CN101620178A - Method for quickly detecting additive chemical component in Chinese patent medicine, health-care food or food based on near-infrared spectrum technique - Google Patents
Method for quickly detecting additive chemical component in Chinese patent medicine, health-care food or food based on near-infrared spectrum technique Download PDFInfo
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Abstract
The invention discloses a method for quickly detecting an additive chemical component in a Chinese patent medicine, a health-care food or a food based on a near-infrared spectrum technique. The method comprises the following six steps: (1) collecting a representative sample and establishing a reference sample library; (2) collecting the near-infrared spectrum of each sample in the reference sample library; (3) qualitatively and quantitatively analyzing each sample in the reference sample library by using a known inspection method; (4) collecting a contrast article of a chemical component to be detected and collecting the near-infrared spectrum; (5) selecting a characteristic spectrum section and establishing a qualitative discrimination model by using an appropriate stoichiometry method; and (6) collecting the near-infrared spectrum of the sample to be detected and utilizing the qualitative discrimination model to analyze the near-infrared spectrum, thereby judging whether the sample to be detected is added with the chemical component or not. The invention has high detection speed, does not destroy the sample, does not need sample pretreatment, does not use a chemical reagent, can detect various chemical components which are illegally added by one experiment simultaneously and can meet the requirement of daily surveillance and inspection.
Description
Technical field
The present invention relates to the analysis technical field of Chinese patent drug, health food or food, be specifically related to a kind of method that Chinese patent drug, health food or food are carried out the quick nondestructive detection, relate in particular to a kind of based on the method for adding chemical constitution in near-infrared spectrum technique fast detecting Chinese patent drug, health food or the food.
Background technology
Advantages such as it is little that Chinese medicine has toxic and side effect, effective, and effect and curative effect are reliable, not only compatriots approve always, and have also risen Chinese medicine heat in the world.Some lawless persons are under the ordering about of interests, utilize that the Western medicine curative effect is fast, effect rapidly and the complicated characteristics of traditional Chinese medicine ingredients, illegal interpolation chemicals in Chinese patent drug, and arbitrarily exaggerative curative effect, sell goods at a high figure and seek exorbitant profit, that gives the people has healthyly caused serious harm, influences the Chinese medicine reputation.The banner current, that a lot of health foods and food are also being sprayed Chinese medicine is mixed the genuine with the fictitious, and is an incompetent person or a person unequal to his task.Though in Chinese patent drug, add chemical constitution itself not in violation of rules and regulations, country had also once ratified a lot of medicines of Chinese and Western medicine combination like this, purpose is that the quick-acting of the opsonic action of Chinese medicine and Western medicine are combined, but Chinese and Western medicine is in conjunction with necessary clinical trial through strictness, adding without authorization is a kind of breakneck behavior, can bring unpredictable harm to patient's life security.
The complicated component of Chinese medicine own, serious interference between each composition, test stone is still far from perfect.The traditional Chinese medicine ingredients of single is very complicated, and its chemical constitution of compound Chinese patent medicine is more complicated various, adds the influence of production technology, makes the discrimination method that adds chemical constitution in the Chinese patent drug require to have more specificity.Technology such as check and analysis means rationalization reaction commonly used at present, thin-layer chromatography, high performance liquid chromatography, high performance liquid chromatography-mass spectrometry, wherein the most effective means are high performance liquid chromatography-mass spectrometry combination methods, but this method exists instrument to cost an arm and a leg, maintenance cost is higher, complex operation, analytical cycle long, to instrumentation personnel's requirement height, and can only be in problems such as the minority testing conditions use in the laboratory preferably.
Be becoming increasingly rampant at the behavior of adding chemical constitution in current Chinese patent drug, health food and the food without authorization, the serious threat people's is healthy, and the existing quality standard of China still can not effectively be supervised this, problems such as the supervision coverage rate is too little, the Fast Detection Technique of greatly developing medicine is one of effective means of head it off.Fast Detection Technique can be carried out fast detecting and examination to medicine at the scene, and suspicious specimen is taken back behind the laboratory with legal method of inspection conclusive evidence.By using Fast Detection Technique, the efficient of supervision and inspection will improve greatly, cost reduces greatly, supervise the big increase of wide coverage, will become the strong instrument that hits illegal interpolation behavior.
