CN106918631B - A kind of age of Chinese rice wine discrimination method based on nano polymer/metal composite material modified electrode array - Google Patents
A kind of age of Chinese rice wine discrimination method based on nano polymer/metal composite material modified electrode array Download PDFInfo
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- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 1
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Abstract
The invention discloses a kind of age of Chinese rice wine discrimination methods based on nano polymer/metal composite material modified electrode array, it is specific as follows: (1) using the electrod-array of tri- groups of modified electrodes of PACBK/Au/GCE, PABSA/Au/GCE and PASP/Pt/GCE composition as working electrode, silver/silver chloride electrode is as reference electrode, and platinum column electrode is as auxiliary electrode.(2) insertion of each electrode is filled in the electrolytic cell of certain volume buffer and yellow rice wine sample, the electrochemical response signal of collecting test sample on the working electrode (s under the excitation of electrochemical workstation multi-frequency scanning signal, and obtains response current curve.(3) area features value is chosen on response current curve, using characteristic value as independent variable, is established age of Chinese rice wine and is identified model, yellow rice wine to be measured is input in model, complete the identification to age of Chinese rice wine.The nano polymer/metal composite material modified electrode array that the present invention develops is sensitive to feature taste compounds certain in yellow rice wine response, and the identification of age of Chinese rice wine can be preferably realized by the model established.
Description
Technical field
The invention belongs to Wine Test Technology In Our methods, and in particular to be based on nano polymer/metal composite material to a kind of
The age of Chinese rice wine discrimination method of modified electrode array.
Background technique
Age of Chinese rice wine refers to the time limit that the finished product former wine after fermentation is stored in wine jar, GB/T 13662-2008 " yellow rice wine "
Wine storage time on national regulations marketing packing label is mark wine storage time, is calculated according to the wine storage time weighted average method of blended liquor, is hooked
At least there is 50% base liquor to reach the wine storage time that product is marked in the yellow rice wine converted, brewery uses several different wine in practical operation
The wine in age is blent, its average wine storage time is made to reach the standard that product is marked.The time of shao-hsing rice wine not only contains abundant go through
History accumulation also represents aromatic strong mouthfeel, more Chen Yuexiang, more Chen Yuegui, but the yellow rice wine blent by this method, wine
The authenticity in age mainly still guarantees by the prestige of enterprise and self-discipline.
The wine storage time judging standard of yellow rice wine mainly includes sensory evaluation, chemical and physical character of quality measurement and precision instrument detection at present
Three kinds of modes.Sensory evaluation suffers from the influence of estimator's subjective factor and external environmental condition, as a result there is certain mould
Paste property；Chemical and physical character of quality measurement is more demanding to operator, and the cumbersome time-consuming of sample pretreatment is not able to satisfy industrialized production
Requirement；Precision instrument detection only detects the content of taste compound, does not consider between a variety of taste compounds
Synergistic function, in addition equipment purchase and maintenance cost are expensive.Also there is research that bare electrode array is applied to age of Chinese rice wine
In identification, but because the feature taste compound in yellow rice wine is mainly the organic substances such as carbohydrate, acids, phenols and amino acid, and it is organic
Object is mostly non-electrolyte or weak electrolyte, and electrolyzing rate in the solution is very low, is based on taste compound when bare electrode array detection
The redox reaction that can occur is very faint, this illustrates bare electrode, and there is also certain limitations.To sum up, finding one kind can
Seem especially urgent by convenient and fast detection method, the nano polymer/metal composite material modified electrode array of this research preparation
Not active enough the disadvantage of bare electrode array chemical property is overcome, has preferable response, Neng Gouke to taste compounds certain in yellow rice wine
Prediction by realizing age of Chinese rice wine.
Summary of the invention
Nano polymer/metal composite wood is based in view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of
Expect the age of Chinese rice wine discrimination method of modified electrode array.Modified electrode array response signal prepared by the present invention is big, high sensitivity,
Stability is good, can reliably realize the prediction of age of Chinese rice wine.
The purpose of the present invention is what is be achieved through the following technical solutions: one kind being based on nano polymer/metal composite material
The age of Chinese rice wine discrimination method of modified electrode array, this method comprises the following steps:
(1) electrod-array for forming tri- groups of modified electrodes of PACBK/Au/GCE, PABSA/Au/GCE and PASP/Pt/GCE
As working electrode, silver/silver chloride electrode is as reference electrode, and platinum column electrode is as auxiliary electrode.
