CN108982636A - Quickly identify the method for cold fresh beef reconciliation chilled beef based on electrochemistry phase spectrum - Google Patents
Quickly identify the method for cold fresh beef reconciliation chilled beef based on electrochemistry phase spectrum Download PDFInfo
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Abstract
The invention belongs to meat products technical field of quality detection, and in particular to quickly identify the method for cold fresh beef reconciliation chilled beef based on electrochemistry phase spectrum.Discrimination method of the present invention to cold fresh beef and solution chilled beef specifically: prepare beef sample and number；The acquisition of electrochemistry phase modal data is carried out to beef sample by CHI660E electrochemical workstation；Dimension-reduction treatment is carried out using electrochemistry phase modal data of the principal component analytical method to acquisition；Based on the phase modal data after dimension-reduction treatment, cold fresh beef is established using chemometrics method and solves the identification model of chilled beef；The acquisition of phase modal data is carried out to unknown beef sample to be measured, the storage mode of unknown beef sample to be measured is predicted using the quick identification model of foundation.It is short the time required to discrimination method of the invention, and detection device is at low cost.To cold fresh beef and when solving the identification of chilled beef, when number of principal components is 8, training set and test set discrimination reach 100%, and recognition correct rate is high, it can be achieved that quickly identifying.
Description
Technical field
The invention belongs to meat products technical field of quality detection, and in particular to quickly be identified based on electrochemistry phase spectrum cold fresh
The method of beef reconciliation chilled beef.
Background technique
Beef is one of main meat products, has high protein, low fat, vitamin and content of mineral substances abundant, contains
There is the features such as all desirable essential amino acids, be a kind of higher health meat product of nutritive value, Shen Shou is international
The favor of domestic market.With the improvement of living standards with the continuous variation of diet structure, need of the people to meat products such as beef
The amount of asking is increasing.
The beef of commercial type is broadly divided into cold fresh meat and chilled meat.Due to circulation cost between both meats and disappear
Take customary difference, selling rice variance is larger, wherein the retail price of cold fresh meat is higher, and chilled meat is on the low side,
Its price difference can reach 50%.In general the nutritive value of cold fresh meat is higher, good in taste；Although chilled meat can store up
Longer time is deposited, but the ice crystal formed inside chilled meat can destroy cell tissue, and chilled meat must first pass through before consumption
Defrosting processing, course of defrosting can cause meat nutrition to be lost serious with more juice loss and protein degradation etc., mouthfeel compared with
Difference.So even if chilled meat price is lower, but consumer still prefers cold fresh meat on the high side.Due to existing meat valence
Lattice difference leads to some illegal retailers and pretends to be cold fresh beef to sell after beef thaws to freeze, adulterates, earn sudden huge profits.Solution
Chilled meat (solution frozen meat) after jelly is difficult to distinguish with cold fresh meat.Cold fresh meat reconciliation frozen meat has on color, smell, elasticity, viscosity
Nuance is difficult from distinguishing in appearance, and difference can be just clearly felt that by being only made into after dish；In recent years, researcher passes through more
Kind method identifies to carry out the differentiation of cold fresh meat reconciliation frozen meat, such as utilizes enzyme process, PCR detection technique, spectral technique or reason
Change property measurement such as detect meat pH value, be waterpower, tenderness index to cold fresh meat conciliate frozen meat distinguish.But these sides
It is not high, cumbersome, costly, time-consuming and the disadvantages of need skilled personnel all to there is detection efficiency in method.Wherein enzyme process is needed sample
Product are broken into gravy, cause destruction to sample；PCR detection technique will receive DNA chain chain rupture and the influence of interchain, therefore PCR
Sensitivity is difficult to be protected technology in the detection process；The impurity such as the bloodstain of sample surface, water stain can cause spectra collection
Larger impact, this brings trouble to work on the spot；Physicochemical test and excessively cumbersome time-consuming are not suitable for market.Therefore, exploitation is fast
Speed is stablized, and accurately, inexpensive detection technique Rapid identification identifies cold fresh beef and conciliates chilled beef, this will be very significant.
Summary of the invention
The present invention is directed to overcome shortcomings and deficiencies existing in the prior art, such as the unstability of: round pcr, enzyme process
Destructive, Physicochemical test time consuming nature etc., the present invention provides quickly identify cold fresh beef reconciliation based on electrochemistry phase spectrometry
The method of chilled beef establishes a kind of low cost with three kinds of electrochemistry phase spectrum, computer technology and Chemical Measurement technologies
, quickly, the discrimination method of efficient cold fresh beef and solution chilled beef, why select phase value rather than impedance magnitude,
Be because by multi-group data discovery: the corresponding impedance magnitude of each frequency differs greatly, this may be since electrode is inserted into
Caused by depth difference.