Publication number patent CN1275038C adopts acidifying extraction, oxidation removal to disturb and the physical and chemical reaction method of three steps of trinitrophenol precipitation detects silaenafil; Publication number patent CN101021483A adopts the physical and chemical reaction method of organic solvent extraction, two steps of concentrated sulphuric acid colour developing to detect Tadalafei and derivant thereof, but existing, these methods need sample is carried out pre-service, need to use chemical reagent, detachment process bothers relatively, can not detect deficiencies such as discriminating to the number of chemical composition that adds simultaneously.
Near-infrared spectrum technique has been one of spectral analysis technique with fastest developing speed, the most prominent since the nineties in 20th century, and it and Chemical Measurement and computer software technology organically combine the back and obtained development rapidly at aspects such as Pharmaceutical Analysis, process control.Frequency multiplication and sum of fundamental frequencies that near infrared spectrum is mainly organic molecule absorb, can obtain the abundant information of sample molecule structure, composition and physical state, it has and need not sample pretreatment, do not use chemical reagent, do not destroy sample, analysis speed is fast, and the acquisition of information amount is big, can only can finish the mensuration of its multinomial performance index in a few minutes by the collection of sample being finished a near infrared spectrum, be very economical and fast for regular quality monitoring.
Different with the conventional analysis technology, near infrared spectrum is a kind of indirect analysis technology, must realize qualitative or quantitative test to unknown sample by setting up calibration model, concrete analytic process mainly comprises following step: the one, and select representational sample and measure its near infrared spectrum; The 2nd, the reference method of employing standard or approval is measured component or the character data of being concerned about; The 3rd, the component measured or character data and near infrared spectrum are carried out related, set up discriminating model with suitable stoechiometric process; The 4th, measure unknown sample component or character.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, provide a kind of based on the method for adding chemical constitution in near-infrared spectrum technique fast detecting Chinese patent drug, health food or the food, detection speed soon, does not destroy sample, need not sample pretreatment, does not use chemical reagent, the number of chemical composition can be detected simultaneously, the needs of day-to-day supervision check can be satisfied.
Above-mentioned purpose of the present invention is achieved by following scheme:
A kind of based on the method for adding chemical constitution in near-infrared spectrum technique fast detecting Chinese patent drug, health food or the food, this method comprises to be set up qualitative discrimination model and unknown sample two stages of detection: setting up the discriminating model stage, need to collect the representative positive and the negative sample of various interpolation known chemical compositions, measure the kind and the quantity of adding the known chemical composition with the known method of inspection, gather near infrared spectrum simultaneously, setting up the incidence relation that adds chemical constitution information and near infrared spectrum by chemometrics method is discriminating model; Detection-phase at unknown sample, gather behind the spectrum of unknown sample with whether having added chemical constitution in the discriminating model judgement sample, model provides the differentiation result after automatically the reference spectra in sample spectra and the modeling sample storehouse being compared, and just the sample rapid screening that is added with chemical constitution can be come out.
Said method specifically comprises the steps:
(1) sample of collecting the different manufacturers different cultivars is set up the reference sample storehouse as representative sample;
(2) near infrared spectrum of each representative sample in the collection reference sample storehouse;
(3) with the known method of inspection each representative sample in the reference sample storehouse is carried out qualitative and quantitative analysis, and distinguish positive and negative sample;
(4) collect the reference substance of chemical constitution to be detected and gather near infrared spectrum;
(5) according to step (2) each spectrum of gained and step (4) gained spectrum, select the feature spectral coverage, set up discriminating model by chemometrics method;
(6) gather the near infrared spectrum of testing sample, and utilize the discriminating model of step (5) foundation to analyze, judge whether add chemical constitution in the testing sample.
