CN103674887A - Analysis identification method of ophiocordyceps sinensis through infrared spectrum - Google Patents
Analysis identification method of ophiocordyceps sinensis through infrared spectrum Download PDFInfo
- Publication number
- CN103674887A CN103674887A CN201310688297.0A CN201310688297A CN103674887A CN 103674887 A CN103674887 A CN 103674887A CN 201310688297 A CN201310688297 A CN 201310688297A CN 103674887 A CN103674887 A CN 103674887A
- Authority
- CN
- China
- Prior art keywords
- cordyceps sinensis
- spectrum
- infrared spectrum
- peak
- sinensis herb
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 241001248610 Ophiocordyceps sinensis Species 0.000 title claims abstract description 121
- 238000002329 infrared spectrum Methods 0.000 title claims abstract description 102
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000001228 spectrum Methods 0.000 claims abstract description 74
- 238000012360 testing method Methods 0.000 claims description 20
- 238000002835 absorbance Methods 0.000 claims description 15
- 238000001965 diffuse reflectance infrared spectroscopy Methods 0.000 claims description 13
- 238000004566 IR spectroscopy Methods 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 230000005540 biological transmission Effects 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 20
- 230000003595 spectral effect Effects 0.000 description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 241000422920 Cordyceps gunnii Species 0.000 description 8
- 238000012937 correction Methods 0.000 description 6
- 238000010606 normalization Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000010076 replication Effects 0.000 description 6
- 238000012545 processing Methods 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 230000001186 cumulative effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 241000190633 Cordyceps Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000008216 herbs Nutrition 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000221751 Claviceps purpurea Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241000130660 Hepialidae Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 206010062717 Increased upper airway secretion Diseases 0.000 description 1
- 244000304222 Melaleuca cajuputi Species 0.000 description 1
- 235000001167 Melaleuca cajuputi Nutrition 0.000 description 1
- 240000001307 Myosotis scorpioides Species 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 210000003056 antler Anatomy 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000012850 discrimination method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 230000023597 hemostasis Effects 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 208000026435 phlegm Diseases 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 235000015961 tonic Nutrition 0.000 description 1
- 230000001256 tonic effect Effects 0.000 description 1
- 229960000716 tonics Drugs 0.000 description 1
Landscapes
- Investigating Or Analysing Materials By Optical Means (AREA)
Abstract
The invention relates to the field of analytical chemistry, particularly to an analysis identification method of ophiocordyceps sinensis through an infrared spectrum, and aims to solve the technical problem that the authenticity of the existing ophiocordyceps sinensis is difficult to distinguish. In order to solve the above technical problem, the invention provides a technical scheme to rapidly and accurately distinguish ophiocordyceps sinensis. The analysis identification method through the infrared spectrum comprises the following steps: a, drawing a standard spectrum of ophiocordyceps sinensis; b, collecting an essential characteristic peak and a common characteristic peak of an infrared spectrum of ophiocordyceps sinensis; c, distinguishing the essential characteristic peak and similarity of the infrared spectrum of measured ophiocordyceps sinensis. The invention provides a novel method for rapidly and accurately distinguishing ophiocordyceps sinensis.
Description
Technical field
The present invention relates to analytical chemistry field.Specifically, the Infrared spectroscopy authentication method that relates to Cordyceps sinensis herb.
Background technology
Cordyceps sinensis is that section ergot fungus cordyceps sinensis bacterium (Cordyceps sinensis (Berk.) Sacc.) colonizes in stroma on Hepialidae insect bat moth larvae and the complex of larva corpse, the effect with kidney tonifying benefit lung, hemostasis and phlegm, with ginseng, pilose antler and be called China's three large tonics.
Cordyceps sinensis growing environment is special, is mainly distributed in mesophorbium, coryphile and the alpine scrub of China's Qinghai-Tibet Platean height above sea level 3000～5000m.Qinghai, Tibet, Sichuan, Gansu and Yunnan are the major production areas of Cordyceps sinensis, and the output in Qinghai and quality occupy first of each provinces and regions, and cajaput, Golog etc. is Cordyceps of Qinghai Province main product ground.Cordyceps sinensis still can not carry out artificial culture at present, and the distributed areas of wild cordyceps are narrow and small, and natural parasitic rate is low, harsh to requirement for environmental conditions, in addition ecological disruption and predation formula in recent years excavated, and the output of Cordyceps sinensis is declined year by year, and price is constantly soaring.Therefore, on market, there is the serious fakement phenomenas such as puppet, weightening finish of mixing.Except Cordyceps sinensis, other Cordyceps sinensis fungus colonize in the complex forming on insect bodies and are also referred to as " Chinese caterpillar fungus ", and some of them are often used as the adulterant of Cordyceps sinensis, and proterties is similar and be difficult to distinguish.Therefore set up Cordyceps sinensis herb true and false product discrimination method fast and accurately, to standard market, guarantee that quality of medicinal material has very important significance.