Specifically, the invention is realized by the following technical scheme:
(1) prepare beef sample and number, be specifically divided into solution frozen meat and cold fresh meat；
(2) acquisition of electrochemistry phase modal data is carried out to the beef sample in step (1) by electrochemical workstation；
(3) dimension-reduction treatment is carried out to the electrochemistry phase modal data that step (2) acquires using principal component analytical method；
(4) based on the phase modal data after step (3) dimension-reduction treatment, using chemometrics method establish cold fresh beef with
Solve the quick identification model of chilled beef；
(5) acquisition of phase modal data is carried out to unknown beef sample to be measured, the quick identification model established using step (4)
The storage mode of unknown beef sample to be measured is quickly identified.
Wherein above-mentioned steps (2) electrochemistry phase modal data acquires method particularly includes: passes through CHI660E electrochemical operation
It stands and carries out the acquisition of impedance module and phase angles data to the beef sample in step (1).In AC impedance (IMP), initially
Current potential init E is set as 0, and potential amplitude Amplitude is set as 5mV, frequency range 10-100KHz, frequency from high frequency to
Low-frequency sweep.
Wherein above-mentioned steps (3) carry out dimension-reduction treatment to electrochemistry phase modal data using principal component analysis: first to ox
The electrochemistry phase modal data of meat sample sheet carries out principal component analysis (PCA), then chooses different number of principal components as model
Input；The principal component analysis specifically: using 48 frequencies in 10-100KHz frequency range as variable, carry out at PCA dimensionality reduction
Reason.
Wherein in above-mentioned steps (4), the method for the Chemical Measurement is reverse transmittance nerve network (BPANN) method.
Wherein above-mentioned steps (5) quickly identify the storage mode of unknown beef sample to be measured, using electrochemistry work
It stands and the acquisition of electrochemistry phase modal data is carried out to unknown beef sample to be measured, then by the electrochemistry phase of beef sample to be measured
Modal data is brought into established identification model, completes the other identification of Beef using Matlab processing software.
The method provided by the invention for quickly identifying cold fresh beef reconciliation chilled beef based on electrochemistry phase spectrometry, it is described fast
The object of fast discrimination method is cold fresh beef and solution chilled beef.
Compared with prior art, beneficial effects of the present invention embody as follows:
(1) present invention uses four needles with existing based on compared with electrochemical impedance spectroscopy beef storage mode authentication technique
Electrode can obtain more three-dimensional more stable phase spectrum and impedance modal data compared to two pin electrodes；Different freshness are added
The sample of different thawing modes is identified, and method more has practicability；The phase spectrum knot stable compared with impedance spectrum is selected
It closes chemometrics method and establishes discrimination model, wherein when using BPANN model, when number of principal components is 5, training set and test
Collection discrimination reaches 100%, and recognition correct rate is high.
(2) for the present invention compared with existing beef storage mode authentication technique, 2min can obtain required phase modal data,
Detection time is short, to testing staff without particular/special requirement, and it is at low cost for realizing the detection device of this method, it is easy to carry, it fits
It closes and is applied to on-site test.
Detailed description of the invention
The apparatus structure schematic diagram of Fig. 1 to realize the present invention；1 is the computer of CHI660E software, and 2 be electrochemical operation
It stands/analyzer, 3 be four bronze medal pin electrodes；
Fig. 2 is four probe electrode schematic diagrames；
Fig. 3 is the phase curve Bode figure for solving frozen meat and cold fresh meat.
Specific embodiment
The present invention is further described below by specific embodiment and in conjunction with attached drawing, but is not intended to limit the present invention.
(1) prepare beef sample:
Prepare beef sample simultaneously number, wherein cold fresh meat be divided into cold fresh 1 day, it is fresh 15 days cold, fresh 30 days cold；Solution frozen meat is divided into
It freezes and thaws within 1 day, thaws within freezing 15 days, thawing within freezing 30 days, obtain cold fresh meat, each 60 pieces of frozen meat of solution altogether.Take different number of days
Sample is incorporated to the cold fresh differentiation with solution frozen meat, makes result with more realistic meaning.
