CN104569244A - Method for constructing liquid chromatographic fingerprint spectrum of tobacco essence perfume - Google Patents
Method for constructing liquid chromatographic fingerprint spectrum of tobacco essence perfume Download PDFInfo
- Publication number
- CN104569244A CN104569244A CN201410268930.5A CN201410268930A CN104569244A CN 104569244 A CN104569244 A CN 104569244A CN 201410268930 A CN201410268930 A CN 201410268930A CN 104569244 A CN104569244 A CN 104569244A
- Authority
- CN
- China
- Prior art keywords
- liquid
- cigarette
- essence spice
- sample
- construction method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
Abstract
The invention discloses a method for constructing a liquid chromatographic fingerprint spectrum of tobacco essence perfume. The liquid chromatographic fingerprint spectrum is analyzed and constructed by utilizing a diode array detector and a refractive index detector in liquid chromatography, and the liquid chromatography comprises the following parameter conditions that a chromatographic column refers to an METACARB H PLUS 300*7.8mm column; a guard column refers to an METACARB H PLUS guard column; the temperature of the column oven is 60 DEG C; the mobile phase refers to 6 mM H2SO4; the flow velocity is equal to 0.4mL/min; and the pumping stop time is 120 minutes. Based on long-term research of the matter characteristics of the tobacco essence perfume, the diode array detector and the refractive index detector in the liquid chromatography are scientifically combined, accurate analysis conditions are summarized in a targeted mode, the liquid chromatographic fingerprint spectrum of the tobacco essence perfume is constructed, the fingerprint characteristics of tobacco essence perfume samples are comprehensively reflected, and the method can be effectively applied to constructing the fingerprint spectrums of tobacco essence perfume samples containing sugar and sugar alcohols and has high actual application values.
Description
Technical field
The invention belongs to Analysis of Tobacco Flavor to detect and Quality Control Technology field, more specifically, relate to a kind of construction method of liquid-phase chromatograph finger print atlas of essence spice for cigarette.
Background technology
Essence spice for cigarette technology is one of important core technology of tobacco business, and essence spice for cigarette is significant to keeping the aromatic style feature of cigarette brand.The change of essence and flavoring agent quality directly affects the quality of cigarette.Essence spice for cigarette has drawn from natural perfume material more, its quality can be subject to the many factors such as original producton location, production technology, and the impact of essence spice for cigarette on cigarette quality comes from the synergy between self Multiple components, so the analytical chemistry composition of system, the finger-print setting up reflection ingredient comprehensively will embody the globality of its chemical composition more effectively.Coming to monitor the quality of essence spice for cigarette qualitatively by similarity between calculated fingerprint collection of illustrative plates, is a kind of important and desirable controlling soil moist.The finger-print that application liquid chromatography sets up essence and flavoring agent can be effectively applied to the security of essence spice for cigarette and quality stability controls and all many-sides such as character distinction, has great importance.The diversity of the chemical composition of essence spice for cigarette and complicacy always are the Focal point and difficult point of its quality control, the acquisition of essence spice for cigarette finger-print, only could stablize after setting up the liquid phase chromatography analytical method of science, easy and effectively obtain.
Finger-print is a kind of technology studying complex material system be on the whole born along with modern analytical technique development, and be applied in the fields such as environmental protection, food evaluation, traditional Chinese medicine quality control at present, especially on Chinese crude drug, Application comparison is extensive.And the application report of finger-print in quality of flavoring essence for tobacco control is relatively less.
Existing research has the chemical composition of coupling to essence spice for cigarette utilizing gas chromatography-GC-MS (GC/MS) two kinds of analytical instrument to analyze, obtain the finger-print of feature, by calculating the numerical value of fingerprint similarity between actual measurement sample and standard model, the degree of closeness of both judgements intrinsic chemical composition.