Summary of the invention
To be solved by this invention is the technical matters that current Cordyceps sinensis herb is difficult to minute true and false.
The technical scheme that the present invention solves the problems of the technologies described above is to provide a kind of method of quick and precisely differentiating Cordyceps sinensis herb, comprises the following steps:
A, Cordyceps sinensis herb standard spectrum are drawn: the standard Cordyceps sinensis herb sample in a plurality of different places of production is pressed into respectively thin slice and carries out transmission test, and the averaged spectrum of all samples is Cordyceps sinensis herb standard spectrum;
The collection of b, the indispensable characteristic peak of Cordyceps sinensis herb infrared spectrum and the common characteristic peak of Cordyceps sinensis herb infrared spectrum;
The diffuse reflectance infrared spectroscopy peak comparison of c, tested Cordyceps sinensis herb sample and the comparison of infrared spectrum similarity: in the infrared spectrum of sample, comprise the indispensable characteristic peak of whole Cordyceps sinensis herb infrared spectrums and the more than 60% of the common characteristic peak of Cordyceps sinensis herb infrared spectrum, and the level of significance between sample spectrum and Cordyceps sinensis herb standard spectrum is that the related coefficient lower threshold of 0.01 o'clock is 0.95, and this sample is genuine piece Cordyceps sinensis herb.
Wherein, in the step a of the Infrared spectroscopy authentication method of above-mentioned Cordyceps sinensis herb, described Cordyceps sinensis herb sample is to be selected from Yushu district, Qinghai state, national main producing region, Forage Land In Guoluo Prefecture, state, Hainan and Tibet, Sichuan and area, 6, Gansu, and each provenance selection is not less than 8 uniform samples.
Wherein, in the step a of the Infrared spectroscopy authentication method of above-mentioned Cordyceps sinensis herb, described Cordyceps sinensis herb sample is by the natural drying rear pulverizing of the polypide part of Cordyceps sinensis, gets fine powder after 200 mesh sieves for examination of infrared spectrum.
Wherein, in the step a of said method, the standard Cordyceps sinensis herb sample in a plurality of different places of production is pressed into respectively thin slice and carries out transmission when test, carries out under the same conditions compressing tablet test, as spectral background with the pure potassium bromide that does not add any sample.
Wherein, in the step a of said method, the transmitance maximal value of every sample infrared spectrum and minimum value differ and should be not less than 60%.
Wherein, in the step a of said method, each sample replication 3～5 times, gets its averaged spectrum as the spectrum of this sample.
Wherein, in the step a of said method, Infrared spectrum scanning scope is 4000～400cm
-1, spectral resolution is 4cm
-1, every spectrum cumulative scan 16 times or 32 times, deducts in real time carbon dioxide and water vapor and disturbs.
Wherein, in the step b of said method, the indispensable characteristic peak of described Cordyceps sinensis herb infrared spectrum refers to the infrared spectrum absorpting peak position of comparison all samples, the indispensable characteristic peak using the absorption peak all occurring in all samples as Cordyceps sinensis herb infrared spectrum.The indispensable characteristic peak of described Cordyceps sinensis herb infrared spectrum is as shown in table 1:
The indispensable characteristic peak of table 1 Cordyceps sinensis herb infrared spectrum
| Peak numbering | Peak position mean value (cm -1） | Deviation (cm in peak position under 99% degree of confidence -1） |
| A01 | 3292 | 6.2 |
| A02 | 2926 | 2.6 |
| A03 | 1657 | 3.6 |
| A04 | 1547 | 4.1 |
| A05 | 1457 | 7.2 |
| A06 | 1083 | 2.6 |
| A07 | 1024 | 3.4 |
| A08 | 930 | 2.1 |
| A09 | 888 | 4.1 |
| A10 | 626 | 6.5 |
Wherein, in the step b of said method, the described common characteristic peak of Cordyceps sinensis herb infrared spectrum refers in the infrared spectrum absorpting peak of all samples, except indispensable characteristic peak, probability of occurrence is not less than to 80% absorption peak, as the common characteristic peak of Cordyceps sinensis herb infrared spectrum.The common characteristic peak of described Cordyceps sinensis herb infrared spectrum is as shown in table 2:
The common characteristic peak of table 2 Cordyceps sinensis herb infrared spectrum
| Peak numbering | Peak position mean value (cm -1） | Deviation (cm in peak position under 99% degree of confidence -1） |
| B01 | 2854 | 1.3 |
| B02 | 1745 | 3.9 |
| B03 | 1378 | 1.3 |
| B04 | 1249 | 5.2 |
| B05 | 1202 | 2.6 |
| B06 | 1152 | 4.9 |
| B07 | 574 | 4.9 |
| B08 | 528 | 8.5 |
| B09 | 416 | 4.4 |
Wherein, in the step c of said method, described related coefficient is calculated by following formula:
In formula 1, R
ijrepresent the related coefficient of infrared spectrum i and infrared spectrum j, x
ikand x
jkrepresentative sample i and sample j are at the absorbance at wave number k place respectively.