Said method mainly is to carry out fast detecting to whether adding chemical constitution in Chinese patent drug, health food or the food, described chemical constitution comprises a lot, mainly be meant more illegal chemical constitutions of adding in Chinese patent drug, health food or food, as the illegal PDE that adds in tonifying kidney and strengthening yang class Chinese patent drug, health food and the food
5Type inhibitor (phosphodiesterase type-5 inhibitor, phosphodiesterase 5 type inhibitor) be exactly wherein a kind of typical case representative, comprise chemical constitutions such as silaenafil class, Tadalafei class, that non-class of red ground, the interpolation situation is general, and fakes increasing at the high-tech of test stone.
In the above-mentioned steps (1), differentiate that whether adding chemical constitution in the sample need compare unknown sample spectrum and reference sample spectrum, therefore set up reliable and stable reference sample storehouse, should collect the sample of various different cultivars, different manufacturers as far as possible from different approach.Generally speaking, the reference sample storehouse should comprise 10 above positive or 10 above negative samples at least.Relatively more difficult as modeling initial stage collection positive, can make positive by oneself according to the effective dose and the consumption adding plan inspection chemical constitution of this chemical constitution.
In the above-mentioned steps (2), should select suitable detection mode at different sample formulation when the sample in the reference sample storehouse is carried out near-infrared spectrum analysis: solid pharmaceutical preparation generally adopts diffuse reflection mode (as optical fiber diffuse reflection and integrating sphere diffuse reflection etc.); Liquid preparation generally adopts transmission mode.For capsule, near infrared luminous energy penetrates capsule shells, can see through the capsule shells measuring samples as required, and the sample that also can collect in the capsule is directly tested; For sugar coated tablet, measure after needing to remove sugar-coat; For Film coated tablets, light film-coating can directly be measured, and measures after black or sepia film-coating need be removed film-coating.
In the above-mentioned steps (3), select national standard method or literature method that each sample in the reference sample storehouse is carried out qualitative and quantitative analysis respectively, whether each sample adds the amount of the chemical constitution of chemical constitution and interpolation in the mensuration reference sample storehouse.General liquid chromatography and the LC-MS method of adopting carried out qualitative and quantitative analysis.
In the above-mentioned steps (4),, can judge what chemical constitution each sample adds in the sample library, collect the reference substance of these chemical constitutions then, gather near infrared spectrum according to the analysis result of step (3);
In the above-mentioned steps (5), near infrared spectrum and above-mentioned steps (2) acquisition near infrared spectrum that above-mentioned steps (4) is obtained compare, and find out the feature spectral coverage that adds chemical constitution.The selection of feature spectral coverage is a committed step of setting up discriminating model, add the feature spectral coverage of chemical constitution in the sample and should be able to distinguish positive and negative sample, therefore should be chosen in when setting up discriminating model in the spectrum of step (4) as far as possible absorption value strong and also in the negative sample spectrum of step (2) glitch-free feature spectral coverage carry out modeling.
In the above-mentioned steps (5), after near infrared spectrum by contrast step (4) and step (2) obtains the characteristic spectrum of chemical constitution, by chemometrics method, the qualitative and quantitative analysis result of integrating step (3) sets up the qualitative discrimination model of whether adding chemical constitution again.Setting up qualitative discrimination model by chemometrics method is the routine operation that present technique field personnel set up model, and common chemical metrology method has nearest neighbor method, techniques of discriminant analysis, principal component analysis (PCA), clustering methodology or the independent soft type method of bunch class (SIMCA) etc.The inventor contrasts discovery by experiment, adopts nearest neighbor method modeling effect best, sets up discriminating model as the IDENT program of the OPUS software that can adopt Bruker company.
The thinking of IDENT program qualitative analysis is to judge the difference of average reference spectrum in unknown sample spectrum and the modeling sample storehouse.Unknown sample collection of illustrative plates and each average reference spectrum compare in analytic process, and result relatively is called spectrum intervals, is also referred to as matching value.Unknown sample spectrum and average reference Spectral matching are good more, and distance is short more, and matching value is more little.The method that multiple relatively unknown sample spectrum and reference spectra are arranged, for example Standardization Act, factorization method, the first scope standardization, reappear horizontal normalization method or principal component analysis (PCA) etc., the present invention preferably adopts the factorization method, and Euclidean distance is adopted in the calculating of spectrum intervals.
