CN101303294A - Application method of near-infrared on-line test technology in Chinese medicine Yiqing granule production - Google Patents
Application method of near-infrared on-line test technology in Chinese medicine Yiqing granule production Download PDFInfo
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Abstract
The present invention relates to a method of application of near infrared on-line measurement technique in the production of the Chinese traditional medicine Yiqing granules, which can effectively solve the problem of inefficient quality analysis and waste of raw material of the Chinese traditional medicine Yiqing granules in the prior art; the technical scheme is: collecting a sample of raw material Baikal skullcap root, a sample of Baikal skullcap root extract and a Yiqing granules sample; scanning the near infrared absorption spectrum of the samples with a near infrared spectrograph to obtain the spectroscopic data; measuring the quality content and taking the quality content as a reference value; preprocessing the spectroscopic data and establishing a multi-element correction model for the near infrared spectrum with a PLS method in chemometrics; analyzing the samples to be analyzed with the established quantitative model, crushing the samples, and scanning the near infrared spectrum to obtain a spectrogram; abstracting a characteristic spectrum and inputting the characteristic spectrum to the correction model on a computer, and obtaining the quality content from the correction model; and storing the model in the computer for future use. The entire process is short, quick, and accurate, and supports real-time on-line measurement, and can reduce the operation cost.
Description
One, technical field
The present invention relates to field of medicaments, the application process of particularly a kind of near infrared online detection technology in the Chinese medicine YIQING KELI is produced.
Two, background technology
The Chinese medicine production run is meant from put into production overall process till the product warehousing of raw material, generally need relate to the raw material evaluation, pulverizing medicinal materials, lixiviate, alcohol precipitation, stir, mix, chromatography, evaporation, dry, preparation, sterilization waits sequence units operation with packing, the mass discrepancy of raw medicinal material, production link is operated the fluctuation of lack of standardization and technological parameter, the capital causes the end product quality instability, batch differences is bigger, directly influence pharmaceutical effectiveness, understand the characteristics of Chinese medicine production run self and influence the various factors of product quality, rational critical control point and effective quality control means are very important for seeking, traditional analysis is from the workshop to the laboratory, so loaded down with trivial details process from the laboratory to the workshop again, being determined in the preparation process of each component in the solid mixture is a very critical step, adopt traditional analytical approach, as chromatogram analysis method, need take a sample, dissolving, analyze, several steps such as report the result, not only needed to spend the more time but also the scientific and technical personnel of the matter that requires to do some training very often finish, how to control the quality of product effectively and enhance productivity, saving production cost is key subjects, the tcm manufacturing process analytical technology has very important meaning for the stable uniform of ensuring drug quality, the conventional mass analysis method is consuming time longer, to personnel, instrument is had relatively high expectations, can not in time reflect active constituent content information in the product, be difficult to instruct production run, can't guarantee the stable uniform of drug quality, YIQING KELI is heat-clearing in the market, purging intense heat, various urgency are treated in detoxifcation, chronic inflammation and aphthae, the first-selected medication that pharyngitis is hemorrhage.The Western medicine microbiotic is produced chemical sproof infectious diseases definite curative effect is also arranged, no obvious toxic-side effects, have no drug resistance, take safety, bacterium is also controlled, eliminate infection symptoms fast, its principal ingredient is a scutelloside, in the YIQING KELI production run is that the laboratory is measured to content of baicalin and quality detection work always, can't on production line, in time measure, the cost height, speed is slow, influence production efficiency and progress greatly, even cause the huge wasting of resources, the mensuration of how effectively to carry out each index composition in the YIQING KELI is the technical barrier of a production always, along with computer technology, the development of process analysis technique and Chemical Measurement and application, the near-infrared spectral analysis technology application enlarges rapidly, be widely used in petrochemical complex at present, agricultural, the qualitative and quantitative analysis of food and medicine, developed into a wonderful work of express-analysis technology, compare other analytical approach, near-infrared spectral analysis technology has significant superiority: 1) a little less than the spectral absorption, make pre-service such as sample to be analyzed need not dilute, can directly analyze, easy and simple to handle, fast; 2) can be to various samples, comprise from gas to transparent or muddy liquid, from homogenate to the powder, from the solid material to the biological tissue etc., qualitative and quantitative analysis is provided fast, accurately and does not damage sample; 3) can in glass or quartz medium, penetrate, can use Optical Fiber Transmission.Near-infrared spectrum wavelength is short, do not absorbed by glass or quartz medium, can use glass or quartz sample pool container and optical fiber, near-infrared analysis fast, non-destructive, pollution-free, favorable reproducibility, so nearly infrared radiation detection apparatus is applied to YIQING KELI Chinese medicine production line Quality Control?
Three, summary of the invention
At above-mentioned situation, the present invention's purpose just provides the application process of a kind of near infrared online detection technology in the Chinese medicine YIQING KELI is produced, can effectively solve the loaded down with trivial details of traditional Chinese medicine YIQING KELI mass analysis method, the production cost height, efficient is low, the problem that wastage of material is too much, the technical scheme of its solution is, collect starting material root of large-flowered skullcap sample, the Radix Scutellariae extractum sample, the YIQING KELI sample, the utilization near infrared spectrometer scans root of large-flowered skullcap sample respectively, the Radix Scutellariae extractum sample, the near-infrared absorption spectrum of YIQING KELI sample, get spectroscopic data, and determine its quality index content, and with this as with reference to the value, pre-processed spectrum data then, PLS (partial least square method) method in the utilization Chemical Measurement is set up the polynary calibration model of near infrared spectrum, utilizing the quantitative model of setting up to treat the cls analysis sample analyzes, for medicinal material sample to be measured, pulverize, scan its near infrared light spectrogram, extract the characteristic light spectrogram by computing machine and be input to calibration model, mensuration through calibration model promptly gets its quality index content, this model is kept in the computing machine, in order to using again, whole process time is short, speed is fast, accurately, can detect by real-time online, improved work efficiency greatly, reduce operating cost.
Four, embodiment
Below the specific embodiment of the present invention is elaborated.
