CN104849323B - A kind of method of fining agent in quick detection fruit juice based on Electronic Nose - Google Patents

A kind of method of fining agent in quick detection fruit juice based on Electronic Nose Download PDF

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CN104849323B
CN104849323B CN201510226487.XA CN201510226487A CN104849323B CN 104849323 B CN104849323 B CN 104849323B CN 201510226487 A CN201510226487 A CN 201510226487A CN 104849323 B CN104849323 B CN 104849323B
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electronic nose
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fruit juice
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CN104849323A (en
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王俊
裘姗姗
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Zhejiang University ZJU
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Abstract

The invention discloses a kind of method of fining agent in quick detection fruit juice based on Electronic Nose.Oranges and tangerines surface is cleaned, is dried, pick out the basically identical oranges and tangerines of size color as detection object.Oranges and tangerines are removed the peel, squeeze the juice, filtered, it is stand-by.Pectase is made into the solution of various concentrations, a certain proportion of mixing is carried out with orange blossom.Take mixed 10 ~ 30ml of solution to be put in the sealing container of 500ml, the solution of each concentration scale respectively takes 24 repeat samples, to the head space of sample, other carry out detection by electronic nose.Electronic Nose sensor settings condition is:Under certain flow rate, the sampling time is 80s, and the air cleaning time is 60s;Using steady-state value as Electronic Nose characteristic value.Using principal component analysis, discriminant analysis, and random forest carry out quantitative analysis to stabilizer in fruit juice.The present invention substantially improves the quick detection of fruit juice internal stabilizer, convenient, objective, and with good discrimination, with popularization higher and value.

Description

A kind of method of fining agent in quick detection fruit juice based on Electronic Nose
Technical field
The invention belongs to food fruit juice clarifier detection technique field, it is related to a kind of based in Electronic Nose quick detection fruit juice The method of fining agent.
Background technology
Fruit juice is susceptible to turbidity and precipitation in long-term storage process, and oxidation deterioration may occur.Muddy the reason for A lot, it is mainly relevant with the material such as naturally occurring phenols.When protein and pectin substance and polyphenols in fruit juice When coexisting for a long time, the phaneroplasm of muddiness will be produced, or even precipitated.So can usually add in the food industry various clear Clear agent, the material of precipitation is easily caused to remove a part or major part, fruit juice is formed more stable solution.
Beverage industry is often added, such as bentonite, diatomite, gelatin, Ludox, pectase clarification aid or they Be used in combination to reach the purpose of clarification.The conventional determining method of stabiliser content has chemical detection, light splitting in current fruit juice Photometry, fluorescence spectrophotometry etc., but the shortcomings of these methods have complex operation, analysis time is long.Therefore, one is explored It is necessary to plant fast and convenient stabilizer detection method.
Electronic Nose quickly provides the whole of sample also known as smell scanner with specific sensor and PRS Body information, indicate sample hidden feature, with high sensitivity, reliability, repeatability, it sample can be quantified, together When some component contents can be carried out fast qualitative quantify.At present, using fruit in olfactory sensor quantitative determination fruit juice The correlative study of glue enzyme content is not yet reported.Present invention aim at stabilizer in Quantitative detection fruit juice, while filling up state The inside and outside blank on the quick detection of stabiliser content in fruit drink.
The content of the invention
Regarding to the issue above, it is an object of the invention to provide a kind of side of fining agent in quick detection fruit juice based on Electronic Nose Method.