The factorization method is the linear combination that spectrogram is expressed as factor spectrum.Factorization method and traditional principal component analysis (PCA) are similar, and difference is that the factorization method adopts the averaged spectrum of each class sample to analyze.When s class sample, the equal spectrum of s Zhang Ping is converted to the linear combination that s opens mutually orthogonal factor spectrum (loadings):
a=t
1a·f
1+t
2a·f
2+t
3a·f
3+...
Spectrum of a vector representation wherein; Factor stave is shown f
1, f
2, f
3Deng; T represents factor score (scores).The contribution of factor spectrum is represented in factor score, and factor score numerical value is big more, contribute greatly more, and the spectral intensity that the corresponding factor is composed is also big more.The factorization method can be carried out dimension-reduction treatment to the near infrared spectrum data of complexity, helps adding the extraction of chemical constitution characteristic spectrum, when setting up discriminating model, selects the factor score of chemical constitution characteristic spectrum to set up model.
In the above-mentioned steps (6), get the sample (as Chinese patent drug, health food or food etc.) that needs detection, gather the near infrared spectrum of testing sample earlier, the discriminating model of setting up with step (5) is analyzed, thereby judges whether add chemical constitution in the testing sample.The comparative analysis method can adopt those skilled in the art's commonly used technology when carrying out near-infrared spectrum analysis, as with the threshold comparison analysis etc.
Threshold value is meant an Euclidean distance limit to each class sample average reference spectra definition in the modeling sample storehouse, is exactly the fiducial interval of giving the definition of average reference spectrum.The process of setting up discriminating model is exactly to make in the reference sample storehouse Euclidean distance of adding with a kind of independent reference spectra of all samples of chemical constitution and their average reference spectrum all less than threshold value, and in the storehouse all other spectrum with the Euclidean distance of this average reference spectrum all greater than threshold value.The spectrum intervals D of spectrum a and spectrum b calculates as follows:
D is more little for spectrum intervals, and spectrum a is similar more to spectrum b.Threshold value D
TComputing method as follows:
D
T=D
Max+S·x
Wherein, D
MaxMaximum range value for each reference spectra in the modeling sample storehouse and average reference spectrum, S is a standard deviation, x is the self-defining confidence level factor (default value is 0.25), if the point of testing sample spectrum drops in the fiducial interval of interpolation with a kind of chemical constitution sample, be that matching value is less than threshold value, so just think that the sample that has added the sort of chemical constitution in testing sample and the reference sample storehouse belongs to same class, otherwise just do not belong to same class.
Above-mentioned steps (6), after by discriminating model testing sample being carried out check and analysis, can tentatively judge and whether illegally add chemical constitution in the testing sample, positive is also needed further examination at random, confirm (as liquid chromatography and LC-MS method) further with national standard method or literature method.Therefore the main effect of the inventive method is to realize that rapid screening goes out the suspicious specimen of whether illegally adding chemical constitution from a large amount of samples.
When concrete application qualitative discrimination model of the present invention, can suitably increase representative sample according to practical situations, expand reference diagram spectrogram storehouse, thereby constantly improve discriminating model.
In the method for the present invention, used sample and the testing sample of setting up discriminating model, but the concentration of its illegal chemical constitution of adding should be in the sensing range of near-infrared spectral analytical method.
Method of the present invention, when utilizing discriminating model that testing sample is detected, can adopt the method for multilayer identification to carry out, when multilayer identification is meant and sets up qualutative model based on a certain feature spectral coverage, preprocessing procedures and chemometrics method, when this condition can not be finished the identification each other of all modeling kinds and wherein a part of kind is discerned each other, can select other one group of condition for identification to be used for distinguishing the kind that last layer model can not be distinguished identification; Such process can repeat repeatedly to use, until all positive and negative sample being distinguished identification fully.As added PDE
5The sample of type inhibitor is called positive, does not add PDE
5The sample of type inhibitor is called negative sample, because PDE
5The type inhibitor is divided into silaenafil class, Tadalafei class and that non-class of red ground etc., so positive can be segmented again, is called the silaenafil positive as what add silaenafil, and that adds Tadalafei is called Tadalafei positive or the like.The near infrared spectrum discriminating model of the present invention identification that all kinds of positive and negative sample should be able to be distinguished from each other can be finished by above-mentioned multilayer identification mode when needing.
