CN111735804B - Ratio type fluorescence method for distinguishing fen-flavor primary pulp from liquid-method white spirit and solid-liquid-method white spirit - Google Patents
Ratio type fluorescence method for distinguishing fen-flavor primary pulp from liquid-method white spirit and solid-liquid-method white spirit Download PDFInfo
- Publication number
- CN111735804B CN111735804B CN202010624105.XA CN202010624105A CN111735804B CN 111735804 B CN111735804 B CN 111735804B CN 202010624105 A CN202010624105 A CN 202010624105A CN 111735804 B CN111735804 B CN 111735804B
- Authority
- CN
- China
- Prior art keywords
- white spirit
- liquid
- fluorescence
- ratio
- solid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N2021/6417—Spectrofluorimetric devices
- G01N2021/6421—Measuring at two or more wavelengths
Landscapes
- Health & Medical Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
A ratio type fluorescence method for distinguishing fen-flavor magma from liquid white spirit and solid-liquid white spirit belongs to the technical field of fluorescence spectrum. Since the main fluorescence emission peaks of each sample were located at 308nm, 330nm and 373nm, respectively, in the fluorescence spectrum. We refer to them as (H) 2 O)(EtOH) n (clusters that are hydrophobic outside and hydrophilic inside), (H) 2 O) m (EtOH) n (hybrid clusters) and (H) 2 O) m (EtOH) (an externally hydrophilic and internally hydrophobic cluster) three clusters. The invention distinguishes the fen-flavor primary pulp (both are more than 1) from the liquid white spirit (both are less than 1) and the solid-liquid white spirit (one is more than 1 and the other is less than 1) based on the size relation of the ratio of the fluorescence intensity 330/308 to the fluorescence intensity 330/373 to 1. The method adopted by the invention has the advantages of high detection speed, simple and convenient operation, simple system, stable signal, high sensitivity, no need of pretreatment, and no need of complex detection instruments except for a simple fluorescence spectrometer. Therefore, the method has very wide application prospect for distinguishing the fen-flavor primary pulp from the liquid-process white spirit and the solid-liquid-process white spirit.
Description
Technical Field
The invention belongs to the technical field of fluorescence spectrum, and particularly relates to a ratio type fluorescence method for distinguishing fen-flavor magma from liquid white spirit and solid-liquid white spirit by the fact that the intensity ratio of each main fluorescence emission peak is different from the magnitude relation of 1.
Background
Chinese white spirit is a unique type in distilled spirit in the world, and is deeply favored by consumers in China because the white spirit is colorless (or slightly yellow) and transparent, has aromatic, mellow and soft taste and remaining fragrance after drinking. The history of the white spirit in China is long, and people can hold cups and celebrate simultaneously and carry singing and dance in the traditional holiday or the modern holiday. The expression "drunk people are not in the sense of wine" means that people not only treat the wine as a drink, but also more people are helped with the emotion of humanity. White spirit has various brands and varieties and various quality and taste due to different production raw materials, auxiliary materials and manufacturing processes. The fragrance type is mainly classified into a strong fragrance type, a faint scent type, a sauce fragrance type and other fragrance types at present because the components are different. White spirit has become an indispensable part of our daily life. However, the white spirit produced by the traditional primary pulp has complex brewing process, long period and higher cost; and more than 98% of the components in the white spirit are ethanol and water, so that a profit opportunity is provided for illegal merchants: they use the scheme of mixing edible ethanol with water, then adding additive into them to make solid-liquid white liquor or pure liquid white liquor, and marking them as raw liquor so as to deceive consumers and obtain violence. At present, no simple and effective objective method for distinguishing raw liquor from liquor by a solid-liquid method and liquor by a liquid method exists due to the limited technical means. Therefore, the invention has very important significance in distinguishing the white spirit technical means of the different brewing processes.
However, with the increasing precision of metering technology and operation technology and automation of procedures, liquid process white spirit and solid-liquid process white spirit are also approaching with raw liquor in chemical composition, which undoubtedly brings greater difficulty and challenge for their differentiation and identification. At present, in the production flow and quality identification of white spirit, besides taste quality identification based on a wine taster, the common analysis and detection is mainly based on a gas chromatography technology and a liquid chromatography technology [1-2] . In addition, scientific research institutions can be assisted by ultraviolet-visible spectrum analysis [3] Near infrared spectroscopy [4-5] Atomic absorption spectrometry [6] Molecular fluorescence spectrometry, atomic fluorescence spectrometry, and the like. The principle on which these analytical instruments are based, apart from the wine tasters, is still itself the chemical composition of the wine, depending onIt is difficult to effectively distinguish the original pulp white spirit from the liquid white spirit and the solid-liquid white spirit. In fact, plasma emission spectrometry is also commonly used to determine the content of metallic elements in wine during the detection and identification of years of wine stored for many years [7] Measuring viscosity of Chinese liquor by using viscometer, measuring compound content of conjugated system by using ultraviolet absorption spectrometry, and identifying Chinese liquor with different flavors by using three-dimensional fluorescence spectrometry. Although these techniques and methods can provide some other physical parameters other than chemical components for white spirit, they still cannot effectively distinguish raw liquor with very similar components from liquid process white spirit and solid-liquid process white spirit. Therefore, a new method for distinguishing the original pulp white spirit from the liquid white spirit and the solid-liquid white spirit, which is quick, effective, low in cost, simple and easy to operate, is imperative to develop.
