CN115792050A - Method for detecting flavor substances of white spirit empty-cup fragrance - Google Patents
Method for detecting flavor substances of white spirit empty-cup fragrance Download PDFInfo
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Abstract
The application relates to the technical field of liquor detection, in particular to a detection method of a white liquor empty cup fragrance flavor substance, which comprises the following steps: (1) Putting a white spirit sample into a container, pouring the white spirit sample out of the container after standing, and adding an internal standard substance after nitrogen blowing treatment of the container to obtain a white spirit empty cup fragrance sample to be detected; (2) And extracting the flavor substances of the white spirit empty cup aroma sample to be detected by adopting a headspace solid-phase microextraction method, and detecting the flavor substances of the white spirit empty cup aroma sample to be detected by adopting a gas chromatograph-mass spectrometer. This application can reduce the interference of volatile substance to the detection, promotes the stability that detects semi-volatile or difficult volatile substance.
Description
Technical Field
The application relates to the technical field of detection of white spirit flavor substances, in particular to a detection method of white spirit empty cup fragrance flavor substances.
Background
The hollow fragrance of the white spirit refers to the phenomenon that the fragrance of the white spirit stays on the wall of a cup filled with high-quality white spirit, so that the aftertaste of people is long. The reason for this phenomenon is twofold: firstly, the flavor substances of the high-quality white spirit are various, and the interaction among the substances is complex, so that the volatilization speed of the high-quality white spirit is low; secondly, the white spirit contains a plurality of flavor substances which are difficult to volatilize, and the aroma of the white spirit can stay in the empty cup for a long time. Researches show that the duration of the empty cup fragrance is a great factor for evaluating the quality of the white spirit, so that the researches on the flavor substances with lasting empty cup fragrance of the white spirit provide technical support and data support for scientifically understanding the sensory characteristics of the empty cup fragrance of the white spirit, and have important significance for the quality evaluation of the white spirit.
In the prior art, a static headspace-gas-mass combination method is adopted to detect and analyze the fragrance components of the empty cup fragrance of Maotai-flavor liquor, and 11 key compounds with fragrance contribution are determined, but the method has the following problems: the method is suitable for analyzing volatile alcohols, aldehydes and the like, is not suitable for analyzing semi-volatile or nonvolatile substances with low content, cannot accurately and effectively detect semi-volatile or nonvolatile substances which contribute more to the empty aroma, has large required wine sample amount, is easy to be influenced by environmental conditions before natural volatilization, and has low detection stability.
Disclosure of Invention
In order to solve the problems, the application provides a detection method of a white spirit empty-cup aroma flavor substance.
The application provides a detection method of white spirit empty glass fragrance flavor substance, which adopts the following technical scheme:
a detection method of white spirit empty-cup fragrance flavor substances comprises the following steps:
(1) Putting a white spirit sample into a container, pouring the white spirit sample out of the container after standing, carrying out nitrogen blowing treatment on the container, and adding an internal standard substance to obtain a white spirit empty cup aroma sample to be detected;
(2) Extracting the flavor substances of the white spirit empty-cup aroma sample to be detected by adopting a headspace solid-phase microextraction method, and detecting the flavor substances of the white spirit empty-cup aroma sample to be detected by adopting a gas chromatography-mass spectrometer;
the flavor substance of the white spirit empty-cup aroma sample to be detected is a semi-volatile or nonvolatile flavor substance.
Preferably, the step (1) comprises: taking 2-4 mL of a white spirit sample in a container, standing for 8-12 min, pouring the white spirit sample out of the container, carrying out nitrogen blowing treatment on the container, and adding an internal standard substance to obtain an empty aroma sample of the white spirit to be detected;
preferably, the step (1) comprises: taking 2mL of a white spirit sample in a container, standing for 10min, pouring out the white spirit sample from the container, carrying out nitrogen blowing treatment on the container, and adding an internal standard substance to obtain a white spirit empty cup aroma sample to be detected.
Preferably, the nitrogen blowing time for performing the nitrogen blowing treatment on the container is determined by the outline of the empty-cup fragrance sensory organ, the total peak area of the volatile substances and the total peak area of the substances with high fragrance intensity which are detected after the nitrogen blowing treatment;
preferably, the nitrogen blowing time for the nitrogen blowing treatment of the container is 20min.
Preferably, the volume of the added internal standard substance is 1-3 μ L;
preferably, the volume of added internal standard is 2. Mu.L.
