CN115236163A - Array electrode system and application thereof in liquor quality grading - Google Patents
Array electrode system and application thereof in liquor quality grading Download PDFInfo
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Abstract
The application provides an array electrode system and application thereof in liquor quality grading. Carrying out electrochemical test on a white spirit sample with a known grade through the array electrode system, and collecting first response signal data; establishing a recognition model for liquor quality grading on the first response signal data by adopting a mathematical statistical model; and carrying out electrochemical test on the white spirit to be tested through an array electrode system to obtain second response signal data, inputting the second response signal data into the recognition model, and determining the final grade of the white spirit. The white spirit quality grading is carried out through the array electrode system, and the white spirit grading device has the advantages of being high in accuracy, high in speed, low in cost and the like.
Description
Technical Field
The application relates to the technical field of liquor quality grading, in particular to an array electrode system and application thereof in liquor quality grading, and specifically relates to rapid grading of liquor quality by utilizing a multi-electrode combination test, an electrochemical test principle and a mathematical statistics method.
Background
The liquor grading is an important link in the brewing process, the accuracy and the efficiency of the liquor grading directly influence the screening result of high-quality products and the subsequent grading cellaring process, and the liquor grading is of great importance to the production benefit of enterprises.
At present, liquor grading is mainly completed by artificial sensory evaluation, the method is non-targeted evaluation of synergistic effect formed by all flavor substances in the liquor, the sensory evaluation method is to judge the quality of the liquor by tasting by a taster, and the main indexes comprise: color of wine, aroma of wine, taste of wine, body of wine, etc. The disadvantages of this method are:
1. the judgment can be made only by a taster with abundant experience, and the factor result of the person is greatly changed;
2. the identification result cannot be quantified;
3. the identification speed is slow, and the requirement of online detection cannot be met.
Sensory evaluation is generally graded by combining the content result of one or more main esters in the gas chromatography detection of the white spirit. The quality grading of the white spirit by using a gas chromatography detection method has the following defects:
1. a large amount of water exists in the white spirit, the existence of the water can damage an instrument, and a sample needs to be subjected to complex pretreatment before testing;
2. chemical components in the white spirit are very complex and have more than 1700 flavor substances, the content of all substances determining the quality of the white spirit cannot be determined by gas chromatography, and the overall 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 using the chromatography, the normalized area size of the substances is used as the content of the substances, and the calculation method has large errors and cannot be used for subsequent analysis;
4. the testing time is long: typically, about 40 minutes is required to test a sample, thus not facilitating on-line testing.
At present, an electronic nose and an electronic tongue are available, and the electronic nose can only detect volatile flavor substances; the electronic tongue is used for carrying out targeted detection on substances which generate sour, salty, bitter and sweet tastes in the white spirit.
Therefore, the detection method is not an overall evaluation of the synergistic effect of all flavor substances in the white spirit, so that the accuracy is poor.
Disclosure of Invention
The application aims to perform in-situ non-targeted evaluation on the synergistic effect of all flavor substances in the white spirit by using an array electrode and an electrochemical detection principle, so that the quality of the white spirit is rapidly graded.
The electrochemical detection is characterized by representing the electrode-solution interface reaction process by obtaining electrode reaction kinetic parameters, further evaluating the characteristics of the electrode or the solution, and has the remarkable advantages of high sensitivity, wide measurement range, small interference on a system, greenness, safety and the like. Flavor substances, alcohol content and ester assembly structures in different grades of white spirit are different, so that electrode-white spirit interfaces are correspondingly changed. When a certain electric signal is applied to the electrode, the electrode interface forms different micro-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 an electrochemical signal, and the feedback information of different grades of white spirits 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 ester content, the oxidation current under the same potential is gradually increased, which is related to the oxidation process of the ester substances after the interface adsorption; different flavor substances form different molecular assembly structures in the solution, and the different molecular assembly structures present different distribution and change of dielectric constant at an electrode interface, so that signal response in electrochemical reaction can also show obvious difference.
The electrochemical signal generated by each electrode in the multi-electrode array electrode system can be divided into a targeting signal directly related to the exact components and a non-targeting signal after being assembled with other substances. Different flavor substances can generate electrochemical signals at an electrode interface, and only the intensity and the parameter interval of the signals 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 capable of responding to all flavors, most of which are non-targeting signals. The multi-electrode array electrode system has the advantages that not only the target signals of the electrodes and main substances such as ethanol, ester, organic acid and the like can be obtained, but also non-target signals after a large amount of trace substances are assembled can be obtained by means of the rest electrodes. The components in the white spirit are also influenced mutually, when the index of one component is changed, the electrochemical test of another index is inevitably influenced, and the multi-electrode array electrode system can effectively reduce the influence degree of the non-targeted signal on the test result by using the database of the non-targeted signal, so that the components are identified more accurately, and the interference of other indexes is avoided.