The present invention uses AssureID software to calculate 1800～800cm
-1in scope, the related coefficient of each sample infrared spectrum and standard spectrum, adds up the distributed area of the related coefficient of each sample infrared spectrum and standard spectrum, determines that level of significance is the related coefficient lower threshold of 0.01 o'clock.
The present invention chooses the typical sample in the different places of production, national main producing region, has determined the common characteristic peak of Cordyceps sinensis herb, has set up Cordyceps sinensis herb standard infrared spectrum, and has determined the correlation coefficient threshold of genuine piece and standard spectrum.Integrated using diffuse reflectance infrared spectroscopy peak differential method and similarity differential method, can be objective, accurate, easy, rapidly Cordyceps sinensis herb is differentiated.
In recent years, infrared spectrum extensively and the true and false that is successfully used to various Chinese crude drugs differentiate, have objective quantification, result accurate, easy and simple to handle, test the plurality of advantages such as rapid, with low cost.The present invention utilizes infra-red sepectrometry to set up the finger-print of Cordyceps sinensis herb, for the Cordyceps sinensis true and false, differentiates objective, accurate, easy, analytical approach is fast provided.
Accompanying drawing explanation
The standard spectrum of Fig. 1 Cordyceps sinensis herb sample.
Fig. 2 Cordyceps gunnii (Berk.) Berk herb infrared spectrum.
Embodiment
The Infrared spectroscopy authentication method of Cordyceps sinensis herb provided by the invention, comprises the following steps:
A, Cordyceps sinensis herb standard spectrum draw: choose 15 parts of Yushu district, Qinghai states |, the Cordyceps sinensis herb sample in 15 parts of Forage Land In Guoluo Prefectures, 15 parts of Hai Nanzhou, 15 parts of Tibet, 15 parts of Sichuan and 8 parts of Gansu, the uniform sample of each provenance selection, adopt pellet technique to carry out transmission test, the averaged spectrum of all samples is Cordyceps sinensis herb standard spectrum.
The mid-infrared spectral data processing of the present invention and Spectrum (v6) and AssureID (v4) software of analyzing use U.S. PerkinElmer company.The sample infrared spectrum initially recording is transmitance figure, comprises the spectrum baseline wander that scattering causes, the spectral intensity difference error factors that amount of samples causes, and need to be eliminated by spectrogram pre-service measures such as baseline correction, normalization.Therefore, use successively the ordinate of Spectrum software to change (transmitance is converted to absorbance), automatic baseline correction, normalization (in full spectral range, high absorbance is 1, and minimum absorbance is 0) function is processed original transmitance spectrogram.The spectrum computing function of use Spectrum software obtains the averaged spectrum of 3～5 replication spectrum of each sample, as the spectrum of this sample.According to the infrared spectrum of all samples, can calculate its averaged spectrum, as the standard spectrum of Cordyceps sinensis herb.
The collection of b, the indispensable characteristic peak of Cordyceps sinensis herb infrared spectrum and the common characteristic peak of Cordyceps sinensis herb infrared spectrum.
Use Spectrum software to read each sample diffuse reflectance infrared spectroscopy peak position, peak intensity threshold value is the strength difference minimum value of the adjacent peak valley of 0.01A(and both sides), use maximum value process (Interpolated Peak) is determined in peak position.Use the characteristic peak positions of Excel or other software analysis all samples.
The diffuse reflectance infrared spectroscopy peak comparison of c, tested Cordyceps sinensis herb sample and the comparison of infrared spectrum similarity: in the infrared spectrum of sample, comprise the indispensable characteristic peak of whole Cordyceps sinensis herb infrared spectrums and the more than 60% of the common characteristic peak of Cordyceps sinensis herb infrared spectrum, and the level of significance between sample spectrum and Cordyceps sinensis herb standard spectrum is that the related coefficient lower threshold of 0.01 o'clock is 0.95, and this sample is genuine piece Cordyceps sinensis herb.
Wherein, in the step a of the Infrared spectroscopy authentication method of above-mentioned Cordyceps sinensis herb, described Cordyceps sinensis herb sample is by the natural drying rear pulverizing of the polypide part of Cordyceps sinensis, gets fine powder after 200 mesh sieves for examination of infrared spectrum.
Wherein, in the step a of said method, the standard Cordyceps sinensis herb sample in a plurality of different places of production is pressed into respectively thin slice and carries out transmission when test, carries out under the same conditions compressing tablet test, as spectral background with the pure potassium bromide that does not add any sample.
