CN103954608A - Method for identifying whether blood-glucose-lowering traditional Chinese medicine contains pioglitazone or rosiglitazone or not - Google Patents
Method for identifying whether blood-glucose-lowering traditional Chinese medicine contains pioglitazone or rosiglitazone or not Download PDFInfo
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- CN103954608A CN103954608A CN201410211927.XA CN201410211927A CN103954608A CN 103954608 A CN103954608 A CN 103954608A CN 201410211927 A CN201410211927 A CN 201410211927A CN 103954608 A CN103954608 A CN 103954608A
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- blood
- rosiglitazone
- pioglitazone
- sugar lowering
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- HYAFETHFCAUJAY-UHFFFAOYSA-N pioglitazone Chemical compound N1=CC(CC)=CC=C1CCOC(C=C1)=CC=C1CC1C(=O)NC(=O)S1 HYAFETHFCAUJAY-UHFFFAOYSA-N 0.000 title claims abstract description 198
- YASAKCUCGLMORW-UHFFFAOYSA-N Rosiglitazone Chemical compound C=1C=CC=NC=1N(C)CCOC(C=C1)=CC=C1CC1SC(=O)NC1=O YASAKCUCGLMORW-UHFFFAOYSA-N 0.000 title claims abstract description 196
- 239000003814 drug Substances 0.000 title claims abstract description 173
- 229960005095 pioglitazone Drugs 0.000 title claims abstract description 99
- 229960004586 rosiglitazone Drugs 0.000 title claims abstract description 98
- 238000000034 method Methods 0.000 title claims abstract description 53
- 238000001228 spectrum Methods 0.000 claims abstract description 47
- 238000004809 thin layer chromatography Methods 0.000 claims abstract description 11
- 229940079593 drug Drugs 0.000 claims description 157
- 238000001069 Raman spectroscopy Methods 0.000 claims description 82
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 claims description 52
- 230000003287 optical effect Effects 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 27
- SUFUKZSWUHZXAV-BTJKTKAUSA-N rosiglitazone maleate Chemical compound [H+].[H+].[O-]C(=O)\C=C/C([O-])=O.C=1C=CC=NC=1N(C)CCOC(C=C1)=CC=C1CC1SC(=O)NC1=O SUFUKZSWUHZXAV-BTJKTKAUSA-N 0.000 claims description 27
- 229960003271 rosiglitazone maleate Drugs 0.000 claims description 27
- 230000001360 synchronised effect Effects 0.000 claims description 21
- 239000012744 reinforcing agent Substances 0.000 claims description 20
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 19
- 229910052709 silver Inorganic materials 0.000 claims description 15
- 239000004332 silver Substances 0.000 claims description 15
- 239000008279 sol Substances 0.000 claims description 11
- 239000000956 alloy Substances 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 230000002035 prolonged effect Effects 0.000 claims description 7
- 238000012937 correction Methods 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 238000004458 analytical method Methods 0.000 claims description 4
- 238000011156 evaluation Methods 0.000 claims 7
- 238000001514 detection method Methods 0.000 abstract description 6
- 238000000479 surface-enhanced Raman spectrum Methods 0.000 abstract 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 230000008569 process Effects 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000002218 hypoglycaemic effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 101710134784 Agnoprotein Proteins 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000010923 batch production Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- GLYLMXARZJNUEY-UHFFFAOYSA-N dichloromethane;methanol;hydrate Chemical compound O.OC.ClCCl GLYLMXARZJNUEY-UHFFFAOYSA-N 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 4
- 239000013558 reference substance Substances 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 229910001961 silver nitrate Inorganic materials 0.000 description 4
- 239000001509 sodium citrate Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 4
- 229940038773 trisodium citrate Drugs 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 206010008190 Cerebrovascular accident Diseases 0.000 description 1
- 208000013016 Hypoglycemia Diseases 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 208000006011 Stroke Diseases 0.000 description 1
- 229940127003 anti-diabetic drug Drugs 0.000 description 1
- 239000003472 antidiabetic agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- -1 contains TLC Chemical compound 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000857 drug effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 208000010125 myocardial infarction Diseases 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Landscapes
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention provides a method for identifying whether a blood-glucose-lowering traditional Chinese medicine contains pioglitazone or rosiglitazone or not. The method comprises the following steps: carrying out thin layer chromatography on a blood-glucose-lowering traditional Chinese medicine to be detected; finding a suspected spot at a corresponding Rf value part of the pioglitazone and the rosiglitazone. The method is characterized by further comprising the following three steps: 1, collecting a series of one-dimensional surface enhanced Raman spectrums of the suspected spot to obtain a dynamic spectrum pattern of the blood-glucose-lowering traditional Chinese medicine to be detected; 2, pre-treating the dynamic spectrum pattern and drawing to obtain a two-dimensional correlation surface enhanced Raman spectrum of the blood-glucose-lowering traditional Chinese medicine to be detected; 3, judging whether the blood-glucose-lowering traditional Chinese medicine contains the pioglitazone or the rosiglitazone or not according to the two-dimensional correlation surface enhanced Raman spectrum of the blood-glucose-lowering traditional Chinese medicine to be detected. According to the technical scheme provided by the invention, whether the blood-glucose-lowering traditional Chinese medicine contains the pioglitazone or the rosiglitazone or not can be identified rapidly; the detection result is accurate and reliable, the cost is low and the operation is convenient.
Description
Technical field
The present invention relates to a kind of method of whether adding Pioglitazone or Rosiglitazone in blood-sugar lowering tcm drug of identifying, belong to medicine analysis technical field.
Background technology
In recent years, some pharmaceutical factories are in order to seek great number interests, in blood-sugar lowering tcm drug, add cheap, drug effect is suitable hypoglycemic Western medicine PIOGITAZONE HYDROCHLORIDE, Rosiglitazone Maleate or the potpourri of the two, although these hypoglycemic Western medicine also can play blood sugar reducing function, but side effect is larger, especially Rosiglitazone Maleate, because of its probability that can significantly increase user's heart attack and apoplexy, food and drug administration is comprehensive this product of undercarriage in 2011.If patient's long-term taking has added these hypoglycemic Western medicine blood-sugar lowering tcm drugs, not only can cause the multiple bad reactions such as hypoglycemia, even entail dangers to is sick, produces serious consequence.Therefore, identify in hypoglycemic class Chinese medicine whether added Pioglitazone or Rosiglitazone, an important process of Shi Yaojian department.
The method of the current detection for adulterate in blood-sugar lowering tcm drug Rosiglitazone Maleate and PIOGITAZONE HYDROCHLORIDE mainly contains TLC, HPLC, LC-MS etc.Although TLC method is simple and quick, but only can make superficial judgement to whether adulterated in antidiabetic drug, to what specifically adulterate in adulterated blood-sugar lowering tcm drug, be that what composition can not be identified, and the method is subject to the impact of Chinese medicine matrix and adulterated amount and demonstrate false positive or false-negative result.Although what HPLC and LC-MS can be to concrete doping in adulterated blood-sugar lowering tcm drug is Pioglitazone or Rosiglitazone or the potpourri of the two judges, but analytical cycle is long, experiment condition is harsh, need specific chromatographic column, mobile equating, testing cost is higher, especially Dang Yaojian department need to be at the scene to whether adding PIOGITAZONE HYDROCHLORIDE or Rosiglitazone Maleate or the two in blood-sugar lowering tcm drug all has to add to make and detects and during judgement, these methods will be difficult to be suitable for.