The method is used for identifying the chemical components and the year of the white spirit, is complex and complicated in operation, and does not exist at present for detecting and distinguishing the fen-flavor primary pulp from the liquid white spirit and the solid-liquid white spirit by a convenient and quick method; the fluorescence spectrum technology for detecting and identifying white spirit is different from other white spirit detection methods, and has a plurality of advantages. The fluorescence spectrum technology has the advantages of high sensitivity, strong selectivity, few required samples, more physical parameters, no need of pretreatment on the samples, and the like, so that the characteristics and the quality of the white spirit can be represented by the fluorescence spectrum. Reported in literature [8] Three-dimensional fluorescence spectroscopy (3 DEEM) has been applied to study structural features of commercially available white spirits and model white spirits. It is well known that neither an ethanol solution nor an aqueous solution alone emits fluorescence, but a solution formed by mixing ethanol and water emits fluorescence, and it is presumed that intermolecular association occurs inside the mixed solution, and a cluster having a fluorescence emission structure is formed, which is also a currently recognized point. According to the structural characteristics of the fluorescent molecules, the molecules are combined into a molecular cluster with a rigid plane structure through hydrogen bonding after ethanol and water are mixed, so that the conjugation degree of chemical bonds is enlarged; at the same time, the structure can reduce the vibration of the molecules, reduce the interaction between the molecules and other molecules in the mixture, reduce the loss of external energy transfer, and facilitate fluorescenceAnd (5) transmitting. It is generally considered that pure ethanol liquid is not a fluorescent substance and does not emit fluorescence, but in our previous experiments, it was found that pure ethanol liquid can absorb excitation light and emit very weak fluorescence, and possible reasons are as follows: (1) Self-association occurs between ethanol molecules to form a planar structure or a conjugated chemical bond; (2) The chromatographic pure ethanol contains a trace of water molecules, and the two molecules are associated to generate a cluster structure capable of emitting fluorescence. Generally, the three-dimensional fluorescence spectrum test time is long, alcohol is seriously volatilized during the test, the drawing is complex, and a conclusion is not easy to directly obtain; therefore, the difference between the fen-flavor magma and the liquid-state white spirit and the solid-liquid white spirit can be revealed more conveniently, clearly and quantitatively by utilizing the one-dimensional fluorescence spectrum and the corresponding ratio graph of the main fluorescence emission peak intensity, and the method can be used for distinguishing the fen-flavor magma from the liquid-state white spirit and the solid-liquid white spirit.
[1] Development of gas chromatography to determine flavour components in white spirit [ J ]. Brewing technology, 2006 (8): 104 to 107.
[2] Hu Guodong gas chromatography is used in white spirit analysis and review [ J ]. Food and fermentation industries, 2003, 29 (10): 65-69.
[3] Zhang Yuxia, dan Junhui, liu Guoqing, et al ultraviolet spectrophotometry to determine the content of furfural in white spirit [ J ]. Journal of the academy of education, xinyang: natural science edition, 2002, 15 (1): 56-57.
[4] Peng Bangzhu, long Minghua, yue Tianli, et al fourier transform near infrared spectroscopy to detect total acids and total fats of white spirits [ J ]. Agricultural engineering journal, 2006, 22 (12): 216 to 219.
[5] Wang Li, ji Keliang, xu Yan. Near infrared spectroscopy and its application in quality control of white spirit are envisaged [ J ]. Brewing, 2005, 32 (5): 17 to 19.
[6] Shenzhi super Wang Fangquan platform graphite oven atomic absorption spectrometry for direct determination of manganese in wine [ J ]. Food industry technology, 2003, 24 (1): 92-93.
[7] Talking about year wine and identification method [ J ]. Sichuan food and fermentation, 2008 (3): 28 to 31.
[8]Qiao H,Zhang S,Wang W.Fluorescence spectroscopic and viscosity studies of hydrogen bonding in Chinese Fenjiu.[J].Journal of bioscience and bioengineering,2013,115(4):405-411.
[9] Wu, liu Ying, han Caiqin, et al, laser raman spectroscopy was used to study the hydration process of liquid ethanol [ J ]. Spectroscopy and spectroscopic analysis, 2011, 31 (10): 2738-2741.
[10]Yui H,Kanoh K,Fujiwara H,etal.Stimulated Raman scattering of liquid water under the strong focusing condition:analysis of local hydration network environments in dilute ethanol solutions.[J].The Journal of Physical Chemistry A,2002,106(50):12041～12044.
Disclosure of Invention
The invention aims to provide a ratio type fluorescence method for distinguishing fen-flavor primary pulp from liquid white spirit and solid-liquid white spirit based on the difference of the magnitude relation between the ratio of the intensities of all main fluorescence emission peaks of fluorescence spectrum and 1, which comprises the following steps:
(1) Sample sources and preparation: the first is faint scent type primary pulp with different alcohol degrees (faint scent type primary pulp with different alcohol degrees is obtained by diluting faint scent type primary pulp with high alcohol degrees with purified water and standing for one week); the second is solid-liquid method white spirit with different alcohol degrees (solid-liquid method white spirit with different alcohol degrees is obtained by diluting solid-liquid method white spirit with high alcohol degrees with purified water and standing for one week); the third is liquid-state white spirit with different alcohol degrees (liquid-state white spirit with different alcohol degrees is obtained by diluting high-volume concentration ethanol solution with purified water and standing for one week as model white spirit);
(2) Fluorescence spectrum test: taking 1 milliliter of the sample in the step (1) for fluorescence spectrometry; the test parameters are as follows: excitation wavelength 240 nm, emission wavelength 280-450 nm, scanning speed: slow; slit: 5 x 10 nm;
(3) According to the fluorescence spectrogram obtained in the step (2), calculating the ratio of the fluorescence intensity at 330nm to the fluorescence intensity at 308nm of the samples with different alcohol degrees, and simultaneously calculating the ratio of the fluorescence intensity at 330nm to the fluorescence intensity at 373 nm;
(4) Judging the type of the wine according to the size relation between the two ratios obtained in the step (3) and 1: if both are more than 1, the wine sample is faint scent type primary pulp; if both are smaller than 1, the liquor sample is liquid method liquor; if one of the two is smaller than 1 and the other is larger than 1, the liquor sample is solid-liquid white liquor.