The purpose of the present invention is achieved through the following technical solutions, and one kind is based on clear in Electronic Nose quick detection fruit juice The method of clear agent, comprises the following steps:
(1) by oranges and tangerines surface treatment it is clean, remove the peel, squeeze the juice, filter, abandon filter residue, the oranges and tangerines filtrate of pure concentration is standby;Respectively The pectase of 3g, 6g, 9g, 12g is weighed, under 40 DEG C of water bath condition, pectase is repeated to dissolve, filter residue is abandoned in filtering;In room Under temperature, during pectinase solution constant volume put into 100ml volumetric flasks, with pure oranges and tangerines solution in mass ratio 1:11 ratio is mixed, Stirring;After static 1 hour of blended fruit juice, it is centrifuged under the centrifugal speed not less than 4000r/min, is abandoned sediment, is taken Clear liquid is stand-by;
(2) take the 10~30ml of fruit juice supernatant after treatment to be put into sealing container of the volume not less than 250ml, sealing, 30min is placed at room temperature, the fragrance level of orange juice is reached saturation in the beaker headspace of sealing;Each concentration The solution of grade is no less than 3 repeat samples respectively, is the regression modeling collection Electronic Nose data in later stage;It is built-in by Electronic Nose Pump by the sensor array passage of the headspace gas suction Electronic Nose in sealing container, with sample gas send out by Electronic Nose sensor Raw reaction produces sensor signal;Electrical conductivity G when the sensor signal is sensor contacts sample gas exists with sensor Electrical conductivity G during by calibration gas0Ratio, i.e. G/G0;The detection time of the Electronic Nose sensor is 80s, scavenging period It is 60s, internal pump gas flow rate is 200ml/min;
(3) the sensor response of detection by electronic nose orange juice is a data matrix, by many responses of sensor Value composition, from each sensor stabilization value as characteristic value, in SPSS softwares, is entered using principal component analysis, discriminant analysis Row analysis;In Matlab softwares, according to characteristic value by bootstrap (boot-strap) resampling technique, training is continuously generated Sample and test sample, some decision trees are generated by training sample, so as to set up Random Forest model;In Random Forest model In, the number to decision tree in the variable number and random forest of the tree node of decision tree is optimized, and test result is by certainly Depending on the average value of plan tree voting results;
(4) the unknown sample to be tested of agent content will be clarified its Electronic Nose sensor response is obtained by step 2, will sensed The Random Forest model that device response steps for importing 3 is obtained, the clarification agent content in final prediction sample to be tested.
Further, in the step 3, by correlation coefficient r, root-mean-square error RMSE value to the random forest after optimization Model is evaluated, specially:
Wherein, N represents the number of samples in modeling process;
XiI-th test value in for modeling process;
It is the average value of the sample responses value in modeling process;
YiIt is i-th predicted value of sample in modeling process;
It is the average value of the sample predictions value in modeling process.
The beneficial effects of the invention are as follows by principal component analysis, discriminant analysis, random forest scheduling algorithm is set up and good determined Property Quantitative Prediction Model, evaluation and pre- is carried out to the pectase of different content in juice solution using intelligent smell sensory system Survey, it is simple to operate, quick, quick indirect evaluation truly has been tested, it is that fruit drink industry additive is determined, carry A kind of new method is supplied.
Brief description of the drawings
The Electronic Nose of Fig. 1 present examples 1 sensor response signal when detection is containing pectase fruit juice;
The principal component analysis result of the pectase samples of juice of the various concentrations of Fig. 2 present examples 1;
The discriminant analysis result of the pectase samples of juice of the various concentrations of Fig. 3 present examples 1;
The random forest regressive prediction model of the pectase samples of juice of the various concentrations of Fig. 4 present examples 1;
The Electronic Nose of Fig. 5 present examples 2 sensor response signal when detection is containing chitin fruit juice
The principal component analysis result of the chitin samples of juice of the various concentrations of Fig. 6 present examples 2;
The discriminant analysis result of the chitin samples of juice of the various concentrations of Fig. 7 present examples 2;
The random forest regressive prediction model of the chitin samples of juice of the various concentrations of Fig. 8 present examples 2.
Specific embodiment
The present invention contains suitable for the various fruit juice stabilizers such as pectase, shitosan, bentonite, diatomite, gelatin, Ludox It is fixed to measure.Electronic Nose quickly provides the Global Information of sample with specific sensor and PRS, indicates sample Hidden feature, with high sensitivity, reliability, repeatability, it sample can be quantified, while can be to some compositions Content carries out fast qualitative and quantifies.Be embodied in case also added based on smell finger print information to fruit juice in shitosan Qualitative and quantitative analysis, so as to further illustrate popularity of the invention.
