CN115236163B - Array electrode system and application thereof in quality classification of white spirit - Google Patents
Array electrode system and application thereof in quality classification of white spirit Download PDFInfo
- Publication number
- CN115236163B CN115236163B CN202210855103.0A CN202210855103A CN115236163B CN 115236163 B CN115236163 B CN 115236163B CN 202210855103 A CN202210855103 A CN 202210855103A CN 115236163 B CN115236163 B CN 115236163B
- Authority
- CN
- China
- Prior art keywords
- electrode
- white spirit
- electrode system
- array electrode
- array
- 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
- 238000000034 method Methods 0.000 claims abstract description 29
- 230000004044 response Effects 0.000 claims abstract description 23
- 238000000840 electrochemical analysis Methods 0.000 claims abstract description 18
- 238000013179 statistical model Methods 0.000 claims abstract description 7
- 235000020097 white wine Nutrition 0.000 claims abstract description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 38
- 230000008685 targeting Effects 0.000 claims description 28
- 238000012360 testing method Methods 0.000 claims description 20
- 229910052697 platinum Inorganic materials 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 238000011156 evaluation Methods 0.000 claims description 14
- 235000014101 wine Nutrition 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 11
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 6
- 239000001913 cellulose Substances 0.000 claims description 6
- 229920002678 cellulose Polymers 0.000 claims description 6
- 239000005543 nano-size silicon particle Substances 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 230000001953 sensory effect Effects 0.000 claims description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229940116333 ethyl lactate Drugs 0.000 claims description 4
- 238000002484 cyclic voltammetry Methods 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 238000000513 principal component analysis Methods 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 claims description 2
- 238000010801 machine learning Methods 0.000 claims description 2
- 238000003062 neural network model Methods 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 238000003860 storage Methods 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims 1
- 239000002131 composite material Substances 0.000 claims 1
- 235000005985 organic acids Nutrition 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 11
- 238000001514 detection method Methods 0.000 abstract description 11
- 239000000126 substance Substances 0.000 description 34
- 239000000796 flavoring agent Substances 0.000 description 15
- 235000019634 flavors Nutrition 0.000 description 15
- 150000002148 esters Chemical class 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 230000002195 synergetic effect Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000003487 electrochemical reaction Methods 0.000 description 5
- 238000007637 random forest analysis Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 238000003066 decision tree Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007405 data analysis Methods 0.000 description 2
- 238000000835 electrochemical detection Methods 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 235000015096 spirit Nutrition 0.000 description 2
- 238000012549 training Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000012952 Resampling Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000013528 artificial neural network Methods 0.000 description 1
- 235000019658 bitter taste Nutrition 0.000 description 1
- 238000013124 brewing process Methods 0.000 description 1
- 238000004422 calculation algorithm Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000019643 salty taste Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000019614 sour taste Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000007619 statistical method Methods 0.000 description 1
- 235000019605 sweet taste sensations Nutrition 0.000 description 1
- 235000019640 taste Nutrition 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/49—Systems involving the determination of the current at a single specific value, or small range of values, of applied voltage for producing selective measurement of one or more particular ionic species
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Abstract
The application provides an array electrode system and application thereof in quality classification of white spirit. Carrying out electrochemical test on a white wine sample with a known grade through the array electrode system, and collecting first response signal data; establishing a recognition model of white spirit quality classification for the first response signal data by adopting a mathematical statistical model; and performing electrochemical test on the white spirit to be tested through the array electrode system to obtain second response signal data, inputting the second response signal data into the identification model, and determining the final grade of the white spirit. The quality classification of the white spirit is carried out through the array electrode system, and the method has the advantages of being high in accuracy, high in speed, low in cost of a detection device and the like.
Description
Technical Field
The application relates to the technical field of white spirit quality grading, in particular to an array electrode system and application thereof in white spirit quality grading, and specifically relates to a method for realizing rapid grading of white spirit quality by utilizing a multi-electrode combination test, an electrochemical test principle and a mathematical statistical method.
Background
The classification of white spirit is an important link in the brewing process, and the accuracy and the efficiency of the white spirit can directly influence the screening result of high-quality products and the subsequent classification cellaring process, so that the white spirit classification method is very important to the production benefit of enterprises.