Wherein, in the step a of said method, the transmitance maximal value of every sample infrared spectrum and minimum value differ and should be not less than 60%.
Wherein, in the step a of said method, each sample replication 3～5 times, gets its averaged spectrum as the spectrum of this sample.
Wherein, in the step a of said method, Infrared spectrum scanning scope is 4000～400cm
-1, spectral resolution is 4cm
-1, every spectrum cumulative scan 16 times or 32 times, deducts in real time carbon dioxide and water vapor and disturbs.
Wherein, in the step b of said method, the indispensable characteristic peak of described Cordyceps sinensis herb infrared spectrum refers to the infrared spectrum absorpting peak position of comparison all samples, the indispensable characteristic peak using the absorption peak all occurring in all samples as Cordyceps sinensis herb infrared spectrum.
Further, in the step b of said method, the indispensable characteristic peak of Cordyceps sinensis herb infrared spectrum has 10.
Wherein, in the step b of said method, the described common characteristic peak of Cordyceps sinensis herb infrared spectrum refers in the infrared spectrum absorpting peak of all samples, except indispensable characteristic peak, probability of occurrence is not less than to 80% absorption peak, as the common characteristic peak of Cordyceps sinensis herb infrared spectrum.
Further, in the step b of said method, the common characteristic peak of Cordyceps sinensis herb infrared spectrum has 9.
Wherein, in the step c of said method, described related coefficient is calculated by following formula:
In formula 1, R
ijrepresent the related coefficient of infrared spectrum i and infrared spectrum j, x
ikand x
jkrepresentative sample i and sample j are at the absorbance at wave number k place respectively.
In step b, the indispensable characteristic peak of Cordyceps sinensis herb infrared spectrum is in Table 3.
The indispensable characteristic peak of infrared spectrum of table 3 Cordyceps sinensis herb
In step b, the common characteristic peak of Cordyceps sinensis herb infrared spectrum is in Table 4.
The common characteristic peak of infrared spectrum of table 4 Cordyceps sinensis herb
The present invention uses AssureID software to calculate 1800～800 cm
-1in scope, the related coefficient of each sample infrared spectrum and standard spectrum, adds up the distributed area of the related coefficient of each sample infrared spectrum and standard spectrum, determines that level of significance is the related coefficient lower threshold of 0.01 o'clock.
Characteristic peak is differentiated the position of only having considered common characteristic peak, does not relate to intensity and the shape information at common characteristic peak, does not also relate to the information of other absorption peaks outside the common characteristic peak that the frequency of occurrences is higher, and needs characteristic peak number relatively more.Therefore, except above-mentioned according to common characteristic peak, differentiate, also need to differentiate according to infrared spectrum similarity, namely with correlation coefficient process, the global similarity degree between sample spectra and standard spectrum is carried out to single quantification comparison.
In the present invention, standard spectrum used is the averaging spectrum of all samples spectrum, because position and the intensity change of some absorption peaks in different samples are larger, when carrying out the discriminating of infrared spectrum similarity, has only chosen 1800～800 cm
-1spectrum in scope, this district inclusion the topmost characteristic peak of sample, and spectrum change is subject to ectocine less.Related coefficient between sample spectra and Cordyceps sinensis herb standard spectrum is carried out to statistical study, determine that level of significance is that the related coefficient lower threshold of 0.01 o'clock is 0.95.That is to say, 99% in the situation that, if testing sample is genuine piece Cordyceps sinensis herb, the related coefficient of its infrared spectrum and standard spectrum is not less than 0.95.
Embodiment 1 Cordyceps sinensis herb standard spectrum drafting, the indispensable characteristic peak of Cordyceps sinensis herb infrared spectrum and the collection of the common characteristic peak of Cordyceps sinensis herb infrared spectrum and determining of related coefficient lower threshold
1) sample source and processing
Choose 15 parts of Yushu district, Qinghai states |, the Cordyceps sinensis sample in 15 parts of Forage Land In Guoluo Prefectures, 15 parts of Hai Nanzhou, 15 parts of Tibet, 15 parts of Sichuan and 8 parts of Gansu, the uniform sample of each provenance selection.
Sample preparation is with reference to Pharmacopoeia of People's Republic of China relevant regulations, by the natural drying rear pulverizing of sample polypide part, gets fine powder after 200 mesh sieves for examination of infrared spectrum.
2) infrared spectrum instrument
In the present invention, U.S. PerkinElmer(platinum Ai Ermo is all used in all samples test) the Spectrum One Fourier transformation infrared spectrometer of company.
Sample test parameter: spectral scan scope 4000～400cm
-1, spectral resolution 4cm
-1, every spectrum cumulative scan 16 times or 32 times, deducts in real time carbon dioxide and water vapor and disturbs.
