CN111693594A - Device and method for quickly detecting physical and chemical indexes of soybean paste based on volt-ampere electronic tongue - Google Patents
Device and method for quickly detecting physical and chemical indexes of soybean paste based on volt-ampere electronic tongue Download PDFInfo
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Abstract
The invention discloses a device and a method for quickly detecting physicochemical indexes of soybean paste based on volt-ampere electronic tongues, belonging to the field of quick detection of food quality. The method comprises the following steps: firstly, collecting electric signal data of the soybean paste by using a taste sensor, and extracting sensor characteristic values such as peak values, inflection values, average values and the like; secondly, measuring the physicochemical indexes of the sample according to a chemical analysis method in national standard to obtain the contents of amino acid nitrogen and ammonium salt; and finally, constructing a model by using the characteristic value obtained by the volt-ampere electronic tongue and the physicochemical index content measured by a national standard method, thereby realizing the rapid and accurate quantitative detection of the physicochemical index of the soybean paste. The invention develops the quick detection device of the physicochemical index of the soybean paste based on the voltammetric electronic tongue, and successfully realizes the quick and simple detection of the physicochemical index of the content of amino acid nitrogen and ammonium salt in the soybean paste.
Description
Technical Field
The invention relates to a method and a device for detecting the quality of soybean paste, in particular to a device and a method for quickly detecting the physicochemical index of the soybean paste by a novel volt-ampere electronic tongue, belonging to the field of quick detection of the quality of food.
Background
The soybean paste is the traditional seasoning paste in China, has strong sauce flavor and ester flavor, is salty and sweet, and is deeply loved by people. The soybean paste is rich in linoleic acid, linolenic acid and soybean lecithin, and is beneficial to reducing cholesterol of a human body and reducing the incidence rate of cardiovascular diseases; the soybean paste also has effects of maintaining blood vessel elasticity, nourishing brain and preventing fatty liver formation. Therefore, the quality guarantee of the soybean paste has very important practical significance for improving the health and the nutrition level of consumers.
The physical and chemical indexes are important references for evaluating the quality of the soybean paste and have important significance for improving the quality and controlling the production of the soybean paste. At present, the physical and chemical indexes of the soybean paste are mainly detected according to a chemical analysis method of national standard (GB/T24399-2009), and the detection indexes comprise amino acid nitrogen, ammonium salt and water. The pretreatment of the detection process of amino acid nitrogen and ammonium salt is complex, time-consuming and labor-consuming, rapid detection cannot be realized, the efficiency is low, and a large amount of toxic reagents of formaldehyde are needed, so that the method is harmful to the body of an operator. Through searching relevant patents, patent numbers: 201711295542.6, in the method for rapidly detecting the contents of amino acid nitrogen and total acid in the soy sauce by using the mid-infrared spectrum, the mid-infrared spectrum technology is adopted for detection, so that not only is the data processing more complicated, but also the spectrum wave band needs to be screened for many times; patent numbers: 201510228898.2 in the method for rapidly detecting benzoic acid in fruit juice based on electronic tongue, the fruit juice is detected by using commercial electronic tongue, the equipment price is high, and the object is fruit juice with simple components. In conclusion, a soybean paste physicochemical index detection method based on the voltammetric electronic tongue is rarely reported.
The electronic tongue obtains sample information by the taste sensor array, and processes the output signals of the sensors by using a multivariate analysis method to realize objective and reliable analysis of the overall quality of the sample. The electronic tongue has the advantages of rapidness, accuracy, good repeatability and the like, and is widely applied to the field of food detection. The volt-ampere electronic tongue has the advantages of simple operation, strong adaptability, high sensitivity, large information amount and the like, and is suitable for detecting food containing complex organic matters.
Aiming at the practical problems, the invention develops the rapid detection device of the soybean paste physicochemical index based on the novel volt-ampere electronic tongue, successfully realizes the rapid and simple detection of the physicochemical index of the content of amino acid nitrogen and ammonium salt in the soybean paste, and the volt-ampere electronic tongue device developed by the invention has simple structure, easy assembly and low cost, and is suitable for mass production and use in factories.