The present invention is realized by following steps:
1. collection sample is collected root of large-flowered skullcap sample and the Radix Scutellariae extractum sample and the YIQING KELI sample of the different places of production, zones of different, different collecting times;
2. set up model, the 80-100 mesh sieve is crossed in the sample of collecting is dry respectively, pulverizing, each sample is got 5g, and the sample powder after sieving is put into the quartz specimen cup, mixes, flatten gently, scan 6700 type near infrared spectrometers of available U.S. ThermoNicolet company with the instrument of near infrared spectrum, light source: halogen tungsten lamp, detecting device: indium gallium arsenic (InGaSn), attached diffuse reflection integrating sphere, sample spinner and quartz specimen cup, test sample mode: integrating sphere diffuse reflection, resolution: 8cm
-1Scanning times: 32 times, sweep limit: 12000-4000cm
-1Room temperature: 25 ℃-30 ℃ serves as with reference to repeatedly scanning, gathering the spectroscopic data of each sample with built-in background, each sample is got two parts, every part of triplicate, averaging is absorption value, obtains the near infrared spectrum of sample sets, therefrom choose most of sample as calibration set, be used to set up the spectrum correction model, remaining sample is as the checking collection, in order to the extrapolability of evaluation model; Determine the starting material root of large-flowered skullcap in the calibration set, Radix Scutellariae extractum (YIQING KELI intermediate), YIQING KELI quality of the pharmaceutical preparations index content, be worth in contrast, pre-processed spectrum data then, NIR spectrum is through pre-service such as single order or second-order differential, the filtering of Norris derivative, level and smooth, the polynary scatter correction of Savitzky-Golay or standard canonical transformations, and the selection range of wavelengths, PLS (partial least square method) method in the utilization Chemical Measurement is set up the polynary calibration model of near infrared spectrum;
3. optimize and check the performance of calibration model, each modeling parameters of loop optimization, to determine best parameter, the precision accuracy that collects testing model then with checking, the index of evaluation model performance has related coefficient (R), calibration set mean square deviation (Root Mean Square Error of Calibration, RMSEC), and checking collection mean square deviation (RootMean SquareError of Validation, RMSEV);
4. tested collection sample determination, the near infrared spectrum of collection sample is with the content of the near infrared spectrum calibration model measurement sample of setting up.
Embodiment 1:
Said sample is the root of large-flowered skullcap, and the mensuration of its raw material quality index is realized by following steps:
(1), the root of large-flowered skullcap sample of selecting 93 different places of production, different collecting time to gather, see Table 1,
The table 1 radix scutellariae medicinal materials place of production and lot number
The root of large-flowered skullcap sample that 93 different places of production, different collecting time are gathered is dry down at 40 ℃, pulverize, cross 100 mesh sieves, sample powder after getting 5g and sieving is put into the quartz specimen cup, mix, flatten gently, instrument with near infrared spectrum scans, 6700 type near infrared spectrometers of available U.S. ThermoNicolet company, light source: halogen tungsten lamp, detecting device: indium gallium arsenic (InGaSn), attached diffuse reflection integrating sphere, sample spinner and quartz specimen cup, test sample mode: integrating sphere diffuse reflection, resolution: 8cm
-1Scanning times: 32 times, sweep limit: 12000-4000cm
-1, room temperature: 25 ℃-30 ℃ serves as that reference repeatedly scans with built-in background, gathers the spectroscopic data of each sample, and each sample is got two parts, every part of triplicate, and averaging is absorption value;
(2), the foundation of radix scutellariae medicinal materials detection by quantitative model
1), the foundation of water content detection model
The assay of A, moisture, because the root of large-flowered skullcap is not for containing or contain the medicinal material of a spot of volatile ingredient, therefore " first method (oven drying method) in an appendix IX of the Chinese pharmacopoeia H aquametry is ground into particle and the fragment that diameter is no more than 3mm to radix scutellariae medicinal materials respectively, and is standby to adopt version in 2005; Get root of large-flowered skullcap sample 4g, be tiled in the flat measuring cup that is dried to constant weight, thickness is no more than 5mm, opens bottle cap 100～105 ℃ of dryings 5 hours, and bottle cap is built, in the dislocation exsiccator, cooled off 30 minutes, again 100～105 ℃ of dryings 1 hour, cooling, weigh, extremely double difference of weighing is no more than till the 5mg; According to the weight that subtracts mistake, calculate water cut in the root of large-flowered skullcap sample, result such as following table 2:
Table 2 93 duplicate samples determination of moisture results
The moisture distribution uniform of 93 batches of root of large-flowered skullcap crude drugs as can be seen from Table 2, moisture is 7.05%-17.10%, meets the basic demand of near infrared modeling;
The pre-service of B, spectroscopic data
Table 6 carries out multiple RMSECV and the R that handles the back model for the spectroscopic data analysis
2Comparison, as can be seen from Table 6, RMSECV and R that the different preprocessing procedures of index composition is obtained
2Remarkable difference is arranged, wherein best with Multiplicative Scattering Correction (MSC multiple scatter correction) treatment effect, MSC can reduce in the experimentation factors such as sample particle size, homogeneity to the influence of near infrared spectrum, original spectrum is carried out more can truly reflect the spectral information of index components meticulously after the pre-service of necessity;
Preprocess method was to RMSECV and R when table 6 adopted the PLS modeling
2Influence
The selection of C, modeling spectral coverage
Although the PLS method can be handled full spectrum information, but result from original near infrared light spectrogram and table 7 cross validation, before the modeling spectral band is screened, can avoid introducing too much redundant information, also can avoid because narrower some the necessary information of losing of band selection, improve model performance, improve computing velocity, the pairing best band scope of moisture is 7502.2-4246.8cm
-1
The selection of table 7 spectral range is to RMSECV and R
2Influence
The foundation of D, water and basis weight model
The PLS method is carried out data processing in the utilization Bruker OPUS/QUANT2 quantitative analysis software, and wherein 83 duplicate samples are as the correcting sample collection, and 10 duplicate samples are carried out internal chiasma checking RMSECV=0.458, R as the prediction sample sets with the correcting sample collection
2=0.943, determine that best number of principal components is 10, the absolute deviation between near infrared spectroscopy measured value and the actual value is between ± 1.1%;
E, water and basis weight verification of model
From all 93 duplicate samples, extract 10 duplicate samples arbitrarily out and form the verification sample collection, the model of setting up is tested result such as table 8;
Table 8 inspection set sample predicts the outcome
Learn that by last table verification sample ensemble average absolute deviation is 0.1059, mean relative deviation is 2.60%, and the foundation of model is successful as can be seen, and it is comparatively accurate to predict the outcome;
2) foundation of root of large-flowered skullcap crude drug alcohol extract detection model