The method of fining agent in a kind of quick detection fruit juice based on Electronic Nose of the present invention, using olfactory sensor to containing not It is used for quickly detecting with the juice solution of concentration pectase, sets up effective Quantitative Prediction Model, is comprised the following steps that:
(1) by oranges and tangerines surface treatment it is clean, remove the peel, squeeze the juice, filter, abandon filter residue, the oranges and tangerines filtrate of pure concentration is standby;Respectively The accurate pectase for weighing 3g, 6g, 9g, 12g, under 40 DEG C of water bath condition, pectase is repeated to dissolve, and filter residue is abandoned in filtering. At room temperature, in pectinase solution constant volume being put into 100ml volumetric flasks.Pressed with 1 with pure oranges and tangerines solution:11 ratio is mixed, Stirring.After static 1 hour of blended fruit juice, it is centrifuged under the centrifugal speed not less than 4000r/min, is abandoned sediment, is taken Clear liquid is stand-by;
(2) take the 10~30ml of fruit juice supernatant after treatment to be put into sealing container of the volume not less than 250ml, sealing, 30min is placed at room temperature, the fragrance level of orange juice is reached saturation in the beaker headspace of sealing.Each concentration The solution of grade is no less than 3 repeat samples respectively, is the regression modeling collection Electronic Nose data in later stage.It is built-in by Electronic Nose Pump by the sensor array passage of the headspace gas suction Electronic Nose in sealing container, with sample gas send out by Electronic Nose sensor Raw reaction produces sensor signal;Electrical conductivity G when the sensor signal is sensor contacts sample gas exists with sensor The ratio of electrical conductivity G0 during by calibration gas, i.e. G/G0;The detection time of the Electronic Nose sensor is 80s, during cleaning Between be 60s, internal pump gas flow rate be 200ml/min;
(3) the sensor response of detection by electronic nose orange juice is a data matrix, by many responses of sensor Value composition, from each sensor stabilization value as characteristic value, in SPSS softwares, is entered using principal component analysis, discriminant analysis Row analysis;In Matlab softwares, according to characteristic value by bootstrap (boot-strap) resampling technique, training is continuously generated Sample and test sample, some decision trees are generated by training sample, so as to set up Random Forest model;In Random Forest model In, the number to decision tree in the variable number and random forest of the tree node of decision tree is optimized, and test result is by certainly Depending on the average value of plan tree voting results;
(4) the unknown sample to be tested of agent content will be clarified its Electronic Nose sensor response is obtained by step 2, will sensed The Random Forest model that device response steps for importing 3 is obtained, the clarification agent content in final prediction sample to be tested.
In the step 3, the Random Forest model after optimization is carried out by correlation coefficient r, root-mean-square error RMSE value Evaluate, specially:
Wherein, N represents the number of samples in modeling process;
XiI-th test value in for modeling process;
It is the average value of the sample responses value in modeling process;
YiIt is i-th predicted value of sample in modeling process;
It is the average value of the sample predictions value in modeling process.