The fluorescence spectrum diagrams of the fen-flavor raw pulp, the solid-liquid white spirit and the liquid white spirit are shown in fig. 1, and the fluorescence spectra (fig. 1 a) of different fen-flavor raw pulp and solid-liquid white spirit are greatly different from the fluorescence spectra (fig. 1 b) of corresponding liquid white spirit, and the main appearance of the fluorescence spectrum diagrams is that the intensity of main fluorescence emission peaks is different.
In the ratio-type fluorescence method based on the difference of the magnitude relation between the ratio of the intensities of all the main fluorescence emission peaks of the fluorescence spectrum and 1, the main fluorescence emission peaks are 308 nanometers, 330 nanometers and 373 nanometers respectively. According to the literature [9-10] We refer to them as (H) 2 O)(EtOH) n (clusters that are hydrophobic outside and hydrophilic inside), (H) 2 O) m (EtOH) n (hybrid clusters) and (H) 2 O) m (EtOH) (an externally hydrophilic and internally hydrophobic cluster) three clusters. The primary pulp with faint scent (more than 1) is distinguished from the white spirit with liquid method (less than 1) and the white spirit with solid-liquid method (more than 1 and less than 1) mainly according to the size relation of the ratio of the fluorescence intensity 330/308 to the fluorescence intensity 330/373 to 1.
The ratio type fluorescence method based on the difference of the magnitude relation between the ratio of the intensities of the main fluorescence emission peaks in the fluorescence spectrum and 1 has the advantages of high detection speed, simple and convenient operation, simple system, stable signal, high sensitivity, no need of pretreatment, and no need of complex detection instrument except for a simple fluorescence spectrometer. Therefore, the method has very wide application prospect for distinguishing the fen-flavor primary pulp from the liquid-process white spirit and the solid-liquid-process white spirit.
Drawings
Fig. 1: (a) The fluorescent spectrum is used for different fen-flavor raw pulp and solid-liquid white spirits (most of commercially available low-price white spirits are solid-liquid white spirits and are suitable for identification by the method of the invention), and the abscissa is fluorescence emission wavelength and the ordinate is fluorescence intensity; (b) The fluorescence spectrum diagrams of the liquid-state white spirit (ethanol solutions with different volume fractions prepared in a laboratory) with different volume concentrations are shown in the horizontal coordinate of fluorescence emission wavelength, and the vertical coordinate of fluorescence intensity.
FIG. 1a is a fluorescence spectrum obtained by taking 1 ml of different fen-flavor raw pulps and solid-liquid white spirits (sources: a part of which is provided by Fenjiu group cooperators and a part of which is commercially available and purchased at low price, verifying that Fenjiu (a) and Daqu #2 are raw pulps and the other is solid-liquid white spirits) in a quartz cell of 4×10×45 cubic millimeters, placing the quartz cell in the fluorescence spectrometer, and setting corresponding parameters;
FIG. 1b is a fluorescence spectrum obtained by taking 1 ml of the prepared aqueous ethanol solution (after one week of standing, in order to achieve stability) in a quartz cell of 4X 10X 45 cubic millimeter, placing in the above-mentioned fluorescence spectrometer, and setting the corresponding parameters. According to FIG. 1a, it can be seen that the main fluorescence emission peaks of different fen-flavor raw stock and solid-liquid white spirit are mainly concentrated between 300 and 350 nanometers, while in FIG. 1b, the main fluorescence emission peaks of ethanol aqueous solution are mainly concentrated between 350 and 400 nanometers, and the main difference between the main fluorescence emission peaks is that the emission peaks of 373 nanometers are very weak, and the emission peaks of 308 nanometers and 330 nanometers are relatively strong in fen-flavor white spirit.
Fig. 2: fluorescent spectrum diagrams of fen wine (a) -53 degrees under different dilution concentrations are shown in the horizontal coordinate of fluorescence emission wavelength and in the vertical coordinate of fluorescence intensity.
Fig. 2 is a fluorescence spectrum obtained by taking a right amount of Fenjiu sample and adding a certain amount of purified water into Fenjiu samples (placed for one week) with different volume concentrations, which are provided by Fenjiu group, wherein the Fenjiu sample is 53 degrees (marked as Fenjiu (a) -53 degrees), placing 1 ml of the above sample in a quartz cell with the volume of 4 x 10 x 45 cubic millimeters, placing the quartz cell in the above fluorescence spectrometer, and setting corresponding parameters. As can be seen from FIG. 2, fenjiu is added with pure water, the fluorescence intensity is continuously reduced, but the basic peak shape is unchanged, and when the concentration is reduced to below 30 degrees, fluorescence emission peaks begin to appear at 400-450 nanometers, which shows that the addition of pure water has an influence on clusters formed in the wine sample, and the fluorescence clusters in the raw wine are destroyed.
Fig. 3: the corresponding ratio of fluorescence intensities at various dilution concentrations of Fenjiu (a) -53 ° (FIG. 3 (a) is the alcohol content on the abscissa and the ratio of fluorescence intensity at 330nm to that at 308nm (fluorescence intensity 330/308) on the ordinate); FIG. 3 (b) is the alcohol content on the abscissa and the ratio of the fluorescence intensity at 330nm to the fluorescence intensity at 373nm (fluorescence intensity 330/373);
as can be seen from FIG. 3a, as the Fenjiu sample is diluted continuously, the fluorescence intensity 330/308 increases and then decreases, but the ratio is greater than 1; as can be seen from FIG. 3b, the fluorescence intensity 330/308 decreases as the Fenjiu sample is diluted, but the ratio is greater than 1, so that Fenjiu (a) -53℃is judged as a fen-flavor puree.