A, the mensuration of root of large-flowered skullcap crude drug alcohol extract is with " method of Chinese pharmacopoeia version in 2005 is measured the alcohol extract (hot dipping) of the root of large-flowered skullcap, gets root of large-flowered skullcap crude drug powder 2g, put in the conical flask of 100～250ml, add mass concentration and be 70% ethanol 50ml, claim to decide weight, leave standstill 1 hour after, the continuous backflow condenser pipe, be heated to boiling, and keep little and boiled 1 hour, put cold after, take off conical flask, close plug claims to decide weight again, is that 70% ethanol is supplied the weight that subtracts mistake with mass concentration, shake up, filter with dry filter, measure filtered fluid 25ml, put in the dry evaporating dish, behind evaporate to dryness in the water-bath, in 105 ℃ of dry 3h, put and cool off 30min in the exsiccator, claim to decide weight rapidly, with the content of alcohol extract in the dry product calculating root of large-flowered skullcap sample, result such as table 3:
93 parts of root of large-flowered skullcap samples of table 3 alcohol extract result
The alcohol extract content distribution of 93 batches of root of large-flowered skullcap crude drugs is more even as can be seen from Table 3, and alcohol extract content is 34.42%-56.00%, meets the basic demand of near infrared modeling;
The pre-service of B, spectroscopic data
Table 9 carries out multiple RMSECV and the R that handles the back model for the spectroscopic data analysis
2Comparison, as can be seen from the table, RMSECV and R that the different preprocessing procedures of index composition is obtained
2Remarkable difference is arranged, wherein best with Vector Normalization (vector normalization) treatment effect, original spectrum is carried out more can truly reflect the spectral information of index components meticulously after the pre-service of necessity;
Preprocess method was to RMSECV and R when table 9 adopted the PLS modeling
2Influence
The selection of C, modeling spectral coverage
Handle full spectrum information with same PLS method, but because the index composition difference of being surveyed, the structure of composition is also different, therefore need to select different wave bands, can be by selecting proper wave band, make the model performance of foundation better, so the pairing best band scope of extract content is 11995.9-7498.4cm
-1And 5450.2-4246.8cm
-1
The selection of table 10 spectral range is to RMSECV and R
2Influence
The foundation of D, extract quantitative model
The PLS method is carried out data processing in the utilization Bruker OPUS/QUANT2 quantitative analysis software, and wherein 83 duplicate samples are as the correcting sample collection, and 10 duplicate samples are carried out internal chiasma checking RMSECV=1.66, R as the prediction sample sets with the correcting sample collection
2=0.9203, determine that best number of principal components is 7, the absolute deviation between near infrared spectroscopy measured value and the actual value is between-4% and 3.5%;
The checking of E, extract quantitative model
From all 93 duplicate samples, extract 10 duplicate samples arbitrarily out and form the verification sample collection, the model of setting up is tested, result such as table 11,
Table 11 inspection set sample predicts the outcome
Can be verified the ensemble average absolute deviation as calculated is 0.2814, and mean relative deviation is 2.11%, is successful with the foundation of finding out model, and it is comparatively accurate to predict the outcome;
3), the foundation of content of baicalin detection model in the root of large-flowered skullcap crude drug
The mensuration of content of baicalin in A, the root of large-flowered skullcap crude drug is with " the high-efficient liquid phase technique method of Chinese pharmacopoeia version in 2005 is carried out assay to radix scutellariae medicinal materials, and chromatographic condition and system suitability test are filling agent with octadecylsilane chemically bonded silica; Methanol-water-phosphoric acid (47: 53: 0.2) is a moving phase; The detection wavelength is 280nm, and number of theoretical plate calculates by the scutelloside peak and should be not less than 2500, and the preparation of reference substance solution is: take by weighing at 4 hours scutelloside reference substance of 60 ℃ of drying under reduced pressure in right amount, add methyl alcohol and make the solution that every 1ml contains 60 μ g, promptly; The preparation of root of large-flowered skullcap sample solution is: get the root of large-flowered skullcap crude drug powder 0.3g that test product is used, it is fixed to claim, adds mass concentration and be 70% ethanol 40ml, reflux 3 hours after the cooling, filters, filtrate is put in the 100ml volumetric flask, is 70% ethanol gradation washing container and residue with mass concentration, and washing lotion is filtered in the same volumetric flask, add mass concentration and be 70% ethanol to 100ml, shake up, measure 1ml, put in the 10ml volumetric flask, add methyl alcohol to 10ml, shake up, promptly; Determination method is: draw each 10 μ l of reference substance solution and root of large-flowered skullcap sample solution respectively, inject liquid chromatograph, measure, promptly; Measurement result such as table 5:
The content of baicalin of table 5 93 duplicate samples
The content of baicalin distribution uniform of 93 batches of root of large-flowered skullcap crude drugs as can be seen from Table 5, content of baicalin is 3.06%-20.19%, meets the basic demand of near infrared modeling;
The pre-service of B, spectroscopic data
Table 10 carries out multiple RMSECV and the R that handles the back model for the spectroscopic data analysis
2Comparison, as can be seen from the table, RMSECV and R that the different preprocessing procedures of index composition is obtained
2Remarkable difference is arranged, wherein best with MSC (polynary scatter correction) treatment effect, original spectrum is carried out more can truly reflect the spectral information of index components meticulously after the pre-service of necessity;
Preprocess method was to RMSECV and R when table 12 adopted the PLS modeling
2Influence
The selection of C, modeling spectral coverage
What adopt is the analysis software that near infrared spectrometer carries, and it will be from 12000cm
-1-4000cm
-1All band scanning combines the basic value of sample with near infrared spectrum, select suitable wave band automatically, and the pairing best band scope of extract content is 7502.2-4246.8cm
-1
The selection of table 13 spectral range is to RMSECV and R
2Influence
The foundation of D, scutelloside quantitative model
The PLS method is carried out data processing in the utilization BrukerOPUS/QUANT2 quantitative analysis software, and wherein 83 duplicate samples are as the correcting sample collection, and 10 duplicate samples are carried out internal chiasma checking RMSECV=1.29, R as the prediction sample sets with the correcting sample collection
2=0.9061, determine that best number of principal components is 10, the absolute deviation between near infrared spectroscopy measured value and the actual value is between 2.8% and-2.2%;
The checking of E, scutelloside quantitative model
From all 93 duplicate samples, extract 10 duplicate samples arbitrarily out and form the check sample collection, model is tested result such as table 14:
Table 14 inspection set sample predicts the outcome
Can obtain the forecast set mean absolute deviation as calculated is 0.0995, and mean relative deviation is 2.47%, and the foundation of model is successful as can be seen, and it is comparatively accurate to predict the outcome;
The quality control of raw material is the source of drug production process quality control, the quality control of Chinese crude drug, except carrying out medicinal material GAP management, for Chinese medicine manufacturing enterprise, in order to guarantee the stable uniform of product quality, before raw material puts into production, also must put screening in order to raw medicinal material, comprise the medicinal material real and fake discrimination, the control medical material quanlity is checked the purity of medicinal material etc.