High performance liquid chromatography is one of very important analytical approach, uses more extensive at tobacco productive corporation and research unit.Along with improving constantly of requiring Product checking, adopt detecting device coupling technique in HPLC, have made some progress, but majority is at the field of Chinese medicines.But current rare application high performance liquid chromatography carries out the finger-print research of essence spice for cigarette.Because in the specific object of concrete analysis, select what kind of detecting device to carry out coupling, how to carry out connection between detecting device, sample should how scientifically pre-service, in described detecting device coupling situation, how to determine that there are a lot of rucial scientific and technological problems in concrete testing conditions etc. needs to go to capture, for chromatographic column, chromatographic column expensive, if carry out simple screening process conditions with reference to existing achievement in research, continuous replacing chromatographic column is to obtain final plan, and expensive research cost is difficult to bear.And interact between each process conditions, check and balance, lower cost how can be used to go to carry out more effectively, analytical work efficiently, it is the technical barrier that annoying the art always, simply can not be applied to another kind of object to reference for the detecting device coupling achievement in research acquired by a kind of object, especially there is for chemical composition the essence spice for cigarette of diversity and complicacy feature.
Have no at present and the coupling of two kinds of detecting device science is realized the correlation technique report that the single injected sampling success chromatographic separation condition that also combination is suitable successfully sets up essence spice for cigarette finger-print.
Summary of the invention
The technical matters that will solve of the present invention sets up the technical deficiency of essence spice for cigarette finger-print, provides a kind of construction method of liquid-phase chromatograph finger print atlas of essence spice for cigarette.
The technical matters that another will solve of the present invention is to provide the application of described construction method.
Object of the present invention is achieved by the following technical programs:
A kind of construction method of liquid-phase chromatograph finger print atlas of essence spice for cigarette is provided, be that the analysis utilizing the diode array detector (PDAD) of liquid chromatography and refractive index detector (RID) to carry out liquid-phase chromatograph finger print atlas builds, the Parameter Conditions of described liquid chromatography is:
Chromatographic column: METACARB H PLUS 300 × 7.8 mm;
Guard column: METACARB H PLUS guard column;
Column oven temperature: 60 DEG C;
Mobile phase: 6 mM H
2sO
4;
Flow velocity: 0.4 mL/min;
The termination of pumping time: 120 min.
Diode array detector determined wavelength: 200 ~ 360 nm;
Refractive index detector optical element temperature: 30 ~ 45 DEG C.
Further preferably, described DAD determined wavelength: 210 nm;
Further preferably, described RID optical element temperature: 35 DEG C.
The construction method of the liquid-phase chromatograph finger print atlas of described essence spice for cigarette, realizes single injected sampling after adopting simple same procedure to carry out pre-treatment to sample, obtains the fingerprint map analyzing of tobacco sample comprehensively.Said method comprising the steps of:
S1. sample pre-treatments;
S2. device builds; Be installed in liquid chromatography instrument by two kinds of detecting devices, wherein diode array detector is front, and refractive index detector is rear; Mobile phase liquid first through diode array detector, then through refractive index detector, finally discharges detecting device as waste liquid;
S3. sample introduction analysis;
Wherein, the sample pre-treatments described in S1 is specifically got 0.1 mL sample and is placed in 10 mL volumetric flasks, with 6 mM H
2sO
4constant volume also filters after mixing.
Preferably, described filtration is filtered through 0.45 μm of nylon leaching film.
Preferably, the amount of described sample introduction is 10 μ L.
The present invention provides the application of described construction method simultaneously, is applied to the finger-print setting up essence spice for cigarette sample.Especially the fingerprint map construction of the essence spice for cigarette sample of sugary and/or sugar alcohol is applied to.