Disclosure of Invention
The invention aims to provide a method and a device for detecting physicochemical indexes of soybean paste by using a novel volt-ampere electronic tongue. The detection scheme adopted by the invention is summarized as follows: firstly, collecting electric signal data of the soybean paste by using a taste sensor, and extracting sensor characteristic values such as peak values, inflection values, average values and the like; secondly, measuring the physicochemical indexes of the sample according to a chemical analysis method in national standard to obtain the contents of amino acid nitrogen and ammonium salt; and finally, constructing a model by using the characteristic value obtained by the volt-ampere electronic tongue and the physicochemical index content measured by a national standard method, thereby realizing the rapid and accurate quantitative detection of the physicochemical index of the soybean paste.
The invention relates to a device for quickly detecting physical and chemical indexes of soybean paste based on a novel volt-ampere electronic tongue, which consists of a sample stage, a sensor array, an excitation signal generator, a signal acquisition circuit, a data acquisition card and a computer, wherein the sensor array is respectively connected with the excitation signal generator and the signal acquisition circuit through leads; the sample platform is square and comprises a magnetic stirrer, a circular groove is formed in the center of the sample platform to fix a sample cell, a support is arranged on the sample platform, a sliding guide rail and a connecting sleeve which keeps vertical are arranged on the support, and the connecting sleeve comprises a screw and a lead and is respectively connected with an excitation signal generator and a working electrode sensor as well as a signal acquisition circuit and an auxiliary electrode sensor; the sensor array includes: the device comprises a graphene-modified gold, silver, palladium and platinum working electrode, a silver chloride/silver reference electrode and a platinum column auxiliary electrode, wherein the graphene-modified gold, silver, palladium and platinum electrode is connected with an excitation signal generator and the silver chloride/silver reference electrode, and the platinum column auxiliary electrode is connected with a signal acquisition circuit; the signal acquisition circuit includes: the constant potential circuit is respectively connected with the working electrode and the silver chloride/silver reference electrode, and the current-voltage conversion circuit is respectively connected with the auxiliary electrode and the program control amplification circuit; the signal acquisition circuit is connected with the data acquisition card, the data acquisition card is connected with the computer, and the acquired data is processed by the computer.
Wherein the sensor array consists of metal electrodes modified with graphene: gold, silver, palladium and platinum electrodes; the modification method comprises the following steps: and cleaning the inert metal electrode by using ethanol and deionized water, drying, dropwise coating 2uL of graphene oxide dispersion liquid (2mg/mL) on the surface of the treated electrode by using a microsyringe, drying under an infrared lamp to obtain the graphene oxide modified electrode, and scanning for 5 periods at the rate of 100mV/s under the potential of-1.7-0.0V by using a cyclic voltammetry method to obtain the graphene modified electrode. The soybean paste has weak response to the excitation current, and the graphene improves the capturing capability of the sensor on weak electric signals, so that the detection effect of the volt-ampere electronic tongue can be improved.
The invention relates to a detection method of a device for quickly detecting physical and chemical indexes of soybean paste based on a novel volt-ampere electronic tongue, which is carried out according to the following steps:
step (1): determining the content of amino acid nitrogen and ammonium salt in the soybean paste by a chemical analysis method in national standard;
step (2): sample pretreatment: grinding the soybean paste until no obvious coarse particles exist, and adding deionized water for dissolving;
and (3): sensor array experiment pretreatment: sequentially ultrasonically cleaning deionized water and ethanol, drying by blowing nitrogen, and initializing by adopting cyclic voltammetry for prescan;
and (4): measuring the soybean paste sample by adopting a novel volt-ampere electronic tongue device, recording the response value of an electronic tongue sensor array, obtaining the response curve of the sensor array to different samples, and storing the response curve in a computer;
and (5): and (3) processing the information of the soybean paste obtained by the volt-ampere electronic tongue in the step (4), extracting a characteristic value, and constructing a quantitative model of the content of the physicochemical index in the step (1).