Set up in the present embodiment based on the rapid assay methods of near-infrared spectral analysis technology content of baicalin, moisture, extract content in the radix scutellariae medicinal materials, result of study shows that the rapid analysis of the near-infrared spectral analysis technology of building is suitable for the fast measuring of radix scutellariae medicinal materials total quality index.
Embodiment 2: said sample is Radix Scutellariae extractum (a YIQING KELI intermediate), and the mensuration of its quality index is realized by following steps:
(1) 60 parts of Radix Scutellariae extractums are pulverized in the collection of Radix Scutellariae extractum near infrared spectrum, cross 100 mesh sieves, sample powder after getting 5g and sieving is put into the quartz specimen cup, mixes, and flattens gently, instrument with near infrared spectrum scans, 6700 type near infrared spectrometers of available U.S. ThermoNicolet company, light source: halogen tungsten lamp, detecting device: indium gallium arsenic (InGaSn), attached diffuse reflection integrating sphere, sample spinner and quartz specimen cup, test sample mode: integrating sphere diffuse reflection, resolution: 8cm
-1Scanning times: 32 times, sweep limit: 12000-4000cm
-1, room temperature: 25 ℃-30 ℃ serves as that reference repeatedly scans with built-in background, gathers the spectroscopic data of each sample, and each sample is got two parts, every part of triplicate, and averaging is absorption value;
(2) foundation of Radix Scutellariae extractum quantitative model
1) foundation of water content detection model
The assay of A, moisture
Because therefore Radix Scutellariae extractum adopts version " first method (oven drying method) in an appendix IXH of the Chinese pharmacopoeia aquametry in 2005 for not containing the medicinal material of volatile ingredient;
Radix Scutellariae extractum is pulverized, crossed 100 mesh sieves, standby, get Radix Scutellariae extractum powder 2g, be tiled in the flat measuring cup that is dried to constant weight, thickness is no more than 5mm, open bottle cap 100～105 ℃ of dryings 5 hours, bottle cap is built, in the dislocation exsiccator, cooled off 30 minutes, again 100～105 ℃ of dryings 1 hour, cooling, weigh, extremely double difference of weighing is no more than till the 5mg, according to the weight that subtracts mistake, calculate water cut (%) in the Radix Scutellariae extractum, determination of moisture result such as following table 15:
60 parts of Radix Scutellariae extractum samples of table 15 moisture measurement result
The moisture distribution uniform of 60 batches of Radix Scutellariae extractums as can be seen from Table 15, moisture is 1.8137%-7.3500%, meets the basic demand of near infrared modeling;
B, spectrogram preprocess method are selected
Table 17 carries out multiple RMSECV and the R that handles the back model for the spectroscopic data analysis
2Comparison, as can be seen from Table 19, RMSECV and R that the different preprocessing procedures of index composition is obtained
2Remarkable difference is arranged, wherein best with MSC+First Derivative processing, original spectrum is carried out more can truly reflect the spectral information of index components meticulously after the pre-service of necessity;
Preprocess method was to RMSECV and R when table 17 adopted the PLS modeling
2Influence
The selection of C, modeling spectral coverage
Handle full spectrum information with same PLS method, but because the index composition difference of being surveyed, the structure of composition is also different, therefore need to select different wave bands, by selecting proper wave band, the model performance of setting up is better, to discover that the pairing best band scope of moisture is 7197.04-4481.76cm in the medicinal extract
-1
The selection of table 18 spectral range is to RMSECV and R
2Influence
The foundation of water and basis weight model in D, the medicinal extract
The PLS method is carried out data processing in the utilization BrukerOPUS/QUANT2 quantitative analysis software, and wherein 53 duplicate samples are as the correcting sample collection, and 7 duplicate samples are carried out internal chiasma checking RMSECV=1.66, R as the verification sample collection with the correcting sample collection
2=0.9203, determine that best number of principal components is 7;
Water and basis weight verification of model in E, the medicinal extract
From all 60 duplicate samples, extract 7 duplicate samples arbitrarily out and form the verification sample collection, the model of setting up is tested result such as table 19:
Table 19 inspection set sample predicts the outcome
Can be verified the ensemble average absolute deviation as calculated is 0.0371, and mean relative deviation is 1.16%, and the foundation of model is successful as can be seen, and it is comparatively accurate to predict the outcome;
2) foundation of content of baicalin detection model
The HPLC of A, content of baicalin measures
Chromatographic condition and system suitability test are filling agent with octadecylsilane chemically bonded silica, are moving phase with methyl alcohol-0.2mol/L phosphate sodium dihydrogen buffer solution (with phosphorus acid for adjusting pH value to 2.7) (42: 58); The detection wavelength is 275nm, and number of theoretical plate calculates by the scutelloside peak should be not less than 5000;
The preparation of reference substance solution takes by weighing scutelloside reference substance 12.5mg, puts in the 250ml volumetric flask, adds methyl alcohol 10ml dissolving, is diluted with water to 250ml, shakes up, and promptly gets (containing scutelloside 50 μ g among every 1ml);
The scutelloside porphyrize is got in the preparation of scutelloside solution, gets 30mg, puts in the 100ml volumetric flask, adds methyl alcohol 10ml, sonicated (power 250W, frequency 50kHz) 10 minutes, and after the cooling, thin up shakes up to 100ml, and is centrifugal, gets supernatant, promptly;
Determination method is drawn each 10 μ l of reference substance solution and scutelloside solution respectively, injects liquid chromatograph, measures, promptly; The content of baicalin measurement result is shown in table 16 in the Radix Scutellariae extractum:
60 parts of Radix Scutellariae extractum samples of table 16 content of baicalin measurement result
Content of baicalin distribution uniform in the 60 batches of Radix Scutellariae extractums as can be seen from Table 16, content of baicalin is 8.1124%-23.6836%, meets the basic demand of near infrared modeling;
The pre-service of B, spectrum
In the gatherer process of near infrared spectrum; through regular meeting because the difference of state, sample state and the measuring condition of instrument causes the trickle variation of near infrared spectrum generation; can be proofreaied and correct it by spectrum is carried out pre-service, table 20 is RMSECV and the R when carrying out modeling with several preprocessing procedures
2Value, as can be seen from the table, RMSECV and R that the different preprocessing procedures of index composition is obtained
2Remarkable difference is arranged, wherein best with Straight Line Subtraction treatment effect, original spectrum is carried out more can truly reflect the spectral information of index components meticulously after the pre-service of necessity;
Preprocess method was to RMSECV and R when table 20 adopted the PLS modeling
2Influence
The selection of C, modeling spectral coverage:
The RMSECV and the R of each the wave band correspondence from table 21
2Value as can be seen: the pairing best band scope of the content of baicalin in the Radix Scutellariae extractum is 6990.0-4050.0cm
-1
The selection of table 21 spectral range is to RMSECV and R
2Influence
The foundation of D, scutelloside quantitative model
The PLS method is carried out data processing in the utilization Bruker OPUS/QUANT2 quantitative analysis software, and wherein 53 duplicate samples are as the correcting sample collection, and 7 duplicate samples are carried out internal chiasma with the correcting sample collection and tested RMSECV=0.262, R as the verification sample collection
2=0.9944, determine that best number of principal components is 10;
The checking of E, scutelloside quantitative model