At present, the wine grading is mainly finished by artificial sensory evaluation, the method is a non-targeted evaluation of the synergistic effect formed by all flavor substances in the wine, the sensory evaluation method judges the quality of the wine by an alcohol taster, and main indexes comprise: the color of the wine, the aroma of the wine, the taste of the wine, the wine body and the like. The disadvantages of this approach are:
1. the wine taster with abundant experience is required to make judgment, and the factor result of the person is greatly changed;
2. the identification result cannot be quantified;
3. the identification speed is low, and the requirement of on-line detection cannot be met.
Sensory evaluation is usually performed by grading in combination with the content results of one or more main esters in the gas chromatography detection of white spirit. The following disadvantages exist in the quality grading of white spirit by using a gas chromatography detection method:
1. the white spirit contains a large amount of water, the existence of the water can damage an instrument, and a complex pretreatment is required to be carried out on a sample before testing;
2. the chemical components in the white spirit are very complex, more than 1700 flavor substances exist, the gas chromatography cannot determine the content of all substances determining the quality of the white spirit at all, and the whole level after the synergistic effect is difficult to measure only by the content of part of substances;
3. the content of substances in the white spirit is measured by utilizing the chromatograph, and the normalized area size of the substances is used as the content of the substances, so that the calculation method has great error and cannot be used for subsequent analysis;
4. the test time is long: a sample is typically tested for about 40 minutes and is therefore not conducive to production on-line testing.
At present, an electronic nose and an electronic tongue are disclosed, and the electronic nose can only detect volatile flavor substances; the electronic tongue is used for targeted detection of substances which generate sour, salty, bitter and sweet tastes in the white spirit.
Therefore, none of the above detection methods is an overall evaluation of the synergistic effect of all the flavor substances in white spirit, and therefore lacks accuracy.
Disclosure of Invention
The method aims at carrying out in-situ non-targeted evaluation on the synergistic effect of all flavor substances in the white spirit by utilizing an array electrode and an electrochemical detection principle, so that the quality of the white spirit is rapidly graded.
The electrochemical detection is to further evaluate the characteristics of the electrode or the solution by obtaining the electrode reaction kinetic parameter to characterize the electrode-solution interface reaction process, and has the remarkable advantages of high sensitivity, wide measurement range, small interference to a system, green safety and the like. The flavor substances, alcohol content and ester assembly structure in the distilled spirit of different grades are different, so that the interface between the electrode and the distilled spirit is correspondingly changed. When a certain electric signal is applied to the electrode, the electrode interface forms different microscopic distributions due to the composition and content difference of the flavor substances, so that the electrode interface has obvious response distinction under the disturbance of electrochemical signals, and feedback information of different grades of white spirit can be obviously distinguished. For example, at the same oxidation potential, there will be a significant difference in oxidation current for white spirit samples of different ester content. With the increase of the content of esters, the oxidation current under the same potential is gradually increased, which is related to the oxidation process of the esters after interfacial adsorption; and different flavours form different molecular assembly structures in the solution, which show differential distribution and change of dielectric constants at the electrode interface, so that signal responses in electrochemical reactions can also show obvious differences.
The electrochemical signal generated by each electrode in a multi-electrode array electrode system can be divided into a targeting signal directly related to the exact component and a non-targeting signal after assembly with other substances. Electrochemical signals can be generated at the electrode interface by different flavor substances, and the intensity of the signals and the parameter interval are changed along with the action mode of the object to be detected and the electrode material. Thus, each electrode in the array electrode system is responsive to all flavors, a substantial portion of which are non-targeted signals. The multi-electrode array electrode system has the advantages that besides the targeting signals of the electrodes and main substances such as ethanol, ester, organic acid and the like, the non-targeting signals of a large number of trace substances after assembly can be obtained by means of the residual electrodes. The components in the white spirit are also affected mutually, when one component index is changed, the electrochemical test of the other index is affected, and the multi-electrode array electrode system can effectively reduce the influence degree of the multi-electrode array electrode system on the test result by utilizing the database of the non-targeting signals, so that the components are accurately identified, and meanwhile, the interference of other indexes is avoided.
The white spirit grade data identification library consists of targeting signals and non-targeting signals of all electrodes, but the parameter interval where the characteristic quantity of the non-targeting signals of each electrode is located is possibly different, so that the degree of cross correlation between the non-targeting signals of the same component by different electrodes becomes the core content for building the non-targeting database. And analyzing the characteristic quantity of the white spirit with known grade by using a mathematical statistical model, establishing a database of standard samples, inputting test data of the sample to be tested into the database, and comparing to obtain a standard sample interval with the least square difference of each characteristic quantity, thereby determining the quality grade of the sample to be tested. The invention can accurately evaluate the content of each substance in the wine and the synergistic effect thereof, thereby realizing the rapid classification of the white wine.
