CN1447110A - Multistage macroscopical fingerprint method for identifying non-separated extracted infrared spectrum of medicinal materials in Chinese traditional medicine - Google Patents
Multistage macroscopical fingerprint method for identifying non-separated extracted infrared spectrum of medicinal materials in Chinese traditional medicine Download PDFInfo
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Abstract
This invention relates to a method for verifying unseparately extracted multilever macro-finger makrs with infrared spectrum of Chinese medicine characterizing in cutting, crushing, and screening medicine to add potassium bromide powder into the medicine powder smaller than 200 mesh for table sampling to determine the middle infrared spectrum, diffuse reflection near infrared, diffuse reflection middle infrared spectrum, reflection spectrum and attenuation total reflection spectrum to get and draw the second-order derivative spectrum diagram of related spectrum, to determine the samples two-dimensional celated infrared spection to be compared in level.
Description
Technical field
Spectral analysis evaluation, discrimination method are extracted in the non-separation that the present invention relates to the extremely complicated mixture solution of a kind of composition, especially relate to the non-separation of a kind of Chinese medicine medicinal material infrared spectrum and extract multistage macroscopical fingerprint identification method, belong to Chinese medicine detection technique field.
Background technology
The quality control of Chinese medicine is to carry forward the basis of the traditional Chinese medical science, science of Chinese materia medica with crucial.In October, 2000 China National Drug Administration has issued " technical requirement (provisional) of traditional Chinese medicine finger-print research " and the research of traditional Chinese medicine fingerprint is made has been instructed and standard.The European Community be the earliest with legislation form regulation finger-print as quality standard (Quality of Herbal Remedies, Eudra/Q/88/028).U.S. FDA is recently clearly with the method for quality control of finger-print as plant herbal medicine compounding substances group.But all still be in practice as the quality of weighing autonomic drug with index components.And people find constantly that also the curative effect of the monomeric compound of separating plant is not so good as crude extract and comes well, even invalid.Yet, but can make method of quality control far away about comprehensive, the clear and definite more science of medicinal material, granule.
The Chinese medicine medicinal material is extremely complicated mixture system.Generally include traditional experience at present and differentiate, basic former discriminating, character identification, microscopical identification, physicochemical identification and chromatogram differentiate that what have differentiates with spectroscopic methodology.Rely on artificial traditional experience to differentiate at most, further former from base, proterties, microscopical identification reach at shape characteristic and identify.Yet this method is to judge the variation of medicine internal component.Dried dried similar to former genseng section in shape such as the section of the genseng of concocting, but its effective constituent can be very different.Therefore it is scientific not enough.This is aided with physicochemical identification often.Adopted thin-layer chromatography (hole C) method to identify, differentiate.It is compared with the position of known Chinese medicine reference substance according to the chromatogram speckle displacement that sample occurs on chromatographic sheet, can be than judging faster, easily, exactly.Yet, because it is subject to multifactorial influence such as experiment condition and environment experimental technique requirement very high so that the repeatability of method is relatively poor.In addition, the someone proposes to utilize the characteristic of the measured spectrogram of spectroscopic methodology (ultraviolet, infrared) to judge with after one group of solvent leaching of opposed polarity or extracting.In " TCD identification ultraviolet spectral line group method and application " (Yuan Jiurong work, People's Health Publisher,, Beijing in 1999), once proposed " ultraviolet spectral line group method " and differentiated Chinese medicine (the UV spectrum of the leaching liquid of four kinds of solvents, derivative UV spectrum).Recently, Tian Jinguo (China Medicine University's journal, 1997,20 (1): 23-28) tens of kinds of Chinese crude drugs are carried out the discriminating of infrared line group.They differentiate, identify after the leaching of Chinese medicine being made in advance multi-solvent separates.Also existing people uses gas chromatography after solvent leaching or extraction, liquid chromatography is separated, and the coupling of available subsequently various instrumental analysis means is obtained effective constituent and judged.Yet these methods have been lost holistic approach, the former person's character and the compatibility of forfeiture system.Though gas chromatography, liquid chromatography has very strong separating power, but because medicinal material itself is because of the difference with conditions such as growths, be that the Chinese medicine medicinal material often just can not strict be controlled from the source, to cause the instability or the reliability deficiency own of its " effective constituent " or " control composition ", thereby add that again n-compound is not easy to obtain to cause being difficult to realizing differentiating when analyzing.In evaluation, discriminating and the quality control of Chinese medicine (medicinal material, granule, injection etc.), the evaluation of medicinal material, discriminating and quality control are stubborn problems the most.
Summary of the invention
The purpose of this invention is to provide a kind of can't harm, need not separation and Extraction, sample is handled simple, fast, easy, do not lose former person's character compatibility on the whole, meet the Chinese medicine differential diagnosis in tcm and execute the non-separation of Chinese medicine medicinal material infrared spectrum of controlling principle and extract multistage macroscopical fingerprint identification method.This method is the method that the relevant spectrum of a kind of collection INFRARED SPECTRUM-derivative spectrum-two-dimensional infrared is analyzed for one.