Summary of the invention
The object of this invention is to provide a kind of method of whether adding Pioglitazone or Rosiglitazone in blood-sugar lowering tcm drug of identifying, to address the above problem.
To achieve these goals, the technical solution adopted in the present invention is:
In a kind of blood-sugar lowering tcm drug, add the authentication method of Pioglitazone or Rosiglitazone, the method comprises that getting blood-sugar lowering tcm drug to be checked carries out thin-layer chromatography, the Rf value place corresponding with Rosiglitazone at Pioglitazone finds doubtful spot, it is characterized in that, also comprises following three steps:
Step 1: the collection of dynamic optical spectrogram
Get surface reinforcing agent point on doubtful spot, adopt Raman spectrometer, the laser of choosing some strength carries out perturbation to doubtful spot prolonged exposure, and gather a series of one dimension Surface enhanced raman spectroscopy of doubtful spot, obtain the dynamic spectrum of blood-sugar lowering tcm drug to be checked, the integral time of every one dimension Surface enhanced raman spectroscopy is identical, some strength is any number between 100mW～200mW, surface reinforcing agent is aurosol, silver sol or gold and silver rubber alloy, and the point sample amount of surface reinforcing agent is 2 μ L～10 μ L;
Step 2: the drafting of two-dimensional correlation Surface enhanced raman spectroscopy figure
Dynamic optical spectrogram is carried out to pre-service, comprise and choose 300cm
-1～1700cm
-1spectral coverage, employing Sgolay method are carried out level and smooth and adopt airPLS method to carry out baseline correction, obtain the pre-service Raman spectrogram of blood-sugar lowering tcm drug to be checked, according to pre-service Raman spectrogram, draw the two-dimensional correlation Surface enhanced raman spectroscopy figure that obtains blood-sugar lowering tcm drug to be checked;
Step 3: to whether adding Pioglitazone or Rosiglitazone is identified
According to the two-dimensional correlation Surface enhanced raman spectroscopy figure of blood-sugar lowering tcm drug to be checked, in this spectrogram, contain the relevant peaks with differ-w～w wave number that goes out peak position of the relevant peaks of Pioglitazone, judge in blood-sugar lowering tcm drug to be checked and contain Pioglitazone, in this spectrogram, contain the relevant peaks with differ-w～w wave number that goes out peak position of the relevant peaks of Rosiglitazone, judge in blood-sugar lowering tcm drug to be checked and contain Rosiglitazone, in this spectrogram, do not contain with Pioglitazone and Rosiglitazone the relevant peaks of differ-w～w wave number that goes out peak position of relevant peaks, judge and in blood-sugar lowering tcm drug to be checked, do not contain Pioglitazone and Rosiglitazone, w is 1cm
-1～5cm
-1between any number, the peak position that goes out of the relevant peaks of Pioglitazone is set to: 414cm
-1, 430cm
-1, 475cm
-1, 824cm
-1, the peak position that goes out of the relevant peaks of Rosiglitazone is set to: 739cm
-1, 1255cm
-1, 1329cm
-1.
The present invention also provides such technical scheme:
In a kind of blood-sugar lowering tcm drug, whether add the authentication method of Pioglitazone or Rosiglitazone, the method comprises: get blood-sugar lowering tcm drug to be checked and carry out thin-layer chromatography, the Rf value place corresponding with Rosiglitazone at Pioglitazone finds doubtful spot, it is characterized in that, also comprises following three steps:
Step 1: the collection of dynamic optical spectrogram
Blood-sugar lowering tcm drug to be checked, Pioglitazone standard items and Rosiglitazone standard items are carried out after thin-layer chromatography, on thin layer plate, find doubtful spot, Pioglitazone and three spots of Rosiglitazone,
Get surface reinforcing agent respectively o'clock on three spots, adopt Raman spectrometer, the laser of choosing some strength carries out perturbation to three spot prolonged exposures respectively, and gather respectively a series of one dimension Surface enhanced raman spectroscopy of three spots, obtain doubtful spot, the dynamic optical spectrogram of Pioglitazone and Rosiglitazone, the integral time of all one dimension Surface enhanced raman spectroscopy of each spot is all identical, some strength is any number between 100mW～200mW, surface reinforcing agent is aurosol, silver sol or gold and silver rubber alloy, the point sample amount of surface reinforcing agent is 2 μ L～10 μ L,
Step 2: the drafting of two-dimensional correlation Surface enhanced raman spectroscopy figure
Respectively the dynamic optical spectrogram of blood-sugar lowering tcm drug to be checked, Pioglitazone standard items and Rosiglitazone standard items is carried out to pre-service, comprise and choose 300cm
-1～1700cm
-1spectral coverage, employing Sgolay method are carried out level and smooth and adopt airPLS method to carry out baseline correction, obtain the pre-service Raman spectrogram of blood-sugar lowering tcm drug to be checked, Pioglitazone standard items and Rosiglitazone standard items, according to pre-service Raman spectrogram, draw respectively the two-dimensional correlation Surface enhanced raman spectroscopy figure that obtains three;
Step 3: the Analysis and judgments of two-dimensional correlation Surface enhanced raman spectroscopy figure
The two-dimensional correlation Surface enhanced raman spectroscopy figure of blood-sugar lowering tcm drug to be checked is compared with the two-dimensional correlation Surface enhanced raman spectroscopy figure of Pioglitazone standard items and Rosiglitazone standard items respectively, in the two-dimensional correlation Surface enhanced raman spectroscopy figure of blood-sugar lowering tcm drug to be checked, contain the relevant peaks with differ-w～w wave number that goes out peak position of the relevant peaks of Pioglitazone standard items, judge in blood-sugar lowering tcm drug to be checked and contain Pioglitazone, in the two-dimensional correlation Surface enhanced raman spectroscopy figure of blood-sugar lowering tcm drug to be checked, contain the relevant peaks with differ-w～w wave number that goes out peak position of the relevant peaks of Rosiglitazone standard items, judge in blood-sugar lowering tcm drug to be checked and contain Rosiglitazone, in the two-dimensional correlation Surface enhanced raman spectroscopy figure of blood-sugar lowering tcm drug to be checked, do not contain with Pioglitazone standard items and Rosiglitazone standard items the relevant peaks of differ-w～w wave number that goes out peak position of relevant peaks, judge and in blood-sugar lowering tcm drug to be checked, do not contain Pioglitazone and Rosiglitazone, w is 1cm
-1～5cm
-1between any number.