Based on the technical principle, the method and the device utilize the response difference of the types and the contents of different flavor substances in the white spirit at the electrode interface to evaluate the integrity of the response characteristics of the white spirit of different grades. And carrying out parameter classification of a standard database by adopting a data system model, and further summarizing the characteristic quantity by utilizing a big data analysis method to obtain 5-20 target indexes and 30-100 characteristic quantities capable of indicating the grade of white spirit. And then, establishing a recognition model of the white spirit grade according to the change interval of the target index and the characteristic quantity. And inputting the parameter value of the electric response signal of the white spirit sample to be tested into a model, and comparing to obtain the section of the standard sample with the minimum square difference of each characteristic quantity, wherein the grade of the white spirit sample to be tested is the quality grade of the section of the standard sample.
In view of the above, the present application provides an array electrode system and its application in quality classification of white spirit, so as to solve or alleviate the above-mentioned part of technical problems.
In a first aspect, the present application provides an array electrode system comprising:
a working electrode; the working electrode is a 2X 2 array electrode system formed by a modified graphite electrode, a glassy carbon electrode, a platinum electrode and a polymer-based electrode;
a reference electrode; the reference electrode is an Ag/AgCl electrode; and
an auxiliary electrode; the auxiliary electrode is a platinum sheet electrode.
In the embodiment of the application, the modified graphite electrode is formed by high-temperature sintering of nano silicon powder, phosphate and cellulose and then coating on a graphite rod; the glassy carbon electrode is a commercial glassy carbon electrode; the platinum electrode is a commercial platinum electrode with a platinum content of greater than 99.9%; the polymer-based electrode is formed by mixing and pressing polyaniline and polypyrrole.
In a second aspect, the present application provides a method for classifying quality of white spirit, specifically including the following steps:
performing electrochemical test on a white wine sample with a known grade through the array electrode system in the first aspect, and collecting first response signal data;
and classifying and summarizing the first response signal data by adopting a mathematical statistical model (namely a general mean regression statistical model), searching a response signal with a larger pearson correlation coefficient with the flavor substance, determining a targeting index and a non-targeting characteristic parameter, and establishing a mean regression model between the flavor substance and the characteristics according to the determined characteristics. Establishing a recognition model (namely a random forest classification model) for classifying the quality of the white spirit according to the target index content and non-target characteristic parameter distribution intervals of the white spirit of different grades, and obtaining an optimal classification recognition model by adjusting parameters in the random forest model;
and carrying out electrochemical test on the white spirit to be tested through the array electrode system in the first aspect to obtain second response signal data, inputting the second response signal data into the identification model, and screening a section where a standard sample with the minimum variance of characteristic parameters is located according to comparison with the targeting indexes of each grade to determine the final grade.
In this embodiment, the known grade white spirit samples are those that have been determined to be of final overall grade by multiple national, provincial, and provincial, wine makers after sensory evaluation during different storage periods.
In embodiments of the present application, the electrochemical test comprises one or a combination of an electrochemical impedance spectroscopy test, a potentiodynamic scanning test, and a cyclic voltammetry test.
In embodiments of the present application, the mathematical statistical model includes one or a combination of principal component analysis, a tree-like neural network model, and unsupervised machine learning.
In the embodiment of the application, the target index comprises substances with mass content higher than 0.1% such as ethanol, ethyl acetate, ethyl lactate, organic acid, higher alcohol and the like; the non-targeted characteristic parameters include potential, current, frequency, capacitance, dispersion coefficient, dielectric constant, real/imaginary impedance and other mathematical deformation values.
In the embodiments of the present application, the number of targeting indexes is preferably 5 to 20, and the number of non-targeting characteristic parameters is preferably 30 to 100.
In a third aspect, the present application provides the use of the array electrode system according to the first aspect and/or the method according to the second aspect for quality classification of white spirit.
In an embodiment of the present application, in the foregoing application, the white spirit is a Xiaoqu white spirit.