Preferably, the internal standard is citronellol or tert-amyl alcohol;
preferably, the internal standard is citronellol;
more preferably, the concentration of citronellol is 238mg/L.
Preferably, the step (2) includes: extracting the flavor substances of the white spirit empty-cup aroma sample to be detected by using an extraction head to obtain the extraction head for extracting the flavor substances; and inserting the extraction head for extracting the flavor substances into a gas chromatography sample inlet, and detecting the flavor substances of the white spirit empty-cup flavor sample to be detected by adopting a gas chromatography-mass spectrometer.
Preferably, the extraction temperature of the flavor substances of the white spirit empty-cup aroma sample to be detected by the extraction head is 70-80 ℃, and the extraction time is 40-50 min;
preferably, the extraction temperature of the flavor substances of the white spirit empty-cup aroma sample to be detected by the extraction head is 70 ℃, and the extraction time is 40min.
Preferably, in the step (2), the gas chromatography parameters are set as: adopting an FFAP chromatographic column, wherein the parameters of the FFAP chromatographic column are 30m multiplied by 0.25mm multiplied by 0.25 mu m, the carrier gas is helium, the flow rate is 0.8-1.2 mL/min, and adopting non-split flow sample injection;
the temperature-raising program is: the initial temperature is 40 ℃, the temperature is kept for 1min, the temperature is increased to 80 ℃ at the speed of 8-12 ℃/min, then the temperature is increased to 140 ℃ at the speed of 3-5 ℃/min, and finally the temperature is increased to 220 ℃ at the speed of 8-12 ℃/min, and the temperature is kept for 10min.
Preferably, the gas chromatography parameters are set as: adopting an FFAP chromatographic column, wherein the parameters of the FFAP chromatographic column are 30m multiplied by 0.25mm multiplied by 0.25 mu m, the carrier gas is helium, the flow rate is 1mL/min, and adopting non-split flow sample injection;
the temperature rising procedure is as follows: the initial temperature was 40 deg.C, held for 1min, ramped to 80 deg.C at a rate of 10 deg.C/min, ramped to 140 deg.C at a rate of 3 deg.C/min, ramped to 220 deg.C at a rate of 10 deg.C/min, and held for 10min.
Preferably, in the step (2), the mass spectrum parameters are set as: the temperature of the four-level bar is 140-160 ℃, the temperature of the EI ion source is 220-240 ℃, an ion scanning mode is adopted, and the scanning range is m/z 30-400 amu;
preferably, the mass spectrometry parameters are set as: the temperature of the quadrupole is 150 ℃, the temperature of the EI ion source is 230 ℃, an ion scanning mode is adopted, and the scanning range is m/z 30-400 amu.
The application has the following beneficial technical effects:
volatile flavor substances are removed through nitrogen blowing treatment, and enrichment detection is carried out through headspace solid phase micro-extraction; the detection interference of the volatile flavor substances on semi-volatile or difficultly-volatile empty-cup-shaped fragrance substances can be reduced, the semi-volatile or difficultly-volatile empty-cup-shaped fragrance substances can be detected, the stability of nitrogen blowing detection is far higher than that of natural volatilization, and the detection result is more accurate and reliable; meanwhile, more semi-volatile or hardly-exerted flavor substances can be detected in a headspace solid phase microextraction mode, and more comprehensive detection can be performed on the white spirit empty-cup flavor substances.
Drawings
FIG. 1 is a comparison of the peak areas measured at different extraction temperatures in example 3;
FIG. 2 is a comparison of the peak areas measured at different extraction times in example 4;
FIG. 3 is a comparison of peak areas detected for different volumes of white spirit samples in example 5;
FIG. 4 is the sensory profile of hollow cup aroma of example 6;
FIG. 5 is a graph of the sensory profile of empty cupule fragrance at different nitrogen blowing times in example 6;
FIG. 6 is a graph comparing the total peak areas of volatile substances at different nitrogen blowing times in example 6;
FIG. 7 is a comparison of total peak areas of the substances with greater fragrance intensity for different nitrogen blowing times in example 6;
FIG. 8 is a graph showing the results of measurement of the static headspace extraction of an empty-cup aroma flavor substance in comparative example 1;
FIG. 9 is a graph showing the results of measuring the headspace solid-phase microextraction of the empty-cup aroma flavor substance in comparative example 1;
FIG. 10 is a graph of the sensory profile of empty cupels in comparative example 2 with different natural volatilization times;
FIG. 11 is a comparison of the total peak areas of the volatile substances for different natural volatilization times in comparative example 2;
FIG. 12 is a comparison of the total peak areas of the substances having higher fragrance intensities at different natural volatilization times in comparative example 2.