Technical scheme of the present invention is further characterized in that: Pioglitazone standard items are PIOGITAZONE HYDROCHLORIDE standard items, and Rosiglitazone standard items are Rosiglitazone Maleate standard items.
The technical scheme of the invention described above is further characterized in that: some strength is 200mW.
The technical scheme of the invention described above is further characterized in that: two-dimensional correlation Surface enhanced raman spectroscopy figure is synchronous spectrum.
The technical scheme of the invention described above is further characterized in that: laser is provided by the LASER Light Source of Raman spectrometer self.
The technical scheme of the invention described above is further characterized in that: surface reinforcing agent is nano silver colloidal sol.
The technical scheme of the invention described above is further characterized in that: the point sample amount of surface reinforcing agent is 4 μ L～6 μ L.
The technical scheme of the invention described above is further characterized in that: w is 5cm
-1.
Compare with background technology, advantage and the good effect of technical scheme of the present invention are as follows:
1. can to whether adding Pioglitazone in blood-sugar lowering tcm drug or Rosiglitazone is differentiated fast
Technical scheme of the present invention adopts laser to carry out perturbation to doubtful spot place, adopt Raman spectrometer to detect the two-dimensional correlation Surface enhanced raman spectroscopy figure that obtains blood-sugar lowering tcm drug to be checked, by judge this dimension relevant surfaces strengthen in Raman spectrogram, whether contain with Pioglitazone or Rosiglitazone go out peak position identical automatic peak or relevant peaks, can realize whether adding Pioglitazone in blood-sugar lowering tcm drug to be checked or Rosiglitazone is judged, compare with LC-MS with HPLC, do not need harsh experiment condition and complicated sample pre-treatments work, can identify fast and in blood-sugar lowering tcm drug to be checked, whether add Pioglitazone or Rosiglitazone.
2. characteristic is strong, and testing result accurately and reliably
Because Raman spectroscopy has extremely strong characteristic, and very low to the content requirement of detection material, therefore the drawn qualification result of technical scheme according to the present invention accurately and reliably, compare with TLC, avoided the appearance of false positive or false negative result, staff that can Wei Yaojian department provides foundation and the guidance of science.
3. cost is low, easy to operate
Technical scheme of the present invention adopts thin layer plate and Raman spectrometer to implement, equipment and experimental situation require simple, cost is low, easy to operate, when the Raman spectrometer adopting is portable or hand-held, can realize whether adding Rosiglitazone Maleate in blood-sugar lowering tcm drug and PIOGITAZONE HYDROCHLORIDE carries out on-the-spot Rapid identification.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of technical scheme of the present invention in embodiment mono-;
Fig. 2 is Raman spectrogram after the pre-service of blood-sugar lowering tcm drug to be checked in embodiment mono-;
Fig. 3 is Raman spectrogram after the pre-service of PIOGITAZONE HYDROCHLORIDE standard items in embodiment mono-;
Fig. 4 is Raman spectrogram after the pre-service of Rosiglitazone Maleate standard items in embodiment mono-;
Fig. 5 is that the two-dimensional correlation surface-enhanced Raman synchronous spectrum of blood-sugar lowering tcm drug to be checked in embodiment mono-is divided into the sync correlation spectrum obtaining after three sections;
Fig. 6 is that the two-dimensional correlation surface-enhanced Raman synchronous spectrum of PIOGITAZONE HYDROCHLORIDE standard items in embodiment mono-is divided into the sync correlation spectrum obtaining after three sections;
Fig. 7 is that the two-dimensional correlation surface-enhanced Raman synchronous spectrum of Rosiglitazone Maleate standard items in embodiment mono-is divided into the sync correlation spectrum obtaining after three sections;
Fig. 8 is the process flow diagram of technical scheme of the present invention in embodiment bis-;
Fig. 9 is Raman spectrogram after the pre-service of blood-sugar lowering tcm drug to be checked in embodiment bis-;
Figure 10 is that the two-dimensional correlation surface-enhanced Raman synchronous spectrum of blood-sugar lowering tcm drug to be checked in embodiment bis-is divided into the sync correlation spectrum obtaining after three sections;
Figure 11 is Raman spectrogram after the pre-service of hypoglycemic sample to be checked in embodiment tri-; And
Figure 12 is that the two-dimensional correlation surface-enhanced Raman synchronous spectrum of hypoglycemic sample to be checked in embodiment tri-is divided into the sync correlation spectrum obtaining after three sections.
Embodiment
Below in conjunction with accompanying drawing, to whether adding the detection method of analogue in medicine involved in the present invention, be described further.
Related concept explanation in following examples:
Synchronous spectrum: sign be direction and the collaborative degree of two wave number place change in signal strength, when two dynamic change homophases (anti-phase), be worth for just (bearing); When dynamic change quadrature, value is zero.
Relevant peaks: diagonal line and off-diagonal region all there will be, comprises automatic peak and intersects peak.
Automatically peak: be positioned at the relevant peaks on principal diagonal, expression be the auto-correlation spectrum peak of the same wave number under same disturbance, the sensitivity that its intensity reflects system is externally disturbed.
Intersection peak: be positioned at the intersection peak on off-diagonal, expression is positioned at the synchronous variation at the peak of different wave numbers, represents that the variation at two peaks has common mechanism and origin.
< embodiment mono->
One, instrument and sample
(1) instrument: BWS415-785H type Portable Raman spectrometer (U.S. Bi Da Imtech), excitation wavelength 785nm;
(2) silver sol preparation: get silver nitrate (AgNO
3) 17mg adds secondary deionized water 100ml and dissolve, and adds 1% trisodium citrate 1.6ml, puts in micro-wave oven with high fire heating 6min, solution is celadon, is cooled to room temperature, adds water to scale place, standby.
(3) preparation of blood-sugar lowering tcm drug solution to be checked and reference substance solution: get the blood-sugar lowering tcm drug of A pharmaceutical factory batch production as blood-sugar lowering tcm drug to be checked, get respectively blood-sugar lowering tcm drug to be checked, PIOGITAZONE HYDROCHLORIDE standard items and Rosiglitazone Maleate standard items appropriate, make the methanol solution of blood-sugar lowering tcm drug to be checked, PIOGITAZONE HYDROCHLORIDE standard items and the Rosiglitazone Maleate standard items of 1mol/L.
Two, blood-sugar lowering tcm drug to be checked is detected
Fig. 1 is the process flow diagram of technical scheme of the present invention in embodiment mono-.
As shown in Figure 1, in the present embodiment one, measure in this blood-sugar lowering tcm drug to be checked whether add PIOGITAZONE HYDROCHLORIDE or Rosiglitazone Maleate, comprise following three steps:
Step 1 (S1): the collection of dynamic optical spectrogram
Get 1 μ l blood-sugar lowering tcm drug to be checked, the methanol solution of PIOGITAZONE HYDROCHLORIDE standard items and Rosiglitazone Maleate standard items is put respectively on silica gel thin-layer plate (hereinafter to be referred as thin layer plate), after methylene chloride-methanol-water (volume ratio 8:2:0.2) launches, taking-up volatilizes, under uviol lamp 254nm, inspect PIOGITAZONE HYDROCHLORIDE standard items and the speckle displacement of Rosiglitazone Maleate standard items on thin layer plate, be labeled as respectively Pioglitazone and Rosiglitazone, inspect in the chromatogram band of this blood-sugar lowering tcm drug to be checked with PIOGITAZONE HYDROCHLORIDE standard items and Rosiglitazone Maleate standard items relevant position also there is chromatogram spot, this chromatogram spot is labeled as to doubtful spot, get 5 μ l silver sols, drip respectively in doubtful spot, on three spots of Pioglitazone and Rosiglitazone.