The data recognition base of the white spirit grade consists of the targeted signals and the non-targeted signals of all the electrodes together, but the parameter intervals of the characteristic quantities of the non-targeted signals of all the electrodes are possibly different, so that the cross-correlation degree between the non-targeted signals of the same component of different electrodes becomes the core content for establishing the non-targeted database. And analyzing the characteristic quantity of the white spirit with the known grade by using a mathematical statistical model, establishing a database of standard samples, inputting the test data of the sample to be tested into the database, comparing to obtain a standard sample interval with the minimum characteristic quantity variance, and determining the quality grade of the sample to be tested. The method can accurately evaluate the content of each substance in the liquor and the synergistic effect thereof, thereby realizing the rapid grading of the liquor.
Based on the technical principle, the response characteristics of the white spirits with different grades are integrally evaluated by utilizing the response difference of the types and the contents of different flavor substances in the white spirits on the electrode interface. And (3) classifying the parameters of the standard database by adopting a numerical model, and 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 the white spirit. And then, establishing a recognition model of the white spirit grade according to the target indexes and the change interval of the characteristic quantity. And inputting the electric response signal parameter values of the white spirit sample to be detected into the model, comparing to obtain the interval where the standard sample with the minimum characteristic quantity variance is located, wherein the grade of the white spirit sample to be detected is the quality grade of the interval where the standard sample is located.
Accordingly, the present application provides an array electrode system and an application thereof in liquor quality grading to solve or alleviate some of the above technical problems.
In a first aspect, the present application provides an array electrode system comprising:
a working electrode; the working electrode forms a 2X 2 array electrode system 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 coating nano silicon powder, phosphate and cellulose 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 the platinum content higher than 99.9%; the polymer-based electrode is formed by mixing and pressing polyaniline and polypyrrole.
In a second aspect, the application provides a method for grading the quality of white spirit, which specifically comprises the following steps:
performing electrochemical test on a white spirit sample with a known grade through the array electrode system in the first aspect, and collecting first response signal data;
and classifying and inducing the data of the first response signal by adopting a mathematical statistical model (namely a general mean regression statistical model), searching for a response signal with a larger correlation coefficient with the flavor substance Pearson, determining a targeted index and a non-targeted characteristic parameter, and establishing a mean regression model between the flavor substance and the characteristic according to the determined characteristic. Establishing a recognition model (namely a random forest classification model) for liquor quality classification according to the targeted index content and the non-targeted characteristic parameter distribution interval of the liquor of different grades, and obtaining an optimal classification recognition model by adjusting parameters in the random forest model;
and performing 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 recognition model, and screening the interval where the standard sample with the minimum variance of the characteristic parameters is located according to comparison with the target indexes of all grades to determine the final grade of the white spirit.
In the embodiment of the application, the white wine samples with known grades are wine samples with final comprehensive grades determined by multiple national and provincial tasters after sensory evaluation in different storage periods.
In the method of the present application, the electrochemical test includes one or a combination of an electrochemical impedance spectroscopy test, a potentiodynamic scanning test and a cyclic voltammetry test.
In the embodiment of the application, the mathematical statistic model comprises 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 indexes comprise substances with the 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 present embodiment, the number of targeted indicators is preferably 5 to 20, and the number of non-targeted characteristic parameters is preferably 30 to 100.
In a third aspect, the application provides the application of the array electrode system of the first aspect and/or the method of the second aspect in liquor quality grading.
In the embodiment of the application, in the application, the white spirit is Xiaoqu white spirit.
Compared with the prior art, this application utilizes the array electrode as working electrode, utilizes the electrochemistry test principle to realize the quick hierarchical of white spirit quality, possesses following advantage at least:
(1) The array electrode system can obtain reaction signals of the electrode and the target indexes, and can also obtain non-target signals assembled by a large amount of trace components by means of the rest electrodes. 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 assembly, establishes recognition databases of white spirits of different grades after integrating the data of the two types of substances, and can avoid the interference of other indexes while accurately recognizing targeted components.
(2) The functional graphite material sintered by nano silicon, phosphate and cellulose has the characteristics of good stability, strong oxidation resistance, high catalytic activity of interfacial electrochemical reaction and the like. The electrode material is doped with multiple elements, so that the charge mobility is high, the electron transmission rate is high, the sensitivity of response signals of flavor substances on an electrode interface can be improved, and the difference of electric response signals under different environments can be accurately identified. Meanwhile, due to the loose carbon structure, the modified graphite electrode can quickly adsorb various flavor substances in the white spirit 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 differentiation basis based on big data operation, and the capacity of the standard database is expanded along with the increase of the number of the test samples, so that the self-correcting function is realized by continuous upgrading, and the accuracy is continuously improved.