In the step (1), the detection method of amino acid nitrogen is a formaldehyde value method, and the principle is that the amphoteric action of amino acid is utilized, formaldehyde is added to fix the alkalinity of amino, so that carboxyl shows acidity, the quantity is determined after titration by sodium hydroxide standard solution, and the end point is measured by an acidimeter;
in the step (1), the detection method of the ammonium salt is a semi-microscale nitrogen determination method, and the principle is that a sample is heated and distilled in an alkaline solution, so that ammonia is free and evaporated out and is absorbed by a boric acid solution, and then the content is calculated by titration with a hydrochloric acid standard solution;
in the step (2), each part of soybean paste sample is 5g in mass; grinding the mixture by using a porcelain mortar for 2 minutes; grinding while maintaining the vertical pestle, crushing large bean grains and grinding;
in the step (2), the mass ratio of the soybean paste to the deionized water is 1: 10;
in the step (3), sequentially performing ultrasonic treatment on the sensor in deionized water and ethanol for half a minute, wherein the electrode tip is suspended in an ultrasonic pool during ultrasonic treatment;
in the step (3), a sensor is used for pre-scanning a mixed solution of 2mmoL/L potassium ferricyanide and 1moL/L potassium nitrate by a cyclic voltammetry method, and a peak current value is used as an index for judging the performance of the sensor;
in the step (4), the detection of the volt-ampere electronic tongue device comprises the following steps: firstly, placing a sample cell in a circular groove corresponding to a sample platform, then sliding down a connecting sleeve provided with a sensor array to ensure that the sensor array is completely submerged in a sample, fixing the connecting sleeve, then opening an excitation signal generator and a computer to set experiment parameters, and finally detecting and recording data;
in the step (4), when the voltammetry electronic tongue is detected, the sensor array is electrochemically cleaned by using deionized water at every two detection intervals;
in the step (4), the experimental parameters of the excitation signal generator mainly comprise signal output waveform, frequency, amplitude and initial phase; the parameters of the computer (data acquisition card) are mainly sampling intervals;
in the step (4), when the first sample detection is carried out, the first two periods are used for determining the collection sensitivity;
in the step (4), detecting each sample for 5 periods by the volt-ampere electronic tongue, and repeatedly detecting each sample for 2-5 times;
in the step (5), data obtained by a voltammetry electronic tongue detection sample is subjected to primary processing, and an average value obtained by peak values and inflection point values of a sensor detection curve in 5 periods is extracted as a characteristic value;
in the step (5), the characteristic value obtained after extracting the detection curve of each sensor is weighted and added as the final parameter value detected by the sensor:
wherein A isiA final parameter value representing the sensor detection;
an average value representing a peak in the sensor detection curve;
an average value representing a inflection point value in the sensor detection curve; m and n are weights; i is the value range of the sensor code number from 1 to 4;
in the step (5), the correlation between the content of each physicochemical component of the soybean paste and the parameter value of each sensor is analyzed by adopting a partial least square method, so as to establish a detection model of the content of each physicochemical component of the soy sauce, and the detection model of the content of each physicochemical component of the soybean paste, which is established by the final parameter value of each sensor and the content of the physicochemical index measured in the step (1), is as follows:
YJ＝kj+aj*A1+bj*A2+cj*A3+dj*A4；
wherein, YJA detection model result representing the content of the physical and chemical component j of the soybean paste; a. the1-4Representing the final parameter values detected by the four sensors; k is a radical ofjA constant in a soybean paste physicochemical component j content detection model is represented; a isjRepresenting the weight corresponding to the silver nano/graphene modified glassy carbon electrode parameter value in a soybean paste physicochemical component j content detection model; bjRepresenting the weight corresponding to the gold electrode parameter value in the soybean paste physicochemical component j content detection model; c. CjExpressed in a soybean paste physicochemical component j content detection modelThe weight corresponding to the platinum electrode parameter value; djAnd representing the weight corresponding to the palladium electrode parameter value in the soybean paste physicochemical component j content detection model.
The invention develops the quick detection device of the physicochemical index of the soybean paste based on the voltammetric electronic tongue, and successfully realizes the quick and simple detection of the physicochemical index of the content of amino acid nitrogen and ammonium salt in the soybean paste.