The laser intensity of Raman spectrometer is adjusted to 200mW, adopt the laser of the 200mW that the LASER Light Source of this Raman spectrometer self provides, doubtful spot place prolonged exposure is carried out to perturbation, gather a series of Surface enhanced raman spectroscopy at doubtful spot place simultaneously, be 5s the integral time of every Surface enhanced raman spectroscopy, a series of Surface enhanced raman spectroscopy of gained are the dynamic spectrum of blood-sugar lowering tcm drug to be checked.In spectra collection process, keep laser intensity constant, illuminated laser spot is constant.
With reference to said method, obtain respectively PIOGITAZONE HYDROCHLORIDE standard items and Rosiglitazone Maleate standard items dynamic spectrum.
Step 2 (S2): the drafting of two-dimensional correlation Surface enhanced raman spectroscopy figure
Fig. 2 is Raman spectrogram after the pre-service of blood-sugar lowering tcm drug to be checked in embodiment mono-.
Fig. 3 is Raman spectrogram after the pre-service of PIOGITAZONE HYDROCHLORIDE standard items in embodiment mono-.
Fig. 4 is Raman spectrogram after the pre-service of Rosiglitazone Maleate standard items in embodiment mono-.
Utilize Matlab7.6 software to carry out pre-service to the dynamic optical spectrogram of this blood-sugar lowering tcm drug to be checked, comprise that spectral coverage chooses (300cm
-1～1700cm
-1), level and smooth (Sgolay method) and baseline correction (airPLS method), obtain the pre-service Raman spectrogram of this blood-sugar lowering tcm drug to be checked as shown in Figure 2, with reference to pre-service aforesaid operations, obtain respectively Raman spectrogram after the pre-service of Raman spectrogram after the pre-service of PIOGITAZONE HYDROCHLORIDE standard items as shown in Figure 3 and Rosiglitazone Maleate standard items as shown in Figure 4.
Fig. 5 is that the two-dimensional correlation surface-enhanced Raman synchronous spectrum of blood-sugar lowering tcm drug to be checked in embodiment mono-is divided into the sync correlation spectrum obtaining after three sections.
Fig. 6 is that the two-dimensional correlation surface-enhanced Raman synchronous spectrum of PIOGITAZONE HYDROCHLORIDE standard items in embodiment mono-is divided into the sync correlation spectrum obtaining after three sections.
Fig. 7 is that the two-dimensional correlation surface-enhanced Raman synchronous spectrum of Rosiglitazone Maleate standard items in embodiment mono-is divided into the sync correlation spectrum obtaining after three sections.
By 2Dshiger version1.3 software, software dynamic spectrum is set to averaged spectrum, contour parameter is 8, pre-service Raman spectrogram to blood-sugar lowering tcm drug to be checked is processed, drafting obtains the two-dimensional correlation surface-enhanced Raman synchronizable optical spectrogram of this blood-sugar lowering tcm drug to be checked, by the two-dimensional correlation surface-enhanced Raman synchronous spectrum (300cm of PIOGITAZONE HYDROCHLORIDE standard items
-1～1700cm
-1) be divided into 300cm as shown in Figure 5
-1～500cm
-1, 500cm
-1～1000cm
-1, and 1000cm
-1～1700cm
-1three sections, wherein 5-a is 1000cm
-1～1700cm
-1section, 5-b is 500cm
-1～1000cm
-1section, 5-c is 300cm
-1～500cm
-1section.
With reference to above-mentioned method for drafting and partition method, draw and obtain the two-dimensional correlation surface-enhanced Raman synchronizable optical spectrogram of PIOGITAZONE HYDROCHLORIDE standard items and Rosiglitazone Maleate standard items and carry out subregion respectively, obtain the two-dimensional correlation surface-enhanced Raman synchronous spectrum of PIOGITAZONE HYDROCHLORIDE as shown in Figure 6 and maleic acid two-dimensional correlation surface-enhanced Raman synchronous spectrum as shown in Figure 7, as shown in Figure 6,6-a is 1000cm in the two-dimensional correlation surface-enhanced Raman synchronous spectrum of PIOGITAZONE HYDROCHLORIDE standard items
-1～1700cm
-1section figure, 6-b is 500cm
-1～1000cm
-1section, 6-c is 300cm
-1～500cm
-1section; As shown in Figure 7,7-a is 1000cm in the two-dimensional correlation surface-enhanced Raman synchronous spectrum of Rosiglitazone Maleate standard items
-1～1700cm
-1section figure, 7-b is 500cm
-1～1000cm
-1section, 7-c is 300cm
-1～500cm
-1section.
Step 3 (S3): to whether adding Pioglitazone or Rosiglitazone is identified
The two-dimensional correlation Surface enhanced raman spectroscopy figure of blood-sugar lowering tcm drug to be checked is compared with the two-dimensional correlation Surface enhanced raman spectroscopy figure of Pioglitazone standard items and Rosiglitazone standard items respectively, in the two-dimensional correlation Surface enhanced raman spectroscopy figure of blood-sugar lowering tcm drug to be checked, contain the relevant peaks with differ-w～w wave number that goes out peak position of the relevant peaks of Pioglitazone standard items, judge in blood-sugar lowering tcm drug to be checked and contain Pioglitazone, in the two-dimensional correlation Surface enhanced raman spectroscopy figure of blood-sugar lowering tcm drug to be checked, contain the relevant peaks with differ-w～w wave number that goes out peak position of the relevant peaks of Rosiglitazone standard items, judge in blood-sugar lowering tcm drug to be checked and contain Rosiglitazone, in the two-dimensional correlation Surface enhanced raman spectroscopy figure of blood-sugar lowering tcm drug to be checked, do not contain with Pioglitazone standard items and Rosiglitazone standard items the relevant peaks of differ-w～w wave number that goes out peak position of relevant peaks, judge and in blood-sugar lowering tcm drug to be checked, do not contain Pioglitazone and Rosiglitazone, w is 5cm
-1.
Contrast Fig. 5,6,7, to whether adding Pioglitazone or Rosiglitazone or the two in this blood-sugar lowering tcm drug to be checked, all there is interpolation to analyze.
Contrast Fig. 5-a, Fig. 6-a, Fig. 7-a, at 1000cm
-1～1700cm
-1section, in blood-sugar lowering tcm drug to be checked, contain with the relevant peaks of Rosiglitazone go out the identical automatic peak 1255cm in peak position
-1and 1329cm
-1.
