CN106092990A - A kind of three-dimensional fluorescence spectrum discrimination method of lycium barbarum - Google Patents
A kind of three-dimensional fluorescence spectrum discrimination method of lycium barbarum Download PDFInfo
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- CN106092990A CN106092990A CN201610424995.3A CN201610424995A CN106092990A CN 106092990 A CN106092990 A CN 106092990A CN 201610424995 A CN201610424995 A CN 201610424995A CN 106092990 A CN106092990 A CN 106092990A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06N—COMPUTING ARRANGEMENTS BASED ON SPECIFIC COMPUTATIONAL MODELS
- G06N3/00—Computing arrangements based on biological models
- G06N3/02—Neural networks
- G06N3/08—Learning methods
- G06N3/084—Backpropagation, e.g. using gradient descent
Abstract
The present invention relates to the three-dimensional fluorescence spectrum discrimination method of a kind of lycium barbarum, it is characterized in, comprise the steps: 1) acquisition correction collection: choose the place of production, at least 10 Ningxia dried fruit of lycium barbarum sample and at least 10 other place of production dried fruit of lycium barbarum samples as Calibration, by all correcting sample heat dryings, it is cooled to room temperature, then it is ground into powder with pulverizer, use fluorescence spectrophotometer and the solid sample test accessories with three-dimensional fluorescence spectrum scan function, gather the three-dimensional fluorescence spectrum figure of the place of production, Ningxia Fructus Lycii powder sample and other place of production Fructus Lycii powder sample successively, calibration set as the place of production, Ningxia Fructus Lycii He other place of production Fructus Lycii.Compared with prior art, the invention provides a kind of easy, analyze method quickly, reliably.
Description
Technical field
The present invention relates to the three-dimensional fluorescence spectrum discrimination method of a kind of lycium barbarum.
Background technology
Fructus Lycii mainly plants area in China Ningxia, Gansu, Xinjiang, Qinghai, the Inner Mongol and Hebei etc., due to ecological ring
The impact of the factor such as border and weather, the Fructus Lycii of different sources there are differences on the content of nutrition and active component, therefore quality and
Effect there is also difference.The most genuine, the most well-known is lycium barbarum, and lycium barbarum market demand is very big, but source confusion
And true and false difficulty distinguishes.The blending of other place of production Fructus Lycii often occurs in Fructus Lycii trade, the situation such as pretends to be, not only upset normal city
Field order, also compromises the interests of consumer.Therefore, it is necessary to the Fructus Lycii of different sources is carried out quality preservation and differentiates to divide
Analysis.
Fructus Lycii physical and chemical index, nutrition and Active Components are mainly studied different sources Fructus Lycii product by domestic existing research
Matter diversity is to realize identification of habitats, and process relates to complicated sample treatment and the use in conjunction of multiple analytical tool, analyzes week
Phase length, instrument configuration cost are high and are unsuitable for popularization and application.And test simple and convenient molecular spectroscopy techniques and combine stoichiometry
Method, is applicable to the qualitatively and quantitatively analysis of multi-component complex sample based on overall spectrum information analysis, in recent years in
Medical herbs qualitative identification aspect is widely used, as mid-infrared/near infrared spectrum has been used for Fructus Lycii identification of habitats and Variety identification, but
Fluorescence spectrum especially three-dimensional fluorescence spectrum does not have Fructus Lycii to differentiate application example.
Three-dimensional fluorescence spectrum (Three-dimensional Fluorescence Spectroscopy) is to have sensitivity
High, amount of samples is little, it is simple and quick to test, be easy to the spectrum test method of the advantages such as finger printing digitized.For containing
For having the complicated Chinese medicine system of multiple fluorescent component, three-dimensional fluorescence spectrum is representation system fluorescent component structure and content information
The best approach.Three-dimensional fluorescence spectrum technology combines chemometrics method, more makes it lead at Chinese medical herb and quality evaluation
The great application advantage in territory and development prospect.Parallel transport (parallel factor analysis, PARAFAC) is profit
A kind of multidimensional data decomposition method realized with alternately least-squares algorithm, it is possible to obtain each component from multicomponent mixed system
Quantitative result accurately, is widely used in three-dimensional fluorescence spectrum analysis.Error backward propagation method (Back
Propagation Network, is called for short BP neutral net) it is most representative in current artificial neural network pattern, apply
Widest a kind of model, has self study, self-organizing, self adaptation and the strongest non-linear mapping capability, it is possible to topotype very well
Intend the non-linear relation of fluorescence excitation-emission process.