Method of the present invention, in order to improve the accuracy of discriminating model, similar sample further can be subdivided into different subclass and distinguish identification respectively, can be divided into silaenafil positive 1 or silaenafil positive 2 again as the silaenafil positive, negative sample is divided into negative sample 1 and negative sample 2.
Compared with prior art, the present invention has following beneficial effect:
1. the present invention adopts near-infrared spectrum technique that illegal chemical constitution of adding in Chinese patent drug, health food or the food is carried out fast detecting, detection speed is fast and do not destroy sample, need not sample pretreatment, also need not to use chemical reagent, can detect the chemical constitution of multiple illegal interpolation simultaneously, can satisfy the needs of day-to-day supervision check, thereby can improve the efficient of supervision and inspection greatly, reduce the cost of supervision and inspection;
2. method of the present invention is collected representative sample and is set up the reference sample storehouse, by selecting to add the characteristic spectrum of chemical constitution, and positive and negative sample be subdivided into class and subclass, and adopt nearest neighbor method and multilayer identification mode to carry out modeling, make qualitative discrimination model more accurate;
3. the present invention is by setting up qualitative discrimination model in advance, follow-up near infrared spectrum that needs to gather testing sample, passing threshold judges whether testing sample spectrum belongs to the reference spectra in the modeling sample storehouse, can detect the chemical constitution that whether contains illegal interpolation in the testing sample rapidly.
Embodiment
At present bibliographical information a large amount of in tonifying kidney and strengthening yang class sample the illegal PDE that add
5The type inhibitor, so present embodiment is to detect in tonifying kidney and strengthening yang class Chinese patent drug, health food or the food whether illegally be added with PDE
5The type inhibitor is an example, introduce the specific implementation process of the inventive method in detail, but present embodiment is not only done any qualification to the present invention as example of the present invention, those skilled in the art can clearly understand the present invention by the description of present embodiment, and are applied to whether contain in other Chinese patent drugs, health food or the food fast detecting of the chemical constitution of illegal interpolation.
PDE
5The type inhibitor can be divided into silaenafil class (as sildenafil citrate, person of outstanding talent silaenafil, hydroxyl person of outstanding talent silaenafil not), Vardenafil class (as Vardenafil, pseudo-Vardenafil), Tadalafei class (as Tadalafei, amino Tadalafei) and that non-class of red ground (as that is non-on red ground, that is non-on hydroxyl red ground) etc. according to chemical constitution, wherein add frequency the highest for silaenafil, be Tadalafei secondly.Illegal formulation of adding chemical constitution is mainly hard capsule, is tablet and pill secondly.