Contrast Fig. 5-b, Fig. 6-b, Fig. 7-b, at 500cm
-1～1000cm
-1section, in blood-sugar lowering tcm drug to be checked, contain with the relevant peaks of Pioglitazone go out the identical automatic peak 627cm in peak position
-1, also contain with the relevant peaks of Rosiglitazone go out the identical automatic peak 739cm in peak position
-1.
Contrast Fig. 5-c, Fig. 6-c, Fig. 7-c, at 300cm
-1～500cm
-1section, contains 475cm in blood-sugar lowering tcm drug to be checked
-1locate automatic peak, and 414cm
-1with 430cm
-1the just intersection peak at place, all with the relevant peaks of Pioglitazone to go out peak situation identical.
Comprehensive 1000cm
-1～1700cm
-1, 500cm
-1～1000cm
-1and 300cm
-1～500cm
-1, in the spectrogram of blood-sugar lowering tcm drug to be checked, there is 414cm in three sections
-1, 430cm
-1, 475cm
-1, 824cm
-1place's relevant peaks, illustrates and contains PIOGITAZONE HYDROCHLORIDE, occurs 739cm
-1, 1255cm
-1, 1329cm
-1place's relevant peaks, illustrates and contains Rosiglitazone Maleate.
According to above analysis result, illustrate that the blood-sugar lowering tcm drug of this this batch of production in pharmaceutical factory is mixed with Pioglitazone and Rosiglitazone.
< embodiment bis->
One, instrument and sample
(1) instrument: BWS415-785H type Portable Raman spectrometer (U.S. Bi Da Imtech), excitation wavelength 785nm;
(2) silver sol preparation: get silver nitrate (AgNO
3) 17mg adds secondary deionized water 100ml and dissolve, and adds 1% trisodium citrate 1.6ml, puts in micro-wave oven with high fire heating 6min, solution is celadon, is cooled to room temperature, adds water to scale place, standby.
(3) preparation of blood-sugar lowering tcm drug solution to be checked and reference substance solution: get the blood-sugar lowering tcm drug of B pharmaceutical factory batch production as blood-sugar lowering tcm drug to be checked, make methyl alcohol (the analyzing pure) solution of the blood-sugar lowering tcm drug to be checked of 1mol/L.
Two, blood-sugar lowering tcm drug to be checked is detected
Fig. 8 is the process flow diagram of technical scheme of the present invention in embodiment bis-.
As shown in Figure 8, in the present embodiment two, measure in this blood-sugar lowering tcm drug to be checked and whether add PIOGITAZONE HYDROCHLORIDE or Rosiglitazone Maleate, the method comprises: get the methanol solution point of 1 μ l blood-sugar lowering tcm drug to be checked on silica gel thin-layer plate (hereinafter to be referred as thin layer plate), after methylene chloride-methanol-water (8:2:0.2) launches, taking-up volatilizes, under uviol lamp 254nm, inspect, at Pioglitazone or the corresponding Rf value place of Rosiglitazone, find doubtful spot (Rf value is 0.9), also comprise following three steps:
Step 1 (S1 '): the collection of dynamic optical spectrogram
Getting 5 μ l silver sols drips on doubtful spot, the laser intensity of Raman spectrometer is adjusted to 200mW, adopt the LASER Light Source Emission Lasers of this Raman spectrometer self, doubtful spot prolonged exposure is carried out to perturbation, gather a series of Surface enhanced raman spectroscopy of doubtful spot simultaneously, obtain the dynamic spectrum of this blood-sugar lowering tcm drug to be checked, be 5s the integral time of every Surface enhanced raman spectroscopy, in spectra collection process, keep laser intensity constant, illuminated laser spot is constant.
Step 2 (S2 '): the drafting of two-dimensional correlation Surface enhanced raman spectroscopy figure
Fig. 9 is Raman spectrogram after the pre-service of blood-sugar lowering tcm drug to be checked in embodiment bis-.
Figure 10 is that the two-dimensional correlation surface-enhanced Raman synchronous spectrum of blood-sugar lowering tcm drug to be checked in embodiment bis-is divided into the sync correlation spectrum obtaining after three sections.
Utilize Matlab7.6 software to carry out pre-service to the dynamic optical spectrogram of this blood-sugar lowering tcm drug to be checked, comprise that spectral coverage chooses (300cm
-1～1700cm
-1), level and smooth (Sgolay method) and baseline correction (airPLS method), obtain the pre-service Raman spectrogram of this blood-sugar lowering tcm drug to be checked as shown in Figure 9.
By 2Dshiger version1.3 software, software dynamic spectrum is set to averaged spectrum, contour parameter is 8, pre-service Raman spectrogram to blood-sugar lowering tcm drug to be checked is processed, drafting obtains the two-dimensional correlation surface-enhanced Raman synchronizable optical spectrogram of this blood-sugar lowering tcm drug to be checked as shown in figure 10, by the two-dimensional correlation surface-enhanced Raman synchronous spectrum (300cm of this blood-sugar lowering tcm drug to be checked
-1～1700cm
-1) be divided into 300cm as shown in figure 10
-1～500cm
-1, 500cm
-1～1000cm
-1, and 1000cm
-1～1700cm
-1three sections, wherein 10-a is 1000cm
-1～1700cm
-1section, 10-b is 500cm
-1～1000cm
-1section, 10-c is 300cm
-1～500cm
-1section.
Step 3 (S3 '): to whether adding Pioglitazone or Rosiglitazone is identified
According to the two-dimensional correlation surface-enhanced Raman synchronizable optical spectrogram of this blood-sugar lowering tcm drug to be checked, in this spectrogram, contain the relevant peaks with differ-w～w wave number that goes out peak position of the relevant peaks of Pioglitazone, judge in blood-sugar lowering tcm drug to be checked and contain Pioglitazone, in this spectrogram, contain the relevant peaks with differ-w～w wave number that goes out peak position of the relevant peaks of Rosiglitazone, judge in blood-sugar lowering tcm drug to be checked and contain Rosiglitazone, in this spectrogram, do not contain with Pioglitazone and Rosiglitazone the relevant peaks of differ-w～w wave number that goes out peak position of relevant peaks, judge and in blood-sugar lowering tcm drug to be checked, do not contain Pioglitazone and Rosiglitazone, w is 5cm
-1, the peak position that goes out of the relevant peaks of Pioglitazone is set to: 414cm
-1, 430cm
-1, 475cm
-1, 824cm
-1, the peak position that goes out of the relevant peaks of Rosiglitazone is set to: 739cm
-1, 1255cm
-1, 1329cm
-1.
From Figure 10-a, 10-b, 10-c, in the two-dimensional correlation surface-enhanced Raman synchronizable optical spectrogram of the blood-sugar lowering tcm drug to be checked that the present embodiment provides at 414cm
-1, 430cm
-1, 475cm
-1, 824cm
-1there is relevant peaks in place, illustrates that the blood-sugar lowering tcm drug of this this batch of production in pharmaceutical factory is mixed with Pioglitazone.