Summary of the invention
It is an object of the invention to provide a kind of simplicity, the three-dimensional fluorescence spectrum discrimination method of lycium barbarum quick, reliable.
The three-dimensional fluorescence spectrum discrimination method of a kind of lycium barbarum, it is particular in that, comprises the steps:
1) acquisition correction collection: choose the place of production, at least 10 Ningxia dried fruit of lycium barbarum sample and at least 10 other place of production Chinese wolfberry fruit dries
Really sample is as Calibration, by all correcting sample heat dryings, is cooled to room temperature, is then ground into powder with pulverizer
End, uses fluorescence spectrophotometer and the solid sample test accessories with three-dimensional fluorescence spectrum scan function, gathers Ningxia successively and produces
Ground Fructus Lycii powder sample and the three-dimensional fluorescence spectrum figure of other place of production Fructus Lycii powder sample, as the place of production, Ningxia Fructus Lycii and other product
The calibration set of ground Fructus Lycii；
2) set up qualitative discrimination model: use computational science software MATLAB to set up qualitative discrimination model, concrete steps and
Model parameter is as follows:
The three-dimensional fluorescence spectrum of correcting sample gathered is derived from the supporting computer test software of fluorescence spectrophotometer,
Importing computational science software MATLAB again, be configured to the initial three-dimensional fluorescent matrix of N × Em × Ex form, wherein N represents school
Just collecting sample number, Em represents and launches wavelength number, and Ex represents excitation wavelength number；
Three-dimensional fluorescence square after initial three-dimensional fluorescent matrix is gone scattering, smooth and normalized are processed
Battle array；
Three-dimensional fluorescence matrix decomposition after utilizing parallel transport to process is score matrix and load matrix；Should
The Fructus Lycii place of production, as input vector, using Fructus Lycii place of production judgement preset value as output vector, and is judged to preset by score matrix
In value, the place of production, Ningxia Fructus Lycii preset value is 1, and other place of production Fructus Lycii preset value is 0, sets up BP neutral net, and carries out network instruction
Practice；
3) measure testing sample: after dried fruit of lycium barbarum sample heat drying to be measured, be ground into powder with pulverizer, use with
Step 1) in identical fluorescence spectrophotometer and solid sample test accessories gather the three-dimensional fluorescence spectrum of dried fruit of lycium barbarum sample to be measured
Figure, then by the three-dimensional fluorescence spectrum of dried fruit of lycium barbarum sample to be measured that gathered from the supporting computer test software of fluorescence spectrophotometer
Derive, be then introduced in computational science software MATLAB, build and step 2) in the three-dimensional fluorescence of testing sample of same form
Matrix, and carry out scattering, smooth and normalized；
Testing sample three-dimensional fluorescence matrix after processing carries out parallel factor analysis, obtains the score square of testing sample
Battle array, is predicted this score matrix as the input vector of the BP neutral net trained, and output vector is to be measured
The place of production of sample judges predictive value；
If the place of production of testing sample judges that predictive value between 0.9-1.1, is then judged to the place of production, Ningxia Fructus Lycii；If treating test sample
The product place of production judges that predictive value between-0.1-+0.1, is then judged to other place of production Fructus Lycii.
Step 1) and step 3) in heat drying specifically refer in drying baker to be dried at 60 DEG C 12h.
Step 2) and step 3) in three-dimensional fluorescence spectrum exported as the identified documentation form of computational science software, this can
Identify file format specifically txt or xls form.
Step 1) and step 3) middle fluorescence spectrophotometer and solid sample test accessories gather the three-dimensional fluorescence of Fructus Lycii powder
The test condition of spectrum is: excitation wavelength Ex scope 200-400nm, sampling interval 5nm, slit 2.5nm；Launch wavelength Em scope
250-550nm, sampling interval 5nm, slit 2.5nm；Scanning speed 12000nm/min；Photomultiplier tube PMT voltage 700V.
Step 2) and step 3) in utilize parallel transport decompose Fructus Lycii powder three-dimensional fluorescence matrix time, function parameter
In because of subnumber be 2.
Step 2) in the foundation of BP neutral net and training parameter be: network structure is 2-3-1；Transmission function is respectively
Tansig and purelin, training function is trainlm；Network training target mean square error is 0.000001, and maximum frequency of training is
1000, pace of learning is 0.01.