Drawings
FIG. 1 is a diagram of a novel voltammetric electronic tongue device;
wherein: 1. a sample stage; 2. a magnetic stirrer; 3. a sample cell; 4. a support; 5. a guide rail; 6. connecting sleeves; 7. a screw; 8. a wire; 9. an array of sensors; 10. an excitation signal generator; 11. a signal acquisition circuit; 12. a data acquisition card; 13. a computer;
FIG. 2 is the result of the quantitative prediction model for detecting the content of amino acid nitrogen by the novel voltammetric electronic tongue;
FIG. 3 is the result of the quantitative prediction model for detecting ammonium salt content by the novel voltammetric electronic tongue.
Detailed Description
The following detailed description will be made with reference to the drawings and preferred embodiments of a method and a device for detecting physicochemical indexes of soybean paste based on voltammetric electronic tongue according to the present invention.
The invention relates to a device for quickly detecting physical and chemical indexes of soybean paste based on volt-ampere electronic tongue, which consists of a sample platform (1), a sensor array (9), an excitation signal generator (10), a signal acquisition circuit (11), a data acquisition card (12) and a computer (13), wherein the sensor array is respectively connected with the excitation signal generator and the signal acquisition circuit through leads, the data acquisition card is connected with the signal acquisition circuit through leads, and the data acquisition card is connected with the computer through a data line; the sample platform is square and comprises a magnetic stirrer (2), a circular groove is formed in the center of the sample platform to fix a sample cell (3), a support (4) is arranged on the sample platform, a sliding guide rail (5) and a connecting sleeve (6) which keeps vertical are arranged on the support, and the connecting sleeve comprises a screw (7) and a lead (8) which are respectively connected with an excitation signal generator and a working electrode sensor, a signal acquisition circuit and an auxiliary electrode sensor; the sensor array includes: the device comprises a graphene-modified gold, silver, palladium and platinum working electrode, a silver chloride/silver reference electrode and a platinum column auxiliary electrode, wherein the graphene-modified gold, silver, palladium and platinum electrode is connected with an excitation signal generator and the silver chloride/silver reference electrode, and the platinum column auxiliary electrode is connected with a signal acquisition circuit; the signal acquisition circuit includes: the constant potential circuit is respectively connected with the working electrode and the silver chloride/silver reference electrode, and the current-voltage conversion circuit is respectively connected with the auxiliary electrode and the program control amplification circuit; the signal acquisition circuit is connected with the data acquisition card, the data acquisition card is connected with the computer, and the acquired data is processed by the computer.
The sensor array consists of metal electrodes modified with graphene: gold, silver, palladium and platinum electrodes; the modification method comprises the following steps: and cleaning the metal electrode by using ethanol and deionized water, drying, dropwise coating 2uL of graphene oxide dispersion liquid (2mg/mL) on the surface of the treated electrode by using a microsyringe, drying under an infrared lamp to obtain a graphene oxide modified electrode, and scanning for 5 periods at a rate of 100mV/s under a potential of-1.7-0.0V by using a cyclic voltammetry method to obtain the graphene modified electrode.