Multistage macroscopical fingerprint identification method is extracted in the non-separation of a kind of Chinese medicine medicinal material infrared spectrum that the present invention proposes, and it is characterized in that this method may further comprise the steps:
(1) earlier the Chinese medicine medicinal material is cut off, pulverizes, sieves;
(2) in less than 200 purpose medicinal powders, add the potassium bromide powder and carry out the compressing tablet sample preparation;
(3) the common infrared spectrum of mensuration compressing tablet sample, near infrared spectrum, diffuse reflection near infrared spectrum, diffuse reflection spectrum, attenuated total reflection spectrum;
(4) obtain and draw the second derivative spectrum of above-mentioned corresponding infrared spectrogram;
(5) two-dimensional correlation infrared spectrum of measuring the compressing tablet sample is composed, and what produce it is any type of disturbance;
(6) classification contrasts corresponding collection of illustrative plates, can directly carry out the non-separation of Chinese medicine medicinal material and extract evaluation, differentiates.
In above-mentioned authentication method, the described two-dimensional correlation infrared spectrum spectrum of step (5) can be synchronous spectrum, or asynchronous spectrum or both dual-purposes; The described two-dimensional correlation infrared spectrum of step (5) spectrum can be various forms of images, is preferably isostrength diagram, fishnet figure, multi-C stereo figure, any in the cromogram or two kinds; One of them of the disturbance that the described disturbance form of step (5) is heat, light, electricity, magnetic, mechanical force.
In above-mentioned authentication method, the described classification contrast of step (6) can be infrared spectrum, second derivative spectrum and three kinds of single comparing of spectrogram of two-dimensional correlation infrared spectrum spectrum, perhaps will be wherein both combine and compare arbitrarily, perhaps triplicity is compared together mutually.
In above-mentioned authentication method, described classification contrast is the one-level contrast, is the secondary contrast, is three grades of contrasts with step (5) gained two-dimensional correlation infrared spectrum spectrum with step (4) gained second derivative spectrum with step (3) gained infrared spectrum.
In above-mentioned authentication method, the one-level infrared spectrum contrast in the described classification contrast is:
(1) observe infared spectrum overall shape or pattern, promptly the similarity of peak position, peak intensity, peak shape is tentatively differentiated;
(2) at 1800～400cm
-1Choose 3～5 strong spectrum peaks bunch in the interval, its peak position fluctuation is at ± 2cm
-1Within, be considered as identically or close, the intensity size of highest peak in the spectrum peak bunch is sorted successively, recently differentiate evaluation according to their ordering and relative intensity;
(3) at 1800～400cm
-1Choose strong spectrum peaks 3～5 times in the above-mentioned peak bunch in interval, its peak position fluctuation is at ± 2cm
-1Within, be considered as identically or close differentiating for assisting.
In above-mentioned authentication method, the secondary second derivative spectrum contrast in the described classification contrast is:
(1) observe derivative spectrum overall shape or pattern, promptly the similarity of peak position, peak intensity, peak shape is tentatively differentiated;
(2) at 1800～400cm
-1Choose respective derivative peak that the strongest spectrum peak-to-peak position in the infared spectrum just occurs in the interval nearby and be considered as identically or close, this derivative spectrum peak-to-peak position fluctuation is at ± 2cm
-1Within, and the size and the order of each strong peak-to-peak relative intensity of comparison;
(3) at 1800～400cm
-1Choose in the infared spectrum both sides, the strongest spectrum peak in the interval and corresponding acromion peak position whether occurs and differentiate, this acromion peak position fluctuation is at ± 2cm
-1Within.
In above-mentioned authentication method, three grades of two-dimensional correlation infrared spectrums spectrums contrast in the described classification contrast is to compare with the two-dimensional correlation spectrum to judge: the automatic peak of choosing strong peak in the sync correlation spectrum or strong peak bunch, contrast their peak position and intensity thereof, and contrast selected automatic peak and the similarities and differences of other automatic peak-to-peak sign of intersecting the peak and differentiate their similarities and differences.
In above-mentioned authentication method, powdered sample can directly be measured near infrared spectrum, diffuse reflection near infrared spectrum, diffuse reflection spectrum, attenuated total reflection spectrum.
Based on infrared itself abundant fingerprint and utilize peak position, peak shape and the variation thereof at Partial Feature peak, the variation of peak intensity or relative peak intensity, the present invention propose directly to carry out with harmless infra-red sepectrometry the evaluation discriminating of Chinese medicine medicinal material.Comprise and the collection of illustrative plates of standard sample comparison method that the multiple technologies of resolving by means of area of computer aided are identified and discerned, and two-dimensional infrared correlation analysis technology is monitored methods such as stability of drug.Thereby can not lose the source person's character, nondestructively, easy, quick, need not to carry out just directly test of detachment process, do not destroy the compatibility of Chinese medicine, can obtain the Global Information of Chinese medicine, and identify, differentiate Chinese medicine with this.This is called macroscopical fingerprint technique.