Embodiment 1
The present embodiment using pectase as analysis object.The PEN2 types Electronic Nose of German AIRSENSE companies is detecting instrument Elaborate, the Electronic Nose is made up of 10 metal oxide sensors, its model is as shown in the table with response characteristic:
Sequence number Title Performance characteristics
1 S1 It is sensitive to fragrance ingredient
2 S2 It is very sensitive to nitrogen oxides
3 S3 It is sensitive to ammoniacal liquor, fragrance ingredient
4 S4 It is selective to hydrogen
5 S5 It is sensitive to alkane, fragrance ingredient
6 S6 It is sensitive to methane
7 S7 It is sensitive to sulfide
8 S8 To alcohol sensible
9 S9 It is sensitive to fragrance ingredient, organic sulfur compound
10 S10 It is sensitive to alkane
Specific detecting step is as follows:
1st, by oranges and tangerines surface treatment it is clean, remove the peel, squeeze the juice, filter, abandon filter residue, the oranges and tangerines filtrate of pure concentration is standby;Respectively The accurate pectase for weighing 3g, 6g, 9g, 12g, under 40 DEG C of water bath condition, pectase is repeated to dissolve, and filter residue is abandoned in filtering. At room temperature, in pectinase solution constant volume being put into 100ml volumetric flasks.Pressed with 1 with pure oranges and tangerines solution:11 ratio is mixed, Stirring.After static 1 hour of blended fruit juice, it is centrifuged under the centrifugal speed not less than 4000r/min, is abandoned sediment, is taken Clear liquid is stand-by;
2nd, take the fruit juice supernatant 10ml after treatment to be put into the beaker of volume 500ml, sealed with double-deck preservative film, in room Temperature is lower to place 30min, the fragrance level of orange juice is reached saturation in the beaker headspace of sealing;Each concentration scale Fruit juice distinguish 24 repeat samples, be the later stage regression modeling collection Electronic Nose data;To be sealed by Electronic Nose internal pump In the sensor array passage of the headspace gas suction Electronic Nose in container, Electronic Nose sensor and sample gas react product Raw sensor signal;Electrical conductivity G when the sensor signal is sensor contacts sample gas is with sensor by calibrating The ratio of electrical conductivity G0 during gas, i.e. G/G0;The detection time of the Electronic Nose sensor is 80s, and scavenging period is 60s, Internal pump gas flow rate is 200ml/min;
3rd, the sensor response of detection by electronic nose orange juice is a data matrix, by many responses of sensor Composition, from each sensor in 60s stationary values as characteristic value, in SPSS softwares, using principal component analysis, discriminant analysis It is analyzed;It is respectively that, based on principal component analysis, linear discriminant analysis is sentenced to the preliminary of chitosan content in fruit juice that Fig. 2, Fig. 3 are It is fixed;In Matlab softwares, according to characteristic value by bootstrap (boot-strap) resampling technique, training sample is continuously generated And test sample, some decision trees are generated by training sample, so as to set up Random Forest model;It is right in Random Forest model The number of decision tree is optimized in the variable number and random forest of the tree node of decision tree, and test result is thrown by decision tree Depending on the average value of ticket result;The substantially step of random forest is as follows:
(1) bootstrap (boot-strap) resampling technique is utilized, T training set S is randomly generated1,S2,...,ST
Bootstrap (boot-strap) resampling:If there is n different sample { x in set1,x2,...,xn, if every time A sample is extracted from set S with putting back to, is extracted n times altogether, form new set S*, then set S*In include certain sample This xi(i=1,2 ..., probability n) isAs n → ∞, have Therefore, the total sample number of new set is identical with former set, but contains repeated sample (putting back to extraction), is only wrapped in new set The sample of former set S collection and about 1-0.368*100%=63.2% is contained;
(2) each training set is utilized, corresponding decision tree C is generated1,C2,...CT;It is being based in each non-leaf nodes Best divisional mode in the Split Attribute collection m of front nodal point enters line splitting to the node (in general, in this random forest Growth course in, the value of m is to maintain constant);
(3) each tree is completely grown up, without being pruned;
(4) for test set sample X, tested using each decision tree, obtained corresponding classification C1(X),C2 (X),...,CT(X);
(5) by the way of ballot, the final result of Random Forest model is by the T average value of decision tree output valve It is fixed.
4th, in Random Forest model, in the variable number and random forest of the tree node of decision tree decision tree Number is optimized, and depending on average value of the test result by decision tree voting results, the result for finally optimizing obtains the change of tree node It is 3 to measure, and the number of decision tree is 40.The Random Forest model after optimization is entered by correlation coefficient r, root-mean-square error RMSE value Row is evaluated, specially:
Wherein, N represents the number of samples in modeling process;
XiI-th test value in for modeling process;
It is the average value of the sample responses value in modeling process;
YiIt is i-th predicted value of sample in modeling process;
It is the average value of the sample predictions value in modeling process.
Shown in Fig. 4, black squares point is the content of the pectase of the sample of the known pectase content model prediction There is good correlation (r=0.9879, RMSE=0.0902) between actual pectase content.
5th, the unknown sample to be tested of pectase content is obtained into its Electronic Nose sensor response by step 2, will be sensed The Random Forest model that device response steps for importing 4 is obtained, the pectase content in final prediction sample to be tested.Such as Fig. 4's is white Triangulation point is the sample of unknown pectase content on color, and Random Forest model has prediction energy well to orange blossom pectase content Power (r=0.9764, RMSE=0.1073).