A method for detecting physicochemical indexes of soybean paste based on volt-ampere electronic tongues comprises the following steps:
(1) preparing a sample to be detected: selecting three soybean paste samples of different brands (Xinhe, Haitian and Lijinji) and three production batches (3 months, 6 months and 9 months), wherein each brand takes 3 soybean pastes of different batches, and each batch has 9 samples;
(2) determining the content of amino acid nitrogen and ammonium salt in the soybean paste sample by adopting a chemical analysis method in the national standard GB/T24399-2009; the detection method of amino acid nitrogen is a formaldehyde value method, and the detection method of ammonium salt is a semi-trace nitrogen determination method;
(3) weighing 5g of soybean paste samples of different brands in a clean and dry mortar, crushing large soybean grains by using a pestle until no obvious soybean grains exist, continuously grinding the soybean grains for 1 minute in clockwise and anticlockwise directions until the sample is uniform and pasty, weighing 4g of ground sample in a sample pool, adding 40mL of deionized water, and uniformly stirring for later use;
(4) taking the bare metal electrode out of the storage box, removing the sealing electrode sleeve, washing twice by using deionized water, placing the electrode in a beaker for ultrasonic cleaning, and carrying out ultrasonic cleaning on the electrode tip in the sequence of deionized water ultrasonic half minute, ethanol ultrasonic half minute and deionized water ultrasonic half minute when the electrode tip is not in contact with the bottom of the beaker; drying the electrode subjected to ultrasonic treatment by using nitrogen for later use;
(5) graphene modified electrode: 2uL of graphene oxide dispersion liquid (2mg/mL) is dripped on the surface of the treated electrode by a dried gold, silver, palladium and platinum electrode and a micro-sampler, the electrode is dried under an infrared lamp to obtain a graphene oxide modified electrode, and then the graphene oxide modified electrode is scanned for 5 periods at the rate of 100mV/s under the potential of-1.7 to 0.0V by using a cyclic voltammetry method to obtain the graphene modified electrode;
(6) placing 40mL of prepared potassium ferricyanide/potassium nitrate (potassium ferricyanide: 2mmoL/L, potassium nitrate: 1moL/L) mixed solution in a sample cell to prepare for electrochemical detection of a sensor array;
(7) setting parameters of an excitation signal generator as cyclic voltammetry, initial potential of-0.2V, maximum potential of 0.6V, minimum potential of-0.2V and period of 32 s; the acquisition interval of the data acquisition card is 0.01 s; each sensor circulates for 5 circles, and the state of the sensor array is determined to be correct by observing the cyclic voltammetry curve and the peak current value;
(8) the device for assembling the volt-ampere electronic tongue comprises a sensor array, an excitation signal generator, a signal acquisition circuit, a data acquisition card, a sample stage and a computer; the sensor array includes: the electrode comprises a silver nano/graphene modified glassy carbon electrode, a gold electrode, a platinum electrode, a palladium electrode, a silver chloride/silver reference electrode and a platinum column auxiliary electrode; the signal acquisition circuit includes: constant potential circuit, current-voltage conversion circuit, program control amplification circuit;
(9) starting sample detection, placing a sample cell filled with a sample in a circular groove corresponding to a sample table, sliding a connecting sleeve provided with a sensor array down along a guide rail to completely submerge the sensor array in the sample, fixing the connecting sleeve, and then opening an excitation signal generator and a computer and setting experiment parameters; the excitation signal generator is set to be a conventional pulse voltammetry, the frequency is 1Hz, the amplitude is 0.8V, the initial phase is 0.8V, and the data acquisition card is set to be a sampling interval of 0.01 s;
(10) pre-testing the sample to determine a sampling sensitivity of 1 × e-4(ii) a In the detection process, the sensor array is electrochemically cleaned by using deionized water every two detection intervals, namely the sensor array is cleaned in the deionized water for 3s under the condition that the set voltage is +/-1.6V respectively; and (3) repeating detection for each sample, wherein each sample acquires 5 periods of data in each detection, and each sensor acquires 500 signal values in each detection, so that the response curve of the sensor array to different detection samples is obtained.
(11) Extracting the characteristics of the obtained sensor array response signals, extracting peak values and inflection point values of each period, and taking the average value obtained by the peak values and the inflection point values of 5 periods after the curve is detected by the sensor as the characteristic value of the sensor; and (3) weighting and adding the characteristic values obtained after extracting the detection curves of each sensor to obtain the final parameter values detected by the sensor:
(12) in this example, the amino acid nitrogen content of the soybean paste obtained in (2) and the final parameter value A of each sensor obtained in (10) were calculated1、A2、A3、A4Analyzing and establishing an amino acid nitrogen content detection model Y of the soybean paste by adopting a least square method1According to the ammonium salt content of the soybean paste obtained in the step (2) and the final parameter value A of each sensor obtained in the step (10)1、A2、A3、A4Analyzing and establishing an ammonium salt content detection model Y of the soybean paste by adopting a least square method2：
Y1＝0.4734+0.2130*A1+0.0596*A2-0.4300*A3+0.0217*A4；
Y2＝0.0921-0.3550*A1+0.2773*A2-0.0527*A3+0.3550*A4；
The detection result of the amino acid nitrogen content detection model is shown in FIG. 2, and R of the model is2A value of 0.9533; the detection result of the ammonium salt content detection model is shown in FIG. 3, and R of the model2A value of 0.9796; the model has good prediction effect. The invention is equally applicable to other brewed foods.