For can be integrally, nondestructively, without separation and Extraction, sample only do simple process, through fast measuring just can be easily, correctly identify, differentiate the Chinese medicine medicinal material and make it standardization, the infra-red sepectrometry that the present invention proposes to adopt comprises that conventional infrared spectrogram, derivative spectrum figure, the two-dimensional correlation infrared spectrum spectrum of measuring sample are multistage macroscopical dactyloscope of one.Obtain not lose the former person's character of sample by this method, therefore the finger print information of the macroscopic view of compatibility has more intuitive.It meets dialectical the executing of traditional Chinese medicine and controls principle.Can obtain the information of stability of drug products and metamorphic mechanism simultaneously in addition, and be convenient to promote.
The present invention is based on such principle, be that the infrared spectrogram of material has fingerprint and can be used as the one-level spectrogram and compare evaluation, when extremely similar its otherness of material possibility is still obvious inadequately, can be by its derivative spectrum, compare as the secondary spectrogram, further check out comparatively small difference, when the difference of above-mentioned two-stage spectrogram still is not enough to difference and identifies, can further compare evaluation with the relevant spectrogram of the higher two-dimensional infrared of resolution.Thereby can identify very intuitively, discriminating and quality control.The non-separation of Chinese medicine medicinal material infrared spectrum of adopting the present invention to propose is extracted multistage macroscopical fingerprint identification method and be need not sample is separated, can be nondestructively, non-destructive ground, apace, easily, lose the foundation that the kind of tested sample, the place of production, cultivation or wild, grade, true and false quality are directly judged in former person's character and compatibility ground.Therefore can be widely used in that the Chinese medicine medicinal material is identified quickly and easily, discriminating and quality control.Its foundation will be quickened Chinese medicine Quality Control process greatly with popularization, quicken the modernization of Chinese medicine and international speed greatly.
Description of drawings
Fig. 1 is the infrared spectrum of the first-class red sage root among the embodiment 1.
Fig. 2 a, 2b are the derivative spectrogram of the first-class red sage root among the embodiment 1.
Fig. 3 a, 3b are the two-dimensional correlation equipotential line spectrogram of the first-class red sage root among the embodiment 1.
Fig. 4 a, 4b are the two-dimensional correlation fishnet figure of the first-class red sage root among the embodiment 1.
Fig. 5 is the infrared spectrum of the second-class red sage root among the embodiment 1.
Fig. 6 a, 6b are the derivative spectrogram of the second-class red sage root among the embodiment 1.
Fig. 7 a, 7b are the two-dimensional correlation equipotential line spectrogram of the second-class red sage root among the embodiment 1.
Fig. 8 a, 8b are the two-dimensional correlation fishnet figure of the second-class red sage root among the embodiment 1.
Fig. 9 is that infrared spectrum first-class among the embodiment 1, the second-class red sage root compares.
Figure 10 a, 10b are that derivative spectrogram first-class among the embodiment 1, the second-class red sage root compares.
(Figure 11 a is 900～1150/cm for two-dimensional correlation equipotential line spectrogram first-class among the embodiment 1, the second-class red sage root compares for Figure 11 a, 11b
-1, Figure 11 b is 1200～1500/cm
-1).
Figure 12 is the infrared spectrum of planted rooted salvia among the embodiment 1.
Figure 13 a, 13b are the derivative spectrogram of planted rooted salvia among the embodiment 1.
Figure 14 a, 14b are the two-dimensional correlation equipotential line spectrogram of planted rooted salvia among the embodiment 1.
Figure 15 a, 15b are the two-dimensional correlation fishnet figure of planted rooted salvia among the embodiment 1.
Figure 16 is the infrared spectrum of wild Radix Salviae Miltiorrhizae among the embodiment 1.
Figure 17 a, 17b are the derivative spectrogram of wild Radix Salviae Miltiorrhizae among the embodiment 1.
Figure 18 a, 18b are the two-dimensional correlation equipotential line spectrogram of wild Radix Salviae Miltiorrhizae among the embodiment 1.
Figure 19 a, 19b are the two-dimensional correlation fishnet figure of wild Radix Salviae Miltiorrhizae among the embodiment 1.
Figure 20 is that the infrared spectrum of cultivation, wild Radix Salviae Miltiorrhizae among the embodiment 1 compares.
Figure 21 a, 21b are that the derivative spectrogram of cultivation, wild Radix Salviae Miltiorrhizae among the embodiment 1 compares.
Relatively (Figure 11 A is 900～1150/cm for the two-dimensional correlation equipotential line spectrogram of cultivation, wild Radix Salviae Miltiorrhizae among the embodiment 1 for Figure 22 a, 22b
-1, Figure 11 B is 1200～1500/cm
-1).
Figure 23 is the infrared spectrum of Patchouli among the embodiment 2.
Figure 24 a, 24b are the derivative spectrogram of Patchouli among the embodiment 2.
Figure 25 a, 25b are the two-dimensional correlation equipotential line spectrogram of Patchouli among the embodiment 2.
Figure 26 a, 26b are the two-dimensional correlation fishnet figure of the second-class red sage root among the Patchouli embodiment 1 among the embodiment 2.
Figure 27 is the infrared spectrum of embodiment 2 Central-South perfume (or spice).