< embodiment tri->
One, instrument and sample
(1) instrument: BWS415-785H type Portable Raman spectrometer (U.S. Bi Da Imtech), excitation wavelength 785nm;
(2) silver sol preparation: get silver nitrate (AgNO
3) 17mg adds secondary deionized water 100ml and dissolve, and adds 1% trisodium citrate 1.6ml, puts in micro-wave oven with high fire heating 6min, solution is celadon, is cooled to room temperature, adds water to scale place, standby.
(3) preparation of blood-sugar lowering tcm drug solution to be checked and reference substance solution: get the blood-sugar lowering tcm drug of C pharmaceutical factory batch production as blood-sugar lowering tcm drug to be checked, make methyl alcohol (the analyzing pure) solution of the blood-sugar lowering tcm drug to be checked of 1mol/L.
Two, blood-sugar lowering tcm drug to be checked is detected
In the present embodiment three, get the methanol solution point of 1 μ l blood-sugar lowering tcm drug to be checked on silica gel thin-layer plate (hereinafter to be referred as thin layer plate), after methylene chloride-methanol-water (8:2:0.2) launches, taking-up volatilizes, under uviol lamp 254nm, inspect, at PIOGITAZONE HYDROCHLORIDE or the corresponding Rf value place of Rosiglitazone Maleate, find doubtful spot, with reference to step 1 in embodiment bis-, to the operation of step 3, doubtful spot is carried out to the collection of dynamic optical spectrogram, the drafting of two-dimensional correlation Surface enhanced raman spectroscopy figure and to whether adding Pioglitazone or Rosiglitazone is identified.
Figure 11 is Raman spectrogram after the pre-service of blood-sugar lowering tcm drug to be checked in embodiment tri-;
Figure 12 is that the two-dimensional correlation surface-enhanced Raman synchronous spectrum of blood-sugar lowering tcm drug to be checked in embodiment tri-is divided into the sync correlation spectrum obtaining after three sections.
By Matlab7.6 software, dynamic optical spectrogram is carried out obtaining after pre-service the pre-service Raman spectrogram of this blood-sugar lowering tcm drug to be checked as shown in figure 11, through 2Dshiger version1.3 Software on Drawing, obtain the two-dimensional correlation surface-enhanced Raman synchronizable optical spectrogram of this blood-sugar lowering tcm drug as shown in figure 12
From Figure 12-a, 12-b, 12-c, in the two-dimensional correlation surface-enhanced Raman synchronizable optical spectrogram of the blood-sugar lowering tcm drug to be checked that the present embodiment provides at 739cm
-1, 1255cm
-1, 1329cm
-1there is relevant peaks in place, illustrates that the blood-sugar lowering tcm drug of this this batch of production in pharmaceutical factory is mixed with Rosiglitazone Maleate.
< embodiment tetra->
One, instrument and sample
(1) instrument: BWS415-785H type Portable Raman spectrometer (U.S. Bi Da Imtech), excitation wavelength 785nm;
(2) silver sol preparation: get silver nitrate (AgNO
3) 17mg adds secondary deionized water 100ml and dissolve, and adds 1% trisodium citrate 1.6ml, puts in micro-wave oven with high fire heating 6min, solution is celadon, is cooled to room temperature, adds water to scale place, standby.
(3) preparation of blood-sugar lowering tcm drug solution to be checked and reference substance solution: get the blood-sugar lowering tcm drug of D pharmaceutical factory batch production as blood-sugar lowering tcm drug to be checked, make methyl alcohol (the analyzing pure) solution of the blood-sugar lowering tcm drug to be checked of 1mol/L.
Two, blood-sugar lowering tcm drug to be checked is detected
In the present embodiment four, get the methanol solution point of 1 μ l blood-sugar lowering tcm drug to be checked on silica gel thin-layer plate (hereinafter to be referred as thin layer plate), after methylene chloride-methanol-water (8:2:0.2) launches, taking-up volatilizes, under uviol lamp 254nm, inspect, at PIOGITAZONE HYDROCHLORIDE or the corresponding Rf value place of Rosiglitazone Maleate, find doubtful spot, with reference to step 1 in embodiment bis-, to the operation of step 3, doubtful spot is carried out to the collection of dynamic optical spectrogram, the drafting of two-dimensional correlation Surface enhanced raman spectroscopy figure and to whether adding Pioglitazone or Rosiglitazone is identified.
By Matlab7.6 software, dynamic optical spectrogram is carried out obtaining after pre-service the pre-service Raman spectrogram of this blood-sugar lowering tcm drug to be checked, through 2Dshiger version1.3 Software on Drawing, obtain the two-dimensional correlation surface-enhanced Raman synchronizable optical spectrogram of this blood-sugar lowering tcm drug, spectrogram shows, at 414cm
-1, 430cm
-1, 475cm
-1, 824cm
-1there is not relevant peaks in place, illustrates in this blood-sugar lowering tcm drug to be checked and do not contain Pioglitazone, at 739cm
-1, 1255cm
-1, 1329cm
-1there is not relevant peaks in place, illustrates and in this blood-sugar lowering tcm drug to be checked, do not contain Rosiglitazone yet yet.
The effect of embodiment and effect
Compare with background technology, the effect and the good effect that in the blood-sugar lowering tcm drug that above-described embodiment one to four provides, add the authentication method of Pioglitazone or Rosiglitazone are:
1. can differentiate fast whether adding the carrying out of Pioglitazone or Rosiglitazone in blood-sugar lowering tcm drug
Technical scheme of the present invention adopts laser to carry out perturbation to doubtful spot place, adopt Raman spectrometer to detect the two-dimensional correlation Surface enhanced raman spectroscopy figure that obtains blood-sugar lowering tcm drug to be checked, by judge this dimension relevant surfaces strengthen in Raman spectrogram, whether contain with Pioglitazone or Rosiglitazone go out peak position identical automatic peak or relevant peaks, can realize whether adding Pioglitazone in blood-sugar lowering tcm drug to be checked or Rosiglitazone is judged, compare with LC-MS with HPLC, do not need harsh experiment condition and complicated sample pre-treatments work, can identify fast and in blood-sugar lowering tcm drug to be checked, whether add Pioglitazone or Rosiglitazone.
2. characteristic is strong, and testing result accurately and reliably
Because Raman spectroscopy has extremely strong characteristic, and very low to the content requirement of detection material, therefore the drawn qualification result of technical scheme according to the present invention accurately and reliably, compare with TLC, avoided the appearance of false positive or false negative result, staff that can Wei Yaojian department provides foundation and the guidance of science.
3. cost is low, easy to operate
Technical scheme of the present invention adopts thin layer plate and Portable Raman spectrometer to implement, equipment and experimental situation require simple, cost is low, easy to operate, can to whether adding Rosiglitazone Maleate in blood-sugar lowering tcm drug and PIOGITAZONE HYDROCHLORIDE carries out on-the-spot Rapid identification.