Beneficial effect of the present invention is embodied in:
Diode array detector (PDAD) is a kind of optical multichannel detectors just occurred the eighties in 20th century, and it can be regarded as a branch of UVD, is applied to the qualitative and quantitative analysis of biological sample, Chinese herbal medicine at present.The sensitivity of diode array detector (PDAD) is better, but the applicant studies discovery, diode array detector (PDAD) has deficiency at analysis essence spice for cigarette, the compound without ultraviolet absorption group is not responded, and a lot of essence spice for cigarette all contains this compounds (such as sugar or glycitols), therefore adopt separately diode array detector (PDAD) that the Fingerprints of sugar or glycitols compound cannot be embodied, differential refraction detector (RID) is a kind of common detector, as long as the refraction index of tested component and eluent has difference just can use.The sensitivity of differential refraction detector (RID) is relatively low, but to not having the material of uv absorption to have good response, also easily use, maintenance cost is low simultaneously.The applicant creatively studies to sum up and finds to utilize the coupling of diode array detector and differential refraction detector to realize the fingerprint map analyzing of essence spice for cigarette.
But in actual applications, because essence spice for cigarette chemical composition has diversity and complicacy feature, the fingerprint map analyzing of sample only can not be realized smoothly based on the coupling design of diode array detector and differential refraction detector.The coupling design of diode array detector and differential refraction detector must rationally, systematically be combined the fingerprint map analyzing that successfully could solve essence spice for cigarette with the sample-pretreating method of science, chromatographic resolution overall technical architecture.
Based on the long-term specific aim further investigation of the applicant to essence spice for cigarette substance characteristics, sum up the H that employing concentration is 6 mM
2sO
4make an addition in proportion in sample and to adopt after constant volume 0.45 μm of nylon leaching film to filter the sample liquid obtained to can be used for single injected sampling and ensure being successfully completed of follow-up separation and fingerprint map analyzing to carrying out dissolving.
Further; the present invention adopts METACARB H PLUS 300 × 7.8 mm as chromatographic column and adopts METACARB H PLUS guard column simultaneously; research for matching sums up suitable Split liquid chromatographic apparatus and accurate technique; obtain the separating effect being applicable to described two kinds of detecting device couplings preferably, finally realize row coupling in conjunction with diode array detector (DAD) and the suitable coupling mode of refractive index detector (RID).
Further, the present invention obtains the sample liquid of sample introduction in conjunction with the sample-pretreating method of science, realizes single injected sampling, to be successfully separated and the associating finger-print realizing two kinds of detecting devices exports.
In sum, the invention provides a kind of system complete, for the fingerprint map construction method of essence spice for cigarette, from the sample-pretreating method of science, obtain research for matching and sum up suitable Split liquid chromatographic apparatus and accurate technique, obtain the separating effect being applicable to described two kinds of detecting device couplings preferably, in conjunction with diode array detector (DAD) and the suitable coupling mode of refractive index detector (RID), obtain the finger-print information of essence spice for cigarette quickly and easily, the fingerprint characteristic of essence spice for cigarette sample can be highlighted, effectively can be applied to the fingerprint map construction containing the essence spice for cigarette sample without ultraviolet absorption group compound, there is important actual application value.
Accompanying drawing explanation
Fig. 1 embodiment 1 finger-print.
Fig. 2 embodiment 1 finger-print partial enlarged drawing.
Embodiment
The present invention is further illustrated below in conjunction with the drawings and specific embodiments.Unless stated otherwise, the embodiment of the present invention adopts equipment, reagent and method are equipment, reagent and the method that this area routine uses.
Embodiment 1
The present embodiment adopts Agilent 1200 liquid chromatograph, joins DAD and RID; The concentrated sulphuric acid (analyzing pure), ultrapure water; 0.45 μm of nylon leaching film.Essence spice for cigarette sample for detecting analysis is provided by Guangdong China Tobacco Industry Co., Ltd, and therefore sample, only for illustration of the inventive method, does not limit the sample scope that the inventive method is suitable for.
Prepare 6 mM H
2sO
4solution (compound method is conventional with reference to this area).