Figure 28 a, 28b are the derivative spectrogram of embodiment 2 Central-South perfume (or spice).
Figure 29 a, 29b are the two-dimensional correlation equipotential line spectrogram of embodiment 2 Central-South perfume (or spice).
Figure 30 a, 30b are the two-dimensional correlation fishnet figure of embodiment 2 Central-South perfume (or spice).
Figure 31 is the infrared spectrum of board perfume (or spice) among the embodiment 2.
Figure 32 a, 32b are the derivative spectrogram of board perfume (or spice) among the embodiment 2.
Figure 33 a, 33b are the two-dimensional correlation equipotential line spectrogram of board perfume (or spice) among the embodiment 2.
Figure 34 a, 34b are the two-dimensional correlation fishnet figure of board perfume (or spice) among the embodiment 2.
Figure 35 is a profound fragrant infrared spectrum among the embodiment 2.
Figure 36 a, 36b are profound fragrant derivative spectrogram among the embodiment 2.
Figure 37 a, 37b are profound fragrant two-dimensional correlation equipotential line spectrogram among the embodiment 2.
Figure 38 a, 38b are profound fragrant two-dimensional correlation fishnet figure among the embodiment 2.
Figure 39 is that the infrared spectrum of four kinds of ageratums among the embodiment 2 compares.
Figure 40 leads figure relatively for four kinds of ageratums among the embodiment 2.
Figure 41 is that the two-dimensional correlation equipotential line spectrogram of four kinds of ageratums among the embodiment 2 compares.
Figure 42 be Chinese anise and thick grass among the embodiment 3 infrared spectrum relatively.
Figure 43 a, 43b be Chinese anise and thick grass among the embodiment 3 the derivative spectrogram relatively.
Figure 44 a, 44b be Chinese anise and thick grass among the embodiment 3 two-dimensional correlation equipotential line spectrogram relatively.
Embodiment
The present invention will be further described below in conjunction with drawings and Examples:
Embodiment 1: the evaluation of the red sage root and discriminating
(1) experiment adopt Spectrum GX FTIR spectrometer (Perkin Elmer, USA), the DTGS detecting device, resolution is 4cm-1, measurement range 4000～400cm-1, scanning adds up for 32 times obtains spectrum.Adopt 50-886 type Portable Controller Programmable Temperature control module (Love Control company);
(2) red sage root sample is pulverized the back and is added KBr, and compressing tablet is made sample, places in the instrument alternating temperature pond, and programmable temperature is from room temperature to 150 ℃, the real-time interval sampling of original position, and infrared spectrum is gathered in 10 ℃ of every intensifications, obtains serial spectrogram-alternating temperature dynamic spectrum continuously;
(3) for the infrared spectrogram of room temperature (～20 ℃), carry out the differentiate of spectrogram and handle, obtain the derivative collection of illustrative plates;
(4) for serial alternating temperature dynamic spectrum, utilize 2D-correlation analysis software processes, obtain the relevant spectrogram of 2D IR: sync correlation spectrum, asynchronous relevant spectrum;
(5) Sichuan Zhong Jiang cultivation first-class, the middle infrared spectrum of the second-class red sage root and synchronous two-dimensional correlation spectrogram (isostrength diagram and three-dimensional fishnet figure) and the description of feature and their the middle infrared spectrum comparison diagram of derivative spectrogram and hot perturbation thereof.Lingbao City, Henan cultivation with wild middle infrared spectrum and the synchronous two-dimensional correlation spectrogram of derivative spectrogram and hot perturbation (isostrength diagram and three-dimensional fishnet figure) and the description of feature and their middle infrared spectrum comparison diagram.Obviously peak position, peak shape, the peak width of mainly composing the peak by spectrograms at different levels made the characteristics that simple contrast has been enough to distinguish the medicinal material that produces with the different places of production, different brackets and the Different Ways of Planting of assert the relevant red sage root.As shown in table 1.Table 1 medicinal material IR (main peak; Submaximum)/cm
-1Derivative (the different peak 2D of main peak (main peak, bunch peak)/cm
-1
The district)/cm
-1 Sichuan Zhong Jiang 1635 2., 1409 4., 1265～1450～1466,1384 1., 1461 the cultivation first-class 5., 1146 3., 1051 1.～1325～1375 red sage root Sichuan Zhong Jiang 1635 3., 1416 4., 1265～1450～1466,1464 1.; 5. 1384,1199,1222 cultivations second-class, 1145 2., 1055 1.～1325～1375 Lingbao City, red sage root Henan 1636 3., 1416 4., 1265～1450～1466,967 1. (just intersecting peak), 1200 planted rooted salvias 5., 1145 2., 1055 1.～1325～1375 1., 1223 2., and 1466 is 3. (negative
Intersect the peak) Lingbao City, Henan 1631 2., 1415 4., 1264～1450～1466,1467 1., negative wild Radix Salviae Miltiorrhizae 5. 1200,1223 2. (, 1149 3., 1050 1.～1325～1375 intersect peak), 1412 4.