3) examination of infrared spectrum method
Sample test adopts potassium bromide (KBr) pressed disc method.Get 1～2 milligram of sample powder and 100 milligrams of spectroscopic pure potassium bromide broken grains ground and mixed in agate mortar is even, with sheeter, mixed-powder is pressed into thin rounded flakes, put into sample holder of Infrared spectrometer and carry out transmission test.With the pure potassium bromide that does not add any sample, carry out under the same conditions compressing tablet test, as spectral background.
The transmitance maximal value of every sample infrared spectrum and minimum value differ and should be not less than 60%.
Each sample replication 3～5 times, gets its averaged spectrum as the spectrum of this sample.
4) ir data is processed
This is studied mid-infrared spectral data processing and analyzes Spectrum (v6) and AssureID (v4) software that uses U.S. PerkinElmer company.
The sample infrared spectrum initially recording is transmitance figure, comprises the spectrum baseline wander that scattering causes, the spectral intensity difference error factors that amount of samples causes, and need to be eliminated by spectrogram pre-service measures such as baseline correction, normalization.Therefore, use successively the ordinate of Spectrum software to change (transmitance is converted to absorbance), automatic baseline correction, normalization (in full spectral range, high absorbance is 1, and minimum absorbance is 0) function is processed original transmitance spectrogram.
5) standard spectrum is drawn
The spectrum computing function of use Spectrum software obtains the averaged spectrum of 3～5 replication spectrum of each sample, as the spectrum of this sample.According to the infrared spectrum of all 30 samples, can calculate its averaged spectrum, as the standard spectrum of Cordyceps sinensis herb.
6) collection of the indispensable characteristic peak of Cordyceps sinensis herb infrared spectrum and the common characteristic peak of Cordyceps sinensis herb infrared spectrum
Use Spectrum software to read each sample diffuse reflectance infrared spectroscopy peak position in embodiment 1, peak intensity threshold value is 0.01 absorbance (with the strength difference minimum value of the adjacent peak valley in both sides), and use maximum value process (Interpolated Peak) is determined in peak position.Use the characteristic peak positions of Excel or all 30 samples of other software analysis.
Relatively the diffuse reflectance infrared spectroscopy peak position of all samples, has 14 absorption peaks all to occur in all samples, can be used as the indispensable characteristic peak of genuine piece Cordyceps sinensis herb infrared spectrum, as shown in table 1.
In the diffuse reflectance infrared spectroscopy peak of all samples, have 9 absorption peak probabilities of occurrence to be not less than in 24～29 sample infrared spectrums in 80%(30 sample and occur), can be used as the common characteristic peak of genuine piece Cordyceps sinensis herb infrared spectrum, as shown in table 2.
7) related coefficient lower threshold determines
Use AssureID software to calculate 1800～800cm
-1the related coefficient of each sample infrared spectrum and standard spectrum in scope, formula is as follows:
In formula, R
ijrepresent the related coefficient of infrared spectrum i and infrared spectrum j, x
ikand x
jkdistinguish representative sample i and sample j at the absorbance at wave number k place,
Add up the distributed area of the related coefficient of each sample infrared spectrum and averaged spectrum, determine that level of significance is the related coefficient lower threshold of 0.01 o'clock.
Related coefficient between sample spectra and Cordyceps sinensis herb standard spectrum is carried out to statistical study, determine that level of significance is that the related coefficient lower threshold of 0.01 o'clock is 0.95.That is to say, 99% in the situation that, if testing sample is genuine piece Cordyceps sinensis polypide herb, the related coefficient of its infrared spectrum and standard spectrum is not less than 0.95.
Embodiment 2 experiment of discerning the false from the genuine
1) sample source and processing
Commercially available Cordyceps gunnii (Berk.) Berk, numbering is respectively G1, G2, G3, G4.
Sample preparation is with reference to Pharmacopoeia of People's Republic of China relevant regulations, by the natural drying rear pulverizing of sample herb part, gets fine powder after 200 mesh sieves for examination of infrared spectrum.
2) infrared spectrum instrument
The Spectrum One Fourier transformation infrared spectrometer of U.S. PerkinElmer company is all used in all samples test.
Sample test parameter: spectral scan scope 4000～400cm
-1, spectral resolution 4cm
-1, every spectrum cumulative scan 16 times, deducts in real time carbon dioxide and water vapor and disturbs.
3) examination of infrared spectrum method
Sample test adopts potassium bromide (KBr) pressed disc method.Get 1～2 milligram of sample powder and 100 milligrams of spectroscopic pure potassium bromide broken grains ground and mixed in agate mortar is even, with sheeter, mixed-powder is pressed into thin rounded flakes, put into sample holder of Infrared spectrometer and carry out transmission test.With the pure potassium bromide that does not add any sample, carry out under the same conditions compressing tablet test, as spectral background.
The transmitance maximal value of every sample infrared spectrum and minimum value differ and should be not less than 60%.