Detailed Description
The duration time of the empty cup fragrance is a great factor for evaluating the quality of the white spirit, so that research on the flavor substances with lasting empty cup fragrance of the white spirit provides technical support and data support for scientifically understanding the sensory characteristics of the empty cup fragrance of the white spirit, and has important significance for quality evaluation of the white spirit. The volatile white spirit flavor substances can be volatilized into the air in a short time, so that the semi-volatile or difficultly-volatile empty-cup fragrance flavor substances greatly contribute to the duration time of the white spirit empty-cup fragrance, and when the white spirit empty-cup fragrance flavor substances are detected, the semi-volatile or difficultly-volatile empty-cup fragrance flavor substances are required to be detected.
In the prior art, a static headspace-gas chromatography-mass spectrometry method is adopted to detect and analyze the components of the empty cup aroma of Maotai-flavor liquor, and 11 key compounds with aroma contribution are determined, but the method has the following problems: the method is suitable for analyzing volatile alcohols, aldehydes and the like, is not suitable for analyzing semi-volatile or nonvolatile substances with low content, cannot accurately and effectively detect semi-volatile or nonvolatile substances with larger contribution to empty glass fragrance, has large required wine sample amount, is easy to be influenced by environmental conditions before natural volatilization, and has low detection stability. Based on the above, the application provides a detection method of white spirit empty-cup aroma flavor substances to solve the above problems.
The present application is further illustrated by the following examples.
Example 1
A detection method of white spirit empty-cup fragrance flavor substances comprises the following steps:
(1) Putting a white spirit sample into a container, pouring the white spirit sample out of the container, performing nitrogen blowing treatment on the container, and adding an internal standard substance to obtain a white spirit empty-cup aroma sample to be detected.
Specifically, 2mL of Maotai-flavor liquor sample is transferred into a container, the container in the embodiment is a 20mL threaded bottle, and in other embodiments, the container can also be a headspace bottle, the liquor sample is poured out of the threaded bottle after standing for 10min, nitrogen blowing treatment is performed on the interior of the threaded bottle for 20min, then 2 μ L of citronellol serving as an internal standard substance is added into the threaded bottle, the concentration of citronellol is 238mg/L, and the liquor empty-cup flavor sample to be detected is obtained.
(2) Extracting flavor substances of the white spirit empty-cup aroma sample to be detected by adopting a headspace solid-phase microextraction method, and detecting the flavor substances of the white spirit empty-cup aroma sample to be detected by adopting a gas chromatography-mass spectrometer (GC-MS); the flavor substance of the white spirit empty-cup aroma sample to be detected is a semi-volatile or nonvolatile flavor substance.
Specifically, extracting flavor substances of the white spirit empty-cup aroma sample to be detected by using an extraction head (50/30 mu m DVB/CAR/PDMS), wherein the extraction temperature is 70 ℃, and the extraction time is 40min, so as to obtain the extraction head for extracting the flavor substances. And inserting the extraction head for extracting the flavor substances into a gas chromatography sample inlet, and detecting the flavor substances of the white spirit empty-cup flavor sample to be detected by adopting a gas chromatography-mass spectrometer.
The gas chromatography parameters were set as: adopting an FFAP chromatographic column, wherein the parameters of the FFAP chromatographic column are 30m multiplied by 0.25mm multiplied by 0.25 mu m, the carrier gas is helium, the flow rate is 1mL/min, and adopting non-split flow sample injection;
the temperature rising procedure is as follows: the initial temperature was 40 deg.C, held for 1min, ramped to 80 deg.C at a rate of 10 deg.C/min, ramped to 140 deg.C at a rate of 3 deg.C/min, ramped to 220 deg.C at a rate of 10 deg.C/min, and held for 10min.
The mass spectrum parameters were set as: the temperature of the four-level bar is 150 ℃, the temperature of the EI ion source is 230 ℃, an ion scanning mode is adopted, and the scanning range is m/z 30-400 amu.