Sichuan Zhong Jiang cultivates the first-class red sage root, 1051 1. 1146 3. 1635 2.=1.15: 0.71: 0.8
Sichuan Zhong Jiang cultivates the second-class red sage root, 1051 1. 1146 3. 1635 2.=1.2: 0.8: 0.66
Lingbao City, Henan planted rooted salvia, 1055 1. 1145 2. 1636 3.=1.25: 0.84: 0.6
Lingbao City, Henan wild Radix Salviae Miltiorrhizae, 1050 1. 1149 3. 1631 2.=1.20: 0.75: 0.78
Annotate: 1. 2. 3. 4. 5.---in order to the relative intensity of mark main peak or main peak bunch.Powerhouse's note weakens successively with 1., 5. is weak person wherein.
Sichuan Zhong Jiang cultivates the first-class red sage root
Fig. 1 cultivates the KBr compressing tablet infrared spectrum of the first-class red sage root for Sichuan Zhong Jiang, and main absorption peak as shown in the figure.Fig. 2 a and 2b are 850～1180cm
-1With 1180～1500cm
-1Second derivative figure in the scope, the spectrum peak as shown in the figure.
Fig. 3 a and Fig. 3 b are 860～1170cm
-1With 1170～1500cm
-1The two-dimensional infrared correlogram of wave-number range.
Among Fig. 3 a, significantly the peak has 7 automatically, respectively at 904cm
-1, 970cm
-1, 1010cm
-1, 1036cm
-1, 1070cm
-1, 1100cm
-1And 1132cm
-1970cm wherein
-1Automatic peak intensity maximum, 1036cm
-1And 1070cm
-1Automatic peak intensity less, other automatic peak intensity is medium.Their intersection peak just is.
Among Fig. 3 b, significantly the peak has 2 automatically, respectively at 1384cm
-1And 1461cm
-11384cm wherein
-1Automatic peak intensity maximum, 1461cm
-1Automatic peak intensity less.Intersection peak between them is for negative.
Second-class red sage root spectrogram explanation is cultivated in the river in the Annex IV river:
Fig. 5 cultivates the KBr compressing tablet infrared spectrum of the second-class red sage root for Sichuan Zhong Jiang, and main absorption peak as shown in the figure.Fig. 6 a and 6b are 850～1180cm
-1With 1180～1500cm
-1Second derivative figure in the scope, the spectrum peak as shown in the figure.
Fig. 7 a and Fig. 7 b are 860～1170cm
-1With 1170～1500cm
-1The two-dimensional infrared correlogram of wave-number range.
Among Fig. 7 a, significantly the peak has 7 automatically, respectively at 905cm
-1, 971cm
-1, 1011cm
-1, 1037cm
-1, 1069cm
-1, 1099cm
-1And 1132cm
-1971cm wherein
-1Automatic peak intensity maximum, 1037cm
-1And 1069cm
-1Automatic peak intensity less, other automatic peak intensity is medium.Their intersection peak just is.
Among Fig. 7 b, significantly the peak has 4 automatically, respectively 1199, and 1222cm
-1, 1384cm
-1And 1464cm
-11464cm wherein
-1Automatic peak intensity maximum, other automatic peak intensity is medium.1464cm
-1Automatic peak with other automatic peak-to-peak intersection peak for negative, other automatic peak-to-peak intersection peak is for just.
Sichuan Zhong Jiang planted rooted salvia relatively
Fig. 9 is the comparison of the KBr compressing tablet infrared spectrum of the Sichuan Zhong Jiang cultivation first-class and the second-class red sage root.Figure 10 a and Figure 10 b are respectively the two kinds of red sage root 850～1180cm
-1With 1180～1500cm
-1The comparison of second derivative figure in the scope.Figure 11 a and Figure 11 b (A, B) are the two kinds of red sage root 860～1170cm
-1With 1170～1500cm
-1The comparison of the two-dimensional infrared correlogram of wave-number range.
Embodiment 2: evaluation of ageratum and discriminating
(1) experiment adopt Spectrum GX FTIR spectrometer (Perkin Elmer, USA), the DTGS detecting device, resolution is 4cm-1, measurement range 4000～400cm-1, scanning 32 adds up and obtains spectrum.Adopt 50-886 type Portable Controller Programmable Temperature control module (Love Control company);
(2) four kinds of ageratum samples add the KBr compressing tablet respectively after pulverizing, and make sample, place in the instrument alternating temperature pond, and programmable temperature is from room temperature to 150 ℃, the real-time interval sampling of original position, and every intensification is gathered infrared spectrum for 10 ℃, obtains serial spectrogram one alternating temperature dynamic spectrum continuously;
(3) for the infrared spectrogram of room temperature (～20 ℃), carry out the differentiate of spectrogram and handle, obtain the derivative collection of illustrative plates;
(4) for serial alternating temperature dynamic spectrum, utilize 2D-correlation analysis software processes, obtain the relevant spectrogram of 2D IR: sync correlation spectrum, asynchronous relevant spectrum;
(5) comparison diagram of the synchronous two-dimensional correlation spectrogram (isostrength diagram) of infrared, derivative spectrogram of the description of the synchronous two-dimensional correlation spectrogram (isostrength diagram and three-dimensional fishnet figure) of the fragrant and profound fragrant middle infrared spectrum of Pogostemon cablin, Nan Xiang, board and derivative spectrogram and hot perturbation and feature thereof and four kinds of wrinkled giant hyssops and hot perturbation.Obviously, peak position, peak shape, the peak width of mainly composing the peak by spectrograms at different levels done simple contrast has been enough to assert and the characteristics of distinguishing relevant wrinkled giant hyssop kind.As shown in table 2.Table 2 medicinal material IR (main peak; Submaximum)/cm
-1Derivative (main difference peak)/cm
-12D (main peak, bunch peak)/cm
-1Pogostemon cablin 1734,1635 2., 1514; 1,059 940 1., and 974,1149 2.