Detection analytical procedure is as follows:
S1. sample pre-treatments: get 0.1 mL essence spice for cigarette sample and be placed in 10 mL volumetric flasks, with 6 mM H
2sO
4constant volume also mixes, after 0.45 μm of nylon leaching film filters, carry out liquid-phase chromatographic analysis in order to subsequent step;
S2. device builds; Be installed in liquid chromatography instrument by two kinds of detecting devices, wherein diode array detector is front, and refractive index detector is rear; Mobile phase liquid first through diode array detector, then through refractive index detector, finally discharges detecting device as waste liquid;
S3. sample introduction analysis;
The present embodiment sample introduction measures 10 μ L.
In experimentation, the present embodiment simultaneously primary study changes DAD determined wavelength to the impact of testing result, and after changing wavelength, the peak height of the chromatographic peak in DAD chromatogram can decrease, and namely detection sensitivity can decrease.The raising of sensitivity, is conducive to obtaining more profile information.Experiment finds when other testing conditions of the present invention are certain, and the wavelength provided, in 200 ~ 360 nm wavelength coverages, is applicable to analyzing multiple compounds, fully can obtains the finger-print information of essence spice for cigarette.The present embodiment simultaneously primary study change RID optical element temperature is tested.Experiment finds, RID optical element temperature is arranged within the scope of 30 ~ 45 DEG C, not obvious on the impact of RID chromatogram, basically identical with former figure.
The factor such as the specific aim of Considering experimental object, the accuracy of experimental result, sensitivity, the analytical parameters condition of the liquid chromatography of the optimum finally determined is:
Chromatographic column: METACARB H PLUS 300 × 7.8 mm;
Guard column: METACARB H PLUS guard column;
Column oven temperature: 60 DEG C;
Mobile phase: 6 mM H
2sO
4;
Flow velocity: 0.4 mL/min;
The termination of pumping time: 120 min;
DAD determined wavelength: 210 nM;
RID optical element temperature: 35 DEG C.
Under above-mentioned analysis condition, obtain finger-print and ask for an interview shown in accompanying drawing 1, wherein upper figure is DAD chromatogram, and figure below is RID chromatogram.Accompanying drawing 2 is finger-prints of partial enlargement.Drawings attached is visible, and the present invention sums up the structure that scientific and reasonable pre-treatment side realizes the liquid-phase chromatograph finger print atlas of essence spice for cigarette.From finger-print, this sample composition is fairly simple, and substantially not sugary or glycitols material, analysis result is consistent with other conventional method testing results.The component colony analysis chart spectrum of the essence sample for tobacco Chemical Characteristics obtained based on the present embodiment combines conventional computational analysis technology to carrying out exclusive, macroscopical, overall chemical feature integrated information analytical calculation research to sample.
Claims (10)
1. the construction method of the liquid-phase chromatograph finger print atlas of an essence spice for cigarette, it is characterized in that, be that the analysis utilizing the diode array detector of liquid chromatography and refractive index detector to carry out liquid-phase chromatograph finger print atlas builds, the Parameter Conditions of described liquid chromatography is:
Chromatographic column: METACARB H PLUS 300 × 7.8 mm;
Guard column: METACARB H PLUS guard column;
Column oven temperature: 60 DEG C;
Mobile phase: 6 mM H
2sO
4;
Flow velocity: 0.4 mL/min;
The termination of pumping time: 120 min;
Diode array detector determined wavelength: 200 ~ 360 nm;
Refractive index detector optical element temperature: 30 ~ 45 DEG C.
2. the construction method of the liquid-phase chromatograph finger print atlas of essence spice for cigarette according to claim 1, it is characterized in that, described diode array detector determined wavelength is 210 nM.
3. the construction method of the liquid-phase chromatograph finger print atlas of essence spice for cigarette according to claim 1, is characterized in that, described refractive index detector optical element temperature: 35 DEG C.