GC-MS is adopted to detect the empty-cup aroma flavor substances of the Maotai-flavor liquor, qualitative detection is carried out on the empty-cup aroma flavor substances of the liquor through a chromatographic Retention Time (RT), a comparison result of a NIST standard spectrum library and a method of combining the aroma substances, each flavor substance content is subjected to semi-quantitative analysis by adopting an internal standard substance citronellol, and 17 semi-volatile or difficult-to-volatile liquor empty-cup aroma flavor substances of the detected Maotai-flavor liquor are shown in Table 1.
TABLE 1 empty cup fragrance flavor materials of Maotai-flavor liquor
Method stability evaluation:
method stability evaluation is expressed as relative standard deviation between days (RSD) and the method for determining relative standard deviation between days is as follows: after 2 days, the detection steps of the embodiment 1 are adopted to detect the white spirit empty-cup fragrance substances, and the total peak area of the empty-cup fragrance substances is calculated. And (3) performing three parallel experiments, and calculating the relative standard deviation (daytime relative standard deviation) according to the total peak area of the white spirit empty-cup flavor substances measured for three times, wherein the daytime relative standard deviation is 2.1%.
Example 2
The difference between the embodiment and the embodiment 1 is that the white spirit sample in the embodiment is a fen-flavor white spirit sample, and the rest detection steps are the same as those in the embodiment 1. The 15 kinds of semi-volatile or non-volatile white spirit empty cup aroma flavor substances of the detected fen-flavor white spirit are shown in table 2.
TABLE 2 fragrant white spirit empty cup fragrant flavor material
As can be seen from the examples 1 and 2, the empty cup fragrance flavor substances of the white spirit samples with different flavor types are different, and the detection method is also suitable for detecting the empty cup fragrance flavor substances of the fen-flavor white spirit.
Example 3 investigation of the Effect of different extraction temperatures of headspace solid phase microextraction on assay results
In this embodiment, the influence of different extraction temperatures on the detection result of the headspace solid-phase microextraction is explored, and the different extraction temperatures include: 50 deg.C, 60 deg.C, 70 deg.C, 80 deg.C. The flavor substances of the empty-cup aroma of the white spirit sample are extracted at 50 ℃, 60 ℃, 70 ℃ and 80 ℃ respectively, and then the detection is carried out, the rest detection steps are the same as the example 1, and the total peak areas detected at different extraction temperatures are shown in figure 1.
It can be seen from fig. 1 that, at an extraction temperature of 50 to 70 ℃, the total peak area of the detected empty aroma flavor substances of the white spirit sample gradually increases with the increase of the extraction temperature and reaches a maximum value at the extraction temperature of 70 ℃, and when the extraction temperature exceeds 70 ℃, the total peak area of the detected empty aroma flavor substances of the white spirit sample shows a descending trend. This shows that the total peak area of the empty-cup-flavor substances of the detected white spirit sample can be significantly increased by adjusting the extraction temperature of the headspace solid-phase microextraction, and the empty-cup-flavor substances of the white spirit sample can be more accurately detected.
Example 4 investigation of the Effect of different extraction times of headspace solid phase microextraction on assay results
In this embodiment, the influence of different extraction times of headspace solid-phase microextraction on the detection result is explored, and the different extraction times include: 20min, 30min, 40min, 50min, 60min. Extracting the flavor substances with the empty cup fragrance of the liquor sample at 20min, 30min, 40min, 50min and 60min respectively, and detecting, wherein the rest detection steps are the same as those in example 1, and the total peak areas detected at different extraction times are shown in FIG. 2.
As can be seen from fig. 2, when the extraction time is 20-40 min, the total peak area of the detected empty-cup aroma flavor substances of the white spirit sample gradually increases with the increase of the extraction time and reaches the maximum value when the extraction time is 40min, and when the extraction time exceeds 40min, the total peak area of the detected empty-cup aroma flavor substances of the white spirit sample tends to decrease. This shows that the total peak area of the empty-cup-flavor substances of the detected white spirit sample can be significantly improved by adjusting the extraction time of the headspace solid-phase microextraction, so that the accuracy of the detection of the empty-cup-flavor substances of the white spirit sample is improved.
Example 5 study of the influence of different volumes of white spirit samples on the test results
This embodiment is for exploring the influence of different volume white spirit samples to the testing result, and the volume of different white spirit samples includes: 0.5mL, 1mL, 1.5mL, 2mL, 2.5mL, 3mL, 4mL. The same procedures as in example 1 were repeated except that 0.5mL, 1mL, 1.5mL, 2mL, 2.5mL, 3mL, and 4mL of each of the white spirit samples were put into a 20mL screw bottle and the nitrogen-blowing treatment was replaced by natural standing and volatilization for 2 hours. The total peak areas detected for different volumes of white spirit samples are shown in fig. 3.