Compared with the prior art, the method has the advantages that the array electrode is used as a working electrode, the electrochemical testing principle is used for realizing quick grading of the quality of the white spirit, and the method has the following advantages:
(1) The array electrode system can obtain the reaction signals of the electrode and the target index, and can also obtain non-target signals assembled by a large number of trace components by means of the residual electrode. The method not only carries out targeted detection on the ethanol content and the main ester content in the wine body, but also carries out overall evaluation on the synergistic effect of other substances after being assembled, establishes an identification database of white spirit of different grades after integrating the two data, and can accurately identify the targeted components and avoid the interference of other indexes.
(2) The functional graphite material formed by sintering nano silicon, phosphate and cellulose has the characteristics of good stability, strong oxidation resistance, high catalytic activity of interface electrochemical reaction and the like. The electrode material has high charge mobility and high electron transmission rate due to multi-element doping, can improve the sensitivity of the flavor substances to response signals on an electrode interface, and accurately identifies the difference of the electric response signals in different environments. Meanwhile, due to a loose carbon structure, the modified graphite electrode can rapidly adsorb various flavor substances in white wine to achieve interface balance, so that the catalytic electrochemical reaction is efficiently carried out, and stable signal data is finally output.
(3) The accuracy of the test result is high, hundreds of characteristic quantities are covered according to the discrimination basis under the big data operation, and the standard database capacity is expanded along with the increase of the number of the test samples, so that the self-correction function is realized by continuous upgrading, and the accuracy is continuously increased.
(4) The method has the advantages that the time required for grading the quality of the white spirit based on the electrochemical test is short, the sum of the total time of all the electrochemical tests is less than 30 minutes, and the method is suitable for on-line rapid detection and full-flow intelligent test.
(5) The method has the advantages that the cost of consumable materials and equipment required by the method is low, the electrode preparation cost is lower than 2000 yuan, the comprehensive cost of a set of rapid white spirit grading device based on electrochemical tests is not more than 5 ten thousand yuan, and the cost is far lower than the price of similar grading equipment.
(6) Aiming at the product difference of different white spirit enterprises, the grading method can ensure that each enterprise obtains a targeted identification model, ensures that various white spirits generate a dedicated data identification library, and meets the customization requirements of the enterprises.
Drawings
The invention will be described in further detail below in connection with the drawings and the preferred embodiments, but it will be appreciated by those skilled in the art that these drawings are drawn for the purpose of illustrating the preferred embodiments only and thus should not be taken as limiting the scope of the invention. Moreover, unless specifically indicated otherwise, the drawings are merely schematic representations, not necessarily to scale, of the compositions or constructions of the described objects and may include exaggerated representations.
Fig. 1 is an electrochemical signal acquisition scanning mode of researching the quality of white spirit by using the array electrode system provided by the embodiment of the application.
Fig. 2 is a schematic diagram of a correspondence relationship between quality of white spirit and electrochemical signals of an array electrode system according to an embodiment of the present application.
Fig. 3 is a schematic diagram of correlation degree of non-targeting signals between electrodes in an array electrode system according to an embodiment of the present application.
Fig. 4 is a schematic diagram of a quantification method of a target index in an array electrode system according to an embodiment of the present application.
Fig. 5 is a schematic diagram of quality classification of white spirit based on electrochemical principles according to an embodiment of the present application.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Array electrode system composition and description
The present application provides an array electrode system comprising:
a working electrode; the working electrode is a 2X 2 array electrode system formed by a modified graphite electrode, a glassy carbon electrode, a platinum electrode and a polymer-based electrode;
a reference electrode; the reference electrode is an Ag/AgCl electrode; and
an auxiliary electrode; the auxiliary electrode is a platinum sheet electrode.
The electrochemical signals generated by each electrode in the array electrode system can be divided into targeting signals directly related to exact components and non-targeting signals assembled by other substances, and the strength of the signals and the parameter interval are changed along with the action mode of the object to be detected and the electrode material. Thus, each electrode in the array electrode system is responsive to all substances, most of which are non-targeted signals.
Taking white spirit as an example, the array electrode system has the advantages that besides the target signals of the electrodes and main substances such as ethanol, ester, organic acid and the like, the non-target signals after assembling a large number of trace substances can be obtained by means of the residual electrodes. The components in the white spirit are also mutually influenced, when one component index is changed, the electrochemical test of the other index is influenced, and the array electrode system can effectively reduce the influence degree of the array electrode system on the test result by utilizing the database of the non-targeting signals, so that the components are accurately identified, and the interference of other indexes is avoided.