Each sample replication 3～5 times, gets its averaged spectrum as the spectrum of this sample.
4) ir data is processed
This is studied mid-infrared spectral data processing and analyzes Spectrum (v6) software that uses U.S. PerkinElmer company.
The sample infrared spectrum initially recording is transmitance figure, comprises the spectrum baseline wander that scattering causes, the spectral intensity difference error factors that amount of samples causes, and need to be eliminated by spectrogram pre-service measures such as baseline correction, normalization.Therefore, use successively the ordinate of Spectrum software to change (transmitance is converted to absorbance), automatic baseline correction, normalization (in full spectral range, high absorbance is 1, and minimum absorbance is 0) function is processed original transmitance spectrogram.
5) Cordyceps gunnii (Berk.) Berk herb diffuse reflectance infrared spectroscopy peak gather, with the comparison of Cordyceps sinensis herb standard spectrum characteristic peak
Use Spectrum software to read each sample diffuse reflectance infrared spectroscopy peak position in embodiment 2, peak intensity threshold value is 0.01 absorbance (with the strength difference minimum value of the adjacent peak valley in both sides), use maximum value process (Interpolated Peak) is determined in peak position, and result is as shown in table 5.
Table 5 Cordyceps gunnii (Berk.) Berk herb diffuse reflectance infrared spectroscopy peak
6) Cordyceps gunnii (Berk.) Berk and the comparison of Cordyceps sinensis herb standard spectrum characteristic peak
Table 6 Cordyceps gunnii (Berk.) Berk and the peak comparison of Cordyceps sinensis herb diffuse reflectance infrared spectroscopy
Table 6 is depicted as in Cordyceps gunnii (Berk.) Berk herb diffuse reflectance infrared spectroscopy peak the part of conform to Cordyceps sinensis herb standard spectrum characteristic peak (in table 1 and table 2 characteristic peak 99% fiducial interval).As can be seen from Table 6, all there is not the indispensable characteristic peak of whole Cordyceps sinensis herbs in four Cordyceps gunnii (Berk.) Berk herbs, illustrates that method of the present invention can effectively carry out true and false discriminating.
Claims (6)
1. the Infrared spectroscopy authentication method of Cordyceps sinensis herb, comprises the following steps:
A, Cordyceps sinensis herb standard spectrum are drawn: the standard Cordyceps sinensis herb sample in a plurality of different places of production is pressed into respectively thin slice and carries out transmission test, and the averaged spectrum of all samples is Cordyceps sinensis herb standard spectrum;
The collection of b, the indispensable characteristic peak of Cordyceps sinensis herb infrared spectrum and the common characteristic peak of Cordyceps sinensis herb infrared spectrum;
The diffuse reflectance infrared spectroscopy peak comparison of c, tested Cordyceps sinensis herb sample and the comparison of infrared spectrum similarity: in the infrared spectrum of sample, comprise the common characteristic peak of Cordyceps sinensis herb the infrared spectrum more than indispensable characteristic peak and 60% of whole Cordyceps sinensis herb infrared spectrums, and the level of significance between sample spectrum and Cordyceps sinensis herb standard spectrum is that the related coefficient lower threshold of 0.01 o'clock is 0.95, and this sample is genuine piece Cordyceps sinensis herb.
2. the Infrared spectroscopy authentication method of Cordyceps sinensis herb according to claim 1, it is characterized in that: in step b, the indispensable characteristic peak of described Cordyceps sinensis herb infrared spectrum refers to the infrared spectrum absorpting peak position of comparison all samples, the indispensable characteristic peak using the absorption peak all occurring in all samples as Cordyceps sinensis herb infrared spectrum.
3. the Infrared spectroscopy authentication method of Cordyceps sinensis herb according to claim 2, is characterized in that: in step b, the indispensable characteristic peak of described Cordyceps sinensis herb infrared spectrum is as shown in table 1:
The indispensable characteristic peak of table 1 Cordyceps sinensis herb infrared spectrum
4. the Infrared spectroscopy authentication method of Cordyceps sinensis herb according to claim 1, it is characterized in that: in step b, the described common characteristic peak of Cordyceps sinensis herb infrared spectrum refers in the infrared spectrum absorpting peak of all samples, except indispensable characteristic peak, probability of occurrence is not less than to 80% absorption peak, as the common characteristic peak of Cordyceps sinensis herb infrared spectrum.