(2) acquisition of phase modal data is carried out to beef sample with electrochemical workstation:
Instrument of the present invention is CHI660E electrochemical workstation (CH Instruments, Inc, Texas, USA), such as
Shown in Fig. 1,1 be CHI660E software computer, by software can be set frequency range, the voltage amplitude of output signal with
And the parameters such as amplitude equalizing value；2 be electrochemical workstation/analyzer, instrument will by frequency range set by computer from high frequency to
Low frequency generates the sine wave signal of continuous multiple and different frequencies, wherein voltage amplitude be 5mV (compare 5mV, 10mV, 15mV,
The supplemental characteristic of 20mV, 25mV, 30mV finally choose relatively stable 5mV), amplitude equalizing value 0, and pass through four needle electrodes
It is applied on sample to be tested；3 be four bronze medal pin electrodes, as shown in Fig. 2, intermediate 1 electrode needle is signal source input terminal, periphery 3
Electrode needle series connection is evenly distributed on using target needle as the center of circle, and radius is on the circle of 1cm.By collet (work red on work station
Make electrode) it is connected on the copper needle at center, green collet (auxiliary electrode) and white collet (reference electrode) are connected to and are connected on
On three copper needles together, copper needle diameter is 1mm, and insertion sample depth is 10mm.
In AC impedance (IMP), initial potential init E is set as 0, and potential amplitude Amplitude is set as 5mV, frequency
Rate range is 10-100KHz (hand capacity of electrode is larger when low frequency, influences measurement result), and frequency is swept from high frequency to low frequency
It retouches.Work station generates sinusoidal voltage and is applied on sample as pumping signal and measures response current with automatic computing impedance value
And phase angle, it obtains real anti-and void and resists simultaneously and make phase spectrum Bode figure.
Fig. 3 is the phase curve Bode figure of the cold fresh meat of the present invention and defrosting meat sample sheet.As seen from Figure 3, cold fresh meat
Phase diagram is more steady compared with solution frozen meat, very poor smaller；Frozen meat phase is solved when low frequency and is slightly above cold fresh meat, and solution frozen meat is lower than when high frequency
Cold fresh meat, this is because the ice crystal in solution frozen meat causes caused by serious destruction cell membrane.If uniquely relying on intuitive point
Analyse difference, this is inadequate science, complete, it is therefore desirable to using chemometrics method establish discrimination model to solution frozen meat with it is cold
Fresh meat is further differentiated.
(3) dimension-reduction treatment is carried out to phase modal data using principal component analysis:
The phase modal data for the beef sample that will acquire first is arranged, with 48 in 10-100KHz frequency range
Frequency is variable, carries out PCA dimension-reduction treatment, then chooses input of the different number of principal components as model.Principal component analysis
(PCA) it is a kind of unsupervised mode identification technology for the purpose of reducing data dimension, multiple variables is melted into a few master
Ingredient, these principal components can react most information of original variable, they are typically expressed as linear group of original variable
It closes.
(4) the quick identification model of solution frozen meat and cold fresh meat based on electrochemistry phase spectrum combination Chemical Measurement is established:
The present invention has chosen two kinds of models, including linear discriminant analysis LDA and reverse transmittance nerve network BPANN differentiates
Model distinguishes solution frozen meat with cold fresh meat；According to the corresponding training set discrimination of different number of principal components come the effect of judgment models
The discrimination of fruit, training set is higher, and modelling effect is better；
Wherein, LDA is a kind of common statistical method that the affiliated type of sample is differentiated based on projection thought；Back propagation neural
The characteristics of network (BPANN) model is to transmitting before signal, and error back propagation has stronger operational capability.
It chooses the 2/3 of total sample and is used as training set (solution frozen meat 40, cold fresh meat 40), the results are shown in Table 1, with master
The increase of component number, discrimination constantly rise (identification error number is reduced).In LDA model, when number of principal components reaches 7, LDA
The training set discrimination of model reaches 96%, and as number of principal components increases, and LDA model discrimination remains unchanged, and works as
When number of principal components is 7, test set differentiation rate is 98% in BPANN model, a sample only occurs and differentiates mistake；In BPANN mould
In type, when number of principal components is 6, discrimination reaches 100%, and when number of principal components is 6 LDA discrimination model training set identification
Rate is 93.75%, shows BPANN to cold fresh meat reconciliation frozen meat by comparing the height and differentiation error sample number of differentiation rate
It distinguishes and is better than LDA model in effect.
(5) quick predict is carried out to the storage mode in unknown beef sample to be measured:
Phase modal data is carried out to beef sample to be measured (20 solution frozen meat, 20 cold fresh meats) using electrochemical workstation to adopt
Then the phase modal data of unknown beef sample to be measured is carried out dimension-reduction treatment first with principal component by collection, then input has been established
LDA and BPANN model in, utilize Matlab processing software complete storage mode identify.