Higher according to the near-infrared spectrum analysis model accuracy that packing and formulation are set up respectively.In conjunction with the actual conditions of collecting sample, present embodiment selects to set up the discriminating model of silaenafil and Tadalafei capsule, whether adds PDE in tonifying kidney and strengthening yang class Chinese patent drug, health food and the food to the capsule packing then
5The type inhibitor carries out fast detecting, and its concrete steps are as follows:
(1) the tonifying kidney and strengthening yang class sample of collecting 59 different manufacturers variable concentrations from market is set up the reference sample storehouse as representative sample, comprises Chinese patent drug, health food and food;
(2) gather the near infrared spectrum of above-mentioned 59 samples: MPA and MATRIX-F type spectrometer with German Bruker company are gathered near infrared spectrum respectively, and metering system is the optical fiber diffuse reflection, and through the capsule shells measuring samples, condition determination is resolution 8cm
-1, scanning times 32 times, data area 4,000 to 12,000cm
-1, detecting device is an indium gallium arsenic, each sample measurement 3 times;
(3) above-mentioned 59 samples are carried out liquid chromatography and LC-MS analysis, negative sample and positive are distinguished in qualitative analysis, (sample of present embodiment definition interpolation silaenafil is the silaenafil positive, the sample that has added Tadalafei is the Tadalafei positive, and the sample that does not add silaenafil and Tadalafei is called negative sample); According to liquid chromatography and LC-MS analysis result, the silaenafil positive is 16 in 59 samples of reference sample, Tadalafei positive 17,26 of negative samples;
(4) collect silaenafil and Tadalafei reference substance, gather near infrared spectrum respectively;
(5) set up discriminating model: adopt the IDENT program of the Bruker OPUS of company software to set up qualitative discrimination model, concrete steps are as follows:
A. according to the analysis result of step (3), according to the kind and the concentration of interpolation chemical constitution, 59 representative capsule samples further are subdivided into silaenafil positive 1, silaenafil positive 2, silaenafil positive 3, Tadalafei positive 1, Tadalafei positive 2, negative sample 1 and 2 seven subclass of negative sample.In 59 samples, 5 is that 1,9 of silaenafil positive is a silaenafil positive 2,2 is that 3,6 of silaenafil positive are that 1,11 of Tadalafei positive is a Tadalafei positive 2,1,14 negative sample 2 of 12 negative samples.Sample size is the employing averaged spectrum modeling more than 5 or 5, be lower than 5 use the original spectrum modeling;
B. select the feature spectral coverage: for tonifying kidney and strengthening yang class sample, the preferred feature spectral coverage of silaenafil positive is 6240cm
-1~5960cm
-1And 5670cm
-1~5635cm
-1, the preferred feature spectral coverage of tadalafil positive is 6120cm
-1~6010cm
-1, 5900cm
-1~5860cm
-1, 5725cm
-1~5690cm
-1And 5670cm
-1~5635cm
-1
C. the correction of spectrum and pre-service: spectrum correction and pre-service are the routine operations of those skilled in the art when spectrum is carried out analyzing and processing, its effect is with the spectrum standardization, eliminates background interference, improves spectral quality, and will be hidden in that signal difference amplifies out in the collection of illustrative plates, make qualitative identification directly perceived more, reliable.Present embodiment selects the combination of " second derivative " and " vector normalization " as preprocess method;
D. select the factorization method to calculate spectrum intervals, generally select 1~2 factor;
E. the optimization of modelling verification and model parameter: whether the fiducial interval of different cultivars averaged spectrum is overlapping in the checking modeling sample storehouse, if find overlappingly, needs by selecting different spectral coverages, factor score, level and smooth point, adjusting methods such as threshold value and remove overlapping; Present embodiment adopts multilayer identification (five layers) that above-mentioned positive and negative sample are distinguished identification fully: ground floor identification silaenafil positive 1 and silaenafil positive 2; Second layer identification silaenafil positive 3; The 3rd layer of identification Tadalafei positive 1; The 4th layer of identification Tadalafei positive 2; Negative sample 1 of layer 5 and negative sample 2 do not need further to distinguish identification, are defined as a class;
With the qualutative model that above-mentioned five layers of recognition method are set up, above-mentioned seven subclass in modeling sample storehouse can be distinguished discriminating fully.