Fig. 4: fluorescent spectrum diagrams of fen wine (b) -53 degrees under different dilution concentrations are shown in the horizontal coordinate of fluorescence emission wavelength and in the vertical coordinate of fluorescence intensity.
FIG. 4 is a graph showing fluorescence spectra obtained by taking 1 ml of a commercially available Fenjiu sample (designated as Fenjiu (b) -53 ℃) of 53 degrees and adding a certain amount of purified water into a Fenjiu sample (one week of standing) of different volume concentrations, placing the sample in a quartz cell of 4X 10X 45 cubic millimeters, placing the quartz cell in the fluorescence spectrometer, and setting corresponding parameters. From fig. 4, it can be seen that the Fenjiu has a continuously decreasing fluorescence intensity with the addition of purified water, a widening of the basic peak shape, and a fluorescence emission peak at 350-400 nm when the concentration is reduced below 30 °, indicating that the clusters formed in the wine sample are affected with the addition of purified water, the fluorescent clusters in the raw wine are destroyed, and the clusters with hydrophilic outside and hydrophobic inside are increased.
Fig. 5: the corresponding fluorescence intensity ratio plots for the various dilutions of Fenjiu (b) -53 °, with the abscissa of FIG. 5 (a) being the alcohol content and the ordinate being the fluorescence intensity 330/308 ratio; the abscissa of FIG. 5 (b) is the alcohol content, and the ordinate is the ratio of fluorescence intensity 330/373.
As can be seen from FIG. 5a, the fluorescence intensity 330/308 increases with the continuous dilution of Fenjiu sample, but the ratio thereof is smaller than 1, and as can be seen from FIG. 5b, the fluorescence intensity 330/308 decreases with the continuous dilution of Fenjiu sample, but the ratio thereof is larger than 1, so that Fenjiu (b) -53 degrees is determined as solid-liquid white spirit.
Fig. 6: fluorescent spectrum diagrams of fen wine (c) -39.9 degrees under different dilution concentrations are shown in the abscissa of fluorescence emission wavelength and in the ordinate of fluorescence intensity.
Fig. 6 is a fluorescence spectrum chart obtained by taking a suitable amount of Fenjiu sample (designated as Fenjiu (c) -39.9 °) provided by Fenjiu group and adding a certain amount of purified water to prepare Fenjiu samples with different volume concentrations (for one week), taking 1 ml of the above sample in a quartz cell of 4×10×45 cubic millimeters, placing in the above fluorescence spectrometer, and setting corresponding parameters. From fig. 6, it can be seen that the Fenjiu has a continuously decreasing fluorescence intensity with the addition of purified water, a widening of the basic peak shape, and a fluorescence emission peak at 350-400 nm when the concentration is reduced below 30 °, indicating that the clusters formed in the wine sample are affected with the addition of purified water, the fluorescent clusters in the raw wine are destroyed, and the clusters that are hydrophilic outside and hydrophobic inside are increased.
Fig. 7: the corresponding fluorescence intensity ratio plots for the various dilutions of Fenjiu (c) -39.9 °, with the abscissa of FIG. 7 (a) being the alcohol content and the ordinate being the fluorescence intensity 330/308 ratio; the abscissa of FIG. 7 (b) is the alcohol content, and the ordinate is the ratio of fluorescence intensity 330/373.
As can be seen from FIG. 7a, as the Fenjiu sample is continuously diluted, the fluorescence intensity 330/308 is increased and then decreased, but the ratio is smaller than 1, and as can be seen from FIG. 7b, as the Fenjiu sample is continuously diluted, the fluorescence intensity 330/308 is decreased and then increased, but the ratio is larger than 1, so that Fenjiu (c) -39.9 degrees is judged as solid-liquid white spirit.
Fig. 8: fluorescent spectrum diagrams of the faint scent type Erguotor at different dilution concentrations are shown in the horizontal coordinate of fluorescence emission wavelength, and the vertical coordinate of fluorescence intensity.
FIG. 8 is a graph showing fluorescence spectra obtained by taking 1 ml of a sample of a commercially available low-valence white spirit (Beijing Erguotou wine (56 DEG) and taking a proper amount of Erguotou wine, adding a certain amount of purified water to prepare samples with different volume concentrations (one week of standing), placing the samples in a quartz cell of 4X 10X 45 cubic millimeters, placing the quartz cell in the fluorescence spectrometer, and setting corresponding parameters. From fig. 8, it can be seen that the Fenjiu has a continuously decreasing fluorescence intensity with the addition of purified water, a broader basic peak shape, a larger influence from concentration, and a fluorescence emission peak at 350-400 nm when the concentration is reduced below 30 °, which indicates that the clusters formed in the Fenjiu have an influence with the addition of purified water, the fluorescent clusters in the raw wine are destroyed, and the clusters with hydrophilic outside and hydrophobic inside are increased.
Fig. 9: FIG. 9 (a) is a graph of the corresponding ratio of fluorescence intensities at various dilution concentrations of Erguotor-56℃with the abscissa of the alcohol content and the ordinate of the ratio of fluorescence intensities 330/308; the abscissa of FIG. 9 (b) is the alcohol content, and the ordinate is the ratio of fluorescence intensity 330/373.
As can be seen from FIG. 9a, the fluorescence intensities 330/308 increase with the continuous dilution of the wine sample, but the ratio is smaller than 1, and as can be seen from FIG. 9b, the fluorescence intensities 330/308 decrease with the continuous dilution of the wine sample, but the ratio is larger than 1, so that the Erguotor-56 DEG is determined to be solid-liquid white spirit.
Fig. 10: fluorescent spectrum diagrams of the faint scent type bamboo leaf green wine at different dilution concentrations are shown in the horizontal coordinate of fluorescence emission wavelength, and the vertical coordinate of fluorescence intensity.