(4) The method is short in time for grading the quality of the white spirit based on electrochemical tests, the sum of all electrochemical tests is less than 30 minutes, and the method is suitable for on-line rapid detection and full-flow intelligent tests.
(5) The method has the advantages of low cost of required consumables and equipment, low electrode preparation cost lower than 2000 yuan, and no more than 5 ten thousand yuan of comprehensive cost of a set of rapid liquor grading device based on electrochemical test, which is far lower than the price of the 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, ensure that each white spirit generates an exclusive data identification database and meet the customization requirements of the enterprises.
Drawings
The present invention will be described in further detail below with reference to the drawings and preferred embodiments, but those skilled in the art will appreciate that the drawings are only drawn for the purpose of illustrating the preferred embodiments and therefore should not be taken as limiting the scope of the invention. Furthermore, unless specifically stated otherwise, the drawings are merely schematic representations based on the concept of a composition or construction of the object being described and may include exaggerated displays and are not necessarily drawn to scale.
Fig. 1 is an electrochemical signal acquisition scanning mode for studying white spirit quality by using an array electrode system provided in an embodiment of the present application.
Fig. 2 is a schematic diagram illustrating a correspondence between the quality of white spirit and the electrochemical signal of the array electrode system provided in the embodiment of the present application.
Fig. 3 is a schematic diagram illustrating the correlation of non-target signals between electrodes in an array electrode system according to an embodiment of the present disclosure.
Fig. 4 is a schematic diagram of a method for quantifying a target indicator in an array electrode system according to an embodiment of the present application.
Fig. 5 is a schematic diagram of liquor quality grading based on an electrochemical principle provided in an embodiment of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit 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 consisting of 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 with other substances, and the intensity and the parameter interval of the signals change along with the action mode of the object to be detected and the electrode material. Thus, each electrode in the array electrode system is capable of responding to all substances, most of which are non-targeting signals.
Taking white spirit as an example, the array electrode system has the advantages that not only the target signals of the electrodes and main substances such as ethanol, ester, organic acid and the like are obtained, but also non-target signals after a large amount of trace substances are assembled can be obtained by means of the rest electrodes. The components in the white spirit are also influenced mutually, when the index of one component is changed, the electrochemical test of another index is inevitably influenced, and the array electrode system can effectively reduce the influence degree of the non-targeted signal on the test result by using the database of the non-targeted signal, so that the components are identified more accurately, and the interference of other indexes is avoided.
In the embodiment of the application, the modified graphite electrode is formed by coating nano silicon powder, phosphate and cellulose 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 the platinum content higher 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 prepared by sintering nano-silicon, phosphate and cellulose, and has the characteristics of good stability, strong oxidation resistance, high catalytic activity of interfacial electrochemical reaction and the like. The electrode material is doped with multiple elements, so that the charge mobility is high, the electron transmission rate is high, the sensitivity of a substance on a response signal on an electrode interface can be improved, and the difference of electric response signals under different environments can be accurately identified. Meanwhile, due to the 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.
The application of the array electrode system in the rapid grading of white spirit quality
1. 400 batches of Xiaoqu white spirit samples with known grades are selected from a certain company, and are subjected to 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 to perform electrochemical test on a white spirit sample, and an electrochemical signal acquisition scanning mode for researching the white spirit quality by using an array electrode system is shown in figure 1.
(1) Performing electrochemical impedance spectroscopy at open circuit potential (current density)Electrode potential at zero, i.e. the potential difference between the working electrode and the reference electrode without load), the disturbing signal is a sinusoidal AC wave with amplitude of 10mV, and the test frequency range is 10 Hz-10 Hz 6 Hz。
(2) And (3) performing potentiodynamic scanning from the cathode to the anode in sequence, wherein the scanning speed is 2mV/s, and the oxidation voltage reaches 3.0V (vs.
(3) And (3) performing cyclic voltammetry, starting reverse scanning from a cathode potential of-3.0V, wherein the scanning speed is 5mV/s, and the scanning times are 3 circles.
2. Adopting Matlab software to summarize the electrochemical response data, and carrying out targeted test on the ethanol content, the ethyl acetate, the ethyl lactate, the long-chain alcohol and the organic acid content to obtain accurate concentration; screening 92 characteristic parameters by using a tree neural network and unsupervised learning calculation, then inducing the change interval of the characteristic parameters corresponding to different grades of white spirit by using a big data analysis method, wherein if the phase angle change range under 10Hz is 48.38-68.39, the real part change range is 6011.01-8605.7, and the current characteristic vector change range under 0.4-0.6V voltage acquired by a voltammetry scanning method is-1.03 multiplied by 10 -6 to-1.97X 10 -7 And then establishing a random forest classification model according to the acquired features. Firstly, dividing all samples into a training set and a testing set, then adopting a self-help resampling technology to construct N subsets from samples returned from the training set and construct corresponding N decision trees, splitting each decision tree according to the information quantity of the selected characteristics, and finally obtaining the final classification result of the random forest algorithm from the result obtained by each decision tree through a voting method.