As can be seen from FIG. 3, when the volume of the white spirit sample is less than 2mL, the residual quantity on the bottle wall is small due to the small volume, and the total peak area of substance response is low; when the volume of the white spirit sample is 2mL or more, the peak area value of the substance response total peak is close, so that the 2mL white spirit sample is selected as the optimal selection.
Example 6 investigation of the Effect of different Nitrogen purge times on the assay results
And (3) transferring 2mL of the Maotai-flavor liquor sample into a 20mL threaded bottle, standing for 10min, and pouring out the liquor sample from the threaded bottle. The dimensions of acid aroma, sweet aroma, flower aroma, nut aroma, dry plant aroma and green grass aroma of the white spirit empty cup aroma in the threaded bottle are evaluated by a 0-3-to-6-point scale method, wherein 0.5 is divided into one scale, 0.5 is divided into one scale for smelling, and 3 is divided into 3 scales with the highest strength. The sensory profile of the empty-cup aroma evaluated is shown in fig. 4, and the sensory characteristics of the empty-cup aroma are mainly a combination of sour, dry, sweet, nut and floral notes.
And (3) searching aroma substances of all dimensions of the empty-cup aroma sensory radar chart by adopting a GC-O aroma smelling method, and detecting representative substances of aroma and corresponding aroma smelling intensity.
The GC-0 fragrance smelling method specifically comprises the following steps:
extracting flavor substances of the white spirit empty-cup aroma sample to be detected by using an extraction head (50/30 mu m DVB/CAR/PDMS), wherein the extraction temperature is 70 ℃, and the extraction time is 40min, so as to obtain the extraction head for extracting the flavor substances. And inserting the extraction head into a gas chromatography-mass spectrometer provided with a fragrance smelling instrument to obtain the fragrance characteristics of each substance. The instrument was equipped with a sniffing port and an air humidifier connected to an Rtx-5 column (30 m x 0.25mm x 0.25 μm).
Gas chromatography conditions: adopting an FFAP chromatographic column, wherein the parameters of the FFAP chromatographic column are 30m multiplied by 0.25mm multiplied by 0.25 mu m, helium is taken as carrier gas, the flow rate is 1mL/min, and non-split flow sample injection is adopted; the temperature-raising program is: the initial temperature was 40 deg.C, held for 1min, ramped to 80 deg.C at a rate of 10 deg.C/min, ramped to 140 deg.C at a rate of 3 deg.C/min, ramped to 220 deg.C at a rate of 10 deg.C/min, and held for 10min.
Mass spectrum conditions: the temperature of the four-level bar is 150 ℃, the temperature of the EI ion source is 230 ℃, an ion scanning mode is adopted, and the scanning range is m/z 30-400 amu.
The column effluent was separated at a ratio of 1. Meanwhile, humid air and hydrogen gas were injected into the sniffing port at flow rates of 40mL/min and 30mL/min, respectively, to rapidly remove the odor of the sniffing port. The results of GC-0 fragrance application are shown in Table 3.
TABLE 3 fragrance results of empty cups GC-O smelling
| Substance(s) | Description of smelling fragrance | GC-O fragrance intensity a | |
| 3-methyl butyraldehyde | Fruit-flavor, slightly nut-flavor | 0.5 | |
| 3-methyl-1-butanol | Burnt incense | 0.5 | |
| Lactic acid ethyl ester | Mushroom and dry plant incense | 2.5 | |
| Trimethylpyrazine | Nut incense | 2.5 | |
| Acetic Acid (AA) | Sour incense | 2.5 | |
| Tetramethylpyrazine | Baking incense and nut incense | 2.5 | |
| Propionic acid | Sour incense | 1.5 | |
| Butyric acid | Sour incense | 2.5 | |
| Isovaleric acid | Sour incense | 2.5 | |
| Phenylacetic acid ethyl | Floral fragrance | 2 | |
| Capric acid ethyl ester | Fruit incense | 1.5 | |
| Phenylethanolic | Rose fragrance | 3 | |
| Nonolactone | Milk candy, sweet fragrance | 2.5 |
As the substances having a large aroma intensity in each aroma dimension, acetic acid, ethyl lactate, nonalactone, tetramethylpyrazine, and phenethyl alcohol were used as the optimization index in table 3.
The influence of different nitrogen blowing time on the detection result is explored, the different nitrogen blowing time comprises 0, 20, 40, 60 and 80min of nitrogen blowing, the nitrogen blowing treatment is respectively carried out on the inner part of the threaded bottle for 0, 20, 40, 60 and 80min, and the other detection steps are the same as those of the embodiment 1 for detection; and detecting the fragrance smelling intensity of the empty cup fragrance by adopting a GC-O fragrance smelling technology. FIG. 5 shows the outline of the empty-cup aroma, FIG. 6 shows the total peak area of volatile substances such as ethanol, n-butanol, 2-methylpropanol, n-butanol, isoamyl alcohol, and amyl alcohol, and FIG. 7 shows the peak area of the response of the substances with higher aroma intensity such as acetic acid, ethyl lactate, nonalactone, tetramethylpyrazine, and phenethyl alcohol.
As can be seen from fig. 5, the sensory intensity of each fragrance dimension gradually decreased with the increase of the nitrogen blowing time, and the sensory intensity of each fragrance dimension was still strong at the time of 20min of nitrogen blowing. As can be seen from FIG. 6, the total peak area of the volatile substances was greatly reduced after 20min of nitrogen purge, which indicates that most of the volatile substances had evaporated, removing the interference from the volatile substances. As can be seen from fig. 7, acetic acid, ethyl lactate, nonalactone, tetramethylpyrazine, and phenethyl alcohol were also effectively detected after 20min of nitrogen-blowing, but acetic acid and nonalactone were not effectively detected after 40min of nitrogen-blowing. In combination with fig. 5 to 7, most of volatile substances can be removed when the nitrogen is blown for 20min, so that the detection interference is reduced, and meanwhile, the empty cup fragrance substances can be effectively detected.
Comparative example 1
Taking 1mL of Maotai-flavor liquor sample, standing for 10min in a 20mL threaded bottle, pouring out, naturally standing and volatilizing for 2h, respectively extracting the empty-cup-flavor substances by adopting static Headspace (HS) and headspace solid-phase microextraction (HS-SPME), and detecting by adopting a gas chromatography-mass spectrometer, wherein the rest detection steps are the same as those in example 1. The results of HS-GC-MS detection are shown in FIG. 8, the results of HS-SPME-GC-MS detection are shown in FIG. 9, and the abscissa of FIGS. 8 and 9 represents the types of substances and the ordinate represents the specific number of substances.
As can be seen from FIGS. 8 and 9, 35 kinds of empty-cup aroma flavor substances were measured by HS-GC-MS and were mostly volatile flavor substances such as acetaldehyde and 3-methylbutanol, while more than 70 kinds of empty-cup aroma substances were measured by HS-SPME-GC-MS. Comparing the two results, the HS-GC-MS is suitable for analyzing volatile aroma substances, and the HS-SPME-GC-MS is beneficial to analyzing semi-volatile and non-volatile aroma substances and has an enrichment effect on the aroma substances.
Comparative example 2 investigation of the Effect of Natural volatilization instead of Nitrogen blowing treatment on the test results
In order to explore the influence of natural volatilization on the detection result by replacing nitrogen blowing treatment, 2mL of Maotai-flavor liquor sample is moved into a 20mL threaded bottle, is poured out of the threaded bottle after being kept stand for 10min, and is kept stand and volatilized for 0, 1, 2, 3 and 4 days (marked as 0d, 1d, 2d, 3d and 4 d) respectively, so as to replace nitrogen blowing treatment, and the rest detection steps are the same as those in the example 1 for detection; and detecting the fragrance smelling intensity of the empty cup fragrance by adopting a GC-O fragrance smelling technology. FIG. 10 shows the outline of the empty-cup aroma sensor, FIG. 11 shows the total peak area of volatile substances such as ethanol, n-butanol, 2-methylpropanol, n-butanol, isoamyl alcohol, and pentanol, and FIG. 12 shows the peak area of the response of substances with high aroma intensity such as acetic acid, ethyl lactate, nonalactone, tetramethylpyrazine, and phenethyl alcohol.
As can be seen from FIG. 10, the intensity of each fragrance only slightly changes after the empty cup is naturally volatilized for 1 day, and the sensory intensity of each fragrance is obviously weakened after the empty cup is naturally volatilized for 2 days, and the flavor profile is greatly different from that of the empty cup in 0 day. As can be seen from FIG. 11, when the empty cup naturally volatilizes for one day, the peak area of the volatile substance is only reduced by half, and the detection of the semi-volatile or non-volatile substance still has great interference. When the hollow cup naturally volatilizes for 2 days, the peak area of the volatile substance is obviously reduced, and the interference effect of the volatile substance on detection is reduced. However, as can be seen from fig. 12, after the empty cup is naturally volatilized for one day, the peak areas of acetic acid, ethyl lactate, nonalactone, tetramethylpyrazine and phenethyl alcohol have been significantly reduced, and after the cup is naturally volatilized for 2 days, the acetic acid, tetramethylpyrazine and phenethyl alcohol are substantially undetectable.
As can be seen from fig. 11 and 12, the detection interference of volatile substances on detection of semi-volatile or non-volatile substances cannot be effectively reduced by using a natural volatilization mode instead of nitrogen blowing, and effective detection of substances with high fragrance intensity, such as acetic acid, ethyl lactate, nonalactone, tetramethylpyrazine and phenethyl alcohol, can be maintained.
The stability of the detection method using natural volatilization instead of nitrogen blowing treatment was expressed as relative standard deviation between days (RSD), which was measured as follows: and (3) transferring 2mL of wine sample into a 20mL threaded bottle after 2 days, standing for 10min, pouring out the wine sample from the threaded bottle, naturally standing and volatilizing for 1 day, adding 2 mu L of citronellol internal standard substance, screwing a cover, detecting the empty-cup fragrance substance by adopting headspace solid-phase microextraction and a gas chromatograph-mass spectrometer, and calculating the total peak area of the empty-cup fragrance substance. And (3) performing three parallel experiments according to the method, calculating the Relative Standard Deviation (RSD) in the daytime by using the total peak area of the white spirit empty-cup aroma flavor substance determined by the three parallel experiments, and calculating the relative standard deviation in the daytime to be 13.23%.
By combining the example 1 and the comparative example 2, the relative standard deviation in daytime of the example 1 is 2.1 percent and less than 5 percent, the stability is good, and the detection result is more stable and reliable. The relative standard deviation between days of the comparative example 2 is 13.23%, the relative standard deviation between days is large, the detection result is greatly influenced by the environment, the detection result is unstable, and the accuracy is low. Therefore, the mode of nitrogen blowing treatment is adopted to compare with natural volatilization, the stability of the empty cup fragrance substance can be improved, and the detection result is more reliable.
Respectively detecting the white spirit empty-cup fragrance flavor substances which are statically placed and naturally volatilized for one day and two days according to the detection method in the comparative example 2; and detecting the GC-0 fragrance smelling strength of the white spirit empty cup fragrance flavor substances which are blown by nitrogen for 20 minutes in example 1 and are stood for naturally volatilizing for one day and naturally volatilizing for two days in comparative example 2 according to the GC-0 fragrance smelling method in example 6. The results of the test comparison are shown in Table 4.
Table 4 example 1 and comparative example 2 test comparative results
As can be seen from the table 4, volatile or non-volatile substances in the white spirit empty-cup fragrance substances can be detected by the nitrogen-blown volatilization for 20min and the standing volatilization for one day, but the fragrance smelling strength of the part of the empty-cup fragrance substances GC-0 blown by the nitrogen for 20min is stronger than the fragrance smelling strength of the white spirit empty-cup fragrance substances volatilized by the standing day. However, as can be seen from FIG. 11, the volatile substances are obviously removed after standing and volatilizing for two days. As can be seen from Table 4, when the mixture is left to volatilize for two days, many substances can not be detected, and the GC-0 fragrance smelling intensity is obviously weaker than that of the nitrogen-blown fragrance smelling intensity for 20min. This shows that neither standing volatilization for one day nor two days is suitable for detecting the flavor substance of the empty glass of the white spirit.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. A detection method of flavor substances of white spirit empty cups is characterized by comprising the following steps:
(1) Putting a white spirit sample into a container, pouring the white spirit sample out of the container after standing, and adding an internal standard substance after nitrogen blowing treatment of the container to obtain a white spirit empty cup fragrance sample to be detected;
(2) Extracting the flavor substances of the white spirit empty-cup aroma sample to be detected by adopting a headspace solid-phase microextraction method, and detecting the flavor substances of the white spirit empty-cup aroma sample to be detected by adopting a gas chromatography-mass spectrometer;
the flavor substance of the white spirit empty-cup aroma sample to be detected is a semi-volatile or nonvolatile flavor substance.
2. The detection method according to claim 1, wherein the step (1) comprises: taking 2-4 mL of white spirit sample in a container, standing for 8-12 min, pouring out the white spirit sample from the container, carrying out nitrogen blowing treatment on the container, and adding an internal standard substance to obtain an empty aroma sample of the white spirit to be detected;
preferably, the step (1) comprises: taking 2mL of a white spirit sample in a container, standing for 10min, pouring the white spirit sample out of the container, carrying out nitrogen blowing treatment on the container, and adding an internal standard substance to obtain a white spirit empty cup aroma sample to be detected.
3. The detection method according to claim 2, wherein the nitrogen-blowing time for the container is determined by a combination of a hollow-cup-fragrance sensory profile, a total peak area of volatile substances, and a total peak area of substances having a high fragrance intensity, which are detected after the nitrogen-blowing treatment;
preferably, the nitrogen blowing time for the nitrogen blowing treatment of the container is 20min.
4. The detection method according to claim 2, wherein the volume of the added internal standard substance is 1 to 3 μ L;
preferably, the volume of added internal standard is 2 μ L.
5. The detection method according to claim 2, wherein the internal standard is citronellol or t-amyl alcohol;
preferably, the internal standard is citronellol;
more preferably, the concentration of citronellol is 238mg/L.
6. The detection method according to claim 1, wherein the step (2) comprises: extracting the flavor substances of the white spirit empty-cup aroma sample to be detected by using an extraction head to obtain the extraction head for extracting the flavor substances; and inserting the extraction head for extracting the flavor substances into a gas chromatography sample inlet, and detecting the flavor substances of the white spirit empty-cup aroma sample to be detected by adopting a gas chromatography-mass spectrometer.
7. The detection method according to claim 6, wherein the extraction temperature of the flavor substances of the white spirit empty-cup aroma sample to be detected by the extraction head is 70-80 ℃, and the extraction time is 40-50 min;
preferably, the extraction temperature of the flavor substances of the white spirit empty-cup aroma sample to be detected by the extraction head is 70 ℃, and the extraction time is 40min.
8. The detection method according to claim 1, wherein in the step (2), the gas chromatography parameters are set as: adopting an FFAP chromatographic column, wherein the parameters of the FFAP chromatographic column are 30m multiplied by 0.25mm multiplied by 0.25 mu m, helium is taken as carrier gas, the flow rate is 0.8-1.2 mL/min, and non-split flow sample injection is adopted;
the temperature rising procedure is as follows: the initial temperature is 40 ℃, the temperature is kept for 1min, the temperature is increased to 80 ℃ at the speed of 8-12 ℃/min, then the temperature is increased to 140 ℃ at the speed of 3-5 ℃/min, and finally the temperature is increased to 220 ℃ at the speed of 8-12 ℃/min, and the temperature is kept for 10min.
9. The detection method according to claim 8, wherein the gas chromatography parameters are set to: adopting an FFAP chromatographic column, wherein the parameters of the FFAP chromatographic column are 30m multiplied by 0.25mm multiplied by 0.25 mu m, helium is taken as carrier gas, the flow rate is 1mL/min, and non-split flow sample injection is adopted;
the temperature-raising program is: the initial temperature was 40 deg.C, held for 1min, ramped to 80 deg.C at a rate of 10 deg.C/min, ramped to 140 deg.C at a rate of 3 deg.C/min, ramped to 220 deg.C at a rate of 10 deg.C/min, and held for 10min.
10. The detection method according to claim 1, wherein in the step (2), the mass spectrum parameters are set as: the temperature of the four-level bar is 140-160 ℃, the temperature of the EI ion source is 220-240 ℃, an ion scanning mode is adopted, and the scanning range is m/z 30-400 amu;
preferably, the mass spectrometry parameters are set as: the temperature of the four-level bar is 150 ℃, the temperature of the EI ion source is 230 ℃, an ion scanning mode is adopted, and the scanning range is m/z 30-400 amu.
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| CN118671240A (en) * | 2024-08-19 | 2024-09-20 | 四川国检检测有限责任公司 | Method for detecting antioxidant component in white spirit |
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| CN118671240A (en) * | 2024-08-19 | 2024-09-20 | 四川国检检测有限责任公司 | Method for detecting antioxidant component in white spirit |
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