(6) discriminating model of utilizing above-mentioned steps (5) to set up is analyzed unknown sample, whether adds PDE in the test sample
5The type inhibitor, decision rule is as follows as a result:
A. the differentiation result of discriminating model has four kinds: " the silaenafil positive " (comprising silaenafil positive 1, silaenafil positive 2 and the silaenafil positive 3), " the Tadalafei positive " (comprising the Tadalafei positive 1 and the Tadalafei positive 2), " feminine gender " (comprising negative 1 and negative 2) and " other " (promptly can not discern); PDE
5The chemical constitution of type inhibitor is more similar, has added other PDE
5The sample of type inhibitor very likely similar feature spectral coverage also occurs at the characteristic spectrum area with silaenafil and Tadalafei positive, so result of determination has been added other PDE that remove silaenafil and Tadalafei for " other " might be in the sample
5The type inhibitor, that is non-, the bold and unconstrained not silaenafil of hydroxyl etc. as Vardenafil, red ground; Though the discriminating model of present embodiment has only been selected silaenafil and Tadalafei positive, also can identify the PDE of other structural similarities simultaneously
5The type inhibitor; When testing sample between the positive fiducial interval of two class silaenafils or between the positive fiducial interval of two class Tadalafeis, when not being positioned at the fiducial interval of negative sample again, result of determination also can be " other "; Therefore, except that feminine gender, " the silaenafil positive ", " the Tadalafei positive " and " other " all are judged to be the positive;
B. there is multiple interpolation PDE in the tonifying kidney and strengthening yang class sample
5The situation of type inhibitor most of is added a kind of chemical constitution, and secondly for adding two kinds of chemical constitutions, the sample that adds three kinds and above chemical constitution is less; Method of the present invention mainly is that sample is carried out rapid screening, and the suspicious specimen that examination is come out need further confirm that also therefore the decision rule of qualitative discrimination model of the present invention is for having added several PDE regardless of in the sample with technology such as liquid chromatography and LC-MS analyses
5The type inhibitor has added wherein a kind of positive that promptly is judged as long as identify;
C. the PDE that adds in the tonifying kidney and strengthening yang class sample
5Type inhibitor kind is a lot, and the overwhelming majority is the derivant of silaenafil, Vardenafil and Tadalafei, when having added other PDE
5When the type inhibitor was judged as the silaenafil positive or the Tadalafei positive, the result was correct.
The tonifying kidney and strengthening yang class sample of collecting 305 different manufacturers variable concentrations from market adopts the method for present embodiment to detect as unknown sample, simultaneously these 305 unknown samples are adopted liquid chromatography and LC-MS analysis, the testing result of two kinds of methods is compared, found that 2 in false positive sample, 2 in false negative sample, rate of accuracy reached to 98.7% illustrates of the present invention based on near-infrared spectrum technique fast detecting Chinese patent drug thus, the method of adding chemical constitution in health food or the food can satisfy supervision and inspection carries out the quick nondestructive examination at the scene to sample requirement.
Claims (6)
1, a kind of based on the method for adding chemical constitution in near-infrared spectrum technique fast detecting Chinese patent drug, health food or the food, it is characterized in that this method comprises to set up discriminating model and testing sample detects two stages, specifically comprise the steps:
(1) sample of collecting the different manufacturers different cultivars is set up the reference sample storehouse as representative sample;
(2) near infrared spectrum of each representative sample in the collection reference sample storehouse;
(3) with the known method of inspection each representative sample in the reference sample storehouse is carried out qualitative and quantitative analysis, and distinguish positive and negative sample;
(4) collect the reference substance of chemical constitution to be detected and gather near infrared spectrum;
(5) according to step (2) each spectrum of gained and step (4) gained spectrum, select the feature spectral coverage, set up discriminating model by chemometrics method;
(6) gather the near infrared spectrum of testing sample, and utilize the discriminating model of step (5) foundation to analyze, judge whether add chemical constitution in the testing sample.
2, according to the described method of claim 1, it is characterized in that in the described step (3), each representative sample in the reference sample storehouse is carried out qualitative and quantitative analysis after, similar sample further is subdivided into different subclass distinguishes identification respectively.
3, according to the described method of claim 1, it is characterized in that in the described step (5), select the feature spectral coverage set up in the reference substance near infrared spectrum that discriminating model is selected at step (4) absorption value strong and also in the near infrared spectrum of step (2) negative sample glitch-free feature spectral coverage.
4,, it is characterized in that the described discriminating model of setting up adopts nearest neighbor method according to the described method of claim 1 step (5).
5, according to the method for claim 1, it is characterized in that in the described step (5), distinguish various modeling kinds by multilayer identification when setting up discriminating model.
6, according to the method for claim 1, it is characterized in that in the described step (6), adopt threshold value to come the judgement sample near infrared spectrum whether to belong to reference spectra in the modeling sample storehouse.
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