1421，1377，1320，1251③；
1159,1055,1036 1. southern fragrant 1647 1., and 1542,1516; 1442,1059 not obvious 942 2., and 1149 1.
1377，1320，1260③；1158，
1059 2., 1035 board perfume (or spice) 1736,1652 2., 1514; 1,059 947 1., and 975 2.
1423，1378，1321，1255
3.; 1158,1055,1037 1. profound fragrant 1735,1646 2., and 1512; 1421,1,059 947 1., and 975 2.
1378,1321 and 1248 1.,
1159,1053,1037 annotate: 1. 2. 3. 4. 5. mark with embodiment 1.
The explanation of attached Pogostemon cablin (starting perfume (or spice)) spectrogram:
Figure 23 is the KBr compressing tablet infrared spectrum of Pogostemon cablin, and main absorption peak as shown in the figure.Figure 24 a and 24b are 850～1180cm
-1With 1180～1530cm
-1Second derivative figure in the scope, the spectrum peak as shown in the figure.
Figure 25 a and Figure 25 b are 860～1160cm
-1With 1160～1510cm
-1The two-dimensional infrared correlogram of wave-number range.
Among Figure 25 a, significantly the peak has 6 automatically, respectively at 887cm
-1, 940cm
-1, 974cm
-1, 998cm
-1, 1092cm
-1And 1149cm
-1940cm wherein
-1Automatic peak intensity maximum, 974cm
-1And 1149cm
-1Automatic peak intensity bigger, other automatic peak intensity is less or medium.Their intersection peak just is.
Among Figure 25 b, significantly the peak has 5 automatically, respectively at 1198cm
-1, 1214cm
-1, 1459cm
-1, 1468cm
-1And 1495cm
-11198cm wherein
-1And 1214cm
-1Automatic peak intensity maximum, 1495cm
-1Automatic peak intensity less, other automatic peak intensity is bigger.1459cm
-1And 1468cm
-1Automatic peak with other automatic peak-to-peak intersection peak for negative, other automatic peak-to-peak intersection peak is for just.
Pogostemon cablin (Nan Xiang)
Figure 27 a is the fragrant KBr compressing tablet infrared spectrum in south, and main absorption peak as shown in the figure.Figure 28 a and 28b are 860～1180cm
-1With 1180～1530cm
-1Second derivative figure in the scope, the spectrum peak as shown in the figure.
Figure 29 a and Figure 29 b are 860～1160cm
-1With 1160～1510cm
-1The two-dimensional infrared correlogram of wave-number range.
Among Figure 29 a, significantly the peak has 7 automatically, respectively at 908cm
-1, 942cm
-1, 973cm
-1, 1022cm
-1, 1037cm
-1, 1088cm
-1And 1149cm
-11149cm wherein
-1Automatic peak intensity maximum, 942cm
-1Automatic peak intensity bigger, other automatic peak intensity is less or medium.1022cm
-1And 1037cm
-1Automatic peak with other automatic peak-to-peak intersection peak for negative, other automatic peak-to-peak intersection peak is for just.
Among Figure 29 b, significantly the peak has 7 automatically, respectively at 1198cm
-1, 1213cm
-1, 1323cm
-1, 1382cm
-1, 1453cm
-1, 1467cm
-1And 1494cm
-11198cm wherein
-1And 1213cm
-1Automatic peak intensity maximum, 1453cm
-1And 1467cm
-1Automatic peak intensity bigger, other automatic peak intensity is medium or less.1198cm
-1, 1213cm
-1And 1494cm
-1Automatic peak with other automatic peak-to-peak intersection peak for negative, other automatic peak-to-peak intersection peak is for just.
Pogostemon cablin (board perfume (or spice))
Figure 31 is the KBr compressing tablet infrared spectrum of board perfume (or spice), and main absorption peak as shown in the figure.Figure 32 a and 32b are 860～180cm
-1With 1180～1530cm
-1Second derivative figure in the scope, the spectrum peak as shown in the figure.
Figure 33 a and Figure 33 b are 860～1160cm
-1With 1160～1510cm
-1The two-dimensional infrared correlogram of wave-number range.
Among Figure 33 a, significantly the peak has 6 automatically, respectively at 886cm
-1, 947cm
-1, 975cm
-1, 1000cm
-1, 1092cm
-1And 1151cm
-1947cm wherein
-1Automatic peak intensity maximum, 975cm
-1Automatic peak intensity bigger, other automatic peak intensity is less or medium.Their intersection peak just is.