(2) the yellow rice wine sample different wine storage time is taken, every kind of wine storage time of the yellow rice wine sample takes 2n at random, and (n is more than or equal to 35 and is less than etc.
It is used as test sample in 50) a, is by volume that 1:4-1:5 is mixed and is put into difference by buffer and each test sample
Electrolytic cell in, the electrochemistry of collecting test sample on the working electrode (s under the excitation of electrochemical workstation multi-frequency scanning signal
Response signal, and obtain response current curve；Wherein, when being detected using PACBK/Au/GCE and PABSA/Au/GCE, buffer
Use concentration for 0.1~0.2mol/L and phosphate solution or Acetate Solution that pH value is 2~2.5；Utilize PASP/Pt/GCE
When detection, buffer uses concentration for the sodium hydroxide solution of 0.05~0.1mol/L.
(3) after acquiring a test sample, the insertion of each electrode is filled in the electrolytic cell of buffer and is cleaned, when cleaning
3~5 circles are scanned under 80~140mV/s scanning speed using cyclic voltammetry, carry out next test specimens after cleaning again
The acquisition of product.
(4) using the area value in the collected response current curve of working electrode and the enclosed region of time shaft as test sample
Characteristic value, using characteristic value as independent variable, establish age of Chinese rice wine identify model, yellow rice wine to be measured is input in model, complete pair
The identification of age of Chinese rice wine.
Further, the form of expression of the multi-frequency scanning signal are as follows: triangular wave, square wave or trapezoidal wave are as scanning wave
Shape chooses one or more of 1Hz, 10Hz, 100Hz and 1000Hz and is used as scan frequency, and potential change section is 0~
1.5V。
Further, the age of Chinese rice wine identifies model using support vector machines, neural network or extreme learning machine method
It establishes.
Further, the extreme learning machine model need to be to optimize within the scope of 10-70 in hidden layer neuron number.
The beneficial effects of the present invention are: being passed compared to sensory evaluation, chemical and physical character of quality measurement and precision instrument detection etc.
System method, modified electrode array approach are more convenient and objective；Compared to bare electrode array, nano polymer/metal composite wood
Expect modified electrode array can more targetedly, more accurately obtain yellow rice wine information；The Current Voltage obtained compared to voltammetry
Curve, the response current curve that multi-frequency scanning signal obtains is more succinct, and area features value is easier to obtain；In conjunction with supporting vector
Machine, neural network or the recognition methods of extreme learning machine isotype can preferably realize the prediction of age of Chinese rice wine.
Detailed description of the invention
Fig. 1 is the square wave multi-frequency scanning signal waveforms used in the embodiment of the present invention 1；
Fig. 2 is the trapezoidal wave multi-frequency scanning signal waveforms used in the embodiment of the present invention 1；
Fig. 3 is the response current curve graph that electrode obtains under square wave multi-frequency scanning signal in the embodiment of the present invention 1；
Fig. 4 is the response current curve graph that electrode obtains under trapezoidal wave multi-frequency scanning signal in the embodiment of the present invention 1；
Fig. 5 is LSSVM training set regression model in the embodiment of the present invention 1 to the prognostic chart of 6 kinds of wine storage time yellow rice wine；
Fig. 6 is LSSVM test set regression model in the embodiment of the present invention 1 to the prognostic chart of 6 kinds of wine storage time yellow rice wine；
Fig. 7 is LIBSVM training set regression model in the embodiment of the present invention 1 to the prognostic chart of 6 kinds of wine storage time yellow rice wine；
Fig. 8 is LIBSVM test set regression model in the embodiment of the present invention 1 to the prognostic chart of 6 kinds of wine storage time yellow rice wine.
Specific embodiment
Following embodiment can make those skilled in the art that the present invention be more fully understood, but the present invention is simultaneously
It is not limited to this.