4. the construction method of the liquid-phase chromatograph finger print atlas of essence spice for cigarette according to claim 1,2 or 3, is characterized in that, comprise the following steps:
S1. sample pre-treatments;
S2. device builds; Be installed in liquid chromatography instrument by two kinds of detecting devices, wherein diode array detector is front, and refractive index detector is rear; Mobile phase liquid first through diode array detector, then through refractive index detector, finally discharges detecting device as waste liquid;
S3. sample introduction analysis;
Wherein, the sample pre-treatments described in S1 is specifically got 0.1 mL sample and is placed in 10 mL volumetric flasks, with 6 mM H
2sO
4constant volume also filters after mixing.
5. the construction method of the liquid-phase chromatograph finger print atlas of essence spice for cigarette according to claim 4, is characterized in that, described filtration is filtered through 0.45 mm nylon leaching film.
6. the construction method of the liquid-phase chromatograph finger print atlas of essence spice for cigarette according to claim 4, it is characterized in that, the amount of described sample introduction is 10 mL.
7. the application of construction method described in claim 1,2 or 3, is characterized in that, be applied to the finger-print setting up essence spice for cigarette sample.
8. the application of construction method described in claim 7, is characterized in that, is applied to the fingerprint map construction of the essence spice for cigarette sample of sugary and/or sugar alcohol.
9. the application of construction method described in claim 4, is characterized in that, is applied to the finger-print setting up essence spice for cigarette sample.
10. the application of construction method described in claim 9, is characterized in that, is applied to the fingerprint map construction of the essence spice for cigarette sample of sugary and/or sugar alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410268930.5A CN104569244B (en) | 2014-06-17 | 2014-06-17 | The construction method of the liquid-phase chromatograph finger print atlas of essence spice for cigarette |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410268930.5A CN104569244B (en) | 2014-06-17 | 2014-06-17 | The construction method of the liquid-phase chromatograph finger print atlas of essence spice for cigarette |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104569244A true CN104569244A (en) | 2015-04-29 |
| CN104569244B CN104569244B (en) | 2016-08-24 |
Family
ID=53085802
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410268930.5A Active CN104569244B (en) | 2014-06-17 | 2014-06-17 | The construction method of the liquid-phase chromatograph finger print atlas of essence spice for cigarette |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104569244B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106404877A (en) * | 2016-08-19 | 2017-02-15 | 陕西中烟工业有限责任公司 | Essence and flavor Fourier transform ion cyclotron resonance mass spectroscopy fingerprint analysis method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004354285A (en) * | 2003-05-30 | 2004-12-16 | Shimamuratekku:Kk | Detection device for preparative liquid chromatography |
| CN101226178A (en) * | 2008-01-21 | 2008-07-23 | 中国烟草总公司郑州烟草研究院 | Method for analyzing liquid phase fingerprint pattern of cigar flavour and perfume |
| CN101566607A (en) * | 2009-06-03 | 2009-10-28 | 川渝中烟工业公司 | Method for measuring organic acid radicals in cigarette paper |
| CN102520094A (en) * | 2011-12-28 | 2012-06-27 | 广东中烟工业有限责任公司 | Method for determining glucose, fructose and saccharose in tobacco essence perfume |
| US20120231514A1 (en) * | 2009-08-31 | 2012-09-13 | Iogen Energy Corporation | Fermentation method to produce a lignocellulose-based sugar stream with enriched pentose content |
-
2014