The invention provides the three-dimensional fluorescence spectrum discrimination method of a kind of lycium barbarum, first gather multiple Ningxia (place of production)
The three-dimensional fluorescence spectrum figure of Fructus Lycii and other place of production Fructus Lycii powder sample multiple is as lycium barbarum, other place of production Fructus Lycii correction
Collection；Then use parallel transport to decompose pretreated calibration set light spectrum matrix and obtain score matrix, and with this score
Matrix as input vector, judge that using the Fructus Lycii place of production preset value is set up as output vector and trains BP neutral net；Finally, profit
Decompose the three-dimensional fluorescence spectrum matrix of testing sample with parallel transport, score matrix is inputted BP neutral net and carries out pre-
Survey, predictive value and preset value compare to determine whether testing sample is lycium barbarum, compared with prior art, the invention provides
A kind of easy, analyze method quickly, reliably.
Accompanying drawing explanation
Fig. 1 is the three-dimensional fluorescence spectrum figure of the typical case place of production, Ningxia Fructus Lycii powder sample；
Fig. 2 is the three-dimensional fluorescence spectrum figure of the typical lycium barbarum powder sample after scattering, smoothing processing；
Fig. 3 is for differentiating BP neural metwork training result in model；
Fig. 4 is the BP neural network prediction result of Fructus Lycii sample to be measured.
Detailed description of the invention
The inventive method by parallel transport and BP neutral net R. concomitans, with parallel factor analysis obtain dense
Degree score matrix builds BP neutral net as network input layer, fast to realize lycium barbarum based on three-dimensional fluorescence spectrum technology
Speed qualitative identification.
Below in conjunction with the accompanying drawings and specific embodiment the present invention is further illustrated, but protection scope of the present invention is not
It is limited to this.
Embodiment 1:
Choose 10 Ningxia (place of production) dried fruit of lycium barbarum samples, 10 Qinghai dried fruit of lycium barbarum samples and 10 Lycium barbarum dry fruits
Sample is as Calibration；Above-mentioned 30 Fructus Lycii samples are placed in drying baker is dried 12h at 60 DEG C after and take out, be placed in dry
Device is cooled to room temperature, then becomes powder stand-by sample comminution with small-sized medicinal material pulverizer, it is not necessary to sieve.
Using Hitachi High-Technologies company model is the fluorescence spectrophotometer of F-4600 and supporting solid
Sample test adnexa gathers three-dimensional fluorescence spectrum figure.Fructus Lycii powder sample is inserted in powder sample pond, rather gather 10 successively
Summer Fructus Lycii sample, the three-dimensional fluorescence spectrum figure of 20 other place of production (Qinghai, Xinjiang) Fructus Lycii samples, respectively as lycium barbarum,
Other place of production Fructus Lycii calibration set.Test condition is: excitation wavelength (Ex) scope 200～400nm, sampling interval 5nm, slit
2.5nm；Launch wavelength (Em) scope 250～550nm, sampling interval 5nm, slit 2.5nm；Scanning speed 12000nm/min；Light
Electricity multiplier tube (PMT) voltage 700V.The three-dimensional fluorescence spectrum figure of typical lycium barbarum powder sample is as shown in Figure 1.
The three-dimensional fluorescence spectrum of 30 calibration set Fructus Lycii samples is soft from the F-4600 supporting computer test of type fluorescence spectrophotometer
Part FL Solutions exports as txt form, imports in MATLAB R2014a (MathWorks, USA), it is configured to 30 ×
The initial three-dimensional fluorescent matrix of 61 × 41 forms, wherein 30 representative sample number, 61 represent transmitting wavelength number, and 41 representatives excite
Wavelength number.
(the MATLAB R2014a of http://www.models.life.ku.dk/algorithms will be downloaded from
In (MathWorks, USA) software) " drEEM " workbox (Murphy KR, Stedmon CA, Graeber D, Bro R.
(2013).Fluorescence spectroscopy and multi-way techniques.PARAFAC.Analytical
Methods 5,6557-6566.) import in MATLAB R2014a operating path.Use in " drEEM " workbox
" smootheem.m " function, goes scattering and smoothing processing, and uses " normeem.m " letter initial three-dimensional fluorescent matrix
Number is normalized, the three-dimensional fluorescence matrix after being processed.Typical lycium barbarum powder sample after smoothing processing
Three-dimensional fluorescence spectrum figure is as shown in Figure 2.
Three-dimensional fluorescence square after utilizing the parallel factor analysis function " parafac.m " in " drEEM " workbox to process
Battle array is decomposed into score matrix A and load matrix B and C, and " because of the subnumber " in function parameter is preferably 2.
The judgement output valve of 10 lycium barbarum samples is preset as 1, the judgement output of 20 other place of production Fructus Lycii samples
Value is preset as 0.Using score matrix A as input vector, the Fructus Lycii place of production judges that preset value, as output vector, uses MATLAB
R2014a carries " newff.m " in " nnet " workbox and sets up BP neutral net net that structure is " 2-3-1 ", transmits function
Being respectively " tansig " and " purelin ", training function is " trainlm ".Call " train.m " function and carry out BP neutral net
Training, network training target mean square error is 0.000001, and maximum frequency of training is 1000, and pace of learning is set to 0.01.BP god
Through network net training result as shown in Figure 3.
Choose the Fructus Lycii sample in 10 known places of production as testing sample collection, to verify the accuracy of qualitative discrimination model.
After testing sample is dried 12h at 60 DEG C in drying baker, it is ground into powder with small-sized medicinal material pulverizer, gathers successively and treat test sample
The three-dimensional fluorescence spectrum figure of product, imports in MATLAB R2014a, builds the three-dimensional fluorescence matrix of testing sample, and carry out and school
Just collecting consistent and going scattering, smooth and normalized.Testing sample three-dimensional fluorescence matrix after processing carries out parallel factor
Analyze, obtain the score matrix A of testing sampleT, by score matrix ATAs the input vector of BP neutral net net, perform
" sim.m " function also returns the predictive value of BP neutral net, and result is as shown in table 1 and Fig. 4.
Table 1
Result shows that 4 lycium barbarum samples are all judged to lycium barbarum, 3 Qinghai Fructus Lycii samples and 3 Lycium barbarums
Sample is all judged to other place of production Fructus Lycii.The above results illustrates: the qualitative discrimination model that the present invention is set up can be quickly accurate
Really differentiate lycium barbarum and other place of production Fructus Lycii.Lycium barbarum three-dimensional fluorescence spectrum discrimination method of the present invention can be used
Qualitative quick discriminating in lycium barbarum.
Above embodiment is only to be described the preferred embodiment of the present invention, not enters the scope of the present invention
Row limits, on the premise of designing spirit without departing from the present invention, and this area ordinary skill technical staff technical side to the present invention
Various deformation that case is made and improvement, all should fall in the protection domain that claims of the present invention determines.
Claims (6)
1. the three-dimensional fluorescence spectrum discrimination method of a lycium barbarum, it is characterised in that comprise the steps:
1) acquisition correction collection: choose the place of production, at least 10 Ningxia dried fruit of lycium barbarum sample and at least 10 other place of production dried fruit of lycium barbarum samples
This, as Calibration, by all correcting sample heat dryings, is cooled to room temperature, is then ground into powder with pulverizer,
Use fluorescence spectrophotometer and the solid sample test accessories with three-dimensional fluorescence spectrum scan function, gather the place of production, Ningxia Chinese holly successively
Qi powder sample and the three-dimensional fluorescence spectrum figure of other place of production Fructus Lycii powder sample, as the place of production, Ningxia Fructus Lycii and other place of production Chinese holly
The calibration set of Qi；
2) qualitative discrimination model is set up: use computational science software MATLAB to set up qualitative discrimination model, concrete steps and model
Parameter is as follows:
The three-dimensional fluorescence spectrum of correcting sample gathered is derived from the supporting computer test software of fluorescence spectrophotometer, then leads
Entering computational science software MATLAB, be configured to the initial three-dimensional fluorescent matrix of N × Em × Ex form, wherein N represents calibration set
Sample number, Em represents and launches wavelength number, and Ex represents excitation wavelength number；
Three-dimensional fluorescence matrix after initial three-dimensional fluorescent matrix is gone scattering, smooth and normalized are processed；
Three-dimensional fluorescence matrix decomposition after utilizing parallel transport to process is score matrix and load matrix；By this score
The Fructus Lycii place of production, as input vector, using Fructus Lycii place of production judgement preset value as output vector, and is judged in preset value by matrix
The place of production, Ningxia Fructus Lycii preset value is 1, and other place of production Fructus Lycii preset value is 0, sets up BP neutral net, and carries out network training；
3) measure testing sample: after dried fruit of lycium barbarum sample heat drying to be measured, be ground into powder with pulverizer, use and step
1) fluorescence spectrophotometer identical in and solid sample test accessories gather the three-dimensional fluorescence spectrum figure of dried fruit of lycium barbarum sample to be measured, then
The three-dimensional fluorescence spectrum of dried fruit of lycium barbarum sample to be measured gathered is derived from the supporting computer test software of fluorescence spectrophotometer,
Be then introduced in computational science software MATLAB, build and step 2) in the three-dimensional fluorescence matrix of testing sample of same form,
And carry out scattering, smooth and normalized；
Testing sample three-dimensional fluorescence matrix after processing carries out parallel factor analysis, obtains the score matrix of testing sample, will
This score matrix is predicted as the input vector of the BP neutral net trained, and output vector is testing sample
The place of production judges predictive value；
If the place of production of testing sample judges that predictive value between 0.9-1.1, is then judged to the place of production, Ningxia Fructus Lycii；If testing sample produces
Ground judges that predictive value between-0.1-+0.1, is then judged to other place of production Fructus Lycii.
The three-dimensional fluorescence spectrum discrimination method of a kind of lycium barbarum the most as claimed in claim 1, it is characterised in that: step 1) and
Step 3) in heat drying specifically refer in drying baker to be dried at 60 DEG C 12h.
The three-dimensional fluorescence spectrum discrimination method of a kind of lycium barbarum the most as claimed in claim 1, it is characterised in that: step 2) and
Step 3) in three-dimensional fluorescence spectrum exported as the identified documentation form of computational science software, this identified documentation form is concrete
It it is txt or xls form.
The three-dimensional fluorescence spectrum discrimination method of a kind of lycium barbarum the most as claimed in claim 1, it is characterised in that: step 1) and
Step 3) in gather Fructus Lycii powder by fluorescence spectrophotometer and solid sample test accessories the test condition of three-dimensional fluorescence spectrum be:
Excitation wavelength Ex scope 200-400nm, sampling interval 5nm, slit 2.5nm；Launch wavelength Em scope 250-550nm, between sampling
Every 5nm, slit 2.5nm；Scanning speed 12000nm/min；Photomultiplier tube PMT voltage 700V.
The three-dimensional fluorescence spectrum discrimination method of a kind of lycium barbarum the most as claimed in claim 1, it is characterised in that: step 2) and
Step 3) in utilize parallel transport decompose Fructus Lycii powder three-dimensional fluorescence matrix time, in function parameter because of subnumber be 2.
The three-dimensional fluorescence spectrum discrimination method of a kind of lycium barbarum the most as claimed in claim 1, it is characterised in that: step 2) in
The foundation of BP neutral net and training parameter be: network structure is 2-3-1；Transmission function is respectively tansig and purelin, instruction
Practicing function is trainlm；Network training target mean square error is 0.000001, and maximum frequency of training is 1000, and pace of learning is
0.01。
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| CN107677647A (en) * | 2017-09-25 | 2018-02-09 | 重庆邮电大学 | Chinese medicine place of production discrimination method based on principal component analysis and BP neural network |
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| CN108627486A (en) * | 2018-05-10 | 2018-10-09 | 江南大学 | A method of measuring the active principle and chemical composition content of Chinese medicine |
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| CN107290315A (en) * | 2017-06-20 | 2017-10-24 | 滁州学院 | A kind of Three-Dimensional Synchronous Fluorescence Spectra detection method for restoring coconut juice |
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| CN108548802A (en) * | 2018-03-27 | 2018-09-18 | 陕西师范大学 | A method of acting on chloropyuril in detection Kiwi berry using fluorescent quenching |
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| CN108827931A (en) * | 2018-04-18 | 2018-11-16 | 宁夏林业研究院股份有限公司 | A kind of Raman spectrum discrimination method of lycium barbarum |
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| CN109900532A (en) * | 2019-01-10 | 2019-06-18 | 青海省农林科学院 | Fructus lycii pre-treating method when a kind of measurement dry fruit fructus lycii stable isotope |
| CN109900532B (en) * | 2019-01-10 | 2021-08-06 | 青海省农林科学院 | Pretreatment method of lycium barbarum during determination of stable isotope of dried lycium barbarum |
| WO2021023211A1 (en) * | 2019-08-05 | 2021-02-11 | Goldway Technology Limited | System and process for diamond authentication |
| CN114364970A (en) * | 2019-08-05 | 2022-04-15 | 金展科技有限公司 | System and process for diamond authentication |
| CN110554013A (en) * | 2019-08-29 | 2019-12-10 | 华夏安健物联科技(青岛)有限公司 | method for realizing rapid identification and comparison by using fluorescence spectrum characteristic information |
| CN110554013B (en) * | 2019-08-29 | 2022-05-20 | 华夏安健物联科技(青岛)有限公司 | Method for realizing rapid identification and comparison by using fluorescence spectrum characteristic information |
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