Embodiment 1:
Using nano polymer/metal composite material modified electrode array to 6 kinds of wine storage time of the Shaoxing Guyue Longshan yellow rice wine (3
Nian Chen, 5 years it is old, 8 years it is old, 10 years it is old, 15 years it is old and 20 years old) predicted, process is as follows:
(1) preparation of modified electrode is carried out first:
The poly- neolan blue K/ Jenner nano composite material modified electrode (PACBK/Au/GCE) of a: glass-carbon electrode is placed in
In 1.2mmol/L gold chloride (containing 0.1mol/L potassium nitrate) solution, deposited under -0.2V constant potential using current time method
Au/GCE is made in 240s；Au/GCE is placed in the 0.5mmol/L acid chromium blue k (phosphoric acid that with concentration be 0.1mol/L and pH value is 6
Salt buffer is prepared) in solution, using cyclic voltammetry in -1.6~2V potential region, swept with the scanning speed of 100mV/s
26 circles are retouched, PACBK/Au/GCE is made.
The poly- p-aminobenzene sulfonic acid of b/Jenner's nano composite material modified electrode (PABSA/Au/GCE): Au/GCE preparation process is same
On；Au/GCE is placed in 2mmol/L p-aminobenzene sulfonic acid (phosphate buffered saline that with concentration be 0.1mol/L and pH value is 7)
In solution, using cyclic voltammetry in -1.5~2.5V potential region, with 12 circle of scanning speed scanning of 100mV/s, it is made
PABSA/Au/GCE。
C poly-aspartate/platinum nanocomposite modified electrode (PASP/Pt/GCE): glass-carbon electrode is placed in 2mmol/L days
In aspartic acid (with the phosphate buffer that concentration is 0.1mol/L and pH value is 6) solution, using cyclic voltammetry -1.2~
In 2V potential region, with 15 circle of scanning speed scanning of 100mV/s, PASP/GCE is made；PASP/GCE is placed in 8mmol/L chlorine platinum
Acid (is prepared) with 0.5mol/L dilute sulfuric acid in solution, using cyclic voltammetry in -0.25~0.4V potential region, with 50mV/s
Scanning speed scanning 24 circle, be made PASP/Pt/GCE.
(2) age of Chinese rice wine identification experiment carries out on electrochemical workstation, using conventional three-electrode system, with PACBK/
Au/GCE), the electricity of tri- kinds of nano polymer/metal composite material modified electrodes of PABSA/Au/GCE and PASP/Pt/GCE composition
Pole array is as working electrode, and silver/silver chloride electrode is as reference electrode, and platinum column electrode is as auxiliary electrode.Each electrode is inserted
In the electrolytic cell for entering to fill buffer and yellow rice wine sample (volume ratio 1:4), square wave and trapezoidal wave two are selected on software kit
Kind multi-frequency scanning signal is applied to electrod-array and is detected, and as depicted in figs. 1 and 2, design parameter is as follows: the present embodiment intermediate frequency
Rate is 1Hz, 10Hz and 100Hz, actually carries out group at least two of 1Hz, 10Hz, 100Hz, 1000Hz these four frequencies
It closes, is likely to be breached technical requirements of the invention, is no longer illustrated repeat one by one here；0~1.5V of potential range, current potential rank
Jumping amount 0.3V, sampling interval are set as 0.002s.Detailed process explanation is carried out by taking 3 years old Guyue Longshan yellow rice wine as an example below,
He analogizes wine storage time yellow rice wine detection process.Prepare 80 glasss of 3 years old Guyue Longshan yellow rice wine samples, label 1~80, each sample first
Product include that 40mL yellow rice wine (for PACBK/Au/GCE and PABSA/Au/GCE, also needs that 10mL pH is added be 2 concentration to be 0.1mol/
The phosphate buffer of L；For PASP/Pt/GCE, then need that 10mL 0.05mol/L sodium hydroxide solution is added, to adjust pH
Value)；Then it for No. 1 sample, is detected under three-electrode system, cyclic voltammetry is finally used in phosphate buffer
It sweeps 3 circle of speed scanning with 80mV/s to clean electrode, 2~No. 80 samples complete 3 years Chen Guyue after detecting in the same way
The detection of Longshan yellow rice wine.