From all 60 duplicate samples, extract 7 duplicate samples arbitrarily out and form the verification sample collection, model is tested result such as table 22;
Table 22 inspection set sample predicts the outcome
Can be verified the ensemble average absolute deviation as calculated is 0.2502, mean relative deviation is 1.84%, the foundation of model still is success as can be seen, and the near infrared spectrum predicted value can be approached the measured value of HPLC accurately, illustrates that the near infrared spectrum quantitative model has good predictive ability;
The main evaluation index of Chinese medicine dry extract quality at first is its active constituent content that includes, and is main at present with HPLC method mensuration.As previously mentioned, the HPLC method needs a large amount of loaded down with trivial details pre-treatment work, the reagent of costliness and skilled experimenter, is difficult to realize fast measuring.In addition, moisture also is the evaluation index of Chinese medicine dry extract quality-critical.Excess moisture content not only influences its biologically active and medical value, also may cause medicine to go mouldy or hydrolysis etc. takes place, the curative effect of medicine is weakened, the storage time shortens, therefore all to have strict control to require present stage the most frequently used determination of moisture method to the content of moisture in the medicine be toluene method and dry weight-loss method to various countries' pharmacopeia, but above-mentioned experimental technique condition harshness, the process complexity, and it is more time-consuming, the near infrared spectrum stability of characteristics, contain much information, the Chinese medicine dry extract is being carried out aspect the total quality evaluation very big potentiality are arranged.Especially hydrone has very strong frequency multiplication of some characteristics and sum of fundamental frequencies absorption band in the near infrared spectrum district, and the frequency multiplication of other various molecules and sum of fundamental frequencies absorb relative a little less than, this makes near-infrared spectral analysis technology have advantage in that the moisture in the dry extract is carried out accurate context of detection.
Present embodiment has been set up based on near-infrared spectral analysis technology content of baicalin, moisture rapid assay methods in the root of large-flowered skullcap dry extract.Result of study shows that the rapid analysis of the near-infrared spectral analysis technology of building is suitable for the fast measuring of root of large-flowered skullcap dry extract total quality index.
Embodiment 3: said sample is the YIQING KELI preparation, and the mensuration of its quality index is realized by following steps:
(1) collection of YIQING KELI near infrared spectrum, the YIQING KELI sample of 50 parts of different recipe quantities of self-control is pulverized, cross 80 mesh sieves, sample powder after getting 5g and sieving, put into the quartz specimen cup, mix, flatten gently, scan 6700 type near infrared spectrometers of available U.S. ThermoNicolet company with near infrared spectrometer, light source: halogen tungsten lamp, detecting device: indium gallium arsenic (InGaSn), attached diffuse reflection integrating sphere, sample spinner and quartz specimen cup), test sample mode: integrating sphere diffuse reflection, resolution: 8cm
-1Scanning times: 32 times, sweep limit: 12000-4000cm
-1, room temperature: 25 ℃-30 ℃ serves as that reference repeatedly scans with built-in background, gathers the spectroscopic data of each sample, and each sample is got two parts, every part of triplicate, and averaging is absorption value;
(2) foundation of YIQING KELI preparation quantitative model
1), the foundation of content of baicalin detection model in the YIQING KELI
Content of baicalin is measured in A, the YIQING KELI, and chromatographic condition and system suitability test are filling agent with octadecylsilane chemically bonded silica, is moving phase with methyl alcohol-0.2mol/L phosphate sodium dihydrogen buffer solution (with phosphorus acid for adjusting pH value to 2.7) (42: 58); The detection wavelength is 275nm, and number of theoretical plate calculates by the scutelloside peak should be not less than 5000; The preparation of reference substance solution is that taking by weighing the scutelloside reference substance is 12.5mg, puts in the 250ml measuring bottle, adds methyl alcohol 10ml dissolving, is diluted with water to 250ml, shakes up, and promptly gets (containing scutelloside 50 μ g among every 1ml); The preparation of YIQING KELI sample solution is, gets the YIQING KELI sample, and porphyrize is got 0.75g, puts in the 100ml measuring bottle, add methyl alcohol 10ml, sonicated (power 250W, frequency 50kHz) 10 minutes, cooling, thin up is to 100ml, shake up, centrifugal, get supernatant, promptly; Determination method is, draws each 10 μ l of reference substance solution and YIQING KELI sample solution respectively, injects liquid chromatograph, measures, promptly; The YIQING KELI sample contains the root of large-flowered skullcap in scutelloside (C21H18011) for every bag, must not be less than 21mg; The content of baicalin measurement result is shown in table 23 in the YIQING KELI:
50 parts-clear particulate samples content of baicalin measurement result of table 23
Content of baicalin distribution uniform in 50 parts of YIQING KELI samples as can be seen from Table 23, scope is bigger, is 0.14%-1.4451%, meets the basic demand of near infrared modeling;
B, spectrogram pre-service
The original spectrum that scanning is obtained carries out spectral manipulation, carries out smoothly, and single order and second derivative are handled, and to abate the noise and the influence of baseline drift, being converted into Chemical Measurement software at last can the recognition data form; The influence certain to establishing of YIQING KELI quantitative model of different preprocess methods finally set up best calibration model after preferred; As follows, best preprocess method is: First Derivative+Msc;
Table 24: different preprocess methods are to the influence of YIQING KELI quantitative model
The selection of C, modeling spectral coverage
Determine the best modeled wave band, as shown in the table, the best modeled spectral coverage is: 6749.63～4987.02cm
-1
Table 25: different spectrums district scope is to the influence of YIQING KELI quantitative model
In Chemical Measurement software, carry out related with each index reference data that standard method obtains spectroscopic data after treatment, corresponding one by one, adopt partial least square method (PLS), set up quantitative model with Chemical Measurement software, the RMSECV value reduces after the raising of calibration model performance gradually along with the increase of main cause subnumber, and taking all factors into consideration the main cause subnumber that calibration model adopts is 15;
Unknown content of baicalin in D, the prediction YIQING KELI sample to be measured:
For YIQING KELI sample to be measured, only need YIQING KELI sample to be measured, scan its near infrared light spectrogram by above-mentioned condition, selection through corresponding spectrum pre-service and spectrum district, these are all the same with the extraction of calibration model spectral signature, spectral signature is input to calibration model, and the mensuration of process calibration model promptly obtains content of baicalin in this YIQING KELI;
Predicting the outcome of table 26 ten batch samples:
Can obtain the forecast set mean absolute deviation as calculated is-0.00239, mean relative deviation is 3.28%, the foundation of model success as can be seen, the near infrared spectrum predicted value can be approached the measured value of HPLC accurately, illustrates that the near infrared spectrum quantitative model has good predictive ability;
The quality control of pelletization is the key point of drug production process quality control, and in order to guarantee to pack the qualified of preceding product quality, stable uniform before the packing of product, also must be measured by midbody particle.