FIG. 10 is a graph showing fluorescence spectra obtained by taking 1 ml of a commercially available low-valent white spirit- -Zhuye Qing wine- -45 degrees and taking a proper amount of a sample of Zhuye Qing wine, adding a certain amount of purified water to prepare samples with different volume concentrations (for one week), placing the samples in a quartz cell of 4 x 10 x 45 cubic millimeters, placing the samples in the fluorescence spectrometer, and setting corresponding parameters. From fig. 10, it can be seen that the green bamboo leaf wine has a continuously increased fluorescence intensity and a widened basic peak shape with the addition of purified water, and when the concentration is reduced below 40 °, a fluorescence emission peak appears at 350-400 nm, which indicates that the addition of purified water has an influence on clusters formed in the wine sample, and the rigid plane of the fluorescent clusters in the raw wine is enhanced.
Fig. 11: the corresponding fluorescence intensity ratio diagrams of the fen-flavor bamboo leaf green wine at different dilution concentrations of-45 degrees are shown in the abscissa of FIG. 11 (a), the alcohol degree is shown, and the ordinate is the ratio of the fluorescence intensity 330/308; the abscissa of FIG. 11 (b) is the alcohol content, and the ordinate is the ratio of fluorescence intensity 330/373.
As can be seen from FIG. 11a, the fluorescence intensities 330/308 increase with the continuous dilution of the wine sample, but the ratio is smaller than 1, and as can be seen from FIG. 11b, the fluorescence intensities 330/373 decrease and then increase with the continuous dilution of the wine sample, but the ratio is larger than 1, so that the Zhuye liqueur-45 DEG is judged as solid-liquid white spirit.
Fig. 12: fluorescent spectrum diagrams of the fen-flavor Daqu wine base (# 1) -65.6 DEG under different dilution concentrations are shown in the horizontal axis of fluorescence emission wavelength, and the vertical axis of fluorescence intensity.
Fig. 12 shows fluorescence spectra obtained by taking a sample of Daqu liquor (# 1-65.6 °) provided by Fenjiu group and taking a proper amount of Daqu liquor, adding a certain amount of purified water, and preparing into samples with different volume concentrations (for one week), taking 1 ml of the above sample into a quartz cell of 4 x 10 x 45 cubic millimeters, placing into the above fluorescence spectrometer, and setting corresponding parameters. From fig. 12, it can be seen that the fluorescence intensity of the Daqu wine base is continuously reduced along with the addition of purified water, the basic peak shape is widened, and when the concentration is reduced to below 50 ℃, a fluorescence emission peak appears at 350-400 nanometers, which indicates that the clusters formed in the wine base are influenced along with the addition of purified water, the fluorescent clusters in the wine base are destroyed, and the clusters with hydrophilic outside and hydrophobic inside are increased.
Fig. 13: the corresponding fluorescence intensity ratio diagrams of the fen-flavor Daqu base wine (# 1) -65.6 DEG at different dilution concentrations are shown in the abscissa of FIG. 13 (a), the alcohol degree is shown, and the fluorescence intensity ratio is shown in the ordinate as 330/308; the abscissa of FIG. 13 (b) is the alcohol content, and the ordinate is the ratio of fluorescence intensity 330/373.
As can be seen from FIG. 13a, the fluorescence intensity 330/308 increases with the continuous dilution of the wine sample, but the ratio is smaller than 1, and the ratio is larger than 1 when the concentration is 20 DEG, and as can be seen from FIG. 13b, the fluorescence intensity 330/373 decreases with the continuous dilution of the wine sample, but the ratio is larger than 1, so that the Daqu base wine (# 1-65.6 DEG) is determined to be solid-liquid white wine.
Fig. 14: fluorescent spectrum diagrams of the fen-flavor Daqu wine base (# 2) -65.8 DEG under different dilution concentrations are shown in the horizontal axis of fluorescence emission wavelength, and the vertical axis of fluorescence intensity.
Fig. 14 shows fluorescence spectra obtained by taking a sample of Daqu liquor (# 2-65.8 °) provided by Fenjiu group and taking a proper amount of Daqu liquor, adding a certain amount of purified water, and preparing into samples with different volume concentrations (for one week), taking 1 ml of the above sample into a quartz cell of 4 x 10 x 45 cubic millimeters, placing into the above fluorescence spectrometer, and setting corresponding parameters. From fig. 14, it can be seen that the fluorescence intensity of the Daqu wine base is continuously reduced along with the addition of purified water, the basic peak shape is widened, and when the concentration is 20 degrees, the main fluorescence emission peak is red shifted, which indicates that the clusters formed in the wine sample are influenced along with the addition of purified water, the fluorescent clusters in the wine base are destroyed, and the clusters with hydrophilic outside and hydrophobic inside are increased.
Fig. 15: the corresponding fluorescence intensity ratio diagrams of the fen-flavor Daqu base wine (# 2) -65.8 DEG at different dilution concentrations are shown in the graph of FIG. 15 (a), wherein the abscissa of the graph is the alcohol degree and the ordinate is the fluorescence intensity 330/308 ratio; the abscissa of FIG. 15 (b) is the alcohol content, and the ordinate is the fluorescence intensity 330/373 ratio.
As can be seen from FIG. 15a, the fluorescence intensities 330/308 increase with the continuous dilution of the wine sample, but the ratio is greater than 1, and as can be seen from FIG. 15b, the fluorescence intensities 330/373 decrease with the continuous dilution of the wine sample, but the ratio is greater than 1, so that Daqu raw wine (# 2-65.8 ℃) is judged as faint scent raw wine.
Fig. 16: fluorescent spectrum diagrams of the fen-flavor Daqu wine base (# 3) -65.3 DEG under different dilution concentrations are shown in the horizontal axis of fluorescence emission wavelength, and the vertical axis of fluorescence intensity.