(3) Fig. 3 and Fig. 4 is respectively that PACBK/Au/GCE electrode is corresponding under two kinds of multi-frequency scanning signals of square wave and trapezoidal wave
The response current curve of acquisition, the response current curve performance form class of other 2 modified electrodes is seemingly；With response current curve with
The area value in the enclosed region of time shaft is as characteristic value, and dash area represents an area features value in figure.Based on area spy
It is flat in 6 kinds of wine storage time yellow rice wine to calculate tri- kinds of electrodes of PACBK/Au/GCE, PABSA/Au/GCE and PASP/Pt/GCE for value indicative
The equal coefficient of variation is respectively 5.61%, 10.75% and 2.23%, and respectively less than 15%, illustrate that modified electrode stability meets the requirements；
PACBK/Au/GCE and PABSA/Au/GCE related coefficient is 0.4619, in positive moderate related (0.4~0.6),
PACBK/Au/GCE and PASP/Pt/GCE related coefficient is -0.3063, in negative weak related (0.2~0.4), PABSA/Au/
GCE and PASP/Pt/GCE related coefficient is -0.1042, in negative extremely weak related (0~0.2), from the above, it can be seen that 3 kinds interelectrode
Pearson correlation coefficient is all little, meets requirement of experiment.
(4) age of Chinese rice wine is predicted using two kinds of algorithm of support vector machine of LSSVM and LIBSVM, from 480 sample datas (6
Kind of wine storage time yellow rice wine, 80 samples of every kind of wine) in choose 300 samples (every kind of wine 50) and be used as training set, 180 samples are (every
Kind of wine 30) be used as test set, choose RBF function as kernel function, respectively in [- 3,7] and [- 10,10] two sections with
Sampling interval 2.5 carries out the penalty factor that grid search determines optimal combination and kernel functional parameter as LSSVM and LIBSVM mould
The final argument of type, two parameters of LSSVM are respectively γ=523.95 and σ2Two parameters of=92.75, LIBSVM are respectively c=
1024 and g=0.0055.LSSVM regression model training set and the corresponding prediction result of forecast set are shown in Fig. 5 and Fig. 6, wherein training
Collect R2=0.9769, MSE=0.7417, test set R2=0.9737, MSE=0.8259, test set effect are slightly better than training set.
LIBSVM regression model training set and the corresponding prediction result of forecast set are shown in Fig. 7 and Fig. 8, wherein training set R2=0.9999, MSE
=0.0044, test set R2=0.9998, MSE=0.0064.Two kinds of forecast result of model are compared, LIBSVM is better than LSSVM,
Especially mean square deviation MSE is smaller.
Embodiment 2:
The preparation of (1) 3 group of modified electrode and embodiment 1 are identical；
(2) age of Chinese rice wine identification experiment carries out on electrochemical workstation, using conventional three-electrode system, with PACBK/
Au/GCE), the electricity of tri- kinds of nano polymer/metal composite material modified electrodes of PABSA/Au/GCE and PASP/Pt/GCE composition
Pole array is as working electrode, and silver/silver chloride electrode is as reference electrode, and platinum column electrode is as auxiliary electrode.Each electrode is inserted
In the electrolytic cell for entering to fill buffer and yellow rice wine sample (volume ratio 1:5), square wave and trapezoidal wave two are selected on software kit
Kind of multi-frequency scanning signal is applied to electrod-array and is detected, and design parameter is as follows: frequency is set as 1Hz, and tri- kinds of 10Hz, 100Hz,
0~1.5V of potential range, potential step increment 0.3V, sampling interval are set as 0.002s.It is with 3 years old Guyue Longshan yellow rice wine below
Example carries out detailed process explanation, other wine storage time yellow rice wine detection process are analogized.Prepare 80 glasss of 3 years old Guyue Longshan yellow rice wine first
Sample, label 1~80, each sample include that 50mL yellow rice wine (for PACBK/Au/GCE and PABSA/Au/GCE, also needs to be added
10mL pH is the phosphate buffer that 2.5 concentration are 0.2mol/L；For PASP/Pt/GCE, then need that 10mL 0.1mol/ is added
L sodium hydroxide solution, to adjust pH value)；Then it for No. 1 sample, is detected under three-electrode system, finally in phosphoric acid
It uses cyclic voltammetry to sweep 5 circle of speed scanning with 140mV/s in salt buffer to clean electrode, 2~No. 80 samples are with same
Mode completes the detection of 3 years old Guyue Longshan yellow rice wine after detecting.
Following step and embodiment 1 are identical, and which is not described herein again.