Present embodiment has been set up based on near-infrared spectral analysis technology YIQING KELI fast Determination method.Result of study shows that the rapid analysis of the near-infrared spectral analysis technology of building is suitable for the fast measuring of content of baicalin in the YIQING KELI.
In a word, the maximum strong point of the present invention is to realize sharing of data resource in whole Chinese medicine industry, though basic data must derive from classical chemical method, but, can save and repeat work in a large number, thereby the digital management of realization traditional Chinese medicine quality in case set up forecast model, later analysis will can't harm, and quick, can in the extremely short time, analyze solid and liquid, this analysis is to be based upon on the basis of the existing near-infrared analysis model system of testing sample.Spectroscopic data by collected specimens and standard spectrum data compare judges whether raw material reaches production requirement; If, then produce smoothly with conformance to standard; Then do not need to adjust if reach.The whole analytical process has realized time synchronized and place original position, harmless characteristics, make the research and the application of near-infrared spectral analysis technology stride forward major step, it will promote modernization of Chinese medicine process, quality detection work in the YIQING KELI production run is that the laboratory is measured always, can't on production line, in time measure, the cost height, speed is slow, influence production efficiency and progress greatly, even cause the huge wasting of resources, its mensuration of how effectively to carry out each index composition in the YIQING KELI is the technical barrier of a production always, the present invention uses modern technologies to solve this difficult problem, in conjunction with concrete condition, creationary will set up model with and infrared spectrum software combine and realized mensuration each index component content, guaranteed the production and the quality of YIQING KELI, meaning is huge.The quick quantitative analytic method that the inventive method utilizes near infrared spectrum to be used for Chinese medicine not only can tested indoor application, its innovative point is scene or on-line analysis in real time, can be used for the online quality monitoring in the Chinese patent drug production run, quality to the control Chinese patent drug has been brought into play vital role, improved Chinese patent drug analysis and detection technology level, the needs that adapted to the modernization of Chinese medicine, set up a kind of quick, easy, the analytical approach that can real-time online detects, solved the chemical pre-treatment of sample needs in traditional quantitative test, problems such as complicated operation, having improved work efficiency greatly, reduced operating cost, is the production of medicine and the creation greatly in the detection.
Claims (4)
1, the application process of a kind of near infrared online detection technology in the Chinese medicine YIQING KELI is produced is characterized in that, realized by following steps:
(1). collect sample, promptly collect root of large-flowered skullcap sample and the Radix Scutellariae extractum sample and the YIQING KELI sample of the different places of production, zones of different, different collecting times;
(2). set up model, the sample of collecting is dry respectively, pulverize, cross the 80-100 mesh sieve, each sample is got 5g, the sample powder after sieving, put into the quartz specimen cup, mix, flatten gently, scan with the instrument of near infrared spectrum, room temperature: 25 ℃-30 ℃, gather the spectroscopic data of each sample, each sample is got two parts, every part of triplicate, average and be absorption value, obtain the near infrared spectrum of sample sets, wherein most sample is used to set up the spectrum correction model as calibration set, another part is as the checking collection, in order to the extrapolability of evaluation model; Determine the starting material root of large-flowered skullcap in the calibration set, Radix Scutellariae extractum, YIQING KELI quality of the pharmaceutical preparations index content, be worth in contrast, pre-processed spectrum data then, NIR spectrum is through single order or second-order differential, the filtering of Norris derivative, level and smooth, the polynary scatter correction of Savitzky one Golay or standard canonical transformation pre-service, and the selection range of wavelengths, the PLS method in the utilization Chemical Measurement is set up the polynary calibration model of near infrared spectrum;
(3). optimize and check the performance of calibration model, each modeling parameters of loop optimization to determine best parameter, collects the precision accuracy of testing model then with checking, and the index of evaluation model performance has related coefficient, calibration set mean square deviation, checking collection mean square deviation;
(4). tested collection sample determination, gather the near infrared spectrum of sample, measure the content of baicalin of sample with the near infrared spectrum calibration model of foundation.