Fig. 16 shows fluorescence spectra obtained by taking a sample of Daqu liquor (# 3-65.3 °) provided by Fenjiu group and taking a sample of Daqu liquor, adding a certain amount of purified water, and preparing samples with different volume concentrations (for one week), taking 1 ml of the above sample in a quartz cell of 4 x 10 x 45 cubic millimeters, placing the sample in the above fluorescence spectrometer, and setting corresponding parameters. From fig. 16, it can be seen that the original wine is added with purified water, the fluorescence intensity is increased first and then is kept unchanged, the main fluorescence emission peak is red shifted, and when the concentration is 55 °, the fluorescence intensity is obviously increased, which indicates that the clusters formed in the original wine are influenced by adding purified water, the fluorescent clusters in the original wine are destroyed, and the clusters with hydrophilic outside and hydrophobic inside are increased.
Fig. 17: the corresponding fluorescence intensity ratio diagrams of the fen-flavor Daqu base wine (# 3) -65.3 DEG at different dilution concentrations are shown in the graph of FIG. 17 (a), wherein the abscissa of the graph is the alcohol degree and the ordinate is the fluorescence intensity 330/308 ratio; the abscissa of FIG. 17 (b) is the alcohol content, and the ordinate is the ratio of fluorescence intensity 330/373.
As can be seen from FIG. 17a, the fluorescence intensities 330/308 increase with the continuous dilution of the wine sample, but the ratio is greater than 1, and as can be seen from FIG. 17b, the fluorescence intensities 330/373 decrease with the continuous dilution of the wine sample, but the ratio is less than 1, so that the Daqu base wine (# 3-65.3 ℃) is determined to be solid-liquid white wine.
Fig. 18: fluorescence spectra of ethanol-water solutions at different dilution concentrations, with the abscissa representing fluorescence emission wavelength and the ordinate representing fluorescence intensity.
FIG. 18 is a series of ethanol-water solutions of volume concentration prepared using chromatographic pure ethanol (. Gtoreq.99.8%) purchased at Allatin corporation and laboratory ultra-pure water (. Rho. =18.2 M.OMEGA.cm, 25 ℃). 1 ml of the sample is taken in a quartz cell with the volume of 4 x 10 x 45 cubic millimeters, placed in the fluorescence spectrometer, and a fluorescence spectrum diagram is obtained by setting corresponding parameters. From fig. 18, it can be derived that the fluorescence intensity of the fluorescence emission peak at 308nm gradually decreases as the ethanol concentration decreases, indicating that the water affects clusters formed in the ethanol solution and damages the fluorescent clusters in the original ethanol solution as the ethanol solution is continuously diluted.
Fig. 19: the corresponding fluorescence intensity ratio plots for various dilutions of the ethanol-water solution, with the abscissa of FIG. 19 (a) being the alcohol content and the ordinate being the fluorescence intensity 330/308 ratio; the abscissa of FIG. 19 (b) shows the alcohol content, and the ordinate shows the fluorescence intensity 330/373 ratio.
As can be seen from FIG. 19a, the fluorescence intensity 330/308 increases with the continuous dilution of the ethanol solution, but the ratio is less than 1 (most white spirits are above 40 DEG) between 65 and 50%, and the ratio is greater than 1 when the ratio is less than or equal to 45%; as can be seen from fig. 17b, the fluorescence intensity 330/373 tends to decrease with the continuous dilution of the ethanol solution, but the ratio is smaller than 1, so that the ethanol solution was judged to be liquid-state white spirit.
Fig. 20: corresponding fluorescence intensity ratio diagrams of different fen-flavor distilled spirits (fen-flavor primary pulp and solid-liquid method distilled spirits can be called fen-flavor distilled spirits) and ethanol-water solutions under different dilution concentrations: the abscissa indicates the fluorescence emission intensity, and the ordinate indicates the fluorescence intensity 330/308. The fluorescence intensities 330/308 of the fen-flavor distilled spirit and the ethanol aqueous solution with different dilution concentrations are plotted with the fluorescence emission wavelength to obtain a graph 20. The ratio is more than 1 and comprises Fenjiu (a), daqu wine base (# 2-65.8 degrees) and Daqu wine base (# 3-65.3 degrees); the ratio is less than 1, and the wine comprises Fenjiu (b, c), daqu wine base (# 1-65.6 degrees), erguotou wine, bamboo leaf green wine and model white wine (ethanol solution).
Fig. 21: corresponding fluorescence intensity ratio diagrams of different fen-flavor distilled spirit and ethanol-water solutions under different dilution concentrations: the abscissa indicates the fluorescence emission intensity, and the ordinate indicates the fluorescence intensity 330/373. The fluorescence intensities 330/373 of the above-mentioned fen-flavor distilled spirit and ethanol aqueous solutions with different dilution concentrations were plotted with fluorescence emission wavelengths to obtain FIG. 21. The ratio is more than 1, and the Fenjiu (a, b and c), daqu wine base (# 1-65.5 degrees), daqu wine base (# 2-65.8 degrees), bamboo leaf green wine and Erguotou wine are included; the ratio is less than 1, and the Daqu wine base (# 3-65.3 DEG) and model white spirit (ethanol solution) are provided.
Detailed Description
The ethanol solution used in the invention is all ordered in the Ama Ding Gongsi with chromatographic purity grade (more than or equal to 99.8 percent); laboratory ultra-pure water (ρ=18.2mΩ cm,25 ℃) was used for both pure water; the wine samples used, fenjiu (a, c) and Daqu base wines (# 1, #2, # 3), were all provided by Fenjiu group, while Fenjiu (b), erguotou wine and Zhuye Qing wine were all commercially available low-priced white spirits purchased.