The above-mentioned prediction result to 6 kinds of Shaoxing Guyue Longshan age of Chinese rice wine shows that nano polymer/metal composite material is repaired
Decorations electrod-array can apply the quality discrimination inspection in the liquid foods such as yellow rice wine and beverage, milk as a kind of reliable method
It surveys.
Above-described embodiment is used to illustrate the present invention, rather than limits the invention, in spirit of the invention and
In scope of protection of the claims, to any modifications and changes that the present invention makes, protection scope of the present invention is both fallen within.
Claims (4)
1. a kind of age of Chinese rice wine discrimination method based on nano polymer/metal composite material modified electrode array, feature exist
In this method comprises the following steps:
(1) by poly- neolan blue K/ Jenner nano composite material modified electrode PACBK/Au/GCE, poly- p-aminobenzene sulfonic acid/gold nano
Composite material modified electrode PABSA/Au/GCE and poly-aspartate/platinum nanocomposite modified electrode PASP/Pt/GCE tri-
The electrod-array of group modified electrode composition is as working electrode, and silver/silver chloride electrode is as reference electrode, and platinum column electrode is as auxiliary
Help electrode；
(2) the yellow rice wine sample different wine storage time is taken, every kind of wine storage time of the yellow rice wine sample takes 2n as test sample at random, and wherein n is big
It is less than or equal to 50 in being equal to 35, is by volume that 1:4-1:5 is mixed and is put into difference by buffer and each test sample
Electrolytic cell in, the electrochemistry of collecting test sample on the working electrode (s under the excitation of electrochemical workstation multi-frequency scanning signal
Response signal, and obtain response current curve；Wherein, poly- neolan blue K/ Jenner nano composite material modified electrode PACBK/ is utilized
When Au/GCE and poly- p-aminobenzene sulfonic acid/Jenner nano composite material modified electrode PABSA/Au/GCE are detected, buffer is using dense
The phosphate solution or Acetate Solution that degree is 0.1~0.2mol/L and pH value is 2~2.5；Utilize poly-aspartate/platinum nanometer
When composite material modified electrode PASP/Pt/GCE is detected, buffer uses concentration molten for the sodium hydroxide of 0.05~0.1mol/L
Liquid；
(3) after acquiring a test sample, the insertion of each electrode is filled in the electrolytic cell of buffer and is cleaned, when cleaning uses
Cyclic voltammetry scans 3~5 circles under 80~140mV/s scanning speed, carries out next test sample after cleaning again
Acquisition；
(4) using the collected response current curve of working electrode and the area value in the enclosed region of time shaft as the spy of test sample
Value indicative establishes age of Chinese rice wine and identifies model, yellow rice wine to be measured is input in model, complete to yellow rice wine using characteristic value as independent variable
Identification wine storage time.
2. the age of Chinese rice wine mirror according to claim 1 based on nano polymer/metal composite material modified electrode array
Other method, which is characterized in that the form of expression of the multi-frequency scanning signal are as follows: selection triangular wave, square wave or trapezoidal wave, which are used as, to be swept
It retouches waveform, chooses one or more of 1Hz, 10Hz, 100Hz and 1000Hz and be used as scan frequency, potential change section is 0~
1.5V。
3. the age of Chinese rice wine mirror according to claim 1 based on nano polymer/metal composite material modified electrode array
Other method, which is characterized in that the age of Chinese rice wine identifies model and uses support vector machines, neural network or extreme learning machine method
It establishes.
4. the age of Chinese rice wine mirror according to claim 3 based on nano polymer/metal composite material modified electrode array
Other method, which is characterized in that extreme learning machine model need to be to optimize within the scope of 10-70 in hidden layer neuron number.
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| CN102967597A (en) * | 2012-09-26 | 2013-03-13 | 江苏大学 | Olfactory imaging sensing technology based yellow wine storage time identification method and identification system |
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| CN104655708B (en) * | 2015-01-30 | 2017-06-06 | 安徽师范大学 | Poly- p-aminobenzene sulfonic acid/trace poly-o-phenylenediamine modified electrode and its preparation method and application |
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| CN102967597A (en) * | 2012-09-26 | 2013-03-13 | 江苏大学 | Olfactory imaging sensing technology based yellow wine storage time identification method and identification system |
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