2, the application process of near infrared online detection technology according to claim 1 in the Chinese medicine YIQING KELI is produced is characterized in that said sample is the root of large-flowered skullcap, and the mensuration of its quality index is to be realized by following steps:
(1), the root of large-flowered skullcap sample of selecting 93 different places of production, different collecting time to gather, the root of large-flowered skullcap sample that 93 different places of production, different collecting time are gathered 40 ℃ dry down, pulverize, cross 100 mesh sieves, sample powder after getting 5g and sieving is put into the quartz specimen cup, mixes, and flattens gently, instrument with near infrared spectrum scans, 25 ℃-30 ℃, gather the spectroscopic data of each sample, each sample is got two parts, every part of triplicate, averaging is absorption value;
(2), set up radix scutellariae medicinal materials detection by quantitative model:
1), set up the water content detection model:
The assay of A, moisture, " first method in an appendix IX of the Chinese pharmacopoeia H aquametry is ground into particle and the fragment that diameter is no more than 3mm to radix scutellariae medicinal materials respectively, and is standby to adopt version in 2005; Get root of large-flowered skullcap sample 4g and put in the flat measuring cup, thickness is no more than 5mm, opens bottle cap 100～105 ℃ of dryings 5 hours, and bottle cap is built, in the dislocation exsiccator, cooled off 30 minutes, again 100～105 ℃ of dryings 1 hour, cooling is weighed, and extremely double difference of weighing is no more than till the 5mg; Water cut is 7.05%-17.10%;
B, spectroscopic data is carried out pre-service, to reduce the influence of sample particle size in the experimentation, homogeneity factor near infrared spectrum with MSC multiple scatter correction method;
C, selection modeling spectral coverage:
Before the modeling spectral band is screened, the pairing best band scope of moisture is 7502.2-4246.8cm
-1
D, set up the water and basis weight model:
The PLS method is carried out data processing in the utilization Bruker OPUS/QUANT2 quantitative analysis software, and wherein 83 duplicate samples are as the correcting sample collection, and 10 duplicate samples are carried out internal chiasma checking RMSECV=0.458, R as the prediction sample sets with the correcting sample collection
2=0.943, determine that best number of principal components is 10, the absolute deviation between near infrared spectroscopy measured value and the actual value is between ± 1.1%.
E, water and basis weight verification of model
Extract 10 duplicate samples arbitrarily out and form the verification sample collection from all 93 duplicate samples, the model of setting up is tested, drawing verification sample ensemble average absolute deviation is 0.1059, and mean relative deviation is 2.60%;
2) set up root of large-flowered skullcap crude drug alcohol extract detection model
A, the mensuration of root of large-flowered skullcap crude drug alcohol extract, with " method of Chinese pharmacopoeia version in 2005 is measured the alcohol extract of the root of large-flowered skullcap, get root of large-flowered skullcap crude drug powder 2g, put in the conical flask of 100～250ml, add mass concentration and be 70% ethanol 50ml, claim to decide weight, after leaving standstill 1 hour, the continuous backflow condenser pipe is heated to boiling, and keep little and boiled 1 hour, put cold after, take off conical flask, close plug, claim to decide weight again, with mass concentration is that 70% ethanol is supplied the weight that subtracts mistake, shakes up, and filters with dry filter, measure filtered fluid 25ml, put in the dry evaporating dish, behind evaporate to dryness in the water-bath, in 105 ℃ of dry 3h, put and cool off 30min in the exsiccator, the content that calculates alcohol extract in the root of large-flowered skullcap sample with dry product is 34.42%-56.00%;
B, spectroscopic data is carried out pre-service with the vector method for normalizing;
C, selection modeling spectral coverage:
Wavelength band is 11995.9-7498.4cm
-1And 5450.2-4246.8cm
-1
D, set up the extract quantitative model:
The PLS method is carried out data processing in the utilization Bruker OPUS/QUANT2 quantitative analysis software, and wherein 83 duplicate samples are as the correcting sample collection, and 10 duplicate samples are carried out internal chiasma checking RMSECV=1.66, R as the prediction sample sets with the correcting sample collection
2=0.9203, determine that best number of principal components is 7, the absolute deviation between near infrared spectroscopy measured value and the actual value is set up the extract quantitative model between-4% and 3.5%;
E, checking extract quantitative model:
Extract 10 duplicate samples arbitrarily out and form the verification sample collection from all 93 duplicate samples, the model of setting up is tested, calculating checking ensemble average absolute deviation is 0.2814, and mean relative deviation is 2.11%, the foundation success of model;
3), set up content of baicalin detection model in the root of large-flowered skullcap crude drug:
The mensuration of content of baicalin in A, the root of large-flowered skullcap crude drug is with " the high-efficient liquid phase technique method of Chinese pharmacopoeia version in 2005 is carried out assay to radix scutellariae medicinal materials, and chromatographic condition and system suitability test are filling agent with octadecylsilane chemically bonded silica; The methanol-water-phosphoric acid volume ratio: be moving phase at 47: 53: 0.2; The detection wavelength is 280nm, and number of theoretical plate calculates by the scutelloside peak should be not less than 2500; The preparation of reference substance solution is: take by weighing at 4 hours scutelloside reference substance of 60 ℃ of drying under reduced pressure in right amount, add methyl alcohol and make the solution that every 1ml contains 60 μ g scutellosides; The preparation of root of large-flowered skullcap sample solution is: get root of large-flowered skullcap sample powder 0.3g, add mass concentration and be 70% ethanol 40ml, reflux 3 hours, after the cooling, filter, filtrate is put in the 100ml volumetric flask, with mass concentration 70% ethanol gradation washing container and residue, washing lotion is filtered in the same volumetric flask, adds mass concentration and be 70% ethanol to 100ml, shakes up, measure 1ml, put in the 10ml volumetric flask, add methyl alcohol, shake up to 10ml; Determination method is: draw each 10 μ 1 of reference substance solution and root of large-flowered skullcap sample solution respectively, inject liquid chromatograph, measure; Test draws the content of baicalin distribution uniform of 93 batches of root of large-flowered skullcap crude drugs, and content of baicalin is 3.06%-20.19%;
B, spectroscopic data is carried out pre-service with the many first scatter correction methods of MSC;
C, selection modeling spectral coverage:
With the analysis software that near infrared spectrometer carries, it will be from 12000cm
-1-4000cm
-1All band scanning combines the basic value of sample with near infrared spectrum, selecting the pairing best band scope of extract content is 7502.2-4246.8cm
-1
D, set up the scutelloside quantitative model:
The PLS method is carried out data processing in the utilization BrukerOPUS/QUANT2 quantitative analysis software, and wherein 83 duplicate samples are as the correcting sample collection, and 10 duplicate samples are carried out internal chiasma checking RMSECV=1.29, R as the prediction sample sets with the correcting sample collection
2=0.9061, determine that best number of principal components is 10, the absolute deviation between near infrared spectroscopy measured value and the actual value is between 2.8% and-2.2%;
E, checking scutelloside quantitative model:
Extract 10 duplicate samples arbitrarily out and form the check sample collection from all 93 duplicate samples, model is tested, can obtain the forecast set mean absolute deviation as calculated is 0.0995, and mean relative deviation is 2.47%, the foundation success of model.