4. perturbation design is ingenious, easy quick, easy operating
Adopt the laser of the required Raman spectrometer self of experiment to carry out prolonged exposure to point sample place, thereby produce heat, testing sample is carried out to perturbation, obtain dynamically SERS spectrogram of series, and then obtain two-dimensional correlation spectrogram.Whole experimentation is without additional interference experiment, only need regulation and control laser energy, avoided people be while applying perturbation measure, may occur because excess Temperature or pH change the shortcoming of the sample system destruction due to excessive etc., and simple to operate, be easy to reappear, be convenient to medicine prison personnel and carry out Site Detection.
Certainly, the authentication method that whether adds Pioglitazone or Rosiglitazone in a kind of blood-sugar lowering tcm drug involved in the present invention is not merely defined in the content in above-described embodiment.Above content is only the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all belongs to protection scope of the present invention.
In addition, in above-described embodiment one to four, the laser intensity of Raman spectrometer is 200mW.Related laser intensity of the present invention can be for guaranteeing that in dynamic spectrum gatherer process any intensity adopting appears in n.s. calcination situation, any number between preferred 100mW～200mW, preferably 200mW.
In addition, in above-described embodiment one to four, w is 5cm
-1, technical scheme w of the present invention can be selected from 1cm
-1to 5cm
-1between any number, preferred 5cm
-1.
In addition, in the above-described embodiments, the point sample amount of surface reinforcing agent is 5 μ L, and in technical scheme of the present invention, the point sample amount of surface reinforcing agent can be selected from any number between 2 μ L～10 μ L, preferably the numerical value between 4 μ L～6 μ L.
In addition, in above-described embodiment one to four, select the synchronous spectrum of two-dimensional correlation surface-enhanced Raman synchronizable optical spectrogram to analyze, technical scheme of the present invention can also be analyzed for the asynchronous spectrum of two-dimensional correlation surface-enhanced Raman synchronizable optical spectrogram.
In addition, in above-described embodiment one to four, the collection of dynamic spectrum be uniformly-spaced the time period gather, technical scheme of the present invention can also be according to increasing progressively interval time or gathering according to successively decreasing interval time, as long as guarantee that the integral time of every spectrogram is identical.
In addition, in above-described embodiment one to four, the surface reinforcing agent adopting is nano silver colloidal sol, and the surface reinforcing agent that technical scheme of the present invention adopts can also be aurosol or gold and silver rubber alloy, preferably nano silver colloidal sol.
In addition, in above-described embodiment one to four, the laser adopting is provided by the LASER Light Source of Raman spectrometer self, and the required laser of technical scheme of the present invention can also provide by additional LASER Light Source.
In addition, in above-described embodiment one to four, adopt Matlab7.6 software dynamic optical spectrogram to be carried out obtaining after pre-service the pre-service Raman spectrogram of blood-sugar lowering tcm drug to be checked, adopt 2Dshiger version1.3 Software on Drawing to obtain the two-dimensional correlation surface-enhanced Raman synchronizable optical spectrogram of blood-sugar lowering tcm drug, the spectrogram process software adopting is only the basic explanation of technical scheme of the present invention, can also select other to process the software that obtains two-dimentional Raman spectrogram to one dimension Raman spectrogram.
In addition, the technical scheme that embodiment mono-adopts can also be identified the blood-sugar lowering tcm drug to be checked that only contains a kind of alloy or do not contain alloy, in the two-dimensional correlation Surface enhanced raman spectroscopy figure of blood-sugar lowering tcm drug to be checked, contain the relevant peaks with differ-w～w wave number that goes out peak position of the relevant peaks of Pioglitazone standard items, in blood-sugar lowering tcm drug to be checked, contain Pioglitazone, in the two-dimensional correlation Surface enhanced raman spectroscopy figure of blood-sugar lowering tcm drug to be checked, contain the relevant peaks with differ-w～w wave number that goes out peak position of the relevant peaks of Rosiglitazone standard items, in blood-sugar lowering tcm drug to be checked, contain Rosiglitazone, in the two-dimensional correlation Surface enhanced raman spectroscopy figure of blood-sugar lowering tcm drug to be checked, do not contain the relevant peaks with differ-w～w wave number that goes out peak position of the relevant peaks of Pioglitazone and Rosiglitazone, in blood-sugar lowering tcm drug to be checked, do not contain Pioglitazone and Rosiglitazone.
In addition, the technical scheme that above-described embodiment two to four adopts, also can be to identifying doped with the blood-sugar lowering tcm drug to be checked of Rosiglitazone and two kinds of adulterants of Pioglitazone.
In addition, in the technical scheme adopting at above-described embodiment two to four, the corresponding Rf value of Pioglitazone or Rosiglitazone is 0.9, and the corresponding Rf value of the Pioglitazone that technical scheme of the present invention is related or Rosiglitazone can exist certain error, between 0.85-0.95.
Claims (9)
1. identify the method for whether adding Pioglitazone or Rosiglitazone in blood-sugar lowering tcm drug for one kind, the method comprises: get blood-sugar lowering tcm drug to be checked and carry out thin-layer chromatography, the Rf value place corresponding with Rosiglitazone at Pioglitazone finds doubtful spot, it is characterized in that, also comprises following three steps:
Step 1: the collection of dynamic optical spectrogram
Get surface reinforcing agent point on described doubtful spot, adopt Raman spectrometer, the laser of choosing some strength carries out perturbation to described doubtful spot prolonged exposure, and gather a series of one dimension Surface enhanced raman spectroscopy of described doubtful spot, obtain the dynamic spectrum of described blood-sugar lowering tcm drug to be checked, the integral time of every one dimension Surface enhanced raman spectroscopy is identical, described some strength is any number between 100mW～200mW, described surface reinforcing agent is aurosol, silver sol or gold and silver rubber alloy, and the point sample amount of described surface reinforcing agent is 2 μ L～10 μ L;
Step 2: the drafting of two-dimensional correlation Surface enhanced raman spectroscopy figure
Described dynamic optical spectrogram is carried out to pre-service, comprise and choose 300cm
-1～1700cm
-1spectral coverage, employing Sgolay method are carried out level and smooth and adopt airPLS method to carry out baseline correction, obtain the pre-service Raman spectrogram of described blood-sugar lowering tcm drug to be checked, according to described pre-service Raman spectrogram, draw the two-dimensional correlation Surface enhanced raman spectroscopy figure that obtains described blood-sugar lowering tcm drug to be checked;
Step 3: identify adding Pioglitazone or Rosiglitazone
According to the described two-dimensional correlation Surface enhanced raman spectroscopy figure of described blood-sugar lowering tcm drug to be checked, in this spectrogram, contain the relevant peaks with differ-w～w wave number that goes out peak position of the relevant peaks of described Pioglitazone, judge in described blood-sugar lowering tcm drug to be checked and contain described Pioglitazone, in this spectrogram, contain the relevant peaks with differ-w～w wave number that goes out peak position of the relevant peaks of described Rosiglitazone, judge in described blood-sugar lowering tcm drug to be checked and contain described Rosiglitazone, in this spectrogram, do not contain with described Pioglitazone and described Rosiglitazone the relevant peaks of differ-w～w wave number that goes out peak position of relevant peaks, judge and in described blood-sugar lowering tcm drug to be checked, do not contain described Pioglitazone and described Rosiglitazone, w is 1cm
-1～5cm
-1between any number, the peak position that goes out of the relevant peaks of described Pioglitazone is set to: 414cm
-1, 430cm
-1, 475cm
-1, 824cm
-1, the peak position that goes out of the relevant peaks of described Rosiglitazone is set to: 739cm
-1, 1255cm
-1, 1329cm
-1.