In the embodiment of the application, the modified graphite electrode is formed by sintering nano silicon powder, phosphate and cellulose at high temperature and then coating the sintered nano silicon powder, phosphate and cellulose on a graphite rod; the glassy carbon electrode is a commercial glassy carbon electrode; the platinum electrode is a commercial platinum electrode with a platinum content of greater than 99.9%; the polymer-based electrode is formed by mixing and pressing polyaniline and polypyrrole.
The functional graphite material in the modified graphite electrode is formed by sintering nano silicon, phosphate and cellulose, and has the characteristics of good stability, strong oxidation resistance, high catalytic activity of interface electrochemical reaction and the like. The electrode material has high charge mobility and high electron transmission rate due to multi-element doping, can improve the sensitivity of a substance to response signals on an electrode interface, and accurately identifies the difference of the electric response signals in different environments. Meanwhile, due to a loose carbon structure, the modified graphite electrode can quickly adsorb various substances in a detection solution to achieve interface balance, so that the catalytic electrochemical reaction is efficiently carried out, and stable signal data is finally output.
Application of the array electrode system in rapid quality classification of white spirit
1. And selecting 400 batches of small-starter liquor samples with known grades from a certain company, and performing electrochemical test to collect standard data.
An array electrode (a modified graphite electrode, a glassy carbon electrode, a platinum electrode and a polymer-based electrode) is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a platinum sheet electrode is used as an auxiliary electrode for carrying out electrochemical test on a white wine sample, and an electrochemical signal acquisition scanning mode for researching the white wine quality by an array electrode system is shown in FIG. 1.
(1) Electrochemical impedance spectrum measurement is carried out under open circuit potential (electrode potential when current density is zero, namely potential difference between working electrode and reference electrode without load), disturbance signal adopts sine alternating current wave with amplitude of 10mV, and test frequency range is 10 Hz-10 6 Hz。
(2) Potentiodynamic scanning is performed sequentially from the cathode to the anode, the scanning speed is 2mV/s, and the oxidation voltage reaches 3.0V (vs. Ag/AgCl) at most.
(3) And (3) performing cyclic voltammetry, namely starting inverse scanning from the cathode potential of-3.0V, wherein the scanning speed is 5mV/s, and the scanning times are 3 circles.
2. Summarizing the electrochemical response data by Matlab software, and carrying out targeted test on the ethanol content, ethyl acetate, ethyl lactate, long-chain alcohol and organic acid content to obtain accurate concentration; using treesThe characteristic parameters 92 are selected by the neural network and the unsupervised learning calculation, and then the change intervals of the characteristic parameters corresponding to the white spirit of different grades are induced by utilizing a big data analysis method, for example, the change range of the phase angle under 10Hz is 48.38-68.39, the change range of the real part is 6011.01-8605.7, and the change range of the characteristic vector of the current under the voltage of 0.4-0.6V obtained by a voltammetry scanning method is-1.03x10 -6 to-1.97X10 -7 And then establishing a random forest classification model according to the acquired characteristics. Firstly dividing all samples into a training set and a testing set, then constructing N subsets from the replaced samples in the training set by adopting a self-help resampling technology, constructing N corresponding decision trees, splitting each decision tree according to the information quantity of the selected features, and finally obtaining a final classification result of a random forest algorithm from the result obtained by each decision tree by a voting method.
3. And selecting 200 batches of unknown grade white spirit samples of the company, numbering, performing the electrochemical test, and inputting the obtained data into the recognition model to obtain the predicted grade of white spirit.
4. According to the GB/T33404-2016 method, artificial sensory evaluation is carried out on an unknown sample, the total content of ethyl acetate and ethyl lactate is tested by using the GB/T10345-2007 method, the two results are combined to obtain the artificial evaluation grade of the white spirit, and the artificial evaluation grade is compared with the evaluation result.
Results: (1) Fig. 2 shows the correspondence between the contents of each substance in the white spirit and the electrochemical signals, from which it can be found that the processed electric signals can accurately reflect the concentration changes of each main component, and the linear regression degree is high.
FIG. 3 shows the correlation of non-targeted signals between electrodes in an array electrode system, and the correlation between signals is distinguished by principal component analysis and machine operation.
FIG. 4 is a quantification method of targeting indexes, wherein the content of the targeting substances is determined by targeting signals of corresponding electrodes and non-targeting signals of other electrodes.