3, the application process of near infrared online detection technology according to claim 1 in the Chinese medicine YIQING KELI is produced is characterized in that said sample is a Radix Scutellariae extractum, and the mensuration of its quality index is to be realized by following steps:
(1) collection of Radix Scutellariae extractum near infrared spectrum, 60 parts of Radix Scutellariae extractums are pulverized, crossed 100 mesh sieves, the sample powder after getting 5g and sieving is put into the quartz specimen cup, mix, flatten gently, scan 25 ℃-30 ℃ with the instrument of near infrared spectrum, gather the spectroscopic data of each sample, each sample is got two parts, every part of triplicate, and averaging is absorption value;
(2) set up the Radix Scutellariae extractum quantitative model:
1) set up the water content detection model:
The assay of A, moisture, adopt version " first method in an appendix IXH of the Chinese pharmacopoeia aquametry in 2005, Radix Scutellariae extractum is pulverized, cross 100 mesh sieves, standby, get Radix Scutellariae extractum powder 2g, be tiled in the flat measuring cup, thickness is no more than 5mm, open bottle cap 100～105 ℃ of dryings 5 hours, bottle cap is built, in the dislocation exsiccator, cooled off 30 minutes, 100～105 ℃ of dryings 1 hour, cooling was weighed again, extremely double difference of weighing is no more than till the 5mg, and water cut is 1.8137%-7.3500%;
B, spectrogram is carried out pre-service with MSC+ First Derivative method;
C, select as the modeling spectral coverage: wavelength band is 7197.04-4481.76cm
-1
D, set up water and basis weight model in the medicinal extract:
The PLS method is carried out data processing in the utilization BrukerOPUS/QUANT2 quantitative analysis software, and wherein 53 duplicate samples are as the correcting sample collection, and 7 duplicate samples are carried out internal chiasma checking RMSECV=1.66, R as the verification sample collection with the correcting sample collection
2=0.9203, determine that best number of principal components is 7;
E, water and basis weight model in the medicinal extract is verified, extract 7 duplicate samples arbitrarily out and form the verification sample collection from all 60 duplicate samples, the model of setting up is tested, can be verified the ensemble average absolute deviation as calculated is 0.0371, mean relative deviation is 1.16%, the modelling success;
2) set up the content of baicalin detection model
The HPLC of A, content of baicalin measures, and is filling agent with octadecylsilane chemically bonded silica, and with methyl alcohol-0.2mol/L phosphate sodium dihydrogen buffer solution, with phosphorus acid for adjusting pH value to 2.7, methyl alcohol and sodium dihydrogen phosphate volume ratio: be moving phase at 42: 58; The detection wavelength is 275nm, and number of theoretical plate calculates by the scutelloside peak should be not less than 5000;
The preparation of reference substance solution takes by weighing scutelloside reference substance 12.5mg, puts in the 250ml volumetric flask, adds methyl alcohol 10ml dissolving, is diluted with water to 250ml, shakes up, and promptly gets the reference substance solution that contains scutelloside 50 μ g among every 1ml;
The scutelloside porphyrize is got in the preparation of scutelloside solution, gets 30mg, puts in the 100ml volumetric flask, adds methyl alcohol 10ml, sonicated, and power 250W, frequency 50kHz, 10 minutes, after the cooling, thin up shakes up to 100ml, and was centrifugal, got supernatant and got scutelloside solution;
Draw each 10 μ l of reference substance solution and scutelloside solution respectively, inject liquid chromatograph, measure in the Radix Scutellariae extractum content of baicalin be 8.1124%-23.6836%;
B, spectrum is carried out pre-service with Straight Line Subtraction method;
C, selection wavelength band are 6990.0-4050.0cm
-1Be the modeling spectral coverage;
D, set up the scutelloside quantitative model
The PLS method is carried out data processing in the utilization Bruker OPUS/QUANT2 quantitative analysis software, and wherein 53 duplicate samples are as the correcting sample collection, and 7 duplicate samples are carried out internal chiasma with the correcting sample collection and tested RMSECV=0.262, R as the verification sample collection
2=0.9944, determine that best number of principal components is 10, sets up the scutelloside quantitative model;
E, the scutelloside quantitative model is verified, extract 7 duplicate samples arbitrarily out and form the verification sample collection from all 60 duplicate samples, model is tested, checking ensemble average absolute deviation is 0.2502, mean relative deviation is 1.84%, and the near infrared spectrum predicted value is approached the measured value of HPLC.
4, the application process of near infrared online detection technology according to claim 1 in the Chinese medicine YIQING KELI is produced is characterized in that said sample is the YIQING KELI preparation, and the mensuration of its quality index is realized by following steps:
(1) gathers the YIQING KELI near infrared spectrum, the YIQING KELI sample of 50 parts of different recipe quantities of self-control is pulverized, cross 80 mesh sieves, sample powder after getting 5g and sieving, put into the quartz specimen cup, mix, flatten gently, scan with near infrared spectrometer, 25 ℃-30 ℃, gather the spectroscopic data of each sample, each sample is got two parts, every part of triplicate, averaging is absorption value;
(2) set up YIQING KELI preparation quantitative model:
1), set up content of baicalin detection model in the YIQING KELI:
Content of baicalin is measured in A, the YIQING KELI, is filling agent with octadecylsilane chemically bonded silica, with methyl alcohol-0.2mol/L phosphate sodium dihydrogen buffer solution, with phosphorus acid for adjusting pH value to 2.7, methyl alcohol and sodium dihydrogen phosphate volume ratio: 42: 58, be moving phase; The detection wavelength is 275nm, and the scutelloside peak is not less than 5000; The preparation of reference substance solution is that taking by weighing the scutelloside reference substance is 12.5mg, puts in the 250ml measuring bottle, adds methyl alcohol 10ml dissolving, is diluted with water to 250ml, shakes up, and promptly gets to contain scutelloside 50 μ g among every 1ml; The preparation of YIQING KELI sample solution is, gets the YIQING KELI sample, and porphyrize is got 0.75g, puts in the 100ml measuring bottle, adds methyl alcohol 10ml, sonicated, and power 250W, frequency 50kHz, 10 minutes, cooling, thin up shakes up to 100ml, and is centrifugal, gets supernatant, promptly; Determination method is to draw each 10 μ l of reference substance solution and YIQING KELI sample solution respectively, injection liquid chromatograph, mensuration; Content of baicalin is 0.14%-1.4451% in the YIQING KELI;
B, spectrogram is carried out pre-service:
The original spectrum that scanning is obtained carries out spectral manipulation, carries out smoothly, and single order and second derivative are handled, and to abate the noise and the influence of baseline drift, being converted into Chemical Measurement software at last can the recognition data form;
C, selection 6749.63～4987.02cm
-1Be the modeling spectral coverage;
D, the sample spectral signature is input to calibration model, promptly obtains content of baicalin in this YIQING KELI through the mensuration of calibration model.
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