The above examples are only examples for clarifying the detection process of the present invention, and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the scope of the invention.
Claims (9)
1. The device for quickly detecting the physical and chemical indexes of the soybean paste based on the novel volt-ampere electronic tongue is characterized by comprising a sample stage, a sensor array, an excitation signal generator, a signal acquisition circuit, a data acquisition card and a computer, wherein the sensor array is respectively connected with the excitation signal generator and the signal acquisition circuit through leads; the sample platform is square and comprises a magnetic stirrer, a circular groove is formed in the center of the sample platform to fix a sample cell, a support is arranged on the sample platform, a sliding guide rail and a connecting sleeve which keeps vertical are arranged on the support, and the connecting sleeve comprises a screw and a lead and is respectively connected with an excitation signal generator and a working electrode sensor as well as a signal acquisition circuit and an auxiliary electrode sensor; the sensor array includes: the device comprises a graphene-modified gold, silver, palladium and platinum working electrode, a silver chloride/silver reference electrode and a platinum column auxiliary electrode, wherein the graphene-modified gold, silver, palladium and platinum electrode is connected with an excitation signal generator and the silver chloride/silver reference electrode, and the platinum column auxiliary electrode is connected with a signal acquisition circuit; the signal acquisition circuit includes: the constant potential circuit is respectively connected with the working electrode and the silver chloride/silver reference electrode, and the current-voltage conversion circuit is respectively connected with the auxiliary electrode and the program control amplification circuit; the signal acquisition circuit is connected with the data acquisition card, the data acquisition card is connected with the computer, and the acquired data is processed by the computer.
2. The device for rapidly detecting the physicochemical index of the soybean paste based on the novel voltammetric electronic tongue as claimed in claim 1, wherein the sensor array is formed by using graphene-modified metal electrodes: gold, silver, palladium and platinum electrodes; the modification method comprises the following steps: cleaning an inert metal electrode by using ethanol and deionized water, drying, dropwise coating 2uL of graphene oxide dispersion liquid (2mg/mL) on the surface of the treated electrode by using a microsyringe, drying under an infrared lamp to obtain a graphene oxide modified electrode, and scanning for 5 periods at a rate of 100mV/s under a potential of-1.7-0.0V by using a cyclic voltammetry method to obtain the graphene modified electrode; the soybean paste has weak response to the excitation current, and the graphene improves the capturing capability of the sensor on weak electric signals, so that the detection effect of the volt-ampere electronic tongue can be improved.
3. The detection method of the device for rapidly detecting the physicochemical index of the soybean paste based on the novel voltammetric electronic tongue as claimed in claim 1, characterized by comprising the following steps:
step (1): determining the content of amino acid nitrogen and ammonium salt in the soybean paste by a chemical analysis method in national standard;
step (2): sample pretreatment: grinding the soybean paste until no obvious coarse particles exist, and adding deionized water for dissolving;
and (3): sensor array experiment pretreatment: sequentially ultrasonically cleaning deionized water and ethanol, drying by blowing nitrogen, and initializing by adopting cyclic voltammetry for prescan;
and (4): measuring the soybean paste sample by adopting a novel volt-ampere electronic tongue device, recording the response value of an electronic tongue sensor array, obtaining the response curve of the sensor array to different samples, and storing the response curve in a computer;
and (5): and (3) processing the information of the soybean paste obtained by the volt-ampere electronic tongue in the step (4), extracting a characteristic value, and constructing a quantitative model of the content of the physicochemical index in the step (1).
4. The method for detecting the physicochemical index of the soybean paste of the novel voltammetric electronic tongue as set forth in claim 3, wherein in the step (1), the detection method of amino acid nitrogen is a formaldehyde value method, and the principle is that the amphoteric action of amino acid is utilized, formaldehyde is added to fix the alkalinity of amino group, so that carboxyl group shows acidity, and after titration with sodium hydroxide standard solution, quantification is performed, and the end point is measured by an acidimeter;
in the step (1), the detection method of the ammonium salt is a semi-micro nitrogen determination method, and the principle is that a sample is heated and distilled in an alkaline solution, so that ammonia is free and distilled out and is absorbed by a boric acid solution, and then the content is calculated by titration with a hydrochloric acid standard solution.