Fig. 5 is a schematic diagram of quality classification of white spirit based on electrochemical principle. Electrochemical signals such as electrochemical impedance spectrum and polarization curve spectrum of the white spirit-electrode interface are collected through electrochemical tests, the electrochemical signals are classified through a mathematical statistics method, characteristic quantities capable of indicating the quality of the wine and the distribution range of the characteristic quantities are obtained, a random forest classification model is established, and finally the quality of the white spirit is predicted.
(2) And comparing the predicted grades of unknown white spirit samples with different numbers with the manual evaluation grade, wherein the coincidence rate reaches 80%.
In summary, the application provides an array electrode system and application thereof in quality classification of white spirit, wherein the array electrode is formed by using an array electrode consisting of a modified graphite electrode, a glassy carbon electrode, a platinum electrode and a polymer-based electrode as a working electrode, an Ag/AgCl electrode as a reference electrode and a platinum sheet electrode as an auxiliary electrode. The array electrode system is applied to the quality grading detection of white spirit and has the advantages of high speed, high accuracy, low cost of a detection device and the like. By applying the method for grading the quality of the white spirit by the array electrode system, each enterprise can obtain a targeted identification model, various white spirits are ensured to generate a dedicated data identification library, and the custom requirements of the enterprise are met.
The foregoing has outlined rather broadly the more detailed description of the invention in order that the detailed description of the invention that follows may be better understood, and in order that the present invention may be better understood. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
Claims (9)
1. An array electrode system comprising a working electrode, a reference electrode, and an auxiliary electrode; the working electrode is a 2X 2 array electrode system formed by a modified graphite electrode, a glassy carbon electrode, a platinum electrode and a polymer-based electrode; the reference electrode is an Ag/AgCl electrode; the auxiliary electrode is a platinum sheet electrode; the method for applying the array electrode system to the quality classification of white spirit comprises the following steps:
performing electrochemical test on a white wine sample with a known grade through the array electrode system, and collecting first response signal data;
classifying and summarizing the first response signal data by adopting a mathematical statistical model, determining a target index and non-target characteristic parameters, and establishing a recognition model for quality classification of the white spirit according to the target index content and non-target characteristic parameter distribution intervals of the white spirit of different grades;
and performing electrochemical test on the white spirit to be tested through the array electrode system to obtain second response signal data, inputting the second response signal data into the identification model, and screening a section where a standard sample with the minimum variance of characteristic parameters is located according to comparison with the targeting indexes of each grade to determine the final grade.
2. The array electrode system of claim 1, wherein the modified graphite electrode is composed of nano silicon powder, phosphate and cellulose, which are coated on a graphite rod after high temperature sintering; the glassy carbon electrode is a commercial glassy carbon electrode; the platinum electrode is a commercial platinum electrode with a platinum content of greater than 99.9%; the polymer-based electrode is formed by mixing and pressing polyaniline and polypyrrole.
3. The array electrode system of claim 1, wherein the known grade white spirit samples are those for which a final composite grade has been determined after sensory evaluation by multiple national, provincial grade wine makers over different storage periods.
4. The array electrode system of claim 1, wherein the electrochemical test comprises one or a combination of an electrochemical impedance spectroscopy test, a potentiodynamic scan test, and a cyclic voltammetry test.
5. The array electrode system of claim 1, wherein the mathematical statistical model comprises one or a combination of principal component analysis, a tree-like neural network model, and unsupervised machine learning.
6. The array electrode system of claim 1, wherein the targeting index comprises ethanol, ethyl acetate, ethyl lactate, organic acids, higher alcohols with a mass content higher than 0.1%; the non-targeting characteristic parameters comprise potential, current, frequency, capacitance, dispersion coefficient, dielectric constant and real/imaginary impedance values.
7. The array electrode system of claim 1, wherein the number of targeting indicators is 5-20 and the number of non-targeting characteristic parameters is 30-100.