5. the Infrared spectroscopy authentication method of Cordyceps sinensis herb according to claim 4, is characterized in that: the common characteristic peak of described Cordyceps sinensis herb infrared spectrum is as shown in table 2:
The common characteristic peak of table 2 Cordyceps sinensis herb infrared spectrum
6. the Infrared spectroscopy authentication method of Cordyceps sinensis herb according to claim 1, is characterized in that: in step c, the computing formula of described related coefficient is:
Wherein, R
ijrepresent the related coefficient of infrared spectrum i and infrared spectrum j, x
ikand x
jkrepresentative sample i and sample j are at the absorbance at wave number k place respectively.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310688297.0A CN103674887B (en) | 2013-12-16 | 2013-12-16 | The Infrared spectroscopy authentication method of Cordyceps sinensis herb |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310688297.0A CN103674887B (en) | 2013-12-16 | 2013-12-16 | The Infrared spectroscopy authentication method of Cordyceps sinensis herb |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103674887A true CN103674887A (en) | 2014-03-26 |
| CN103674887B CN103674887B (en) | 2016-01-27 |
Family
ID=50313097
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310688297.0A Active CN103674887B (en) | 2013-12-16 | 2013-12-16 | The Infrared spectroscopy authentication method of Cordyceps sinensis herb |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103674887B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108204954A (en) * | 2016-12-20 | 2018-06-26 | 松下知识产权经营株式会社 | Resin determination method and resin decision maker |
| CN109781647A (en) * | 2018-12-13 | 2019-05-21 | 康美药业股份有限公司 | A kind of differentiating method of caulis piperis futokadsurae He Hance Pepper Stem and Leaf |
| CN109932332A (en) * | 2019-03-18 | 2019-06-25 | 陇西保和堂药业有限责任公司 | A kind of method of infrared spectroscopy detection Chinese medicine |
| WO2019223364A1 (en) * | 2018-05-25 | 2019-11-28 | 深圳市太赫兹科技创新研究院有限公司 | Method for detecting quality of cordyceps sinensis based on electromagnetic wave in terahertz band |
| CN111458306A (en) * | 2019-01-22 | 2020-07-28 | 吉林农业大学 | Method for identifying different cartialgenous flowers by combining infrared spectrum with P L S-DA |
| CN112649393A (en) * | 2021-01-14 | 2021-04-13 | 中国林业科学研究院木材工业研究所 | Infrared spectrum-based method for identifying small ornament of dalbergia odorifera |
| CN112697744A (en) * | 2021-01-14 | 2021-04-23 | 中国林业科学研究院木材工业研究所 | Infrared spectrum-based identification method for Dongfei yellow sandalwood artware |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020027444A (en) * | 2002-03-12 | 2002-04-13 | 김광학 | The process of Vegetable worms season laver |
| US20060269567A1 (en) * | 2005-05-16 | 2006-11-30 | Liu Yuen | Universal detoxifying composition |
| CN101852730A (en) * | 2010-03-25 | 2010-10-06 | 丽珠集团利民制药厂 | Infrared spectrum detection method of ginseng and astragalus injection liquid |
| CN102288551A (en) * | 2011-04-01 | 2011-12-21 | 尚振刚 | Method for distinguishing traditional Chinese medicinal material by utilizing hyperspectral data |
| CN103105374A (en) * | 2011-11-15 | 2013-05-15 | 天津天狮生物发展有限公司 | Method for quickly identifying true and false cordyceps mycelia |
-
2013
- 2013-12-16 CN CN201310688297.0A patent/CN103674887B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020027444A (en) * | 2002-03-12 | 2002-04-13 | 김광학 | The process of Vegetable worms season laver |
| US20060269567A1 (en) * | 2005-05-16 | 2006-11-30 | Liu Yuen | Universal detoxifying composition |
| CN101852730A (en) * | 2010-03-25 | 2010-10-06 | 丽珠集团利民制药厂 | Infrared spectrum detection method of ginseng and astragalus injection liquid |
| CN102288551A (en) * | 2011-04-01 | 2011-12-21 | 尚振刚 | Method for distinguishing traditional Chinese medicinal material by utilizing hyperspectral data |
| CN103105374A (en) * | 2011-11-15 | 2013-05-15 | 天津天狮生物发展有限公司 | Method for quickly identifying true and false cordyceps mycelia |
Non-Patent Citations (1)
| Title |
|---|
| 徐永群 等: "红外指纹图谱库与阵列相关系数法快速鉴别中药材", 《光谱实验室》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108204954A (en) * | 2016-12-20 | 2018-06-26 | 松下知识产权经营株式会社 | Resin determination method and resin decision maker |
| WO2019223364A1 (en) * | 2018-05-25 | 2019-11-28 | 深圳市太赫兹科技创新研究院有限公司 | Method for detecting quality of cordyceps sinensis based on electromagnetic wave in terahertz band |
| CN109781647A (en) * | 2018-12-13 | 2019-05-21 | 康美药业股份有限公司 | A kind of differentiating method of caulis piperis futokadsurae He Hance Pepper Stem and Leaf |
| CN111458306A (en) * | 2019-01-22 | 2020-07-28 | 吉林农业大学 | Method for identifying different cartialgenous flowers by combining infrared spectrum with P L S-DA |