Example 1:
1 ml of wine base sample is respectively added into a quartz pool with the volume of 4 x 10 x 45 cubic millimeters, the quartz pool is placed in a fluorescence spectrometer, the wavelength of incident light is set to be 240 nanometers, the wavelength of emitted light is in the range of 280-450 nanometers, and a slit is set to be 5 x 10 nanometers, so that a fluorescence emission spectrum is obtained (figure 1 a). For a model white spirit sample, preparing an ethanol-water solution with corresponding concentration, vibrating for half a minute by a vortex oscillator, standing for one week at room temperature for fluorescence test to obtain a corresponding fluorescence spectrogram (figure 1 b), wherein the fluorescence intensity of the ethanol-water solution is weaker, and the adopted slit is 10 x 10 nanometers so as to enhance the fluorescence intensity.
Example 2:
preparing raw liquor solutions with different alcohol degrees: preparing a sample with a final volume of 1.5 milliliters, firstly calculating the volume of the raw wine required by the wine with different alcohol degrees with the final volume of 1.5 milliliters, taking the raw wine sample with different volumes, supplementing the rest with laboratory purified water (rho=18.2M omega cm,25 ℃), vibrating the raw wine sample with a vortex oscillator for half a minute to mix the sample uniformly, and standing for one week for fluorescence test (figures 2, 4, 6, 8, 10, 12, 14 and 16).
And (3) preparation of model white spirit: a series of ethanol solutions with a final volume of 1.5 ml and a volume concentration of 15-65% (interval of 5%) were prepared by calculation from a certain amount of chromatographic pure ethanol (99.8%) and laboratory ultra-pure water (ρ=18.2 mΩ cm,25 ℃), and after shaking for half a minute with a vortex shaker, were left for one week for fluorescence testing (fig. 18).
Example 3:
establishing a fluorescence method based on different magnitude relations between the ratio of the intensities of the main fluorescence emission peaks of the fluorescence spectrum and 1: fluorescence emission spectra obtained from the wine base solutions of different alcohol degrees prepared in example 2 were taken to have three main fluorescence emission peaks: the fluorescence intensities at different concentrations of 308nm, 330nm and 373nm were obtained by respectively comparing the intensities of the main fluorescence peak of 330nm with the intensities of the other two main fluorescence emission peaks to obtain fluorescence intensities 330/308 and 330/373 as ordinate, and different alcohol degrees as abscissa (FIGS. 3, 5, 7, 9, 11, 13, 15, 17). And then comparing the ratio chart with a corresponding model white spirit ratio chart (figure 19). As shown in fig. 20 and 21, the results show that the ratio of the fen-flavor raw stock to the liquid white spirit and the solid-liquid white spirit is obviously different: when the fluorescence intensity is 330/308 and the fluorescence intensity is 330/373 are both more than 1, the light-scent type primary pulp is obtained; when both are smaller than 1, the white spirit is prepared by liquid method; one is smaller than 1, and the other is larger than 1, and the white spirit is obtained by a solid-liquid method. Meanwhile, different types of fen-flavor liquor are selected and well distinguished, so that the invention adopts the difference of the ratio of the intensity of each main fluorescence emission peak of the fluorescence spectrum to the magnitude relation of 1 to distinguish the fen-flavor primary pulp, the liquor with a liquid method and the liquor with a solid-liquid method, and has universality for different types of fen-flavor liquor.
It should also be noted that the specific embodiments of the present invention are provided for illustration only and not to limit the scope of the present invention in any way, and that modifications or variations can be made by persons skilled in the art in light of the above description, and all such modifications or variations are intended to fall within the scope of the appended claims.
Claims (3)
1. A ratio type fluorescence method for distinguishing fen-flavor magma from liquid-process white spirit and solid-liquid-process white spirit comprises the following steps:
(1) Fluorescence spectrum test: taking 1 milliliter of fen-flavor raw stock with different alcohol degrees, and carrying out fluorescence spectrum measurement on a liquid-method white spirit or solid-liquid-method white spirit sample; excitation wavelength of 240 nm measured by fluorescence spectrum;
(2) According to the fluorescence spectrogram obtained in the step (1), respectively calculating the ratio of the fluorescence intensity at 330nm to the fluorescence intensity at 308nm of the samples with different alcohol degrees, and simultaneously calculating the ratio of the fluorescence intensity at 330nm to the fluorescence intensity at 373 nm;
(3) Judging the type of the wine according to the size relation between the two ratios obtained in the step (2) and 1, and if the two ratios are larger than 1, obtaining the sample as faint scent type primary pulp; if both are smaller than 1, the sample is liquid white spirit; if one of the two is smaller than 1 and the other is larger than 1, the sample is the solid-liquid white spirit.
2. The ratio-based fluorescence method for distinguishing fen-flavor magma from liquid-process white spirit and solid-liquid-process white spirit according to claim 1, wherein the ratio-based fluorescence method is characterized by: emission wavelength of fluorescence spectrometry: 280-450 nanometers; scanning speed: slow; slit: 5 x 10 nm.