3. 200 batches of liquor samples with unknown grades of the company are selected, the electrochemical test is carried out after the liquor samples are numbered, and the obtained data are input into an identification model to obtain liquor prediction grades.
4. Carrying out artificial sensory evaluation on an unknown sample according to a GB/T33404-2016 method, testing the total content of ethyl acetate and ethyl lactate by using the GB/T10345-2007 method, synthesizing two results to obtain an artificial evaluation grade of the white spirit, and comparing the artificial evaluation grade with the evaluation result.
As a result: (1) FIG. 2 is the corresponding relationship between the contents of various substances in the white spirit and electrochemical signals, from which it can be found that the processed electrical signals can accurately reflect the concentration change of various main components, and the linear regression degree is high.
Fig. 3 shows the correlation degree of the non-target signals between the electrodes in the array electrode system, and the correlation between the signals is distinguished by the principal component analysis method and the machine calculation.
Fig. 4 is a method for quantifying the target index, and the content of the target substance is determined by the target signal of the corresponding electrode and the non-target signal of the other electrode.
Fig. 5 is a schematic diagram of liquor quality grading based on electrochemical principle. Collecting electrochemical signals such as electrochemical impedance spectrum and polarization curve spectrogram of the liquor-electrode interface through electrochemical test, classifying the electrochemical signals by a mathematical statistics method to obtain characteristic quantity capable of indicating liquor quality and distribution range thereof, establishing a random forest classification model, and finally predicting the liquor quality.
(2) The predicted grades and the manual evaluation grades of unknown white wine samples with different numbers are compared, and the coincidence rate reaches 80%.
In summary, the application provides an array electrode system and application thereof in liquor quality grading, the array electrode uses an array electrode composed 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 graded detection of the white spirit quality, and has the advantages of high speed, high accuracy, low cost of a detection device and the like. The method for grading the quality of the white spirit by applying the array electrode system can enable enterprises to obtain targeted identification models, ensure that various white spirits generate exclusive data identification databases, and meet the customization requirements of the enterprises.
The present invention has been described in detail, and the principles and embodiments of the present invention have been described herein using specific examples, which are provided only to assist in understanding the present invention and the core concepts. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (10)
1. An array electrode system, comprising:
a working electrode; the working electrode is a 2X 2 array electrode system consisting of 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.
2. The array electrode system of claim 1, wherein the modified graphite electrode is formed by coating nano silicon powder, phosphate and cellulose 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 the platinum content higher than 99.9%; the polymer-based electrode is formed by mixing and pressing polyaniline and polypyrrole.
3. A method for grading the quality of white spirit specifically comprises the following steps:
performing electrochemical test on a white spirit sample with a known grade through the array electrode system of any one of claims 1 or 2, and collecting first response signal data;
classifying and inducing the first response signal data by adopting a mathematical statistic model, determining a targeted index and a non-targeted characteristic parameter, and establishing a liquor quality grading identification model according to targeted index contents and non-targeted characteristic parameter distribution intervals of different grades of liquor;
carrying out electrochemical test on the white spirit to be tested through the array electrode system of any one of claims 1 or 2 to obtain second response signal data, inputting the second response signal data into the identification model, and screening the interval where the standard sample with the minimum variance of the characteristic parameters is located according to comparison with the target indexes of all grades to determine the final grade of the white spirit.
4. The method of claim 3, wherein the known grade of white spirit sample is a wine sample for which a final composite grade has been determined by multiple national, provincial tasters after sensory evaluation at different periods of storage.
5. The method of claim 3, wherein the electrochemical test comprises one or a combination of an electrochemical impedance spectroscopy test, a potentiodynamic scanning test, and a cyclic voltammetry test.
6. The method of claim 3, wherein the mathematical statistical model comprises one or a combination of principal component analysis, a tree neural network model, and unsupervised machine learning.
7. The method according to claim 3, wherein the target index comprises substances with mass content higher than 0.1% such as ethanol, ethyl acetate, ethyl lactate, organic acids and higher alcohols; the non-targeted characteristic parameters include potential, current, frequency, capacitance, dispersion coefficient, dielectric constant, real/imaginary impedance and other mathematical deformation values.
8. A method according to claim 3, wherein the number of targeted markers is preferably 5 to 20 and the number of non-targeted characteristic parameters is preferably 30 to 100.
9. Use of an array electrode according to any one of claims 1 or 2 and/or a method according to any one of claims 3 to 8 for grading the quality of liquor.
10. The use according to claim 9, wherein the white spirit is Xiaoqu white spirit.
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