2. identify the method for whether adding Pioglitazone or Rosiglitazone in blood-sugar lowering tcm drug for one kind, the method comprises: get blood-sugar lowering tcm drug to be checked and carry out thin-layer chromatography, the Rf value place corresponding with Rosiglitazone at Pioglitazone finds doubtful spot, it is characterized in that, also comprises following three steps:
Step 1: the collection of dynamic optical spectrogram
Described blood-sugar lowering tcm drug to be checked, Pioglitazone standard items and Rosiglitazone standard items are carried out after thin-layer chromatography, on thin layer plate, find doubtful spot, Pioglitazone and three spots of Rosiglitazone,
Get surface reinforcing agent respectively o'clock on three described spots, adopt Raman spectrometer, the laser of choosing some strength carries out perturbation to three described spot prolonged exposures respectively, and gather respectively a series of one dimension Surface enhanced raman spectroscopy of three described spots, obtain described doubtful spot, the dynamic optical spectrogram of described Pioglitazone and described Rosiglitazone, the integral time of all one dimension Surface enhanced raman spectroscopy of each spot is all identical, described some strength is any number between 100mW～200mW, described surface reinforcing agent is aurosol, silver sol or gold and silver rubber alloy, the point sample amount of described surface reinforcing agent is 2 μ L～10 μ L,
Step 2: the drafting of two-dimensional correlation Surface enhanced raman spectroscopy figure
Respectively the described dynamic optical spectrogram of described blood-sugar lowering tcm drug to be checked, described Pioglitazone standard items and described Rosiglitazone standard items is carried out to pre-service, comprise and choose 300cm
-1～1700cm
-1spectral coverage, employing Sgolay method are carried out level and smooth and adopt airPLS method to carry out baseline correction, obtain the pre-service Raman spectrogram of described blood-sugar lowering tcm drug to be checked, described Pioglitazone standard items and described Rosiglitazone standard items, according to described pre-service Raman spectrogram, draw respectively the two-dimensional correlation Surface enhanced raman spectroscopy figure that obtains three;
Step 3: the Analysis and judgments of two-dimensional correlation Surface enhanced raman spectroscopy figure
The two-dimensional correlation Surface enhanced raman spectroscopy figure of described blood-sugar lowering tcm drug to be checked is compared with the two-dimensional correlation Surface enhanced raman spectroscopy figure of described Pioglitazone standard items and described Rosiglitazone standard items respectively, in the two-dimensional correlation Surface enhanced raman spectroscopy figure of described blood-sugar lowering tcm drug to be checked, contain the relevant peaks with differ-w～w wave number that goes out peak position of the relevant peaks of described Pioglitazone standard items, judge in described blood-sugar lowering tcm drug to be checked and contain Pioglitazone, in the two-dimensional correlation Surface enhanced raman spectroscopy figure of described blood-sugar lowering tcm drug to be checked, contain the relevant peaks with differ-w～w wave number that goes out peak position of the relevant peaks of described Rosiglitazone standard items, judge in described blood-sugar lowering tcm drug to be checked and contain Rosiglitazone, in the two-dimensional correlation Surface enhanced raman spectroscopy figure of described blood-sugar lowering tcm drug to be checked, do not contain with described Pioglitazone standard items and described Rosiglitazone standard items the relevant peaks of differ-w～w wave number that goes out peak position of relevant peaks, judge in described blood-sugar lowering tcm drug to be checked and do not contain Pioglitazone and Rosiglitazone, w is 1cm
-1～5cm
-1between any number.
3. the method for whether adding Pioglitazone or Rosiglitazone in evaluation blood-sugar lowering tcm drug according to claim 2, it is characterized in that: described Pioglitazone standard items are PIOGITAZONE HYDROCHLORIDE standard items, described Rosiglitazone standard items are Rosiglitazone Maleate standard items.
4. the method for whether adding Pioglitazone or Rosiglitazone in evaluation blood-sugar lowering tcm drug according to claim 1 and 2, is characterized in that: described some strength is 200mW.
5. the method for whether adding Pioglitazone or Rosiglitazone in evaluation blood-sugar lowering tcm drug according to claim 1 and 2, is characterized in that: described two-dimensional correlation Surface enhanced raman spectroscopy figure is synchronous spectrum.
6. the method for whether adding Pioglitazone or Rosiglitazone in evaluation blood-sugar lowering tcm drug according to claim 1 and 2, is characterized in that: described laser is provided by the LASER Light Source of Raman spectrometer self.
7. the method for whether adding Pioglitazone or Rosiglitazone in evaluation blood-sugar lowering tcm drug according to claim 1 and 2, is characterized in that: described surface reinforcing agent is nano silver colloidal sol.
8. the method for whether adding Pioglitazone or Rosiglitazone in evaluation blood-sugar lowering tcm drug according to claim 1 and 2, is characterized in that: the point sample amount of described surface reinforcing agent is 4 μ L～6 μ L.
9. the method for whether adding Pioglitazone or Rosiglitazone in evaluation blood-sugar lowering tcm drug according to claim 1 and 2, is characterized in that: w is 5cm
-1.
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| CN106525809A (en) * | 2016-09-30 | 2017-03-22 | 中国人民解放军第二军医大学 | Method for identifying whether one or more chemicals of theophylline, caffeine and theobromine are added into traditional Chinese medicines for relieving cough and asthma |
| CN107525859A (en) * | 2017-07-26 | 2017-12-29 | 中国人民解放军第二军医大学 | A kind of method that compound derivatives quick detection condition is illegally added in screening health products |
| CN108732292A (en) * | 2018-04-27 | 2018-11-02 | 中国人民解放军第二军医大学 | The rapid detection method and device of sufentanil in blood plasma |
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| CN105241861A (en) * | 2015-09-18 | 2016-01-13 | 中国人民解放军第二军医大学 | Method for rapidly and simultaneously detecting ten adulterated components in lipid lowering Chinese patent medicine |
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| CN108732292A (en) * | 2018-04-27 | 2018-11-02 | 中国人民解放军第二军医大学 | The rapid detection method and device of sufentanil in blood plasma |
| CN108732292B (en) * | 2018-04-27 | 2020-07-14 | 中国人民解放军第二军医大学 | Method and device for rapidly detecting sufentanil in blood plasma |
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| CN113340870A (en) * | 2021-06-09 | 2021-09-03 | 河北省食品检验研究院 | Rapid detection method for illegally added pioglitazone in health food |
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