3. The ratio-based fluorescence method for distinguishing fen-flavor magma from liquid-process white spirit and solid-liquid-process white spirit according to claim 1, wherein the ratio-based fluorescence method is characterized by: the faint scent type primary pulp with different alcohol degrees is obtained by diluting faint scent type primary pulp with high alcohol degrees with purified water and standing for one week; the solid-liquid method white spirit with different alcohol degrees is obtained by diluting solid-liquid method white spirit with high alcohol degrees with purified water and standing for a week; the liquid-state white spirit with different alcohol degrees is obtained by diluting high-volume concentration ethanol solution with purified water and standing for one week.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010624105.XA CN111735804B (en) | 2020-07-01 | 2020-07-01 | Ratio type fluorescence method for distinguishing fen-flavor primary pulp from liquid-method white spirit and solid-liquid-method white spirit |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010624105.XA CN111735804B (en) | 2020-07-01 | 2020-07-01 | Ratio type fluorescence method for distinguishing fen-flavor primary pulp from liquid-method white spirit and solid-liquid-method white spirit |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111735804A CN111735804A (en) | 2020-10-02 |
| CN111735804B true CN111735804B (en) | 2023-09-22 |
Family
ID=72652540
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010624105.XA Active CN111735804B (en) | 2020-07-01 | 2020-07-01 | Ratio type fluorescence method for distinguishing fen-flavor primary pulp from liquid-method white spirit and solid-liquid-method white spirit |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111735804B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114279991B (en) * | 2021-12-30 | 2023-05-12 | 宜宾五粮液股份有限公司 | White spirit brand identification method |
| CN114634812B (en) * | 2022-03-09 | 2023-08-18 | 四川光良酿造科技有限公司 | Application of dansyl AA in visual monitoring, visual distinguishing and stability detection of ethanol-water supermolecular cluster |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101825572A (en) * | 2010-06-11 | 2010-09-08 | 重庆大学 | Method for differentiating Chinese spirits with different flavor types with fluorescein |
| CN104677875A (en) * | 2015-03-24 | 2015-06-03 | 江南大学 | Method for identifying baijiu of different brands by combining three-dimensional fluorescence spectrum and parallel factor |
| CN110455763A (en) * | 2019-08-22 | 2019-11-15 | 四川省绵阳市丰谷酒业有限责任公司 | The spectrogram measuring method and difference analysis method of white wine |
-
2020
- 2020-07-01 CN CN202010624105.XA patent/CN111735804B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101825572A (en) * | 2010-06-11 | 2010-09-08 | 重庆大学 | Method for differentiating Chinese spirits with different flavor types with fluorescein |
| CN104677875A (en) * | 2015-03-24 | 2015-06-03 | 江南大学 | Method for identifying baijiu of different brands by combining three-dimensional fluorescence spectrum and parallel factor |
| CN110455763A (en) * | 2019-08-22 | 2019-11-15 | 四川省绵阳市丰谷酒业有限责任公司 | The spectrogram measuring method and difference analysis method of white wine |
Non-Patent Citations (2)
| Title |
|---|
| Supramolecular Clusters Clarification in Ethanol-water Mixture by Using Fluorescence Spectroscopy and 2D Correlation Analysis;Xiao-Qi Jia et al.;《Journal of Molecular Structure》;20200604;第1219卷;第1-3页 * |
| 基于荧光光谱研究清香型白酒中乙醇-水缔合行为;乔华 等;《食品科学》;20141231;第35卷(第15期);第83-88页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111735804A (en) | 2020-10-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111735804B (en) | Ratio type fluorescence method for distinguishing fen-flavor primary pulp from liquid-method white spirit and solid-liquid-method white spirit | |
| Magdas et al. | Wine discrimination based on chemometric analysis of untargeted markers using FT-Raman spectroscopy | |
| CN101806740B (en) | Detection method of human plasma surface enhanced raman spectroscopy by integrating main component analysis | |
| Ravandi et al. | Green effervescence assisted dispersive liquid–liquid microextraction based on a hydrophobic deep eutectic solvent for determination of Sunset Yellow and Brilliant Blue FCF in food samples | |
| TWI507672B (en) | Method for manufacturing and using a test paper and chemical composition thereof | |
| CN110455769B (en) | Quantitative analysis method for surface enhanced Raman spectroscopy of core-shell nanoparticles with shell as internal standard | |
| Yin et al. | Rapid colorimetric detection of melamine by H 2 O 2–Au nanoparticles | |
| De Almeida et al. | Expedite SERS fingerprinting of Portuguese white wines using plasmonic silver nanostars | |
| CN113201336A (en) | Preparation method based on nitrogen-phosphorus doped carbon quantum dots and application of preparation method in rapid detection of tartrazine | |
| Qiao et al. | Fluorescence spectroscopic and viscosity studies of hydrogen bonding in Chinese Fenjiu | |
| Qu et al. | Chemical profiling of red wines using surface-enhanced Raman spectroscopy (SERS) | |
| Jia et al. | Differentiation of ethanol–water clusters in Fenjiu by two-dimensional correlation fluorescence and Raman spectra | |
| Yin et al. | Preliminary investigation on variety, brewery and vintage of wines using three-dimensional fluorescence spectroscopy | |
| Sochorova et al. | Electrochemical and others techniques for the determination of malic acid and tartaric acid in must and wine | |
| CN109781694A (en) | The rapid detection method of metal ion in a kind of grape wine | |
| Ziyatdinova et al. | New electrochemistry-based approaches to brandy quality evaluation using antioxidant parameters | |
| Zhang et al. | Using in situ untargeted flavoromics analysis to unravel the empty cup aroma of Jiangxiang-type Baijiu: A novel strategy for geographical origin traceability | |
| CN108956593A (en) | A method of without aptamer nanogold hydrosol Visual retrieval melamine | |
| Muñoz-Muñoz et al. | Identification and quantification of furanic compounds in tequila and mezcal using spectroscopy and chemometric methods | |
| CN108088830B (en) | Method for accurately measuring content of chitosan oligosaccharide by resonance Rayleigh scattering method | |
| Neng et al. | Rapid Detection of Tetrodotoxin Using Surface-Enhanced Raman Spectroscopy and Fe 3 O 4/SiO 2/Au Gold/Magnetic Nanoparticles | |
| CN111562227B (en) | Nanogold colorimetric method for detecting lysine | |
| CN108148596B (en) | Method for distinguishing red wine by utilizing fluorescence quenching of up-conversion fluorescent material | |
| Sádecká et al. | Fluorescence spectroscopy for the analysis of spirit drinks | |
| Yang et al. | Development of an iodine sensor based on fluorescence energy transfer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |