CN107340241A - A kind of method based on shortwave imaging spectral technology detection content of ginsenoside - Google Patents

A kind of method based on shortwave imaging spectral technology detection content of ginsenoside Download PDF

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CN107340241A
CN107340241A CN201710097728.4A CN201710097728A CN107340241A CN 107340241 A CN107340241 A CN 107340241A CN 201710097728 A CN201710097728 A CN 201710097728A CN 107340241 A CN107340241 A CN 107340241A
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sample
ginseng
collection
ginsenoside
spectrum
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宁晓锋
冯雨龙
王芳
刘诗曼
培军强
潘明忠
宫元娟
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Shenyang Agricultural University
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/33Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
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Abstract

The invention discloses a kind of method based on shortwave imaging spectral technology detection content of ginsenoside, this method is to carry out spectra collection in characteristic wave bands 910nm 2500nm, and the spectral information for gathering reference white plate is used as with reference to spectrum, distance of the distance of light source and reference white plate as sample collection spectrum, each sample carries out collection twice and averaged is as last spectroscopic data, so that the data arrived are more complete and representative.Establish forecast model, and the content of ginsenoside and model obtained by stechiometry obtain come predicted value verified that illustrate that forecast model is reasonable, this detection method is feasible.Detection method provided by the invention, have the advantages that simple to operate, easily controllable, analysis efficiency is high, analysis quality is good, and detect in this way without using chemical reagent, sample is not polluted and lost, it is also free from environmental pollution so as to save resource, the method for being used as detecting content of ginsenoside, reliable foundation is provided for ginseng attributional analysis.

Description

A kind of method based on shortwave imaging spectral technology detection content of ginsenoside
Technical field
The present invention applies spectral detection and analytical technology, is related to a kind of ginseng quality's determination techniques, specifically one kind is based on The method that shortwave imaging spectral technology detects ginsenoside saponin content.
Technical background
Ginseng is otherwise known as Asia ginseng, because its root is similar to human nature, so it is referred to as ginseng by people, because it Good effects, be often " kings of hundred grass ", " northeast Triratna " by person, be a kind of to be mainly grown in East Asia particularly cold district The root with meat.Ginseng is the common big tonic material in Asia, frequently as medicinal, in most swath and some supermarkets all Various ginseng drinks or the health products that ginseng extract is made can be seen.
Ginseng has had won fame both at home and abroad as a kind of tonic being highly profitable to human body, and ginseng likes gentle shady and cool weather, Be grown in the shaw in the small hillside of 500 to 1100 meters of day and night temperatures of height above sea level more, and Changbai Mountain across Jilin, Liaoning and Three, Heilungkiang province, position, temperature, precipitation and soil slackness here are all the preferable milpas of ginseng.Root According to the data of China's Industry Information Network, the fresh ginseng yield in Jilin Province accounts for the 80% of China, and yield is at 20000 tons or so, according to Jilin Province Public data, Jilin possesses about 6000 hectares of cultivated area, and the content of China's general ginsenoside is also very high.
And the active ingredient in ginseng is exactly saponin(e, the content in ginseng about accounts for 4% or so, and ginsenoside is one Kind steroid compound, the active component being counted as in ginseng, so as to be adjusted as research object now, ginsenoside Save the tumor cell proliferation cycle, carry out tumor cell induction to be divided into normal cell, so as to reach antineoplastic action.And And ginsenoside has the apoptosis for promoting leukaemia, suppression cancer metastasis, enhancing body immunity, rapid recovery tired Labor, strengthen the functions such as myocardial function, be the tonic with health effect.
China ginseng main exit area is Japan, Italy, Holland, Germany and Hong-Kong and TaiWan, China etc., Although China's ginseng has increased in export volume and export price in recent years, growth rate is but more slow, Er Qiehan The exporting country of state and the exporting country in China are substantially similar, but the ginseng export volume and price in China are even more to be less than South Korea The export volume and price of red ginseng, in the same export area, the red ginseng of South Korea is in occupation of high-end market, and China's ginseng can only account for The low market in, but the saponin content of China's ginseng and the saponin content for being not less than South Korea's red ginseng, govern China's ginseng and go out The reason for mouth amount and price, is not only us and does not exploit market, it is often more important that contains without a set of advanced detection ginsenoside The method of amount, exactly because so, customers do not know Chinese people ginseng added value which, advantage which, so international competition Power is relatively low.
Shortwave imaging spectral technology, can be before not causing damage and polluting to material as a kind of non-destructive testing technology Put and material is detected, and the spectroscopic data to detecting is analyzed, relative to existing conventional detection analytical technology For have the characteristics that it is simple to operate it is quick, analysis efficiency is high, analytical effect is good and advantage.The present invention is attempted shortwave imaging Spectral technology is applied in the quick detection of content of ginsenoside, and reliable foundation is provided for the quality evaluation of ginseng.
The content of the invention
The invention aims to provide a kind of shortwave imaging spectral technology that is based on to be directed to saponin content progress in ginseng The method of Non-Destructive Testing, this method application shortwave imaging spectrometer and ENVI spectra collections software are in 910nm -2500nm features Spectra collection is carried out to Ginseng Root Powder sample in wavelength band, and also uses a powerful DAS The Unscrambler 9.7 is pre-processed to the spectral information collected, and shortwave imaging spectral technology is utilized on verifying bench Special remote sensing image processing function, comprehensive detection is carried out to Ginseng Root Powder, can be very good to realize to ginsenoside Non-Destructive Testing, the quality of ginsenoside can quickly be tested and analyzed, and pretreatment is carried out to ginsenoside quality and built Mould, applied forecasting model are predicted, and carry out evaluation test to predicted value, weigh the predictive ability of forecast model, are examined pre- Survey ratio of precision is more reasonable, and the method for inspection is scientific and reasonable, simple and easy to control, accuracy of detection is excellent, is adapted to promote, and can be very good to help Help the economy and competitiveness for improving ginseng market.
The technical scheme of use:
A kind of method based on shortwave imaging spectral analytical technology detection content of ginsenoside, it is characterised in that it is included Following steps:
(1) sample needed for detection is prepared:Fresh ginseng is carried out at crushing using LD-Y400A high speed Universal pulverizer Reason, chooses 24 test set samples and 12 forecast set sample totally 36 samples, and being numbered successively, and pack preserves.
(2) preparation before the collection of spectral information and collection:
(2.1) half-light spectrum is deducted:The equipment for gathering spectral information is connected, when the light and temperature that light source is sent are put down After slow stabilization, the curve of spectrum now is gathered, the half-light spectrum of this environment is deducted, spectra collection is had a good camera bellows light Spectrum basis.
(2.2) reference spectra is stored:After dark spectral subtraction, being put into reference to blank in spectra collection area, joined The collection of irradiation spectrum, platform regulation the distance between blank and light source are moved up and down, when spectral intensity curve is without substantially beating, do not have When having spilling, what is obtained is exactly the reference curve of spectrum, and now the distance between blank and light source are with regard to generally carrying out sample Required distance during this collection.
(2.3) collection of spectral information:The Ginseng Root Powder sample that will be detected is placed on lifting platform, and adjusts lifting Platform position makes the distance between collected point and light source and previous step obtain sample with reference to identical distance between blank and light source Corresponding detection data.
(3) observable spectrogram is obtained:Due to the imaging function of shortwave imaging spectrometer, by spectrometer to ginseng Detection, can obtain a series of data during Ginseng Root Powder pattern detection, by processing, obtain observing obvious spectrogram.
(4) spectroscopic data is arranged and pre-processed:Obtained spectroscopic data is averaging processing, and utilizes The Good data transfer between the softwares of Unscrambler 9.7 and Microsoft Office, to obtained sample light Spectrum is pre-processed and utilizes PLS founding mathematical models.
(5) inspection of gained mathematical modeling:The ginseng soap of forecast sample can be obtained using mathematical modeling obtained above Glycosides content prediction value, and forecast sample is tested to obtain actual value, checking mathematical modulo is compared by predicted value and actual value The predictive ability of type.
Spectra collection equipment is shortwave imaging spectrometer in above-mentioned steps (2).
Spectra collection software is the ENVI softwares with remote sensing image processing function in above-mentioned steps (3).
The mathematical modeling established in above-mentioned steps (4) is primarily directed to total saposins concentration, and for different information compared with Suitable optimal preprocess method is different, is standard normal variable for the optimal pretreatment mode of Ginseng Root Powder total saposins concentration Conversion combines second-order differential spectroscopic data preprocess method.
It is to calculate the residual sum between the predicted value of gained and actual value to mathematics model verification method in above-mentioned steps (5) Relative error, the reliability of evaluation gained model.
The invention has the advantages that:The most fast sample rate of shortwave imaging spectrometer is 1ms, 1000 width spectrum of storage per second Figure, is the application of a high speed processing, and establishes forecast model by analyzing ginsenoside data, as long as the unknown sample collection The spectral information of product can obtain corresponding predicted value by forecast model, and empirical tests precision of prediction meets the requirements.This hair The detection of bright content of ginsenoside, fast with analysis process and impracticable chemical reagent, it is a variety of not produce waste and pollution etc. Advantage.
Embodiment
The shortwave imaging spectrometer that the present invention is produced using Changchun Institute of Optics, Fine Mechanics and Physics, CAS, Comprehensive foregoing inventive method and requirement, carry out spectrum extraction, spectra collection is respectively to test set and forecast set sample ENVI spectra collection softwares with remote sensing image processing function, all spectroscopic data information processings are all to apply CAMO companies The data processing software The Unscrambler 9.7 of exploitation.
A kind of method based on shortwave imaging spectral technology detection ginseng content, this method can be realized to ginsenoside Content carries out Non-Destructive Testing, and this method comprises the following steps:
(1) testing sample is chosen:Material selection Ginseng Root Powder chooses 36 samples the most total, at this as detection object Centre selects 24 and is used as test set sample, and 12 are forecast set sample, carries out number consecutively to test set and forecast set respectively And pack and give over to detection.
(2) spectral information is gathered:
(2.1) preparation before collecting sample spectrum:First open spectrometer to preheat 20 minutes by it, there is stable light The sample spectra that source temperature can just make next to survey has relatively stable wave band, then shortwave imaging spectrometer and computer phase Connection, forms complete on-line detecting system, sets corresponding parameter, environment is handled, make in gatherer process not Disturbed by environment, then reference white plate is put into detection platform, the position adjusted between blank and light source is beneficial to light intensity Sensitive change occurs for spectrum without regard to the position of spilling, the reference information that this information is gathered as sample information, and Now the distance between blank and light source are recorded, in case subsequent detection uses.Obtain the correlation test information of sample.
(2.2) the spectral information collection of sample:Reference white plate is removed, is put into the testing sample of 24 test sets, is adjusted The blank that the distance between testing sample and light source and previous step are recorded is equal with the distance between light source, other ginsengs Number gathers spectral information at the two of each sample, then utilizes the good of shortwave imaging spectrometer respectively with above Imaging function, records done experiment process, next just needs to utilize ENVI spectra collection softwares, the experiment institute before Obtain related data to import in ENVI softwares, corresponding spectrogram is obtained according to data.
(3) content of ginsenoside stechiometry measures:Precision weighs reference substance ginsenoside 10.5mg, is placed in 10ml appearances In measuring bottle, dissolved with methanol and be diluted to scale, measure different amounts of ginsenoside Re's reference substance solution, using deionized water as sky White sample, 5% vanillic aldehyde glacial acetic acid solution 0.5ml and 70% aqueous sulfuric acid 5.0ml are separately added into, are placed in 60 DEG C of waters bath with thermostatic control and add Hot 15min, then water-bath cooling 10min, places 10min again at room temperature.With TU-1810 types ultraviolet-uisible spectrophotometer in Absorption value is determined at 544nm wavelength and draws out standard curve.Gained regression equation is:Y=0.47998+2.83571X, and by Normal equation obtains corresponding total Ginsenosides Content.
(4) analysis testing result establishes forecast model:
(4.1) mathematical modeling of Ginseng Root Powder saponin concentrations is established, finds suitable preprocess method, will be counted through chemistry It is as shown in table 1 that amount learns 36 Ginseng Root Powder saponin contents statistics that measurement obtains.
The Ginseng Root Powder saponin content statistical form of table 1
As shown in Table 1, between 58.48-63.96, average value is 24 ginseng Powder samples saponin contents of test set 60.84, standard deviation 1.2;Between 59.85-63.16, average value is 12 ginseng Powder samples saponin contents of forecast set 60.89, standard deviation 1.05;And for 36 total sample saponin contents between 58.476-63.957, average value is 60.834.The characteristics of content of ginsenoside is very abundant is also demonstrated from analysis above.
(4.2) next spectroscopic data is pre-processed, denoising Processing, light path correction process is carried out to data respectively It is as shown in table 2 with differential process and combined treatment, data handling procedure.Find out from data processing:By Moving After the smooth two kinds of denoising Processings of average and S-G convolution, its modelling effect is also just said not as good as the model without denoising Processing Understand that the removal built in ENVI spectra collection softwares can be good at eliminating influence of noise by functions such as noise and flare corrections, So denoising Processing need not be carried out when being pre-processed to spectroscopic data;But by analysis it can be found that the pre- place of light path correction Reason and differential pretreating effect or obvious, but RMSEP>RMSEC, prediction effect or undesirable;For their 4 Kind combination pretreatment, is further explored, and the spectroscopic data that discovery standard normal variable conversion combines second-order differential is located in advance Reason method coefficient of determination (R2=0.9972) it is of a relatively high, correction root-mean-square error (RMSEC=0.0628) and prediction root mean square Error (RMSEP=1.5268) is relatively small, and model prediction ability is more prominent, better.So better suited spectroscopic data Preprocess method is that standard normal variable conversion combines second-order differential.
The Ginseng Root Powder saponin content preprocess method statistical form of table 2
(4.3) foundation of mathematical modeling is carried out, selection should with the optimal data after most suitable preprocess method processing It is modeled with PLS and records the model measurement index under each model.
(5) Ginseng Root Powder saponin content forecast model detects:Spectroscopic data carries out PLS and built after best mode pre-processes Mould.First have to carry out the determination of number of principal components, in order to avoid omitting, first obtain the prediction residual absolute value under each component number, people Join powder saponin content number of principal components histogram corresponding with prediction residual absolute value.It can be seen that when number of principal components is 8, Its prediction residual absolute value is minimum, and the forecast model of foundation is also more accurate, and predictive ability is also stronger.So determine model Number of principal components is 8.Using the saponin content of 12 Ginseng Root Powder forecast set samples of PLS model predictions of above-mentioned foundation, obtain pre- Survey the predicted value scatter diagram corresponding with actual value of collection sample.Forecast set Ginseng Root Powder sample is in total saposins concentration PLS forecast models Under obtained predicted value and actual value statistical form it is as shown in table 3.And calculate residual sum relative error.
The Ginseng Root Powder saponin content forecast set sample actual value of table 3 and predicted value statistical form
By the actual value and predicted value statistical form of Ginseng Root Powder saponin content above it can be calculated that forecast set 12 Residual error (actual value-residual values) absolute value sum of Ginseng Root Powder sample is 13.384, and the statistical result in table 3 is built Corresponding residual distribution figure is found.The residual values of most samples are ± 0.4 in the range of this, and this residual values pair The relative error answered is 3.51%, and this result meets the requirement of ginseng quality's accuracy of detection, so this model meets actual market The demand of upper detection content of ginsenoside, can be used for the detection of content of ginsenoside.It is comprehensive foregoing to forecast set judgement system Checking of the test on multi-tenns such as number, root-mean-square error, residual distribution, relative error index to model, shows forecast set sample predictions Value is higher with actual value correlation, and predicted value and actual value contrast find that both are closer to numerical value, illustrate model prediction Ability is good, and prediction is reliable, and the method substantially meets requirement of ginseng quality's on-line checking to content of ginsenoside.
The present invention and specific embodiment are simply described by above description, this is simply to this invention The substantially description of implementation thinking, but this is not the absolute execution sequence of method.

Claims (5)

1. a kind of method based on shortwave imaging spectral technology detection content of ginsenoside, it is characterised by that it is included and walked Suddenly:
(1) sample needed for detection is prepared:Pulverization process, choosing are carried out to fresh ginseng using LD-Y400A high speed Universal pulverizer 24 test set samples and 12 forecast set sample totally 36 samples, and being numbered successively are taken, pack preserves.
(2) preparation before the collection of spectral information and collection:
(2.1) half-light spectrum is deducted:The equipment for gathering spectral information is connected, the light and temperature sent when light source is gently steady After fixed, the curve of spectrum now is gathered, the half-light spectrum of this environment is deducted, spectra collection is had a good camera bellows spectrum base Plinth.
(2.2) reference spectra is stored:After dark spectral subtraction, being put into reference to blank in spectra collection area, progress reference light The collection of spectrum, platform regulation the distance between blank and light source are moved up and down, when spectral intensity curve is beated, without excessive without obvious When going out, what is obtained is exactly with reference to the curve of spectrum, and now the distance between blank and light source are just about progress sample and adopted Required distance during collection.
(2.3) collection of spectral information:The Ginseng Root Powder sample that will be detected is placed on lifting platform, and adjusts lifting platform position Putting makes the distance between collected point and light source and previous step that it is corresponding to obtain sample with reference to identical distance between blank and light source Detection data.
(3) observable spectrogram is obtained:Due to the imaging function of shortwave imaging spectrometer, by inspection of the spectrometer to ginseng Survey, a series of data during Ginseng Root Powder pattern detection can be obtained, by processing, obtain observing obvious spectrogram.
(4) spectroscopic data is arranged and pre-processed:Obtained spectroscopic data is averaging processing, and utilizes The Good data transfer between the softwares of Unscrambler 9.7 and Microsoft Office, to obtained sample light Spectrum is pre-processed and utilizes PLS founding mathematical models.
(5) inspection of gained mathematical modeling:The ginsenoside that forecast sample can be obtained using mathematical modeling obtained above is contained Predicted value is measured, and forecast sample is tested to obtain actual value, checking mathematical modeling is compared by predicted value and actual value Predictive ability.
2. a kind of method based on shortwave imaging spectral technology detection ginseng content according to claim 1, its feature exist In:Spectra collection equipment is shortwave imaging spectrometer in above-mentioned steps (2).
3. a kind of method based on shortwave imaging spectral technology detection ginseng content according to claim 1, its feature exist In:Spectra collection software is the ENVI softwares with remote sensing image processing function in above-mentioned steps (3).
4. a kind of method based on shortwave imaging spectral technology detection ginseng content according to claim 1, its feature exist In:The mathematical modeling established in above-mentioned steps (4) is primarily directed to total saposins concentration, and better suited for different information Optimal preprocess method is different, is standard normal variable conversion knot for the optimal pretreatment mode of Ginseng Root Powder total saposins concentration Close second-order differential spectroscopic data preprocess method.
5. a kind of method based on shortwave imaging spectral technology detection ginseng content according to claim 1, its feature exist In:In above-mentioned steps (5) to mathematics model verification method be calculate gained predicted value and actual value between residual sum it is relative Error, it is capable of the reliability of model obtained by rational evaluation.
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Application publication date: 20171110