Embodiment 2
Present case is using the shitosan commonly used in fruit juice as analysis object.The PEN2 type Electronic Noses of German AIRSENSE companies For detecting instrument has elaborated in case 1.
1st, it is oranges and tangerines surface treatment is clean, lesion is rejected, get colors, the sample that size, shape are consistent.Oranges and tangerines go Skin, squeezes the juice, filtering, abandons filter residue, and the oranges and tangerines filtrate of pure concentration is standby.
2nd, accurate accurate title 3g, 6g, 9g, 12g shitosan, pours into cold water, is soaked through 10 minutes, adds in 45 DEG C of hot bath methods Thermal agitation is fully dissolved, at room temperature, during chitosan solution constant volume put into 100ml volumetric flasks.With the pure oranges and tangerines solution of step (1) By 1:11 ratios repeat to mix, and treat and detection by electronic nose.
3rd, take the fruit juice 10ml after treatment to be put into the beaker of volume 500ml, sealed with double-deck preservative film, put at room temperature 30min is put, the fragrance level of orange juice is reached saturation in the beaker headspace of sealing;The fruit juice of each concentration scale 24 repeat samples, are the regression modeling collection Electronic Nose data in later stage respectively;By Electronic Nose internal pump by sealing container Headspace gas suction Electronic Nose sensor array passage in, Electronic Nose sensor and sample gas react generation sensing Device signal;Electrical conductivity G when the sensor signal is sensor contacts sample gas is with sensor when by calibration gas Electrical conductivity G0 ratio, i.e. G/G0;The detection time of the Electronic Nose sensor is 80s, and scavenging period is 60s, internal pump Gas flow rate is 200ml/min;
4th, the sensor response of detection by electronic nose orange juice is a data matrix, by many responses of sensor Composition, from each sensor stabilization value as characteristic value, in SPSS softwares, is carried out using principal component analysis, discriminant analysis Analysis;Fig. 6, Fig. 7 are to be respectively based on principal component analysis, preliminary judgement of the linear discriminant analysis to chitosan content in fruit juice; In Matlab softwares, according to characteristic value by bootstrap (boot-strap) resampling technique, be continuously generated training sample and Test sample, some decision trees are generated by training sample, so as to set up Random Forest model;In Random Forest model, fight to the finish The number of decision tree is optimized in the variable number and random forest of the tree node of plan tree, and test result is voted by decision tree Depending on the average value of result;The substantially step of random forest is as follows:
(1) bootstrap (boot-strap) resampling technique is utilized, T training set S is randomly generated1,S2,...,ST
Bootstrap (boot-strap) resampling:If there is n different sample { x in set1,x2,...,xn, if every time A sample is extracted from set S with putting back to, is extracted n times altogether, form new set S*, then set S*In include not individual sample This xi(i=1,2 ..., probability n) isAs n → ∞, have Therefore, the total sample number of new set is identical with former set, but contains repeated sample (putting back to extraction), is only wrapped in new set The sample of former set S collection and about 1-0.368*100%=63.2% is contained;
(2) each training set is utilized, corresponding decision tree C is generated1,C2,...CT;It is being based in each non-leaf nodes Best divisional mode in the Split Attribute collection m of front nodal point enters line splitting to the node (in general, in this random forest Growth course in, the value of m is to maintain constant);
(3) each tree is completely grown up, without being pruned;
(4) for test set sample X, tested using each decision tree, obtained corresponding classification C1(X),C2 (X),...,CT(X);
(5) by the way of ballot, depending on the average value of the head piece result exported in T decision tree.
4th, in Random Forest model, in the variable number and random forest of the tree node of decision tree decision tree Number is optimized, and depending on average value of the test result by decision tree voting results, the result for finally optimizing obtains the change of tree node It is 3 to measure, and the number of decision tree is 50.The Random Forest model after optimization is entered by correlation coefficient r, root-mean-square error RMSE value Row is evaluated, specially:
Wherein, N represents the number of samples in modeling process;
XiI-th test value in for modeling process;
It is the average value of the sample responses value in modeling process;
YiIt is i-th predicted value of sample in modeling process;
It is the average value of the sample predictions value in modeling process.