5. The method for detecting the physicochemical index of the soybean paste of the novel voltammetric electronic tongue as set forth in claim 3, wherein in the step (2), the mass of each soybean paste sample is 5 g; grinding the mixture by using a porcelain mortar for 2 minutes; grinding while maintaining the vertical pestle, crushing large bean grains and grinding;
in the step (2), the mass ratio of the soybean paste to the deionized water is 1: 10.
6. the detection method of the novel quick detection device for the physicochemical index of the soybean paste of the voltammetric electronic tongue as claimed in claim 3, wherein in the step (3), the sensor sequentially performs ultrasound in deionized water and ethanol for half a minute, respectively, and the electrode tip is suspended in the ultrasonic tank during the ultrasound;
in the step (3), the cyclic voltammetry uses a sensor to pre-scan a mixed solution of 2mmoL/L potassium ferricyanide and 1moL/L potassium nitrate, and the peak current value is used as an index for judging the performance of the sensor.
7. The method for detecting the physicochemical index of the soybean paste of the novel voltammetric electronic tongue as claimed in claim 3, wherein in the step (4), the step of detecting the voltammetric electronic tongue device is as follows: firstly, placing a sample cell in a circular groove corresponding to a sample platform, then sliding down a connecting sleeve provided with a sensor array to ensure that the sensor array is completely submerged in a sample, fixing the connecting sleeve, then opening an excitation signal generator and a computer to set experiment parameters, and finally detecting and recording data;
in the step (4), when the voltammetry electronic tongue is detected, the sensor array is electrochemically cleaned by using deionized water at every two detection intervals;
in the step (4), the experimental parameters of the excitation signal generator mainly comprise signal output waveform, frequency, amplitude and initial phase; the parameters of the computer (data acquisition card) are mainly sampling intervals;
in the step (4), when the first sample detection is carried out, the first two periods are used for determining the collection sensitivity;
in the step (4), the voltammetric electronic tongue detects each sample for 5 periods, and each sample is repeatedly detected for 2-5 times.
8. The method for detecting the physicochemical index of the soybean paste of the novel voltammetric electronic tongue as set forth in claim 3, wherein in step (5), the data obtained from the voltammetric electronic tongue detection sample is subjected to preliminary processing, and the average value obtained by extracting the peak value and inflection point value of the sensor detection curve for 5 periods is taken as the characteristic value;
in the step (5), the characteristic value obtained after extracting the detection curve of each sensor is weighted and added as the final parameter value detected by the sensor:
wherein A isiA final parameter value representing the sensor detection;
an average value representing a peak in the sensor detection curve;
an average value representing a inflection point value in the sensor detection curve; m and n are weights; i is the value range of the sensor code number from 1 to 4.
9. The method for detecting the physicochemical index of the soybean paste of the novel voltammetric electronic tongue as claimed in claim 3, wherein in step (5), the correlation between the physicochemical component content of the soybean paste and the parameter value of each sensor is analyzed by a partial least squares method, so as to establish a detection model for the physicochemical component content of the soy sauce, and the detection model for the physicochemical component content of the soybean paste established by the final parameter value of each sensor and the physicochemical index content measured in step (1) is:
YJ＝kj+aj*A1+bj*A2+cj*A3+dj*A4；
wherein, YJA detection model result representing the content of the physical and chemical component j of the soybean paste; a. the1-4Representing the final parameter values detected by the four sensors; k is a radical ofjA constant in a soybean paste physicochemical component j content detection model is represented; a isjRepresenting the weight corresponding to the silver nano/graphene modified glassy carbon electrode parameter value in a soybean paste physicochemical component j content detection model; bjRepresenting the weight corresponding to the gold electrode parameter value in the soybean paste physicochemical component j content detection model; c. CjRepresenting the weight corresponding to the platinum electrode parameter value in the soybean paste physicochemical component j content detection model; djAnd representing the weight corresponding to the palladium electrode parameter value in the soybean paste physicochemical component j content detection model.
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