8. Use of the array electrode system of claim 1 in the quality classification of white spirit.
9. The use according to claim 8, wherein the white spirit is a small starter white spirit.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210855103.0A CN115236163B (en) | 2022-07-20 | 2022-07-20 | Array electrode system and application thereof in quality classification of white spirit |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210855103.0A CN115236163B (en) | 2022-07-20 | 2022-07-20 | Array electrode system and application thereof in quality classification of white spirit |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115236163A CN115236163A (en) | 2022-10-25 |
| CN115236163B true CN115236163B (en) | 2024-01-16 |
Family
ID=83674007
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210855103.0A Active CN115236163B (en) | 2022-07-20 | 2022-07-20 | Array electrode system and application thereof in quality classification of white spirit |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115236163B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101149362A (en) * | 2007-09-27 | 2008-03-26 | 北京市产品质量监督检验所 | Brewing white spirit and alcohol concocted white spirit discrimination method |
| CN106501470A (en) * | 2016-11-23 | 2017-03-15 | 广东嘉豪食品有限公司 | Using gustatory system and the method for Electronic Nose association evaluation mustard chilli sauce local flavor grade |
| CN112213303A (en) * | 2020-09-30 | 2021-01-12 | 青岛啤酒股份有限公司 | Method for rapidly detecting key quality index of beer |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020118732A1 (en) * | 2018-12-15 | 2020-06-18 | 深圳先进技术研究院 | Composite array electrode, preparation method therefor and application thereof |
-
2022
- 2022-07-20 CN CN202210855103.0A patent/CN115236163B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101149362A (en) * | 2007-09-27 | 2008-03-26 | 北京市产品质量监督检验所 | Brewing white spirit and alcohol concocted white spirit discrimination method |
| CN106501470A (en) * | 2016-11-23 | 2017-03-15 | 广东嘉豪食品有限公司 | Using gustatory system and the method for Electronic Nose association evaluation mustard chilli sauce local flavor grade |
| CN112213303A (en) * | 2020-09-30 | 2021-01-12 | 青岛啤酒股份有限公司 | Method for rapidly detecting key quality index of beer |
Non-Patent Citations (1)
| Title |
|---|
| 基于电子舌的白酒检测与区分研究;王永维;王俊;朱晴虹;;包装与食品机械(05);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115236163A (en) | 2022-10-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103134850B (en) | A kind of tea leaf quality method for quick based on characteristic perfume | |
| CN102879445B (en) | Method for identifying millet wine storage time based on multi-electrode sensing technology | |
| CN102778442B (en) | Method for rapidly identifying type of balsam material liquid for cigarette | |
| CN110018203A (en) | Aromatic vinegar flavor quantitatively characterizing method based on electronic nose electronic tongues intelligent sensory technology | |
| Pigani et al. | Pedot modified electrodes in amperometric sensing for analysis of red wine samples | |
| JP7090184B2 (en) | Biometric concentration measurement method using artificial intelligence deep learning learning | |
| CN111521722A (en) | Method for identifying storage years of fragrant odor type finished product white spirit bottles | |
| CN111505097A (en) | Electrochemical method for measuring nicotine content in tobacco and tobacco related products | |
| CN107656181A (en) | A kind of method of quantitative Diagnosis paper oil insulation degree of aging | |
| CN101685092A (en) | Method for judging alcoholization quality of flue-cured tobacco by pH detection value of tobacco leaf | |
| CN115236163B (en) | Array electrode system and application thereof in quality classification of white spirit | |
| CN109884146B (en) | Method for rapidly identifying vintage by electrochemical impedance spectroscopy | |
| CN110887944A (en) | Tea-seed oil quality short-term test device | |
| Lazaro et al. | Chemometric data analysis for black tea fermentation using principal component analysis | |
| CN111707728A (en) | Method for identifying white peony tea with different grades based on HS-PTR-TOF-MS | |
| CN110954584B (en) | Taste testing method and verification method based on electronic tongue | |
| CN110084420B (en) | Method for detecting total sugar, total acid and alcoholic strength of yellow water in strong aromatic Chinese spirit fermentation | |
| Huang et al. | Study on grading of Xiaoqu Baijiu based on in-situ untargeted detection of electrochemical measurements | |
| CN202794093U (en) | Device for fast detecting quality of baked food based on bionic olfaction | |
| CN108241016B (en) | Method and device for rapidly detecting theaflavin content in black tea | |
| Liu et al. | Taste analog perception system based on impedance spectrum sensor array and human-like fuzzy evaluation cloud model | |
| Huang et al. | Cluster and discriminant analysis of electrochemical noise statistical parameters | |
| Sarkar et al. | Taste recognizer by multi sensor electronic tongue: a case study with tea quality classification | |
| CN107884360B (en) | Cigarette paper combustion improver detection method | |
| Wójcik et al. | A new approach in voltammetric profiling of wines and whiskies based on a useful faradaic signal component |
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 |