded cap of the headspace bottle. The bottle body 2 and bottle neck 4 are U-shaped. The height of the bottle neck 4 allows the extraction fibers to extend approximately 2 cm above the bottom of the bottle. This tulip-shaped glass headspace bottle of this embodiment provides a structure for creating the aroma of baijiu in an empty glass, reducing the negative impact of the bottle shape on the formation of this aroma, ensuring the airtightness of the headspace bottle, and minimizing the loss of flavor components extracted using other shaped headspace bottles / glasses or similar devices.

[0035] Example 1 A method for enriching and extracting flavor components from an empty glass of baijiu (Chinese liquor) and its application, comprising the following steps: (1) Take about 15 mL of the sauce-flavored baijiu sample and pour it into a tulip-shaped glass headspace bottle. Gently shake the headspace bottle to form a coating on the wall and let it stand for 5 minutes. After standing, pour out the baijiu sample from the special headspace bottle and let it air dry naturally for 1.5 minutes.

[0036] (2) The headspace vial that has been air-dried was heated in a water bath at 50°C and extracted using an extraction head (50 / 30μm DVB / CAR / PDMS) at 50°C for 15 min to obtain an extraction head for extracting flavor components once.

[0037] (3) The above extraction process is repeated twice to obtain an extraction head that can continuously extract the flavor components of the empty glass of baijiu three times. The extraction head is quickly inserted into the gas chromatograph injection port, and then the flavor components of the empty glass of baijiu sample are detected by gas chromatography-mass spectrometry.

[0038] The gas chromatography parameters were set as follows: DB-WAX column (30 m × 0.25 mm × 0.25 µm), high-purity helium (99.999%) as carrier gas, and constant flow rate of 1.0 mL / min.

[0039] The temperature program was set as follows: starting at 40℃, increasing to 50℃ at 10℃ / min (holding for 5 min); then increasing to 80℃ at 3℃ / min (holding for 5 min); and finally increasing to 230℃ at 5℃ / min (holding for 5 min).

[0040] The mass spectrometry parameters were set as follows: the mass spectrometer used an electron impact (EI) source, the ion source temperature was 230 °C, the electron energy was set to 70 eV, the quadrupole temperature was 150 °C, and a full scan mode was used.

[0041] GC-MS was used to detect and analyze the flavor components of the empty glass aroma of Maotai-flavor liquor. The flavor components were qualitatively identified by comparing with the NIST standard library and the retention index. The detected flavor components are shown in Table 1.

[0042] Table 1 Example 2 The same method and application of the extraction and enrichment of aroma components in empty glass of baijiu as in Example 1 were adopted, except that the three consecutive repeated extractions were changed to two consecutive repeated extractions.

[0043] Table 2 Example 3 The same method for enriching and extracting the aroma components of baijiu in an empty glass as in Example 1 was used, except that the three consecutive extractions were changed to four consecutive extractions.

[0044] Table 3 Example 4 The same method for enriching and extracting the aroma components of baijiu in an empty glass as in Example 1 was used, except that the three consecutive extractions were changed to five consecutive extractions.

[0045] Table 4 Comparative Example 1 The same method for enriching and extracting the aroma components of baijiu in an empty glass as in Example 1 was used, except that the extraction was not repeated continuously and was performed only once.

[0046] Table 5 The test results from Examples 1-4 and Comparative Example 1 (Tables 1-5) show that, with repeated extractions of 1-3 times, the number of detectable flavor components gradually increases with the number of extractions. Beyond 3 extractions, the extraction effect decreases due to the limited adsorption capacity of the extraction head. By adjusting the number of repeated extractions, the number of flavor components detected in the empty glass of baijiu can be significantly increased, thereby improving the comprehensiveness of the analysis of the aroma characteristics of baijiu in an empty glass.

[0047] Comparative Example 2 The method and application of the enrichment and extraction of aroma components in empty cups of baijiu were adopted using the same comparative ratio 1. The difference is that commercially available cylindrical top-empty bottles were used, and only 25 types were detected.

[0048] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for enriching and extracting flavor components from an empty glass of baijiu (Chinese liquor), characterized in that, include: 1) Pour the wine sample to be tested into a tulip-shaped headspace bottle, let it stand, and then pour out the wine sample; 2) The headspace vial was air-dried and heated in a water bath, and flavor components were extracted using headspace solid-phase microextraction; 3) Repeat steps 1) and 2) at least twice to continuously extract the baijiu aroma sample from the empty glass.

2. The method according to claim 1, characterized in that, The repetition is performed 2-5 times; preferably, it is performed 3 times.

3. The method according to claim 1 or 2, characterized in that, Pour 12-18 mL of wine sample into the headspace bottle, gently shake 3-8 times, let stand for 4-6 minutes, pour out the wine sample, and let it air dry naturally for 1-2 minutes.

4. The method according to any one of claims 1-3, characterized in that, The water bath heating and / or the extraction temperature is 50-70℃, and the extraction time for a single extraction is 8-15 min.

5. The method according to any one of claims 1-4, characterized in that, The headspace bottle is shaped like a tulip cup.

6. A method for detecting the aroma components remaining in an empty glass of baijiu (Chinese liquor), characterized in that, A sample of baijiu (Chinese liquor) with lingering aroma in an empty glass is obtained by the method described in claims 1-5. The flavor components of the sample are detected by gas chromatography. Preferably, the extraction head is inserted into the inlet of a gas chromatograph-mass spectrometer, and the flavor components in the sample are detected by gas chromatography-mass spectrometry.

7. The detection method according to claim 6, characterized in that, The temperature program for the gas chromatograph includes: increasing the temperature from 35-42℃ to 45-60℃ at 9-12℃ / min and holding for 3-7 min; increasing the temperature to 70-90℃ at 2-5℃ / min and holding for 3-7 min; and increasing the temperature to 200-250℃ at 4-6℃ / min and holding for 3-7 min.

8. The detection method according to claim 6 or 7, characterized in that, The gas chromatography used a DB-WAX column with dimensions of 30-50m × 0.25mm × 0.25µm, and high-purity helium as the carrier gas, with a constant flow rate of 1-1.5mL / min.

9. The detection method according to any one of claims 6-8, characterized in that, The mass spectrometry parameters include: an electron impact source, an ion source temperature of 220-230℃, an electron energy of 60-80 eV, a quadrupole temperature of 140-160℃, and a full scan mode.

10. The application of the method according to any one of claims 1-5 or the detection method according to any one of claims 6-9 in analyzing the aroma characteristics of baijiu left in an empty glass; preferably, the number of flavor components detected in the baijiu left in an empty glass is ≥50.

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