Identification result is as shown in table 1, in LDA model, it can be seen that preceding 7 principal components of selection are best, and test set is known
Rate is not 92.5%, three specimen discerning mistakes occurs, and when number of principal components is 7, test set differentiation rate is in BPANN model
97.5%, only there is a sample and differentiates mistake；In BPANN model, it can be seen that best number of principal components is 8, test set
Discrimination has reached 100%.BPANN model can successfully identify 20 cold fresh meats and 20 frost meat, and modelling effect is best,
Identification result is consistent with the actual storage mode of corresponding sample, and LDA model highest differentiation rate is 92.5%, is shown by comparing
BPANN model is better than LDA model to the differentiation of cold fresh beef reconciliation chilled beef, can be used for practical application.
The result of table 1 LDA, BPANN model training set and test set under different number of principal components
Electrical Bioimpedance Measurement Technology (Electrical Bio-impedance Measuring Technology) is benefit
With a kind of detection technique of electrical characteristics and its change detection biological information relevant to organism physiological status of biological tissue.It is raw
Object impedance bioelectrical measurement principle includes the frequency of the tri- element equivalent-circuit model of R-C of biological tissue, Cole-Cole theory and Schwan
Theory is dissipated, they are the theoretical basis of entire bio-electrical impedance measuring.For meat when freezing, inside will form ice crystal, ice
Crystalline substance can damage meat fibre structure and cell membrane, and along with a large amount of juice loss in course of defrosting, this
The electrical characteristics of beef will be caused to change, thus propose electrochemistry phase spectrum combination BPANN discrimination model to cold fresh meat
The method that reconciliation frozen meat distinguishes.
Claims (8)
1. quickly identifying the method for cold fresh beef reconciliation chilled beef based on electrochemistry phase spectrometry, which is characterized in that including following
Step:
(1) prepare beef sample and number, be specifically divided into solution frozen meat and cold fresh meat；
(2) acquisition of electrochemistry phase modal data is carried out to the beef sample in step (1) by electrochemical workstation；
(3) dimension-reduction treatment is carried out to the electrochemistry phase modal data that step (2) acquires using principal component analytical method；
(4) based on the phase modal data after step (3) dimension-reduction treatment, cold fresh beef is established using chemometrics method and is thawed
The quick identification model of beef；
(5) acquisition of phase modal data is carried out to unknown beef sample to be measured, the quick identification model established using step (4) is not to
Know that the storage mode of beef sample to be measured is quickly identified.
2. the method according to claim 1 for quickly identifying cold fresh beef reconciliation chilled beef based on electrochemistry phase spectrometry,
It is characterized in that, in step (2), the electrochemistry phase modal data acquisition method particularly includes: pass through CHI660E electrochemistry work
It stands and carries out the acquisition of impedance module and phase angles data to the beef sample in step (1).
3. the method according to claim 1 for quickly identifying cold fresh beef reconciliation chilled beef based on electrochemistry phase spectrometry,
It is characterized in that, in step (2), the parameter of the electrochemical workstation are as follows: initial potential init E is set as 0, potential amplitude
Amplitude is set as 5mV, and frequency range 10-100KHz, frequency is from high frequency to low-frequency sweep.
4. the method according to claim 1 for quickly identifying cold fresh beef reconciliation chilled beef based on electrochemistry phase spectrometry,
It is characterized in that, in step (3), the dimension-reduction treatment specifically: the electrochemistry phase modal data of beef sample is carried out first
Then input of the different number of principal components as model is chosen in principal component analysis.
5. the method according to claim 4 for quickly identifying cold fresh beef reconciliation chilled beef based on electrochemistry phase spectrometry,
It is characterized in that, in step (3), the principal component analysis specifically: with 48 frequencies in 10-100KHz frequency range be to become
Amount carries out principal component analysis dimension-reduction treatment.
6. the method according to claim 1 for quickly identifying cold fresh beef reconciliation chilled beef based on electrochemistry phase spectrometry,
It is characterized in that, the method for the Chemical Measurement is reverse transmittance nerve network method in step (4).
7. the method according to claim 1 for quickly identifying cold fresh beef reconciliation chilled beef based on electrochemistry phase spectrometry,
It is characterized in that, in step (5), the quick identification specifically: using electrochemical workstation to unknown beef sample to be measured into
The acquisition of row electrochemistry phase modal data, then brings the electrochemistry phase spectrum data of beef sample to be measured into established identification mould
In type, the other identification of Beef is completed using Matlab processing software.
8. the method according to claim 1 for quickly identifying cold fresh beef reconciliation chilled beef based on electrochemistry phase spectrometry,
It is characterized in that, the object of the method for quick identification is cold fresh beef and solution chilled beef.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111562359A (en) * | 2020-04-10 | 2020-08-21 | 中国农业大学 | Automatic detector and detection method for rapidly and nondestructively detecting fish body storage mode |
| CN112986422A (en) * | 2021-02-08 | 2021-06-18 | 中国检验检疫科学研究院 | Method for identifying fresh meat and repeatedly freezing and thawing meat |
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