Shown in Fig. 8, black squares point is the content of the pectase of the sample of the known chitosan content model prediction There is good correlation (r=0.9950, RMSE=0.0542) between actual chitosan content.
6th, the unknown sample to be tested of chitosan content is obtained into its Electronic Nose sensor response by step 3, will be sensed The Random Forest model that device response steps for importing 5 is obtained, the chitosan content in final prediction sample to be tested.Such as Fig. 4's is white Triangulation point is the sample of unknown chitosan content on color, and Random Forest model has prediction energy well to orange blossom pectase content Power (r=0.9721, RMSE=0.1449).

Claims (2)

1. in a kind of quick detection fruit juice based on Electronic Nose fining agent method, it is characterised in that comprise the following steps:
(1) by oranges and tangerines surface treatment it is clean, remove the peel, squeeze the juice, filter, abandon filter residue, the oranges and tangerines filtrate of pure concentration is standby;Weigh respectively The pectase of 3g, 6g, 9g, 12g, under 40 DEG C of water bath condition, pectase is repeated to dissolve, and filter residue is abandoned in filtering;In room temperature Under, during pectinase solution constant volume put into 100ml volumetric flasks, with pure oranges and tangerines solution in mass ratio 1:11 ratio is mixed, and is stirred Mix;After static 1 hour of blended fruit juice, it is centrifuged under the centrifugal speed not less than 4000r/min, is abandoned sediment, is taken supernatant Liquid is stand-by;
(2) take the 10~30ml of fruit juice supernatant after treatment to be put into sealing container of the volume not less than 250ml, sealing, in room Temperature is lower to place 30min, the fragrance level of orange juice is reached saturation in the beaker headspace of sealing;Each concentration scale Solution respectively be no less than 3 repeat samples, be the later stage regression modeling collection Electronic Nose data;Will by Electronic Nose internal pump In the sensor array passage of the headspace gas suction Electronic Nose in sealing container, Electronic Nose sensor occurs anti-with sample gas Sensor signal should be produced;Electrical conductivity G when the sensor signal is sensor contacts sample gas is passing through with sensor Electrical conductivity G during calibration gas0Ratio, i.e. G/G0;The detection time of the Electronic Nose sensor is 80s, and scavenging period is 60s, internal pump gas flow rate is 200ml/min;
(3) the sensor response of detection by electronic nose orange juice is a data matrix, by many response groups of sensor Into from each sensor stabilization value as characteristic value, in SPSS softwares, being divided using principal component analysis, discriminant analysis Analysis;In Matlab softwares, according to characteristic value by bootstrap (boot-strap) resampling technique, training sample is continuously generated And test sample, some decision trees are generated by training sample, so as to set up Random Forest model;It is right in Random Forest model The number of decision tree is optimized in the variable number and random forest of the tree node of decision tree, and test result is thrown by decision tree Depending on the average value of ticket result;
(4) the unknown sample to be tested of agent content will be clarified its Electronic Nose sensor response is obtained by step (2), by sensor The Random Forest model that response steps for importing (3) is obtained, the clarification agent content in final prediction sample to be tested.
2. in a kind of quick detection fruit juice based on Electronic Nose according to claim 1 fining agent method, it is characterised in that In the step (3), the Random Forest model after optimization is evaluated by correlation coefficient r, root-mean-square error RMSE value, had Body is:
r = Σ i = 1 N ( X i - X ‾ ) ( Y i - Y ‾ ) Σ i = 1 N ( X i - X ‾ ) 2 Σ i = 1 N ( Y i - Y ‾ ) 2
R M S E = 1 N Σ i = 1 N ( X i - Y i ) 2
Wherein, N represents the number of samples in modeling process;
XiI-th test value in for modeling process;
It is the average value of the sample responses value in modeling process;
YiIt is i-th predicted value of sample in modeling process;
It is the average value of the sample predictions value in modeling process.
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