| CN109932332A (en) * | 2019-03-18 | 2019-06-25 | 陇西保和堂药业有限责任公司 | A kind of method of infrared spectroscopy detection Chinese medicine |
| CN112649393A (en) * | 2021-01-14 | 2021-04-13 | 中国林业科学研究院木材工业研究所 | Infrared spectrum-based method for identifying small ornament of dalbergia odorifera |
| CN112697744A (en) * | 2021-01-14 | 2021-04-23 | 中国林业科学研究院木材工业研究所 | Infrared spectrum-based identification method for Dongfei yellow sandalwood artware |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103674887B (en) | 2016-01-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103674887B (en) | The Infrared spectroscopy authentication method of Cordyceps sinensis herb | |
| Li et al. | Quality control of Lonicerae Japonicae Flos using near infrared spectroscopy and chemometrics | |
| Woo et al. | Discrimination of herbal medicines according to geographical origin with near infrared reflectance spectroscopy and pattern recognition techniques | |
| CN103760126B (en) | The Infrared spectroscopy authentication method of Cordyceps sinensis polypide | |
| Peng et al. | Fingerprint profile of active components for Artemisia selengensis Turcz by HPLC–PAD combined with chemometrics | |
| WO2021056814A1 (en) | Chemical pattern recognition method for evaluating quality of traditional chinese medicine based on medicine effect information | |
| Cheng et al. | Infrared spectroscopic studies of Chinese medicines | |
| CN102706813B (en) | Poa pratensis variety identification method based on hyper-spectral image | |
| Chen et al. | Rapid and automatic chemical identification of the medicinal flower buds of Lonicera plants by the benchtop and hand-held Fourier transform infrared spectroscopy | |
| CN101961379A (en) | Near infrared spectrum identification method for red sage roots | |
| CN102288551A (en) | Method for distinguishing traditional Chinese medicinal material by utilizing hyperspectral data | |
| CN107917896A (en) | Radix glycyrrhizae method for quick identification based near infrared spectrum and Clustering Analysis Technology | |
| Cheng et al. | Classification of two species of Bidens based on discrete stationary wavelet transform extraction of FTIR spectra combined with probability neural network | |
| CN103698296B (en) | The Infrared spectroscopy authentication method of Cordyceps sinensis stroma | |
| Chen et al. | Application of UV-Vis and infrared spectroscopy on wild edible bolete mushrooms discrimination and evaluation: a review | |
| CN103105374A (en) | Method for quickly identifying true and false cordyceps mycelia | |
| Hu et al. | A review of the application of vibrational spectroscopy combined with chemometrics in genus Panax | |
| CN105334183A (en) | Method for identifying certifiable Herba Ephedrae based on near infrared spectroscopy | |
| CN110823828A (en) | Method for identifying Wumai green wormwood in different producing areas | |
| CN103076300A (en) | Method for judging and analyzing traditional Chinese medicine resource fingerprint information by specific mode identification model | |
| CN105527241A (en) | Non-destructive method for detecting authenticity of raw cordyceps sinensis | |
| Gu et al. | Identification of Panax notoginseng origin using terahertz precision spectroscopy and neural network algorithm | |
| Lu et al. | Rapid analysis of Radix Astragali using a portable Raman spectrometer with 1064-nm laser excitation and data fusion with PLS-DA | |
| Wu et al. | Identify production area, growth mode, species, and grade of Astragali radix using metabolomics “big data” and machine learning | |
| Liu et al. | Discrimination and feature selection of geographic origins of traditional Chinese medicine herbs with NIR spectroscopy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: QINGHAI SPRING MEDICINAL RESOURCES SCI-TECH UTILIZ Free format text: FORMER OWNER: ZHANG XUEFENG Effective date: 20140516 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 610041 CHENGDU, SICHUAN PROVINCE TO: 810000 XINING, QINGHAI PROVINCE |
|
| TA01 | Transfer of patent application right |
Effective date of registration: 20140516 Address after: 810000 No. 1, Dongxin Road, Xining economic and Technological Development Zone, Qinghai, China Applicant after: QINGHAI CHUNTIAN MEDICAL RESOURCE TECHNOLOGY UTILIZATION CO., LTD. Address before: 610041, No. 1, building 3, 85 Confucious'Temple Street, Qingyang District, Sichuan, Chengdu, 1 Applicant before: Zhang Xuefeng |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190904 Address after: 810007 No. 1, Dongxin Road, Xining economic and Technological Development Zone, Qinghai, China Patentee after: Qinghai Spring Medical Resources Science and Technology Co., Ltd. Address before: 810000 No. 1, Dongxin Road, Xining economic and Technological Development Zone, Qinghai, China Patentee before: QINGHAI CHUNTIAN MEDICAL RESOURCE TECHNOLOGY UTILIZATION CO., LTD. |
|
| TR01 | Transfer of patent right |