Among Figure 33 b, significantly the peak has 6 automatically, respectively at 1200cm
-1, 1214cm
-1, 1325cm
-1, 1458cm
-1, 1468cm
-1And 1494cm
-11214cm wherein
-1Automatic peak intensity maximum, 1200cm
-1, 1458cm
-1And 1468cm
-1Automatic peak intensity bigger, other automatic peak intensity is less.1325cm
-1, 1458cm
-1And 1468cm
-1Automatic peak with other automatic peak-to-peak intersection peak for negative, other automatic peak-to-peak intersection peak is for just.
Pogostemon cablin (profound fragrant)
Figure 35 a is profound fragrant KBr compressing tablet infrared spectrum, and main absorption peak as shown in the figure.Figure 36 a and 36b are 860～1180cm
-1With 1180～1530cm
-1Second derivative figure in the scope, the spectrum peak as shown in the figure.
Figure 37 a and Figure 37 b are 860～1160cm
-1With 1160～510cm
-1The two-dimensional infrared correlogram of wave-number range.
Among Figure 37 a, significantly the peak has 6 automatically, respectively at 886cm
-1, 947cm
-1, 975cm
-1, 1000cm
-1, 1092cm
-1And 1151cm
-1947cm wherein
-1Automatic peak intensity maximum, 975cm
-1Automatic peak intensity bigger, other automatic peak intensity is less or medium.Their intersection peak just is.
Among Figure 37 b, significantly the peak has 6 automatically, respectively at 1200cm
-1, 1214cm
-1, 1325cm
-1, 1458cm
-1, 1468cm
-1And 1494cm
-11214cm wherein
-1Automatic peak intensity maximum, 1200cm
-1, 1458cm
-1And 1468cm
-1Automatic peak intensity less, other automatic peak intensity is less.1325cm
-1, 1458cm
-1And 1468cm
-1Automatic peak with other automatic peak-to-peak intersection peak for negative, other automatic peak-to-peak intersection peak is for just.
Embodiment 3: evaluation of Chinese anise and thick grass and discriminating
(1) experiment adopt Spectrum GX FTIR spectrometer (Perkin Elmer, USA), the DTGS detecting device, resolution is 4cm-1, measurement range 4000～400cm-1, scanning adds up for 32 times obtains spectrum.Adopt 50-886 type Portable Controller Programmable Temperature control module (Love Control company);
(2) Chinese anise and thick grass sample are pulverized the back and are added KBr, and compressing tablet is made sample, place in the instrument alternating temperature pond, and programmable temperature is from room temperature to 150 ℃, the real-time interval sampling of original position, and infrared spectrum is gathered in 10 ℃ of every intensifications, obtains serial spectrogram one alternating temperature dynamic spectrum continuously;
(3) for the infrared spectrogram of room temperature (～20 ℃), carry out the differentiate of spectrogram and handle, obtain the derivative collection of illustrative plates;
(4) for serial alternating temperature dynamic spectrum, utilize 2D-correlation analysis software processes, obtain the relevant spectrogram of 2D IR: sync correlation spectrum, asynchronous relevant spectrum;
(5) description of the synchronous two-dimensional correlation spectrogram (isostrength diagram) of the middle infrared spectrum of Chinese anise and thick grass and derivative spectrogram and hot perturbation and feature thereof and comparison diagram separately in twos.Obviously, peak position, peak shape, the peak width of mainly composing the peak by spectrograms at different levels done simple contrast has been enough to assert and has distinguished in twos the true and false separately.As shown in table 3.
Table 3 medicinal material IR (main peak; Submaximum)/cm
-1Derivative (the different peak 2D of main peak (main peak, bunch
The district)/cm
-1The peak)/cm
-1Anistree 3392,1613 2.; 1444,1376,1,248 960, (1055) 1374 1.; 3. 1290 fennels wide; 1093,1059 1. thick grass 3482,33871647 is 2.; 1444,1386,948,1055,1092,1,131 1385,1351 1.;
1294，1276，1238③；1091，1070，1294，1273
1. 1035,1018 annotate: 1. 2. 3. 4. 5. mark with embodiment 1.
Annex VIII angle fennel and thick grass is the spectrogram explanation relatively;
Figure 42 is the comparison of the KBr compressing tablet infrared spectrum of Chinese anise and pseudo-product thick grass thereof.Figure 43 a and Figure 43 b are respectively them at 850～1180cm
-1With 1180～1500cm
-1The comparison of second derivative figure in the scope.Figure 44 a and Figure 44 b (A, B) are that they are at 860～1170cm
-1With 1170～1500cm
-1The comparison of the two-dimensional infrared correlogram of wave-number range.
Claims (10)
1, multistage macroscopical fingerprint identification method is extracted in the non-separation of Chinese medicine medicinal material infrared spectrum, it is characterized in that this method may further comprise the steps:
(1) earlier the Chinese medicine medicinal material is cut off, pulverizes, sieves;
(2) in less than 200 purpose medicinal powders, add the potassium bromide powder and carry out the compressing tablet sample preparation;
(3) middle infrared spectrum of mensuration compressing tablet sample, near infrared spectrum, diffuse reflection near infrared spectrum, diffuse reflection spectrum, attenuated total reflection spectrum;
(4) obtain and draw the second derivative spectrum of above-mentioned corresponding infrared spectrogram;
(5) two-dimensional correlation infrared spectrum of measuring the compressing tablet sample is composed, and what produce it is any type of disturbance;
(6) classification contrasts corresponding collection of illustrative plates successively, can directly carry out the non-separation of Chinese medicine medicinal material and extract evaluation, differentiates.
2, multistage macroscopical fingerprint identification method is extracted in the non-separation of Chinese medicine medicinal material infrared spectrum according to claim 1, it is characterized in that: the described two-dimensional correlation infrared spectrum spectrum of step (5) can be synchronous spectrum, or asynchronous spectrum or both dual-purposes.
3, multistage macroscopical fingerprint identification method is extracted in the non-separation of Chinese medicine medicinal material infrared spectrum according to claim 1, it is characterized in that: the described two-dimensional correlation infrared spectrum spectrum of step (5) can be various forms of images, be preferably isostrength diagram, fishnet figure, multi-C stereo figure, any in the cromogram or two kinds.
4, multistage macroscopical fingerprint identification method is extracted in the non-separation of Chinese medicine medicinal material infrared spectrum according to claim 1, it is characterized in that: the described disturbance form of step (5) is one of them of disturbance of heat, light, electricity, magnetic, mechanical force.
5, multistage macroscopical fingerprint identification method is extracted in the non-separation of Chinese medicine medicinal material infrared spectrum according to claim 1, it is characterized in that: the described classification contrast of step (6) can be infrared spectrum, second derivative spectrum and three kinds of single comparing of spectrogram of two-dimensional correlation infrared spectrum spectrum, perhaps will be wherein both combine and compare arbitrarily, perhaps triplicity is compared together mutually.
6, multistage macroscopical fingerprint identification method is extracted in the non-separation of Chinese medicine medicinal material infrared spectrum according to claim 1, it is characterized in that: described classification contrast is the one-level contrast, is the secondary contrast, is three grades of contrasts with step (5) gained two-dimensional correlation infrared spectrum spectrum with step (4) gained second derivative spectrum with step (3) gained infrared spectrum.
7, extract multistage macroscopical fingerprint identification method according to claim 1 or the non-separation of 5 or 6 described Chinese medicine medicinal material infrared spectrums, it is characterized in that, the one-level infrared spectrum contrast in the described classification contrast is:
(1) observe infared spectrum overall shape or pattern, promptly the similarity of peak position, peak intensity, peak shape is tentatively differentiated;
(2) at 1800～400cm
-1Choose 3～5 strong spectrum peaks bunch in the interval, its peak position fluctuation is at ± 2cm
-1Within, be considered as identically or close, the intensity size of highest peak in the spectrum peak bunch is sorted successively, recently differentiate evaluation according to their ordering and relative intensity;
(3) at 1800～400cm
-1Choose strong spectrum peaks 3～5 times in the above-mentioned peak bunch in interval, its peak position fluctuation is at ± 2cm
-1Within, be considered as identically or close differentiating for assisting.
8, extract multistage macroscopical fingerprint identification method according to claim 1 or the non-separation of 5 or 6 described Chinese medicine medicinal material infrared spectrums, it is characterized in that, the secondary second derivative spectrum contrast in the described classification contrast is:
(1) observe derivative spectrum overall shape or pattern, promptly the similarity of peak position, peak intensity, peak shape is tentatively differentiated;
(2) at 1800～400cm
-1Choose respective derivative peak that the strongest infrared spectrum peak-to-peak position just occurs in the interval nearby and be considered as identically or close, this derivative spectrum peak-to-peak position fluctuation is at ± 2cm
-1Within, and the size and the order of each strong peak-to-peak relative intensity of comparison;
(3) at 1800～400cm
-1Choose in the infared spectrum both sides, the strongest spectrum peak in the interval and corresponding acromion peak position whether occurs and differentiate, this acromion peak position fluctuation is at ± 2cm
-1Within.
9, extract multistage macroscopical fingerprint identification method according to claim 1 or the non-separation of 5 or 6 described Chinese medicine medicinal material infrared spectrums, it is characterized in that, three grades of two-dimensional correlation infrared spectrums spectrums contrast in the described classification contrast is to compare with the two-dimensional correlation spectrum to judge: the automatic peak of choosing strong peak in the sync correlation spectrum or strong peak bunch, contrast their peak position and intensity thereof, and selected automatic peak and the similarities and differences of other automatic peak-to-peak sign of intersecting the peak are differentiated their similarities and differences.
10, multistage macroscopical fingerprint identification method is extracted in the non-separation of Chinese medicine medicinal material infrared spectrum according to claim 1, it is characterized in that powdered sample can directly be measured near infrared spectrum, diffuse reflection near infrared spectrum, diffuse reflection spectrum, attenuated total reflection spectrum.
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