- 2014-06-17 CN CN201410268930.5A patent/CN104569244B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004354285A (en) * | 2003-05-30 | 2004-12-16 | Shimamuratekku:Kk | Detection device for preparative liquid chromatography |
| CN101226178A (en) * | 2008-01-21 | 2008-07-23 | 中国烟草总公司郑州烟草研究院 | Method for analyzing liquid phase fingerprint pattern of cigar flavour and perfume |
| CN101566607A (en) * | 2009-06-03 | 2009-10-28 | 川渝中烟工业公司 | Method for measuring organic acid radicals in cigarette paper |
| US20120231514A1 (en) * | 2009-08-31 | 2012-09-13 | Iogen Energy Corporation | Fermentation method to produce a lignocellulose-based sugar stream with enriched pentose content |
| CN102520094A (en) * | 2011-12-28 | 2012-06-27 | 广东中烟工业有限责任公司 | Method for determining glucose, fructose and saccharose in tobacco essence perfume |
Non-Patent Citations (5)
| Title |
|---|
| ARMANDO SAMPAIO ET AL.: "Production, chemical characterization, and sensory profile of a novel spirit elaborated from spent coffee ground", 《FOOD SCIENCE AND TECHNOLOGY》 * |
| ARMANDO SAMPAIO ET AL.: "Production, chemical characterization, and sensory profile of a novel spirit elaborated from spent coffee ground", 《FOOD SCIENCE AND TECHNOLOGY》, vol. 54, 31 December 2013 (2013-12-31), pages 557 - 563, XP028691364, DOI: doi:10.1016/j.lwt.2013.05.042 * |
| 廖堃 等: "烟用香精的高效液相色谱指纹图谱分析", 《烟草科技》 * |
| 薛芳 等: "高效液相色谱法测定卷烟纸中的6种有机酸根", 《烟草科技》 * |
| 黄菲 等: "高效液相色谱测定烟用香精及料液中保润剂方法的改进", 《现代食品科技》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106404877A (en) * | 2016-08-19 | 2017-02-15 | 陕西中烟工业有限责任公司 | Essence and flavor Fourier transform ion cyclotron resonance mass spectroscopy fingerprint analysis method |
| CN106404877B (en) * | 2016-08-19 | 2019-05-03 | 陕西中烟工业有限责任公司 | Flavors and fragrances Fourier Transform Ion cyclotron Resonance mass spectrum fingerprint pattern analysis method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104569244B (en) | 2016-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103808840B (en) | A kind of method for building up of ginseng and astragalus injection for strengthening body finger-print | |
| CN104181248B (en) | A kind of fingerprint atlas detection method of Ganmaoling Granules | |
| CN103808846A (en) | Series quadrupole-rod gas-chromatographic mass spectrometry detection method for 35 toxic medicaments in urine | |
| CN111024643B (en) | Near infrared spectrum detection method for quality evaluation of gentiana straminea maxim medicinal materials | |
| CN102370891A (en) | Method for authenticating dendrobium officinale by using HPLC fingerprint | |
| CN104198619B (en) | A kind of quality determining method of P-Cymene | |
| CN103115892A (en) | Method for preparing ginkgo leaf extract by using near infrared spectroscopy analysis technology | |
| CN104749306A (en) | Epimedium extract fingerprint spectrum construction method | |
| Wang et al. | A hierarchical screening method for detection of illegal adulterants in Fur seal ginseng pills by profiling analysis of HPLC multi‐dimensional fingerprints | |
| CN106353275A (en) | Method for quickly measuring alkaloids of ephedra herb medicinal material based on ultraviolet spectrum | |
| CN105842353A (en) | Establishing method of fingerprint spectrum of honeysuckle-fructus forsythiae heat-clearing tablets and fingerprint spectrum | |
| CN103675147B (en) | Method for rapidly determining caffeine in drink | |
| CN108169385A (en) | A kind of method using six kinds of glucides in ultra performance liquid chromatography concatenation QDa simultaneously quick detection health liquor | |
| Tao et al. | Mid-infrared and near-infrared spectroscopy for rapid detection of Gardeniae Fructus by a liquid-liquid extraction process | |
| CN101408501A (en) | Method for quantitatively detecting DNA base by using near-infrared spectrum-partial least squares method | |
| CN102879351A (en) | Near-infrared transmission spectroscopy method for measuring content of salvianolic acid B in salvianolic acid extractive | |
| CN101256176A (en) | Method for analysis of chromatographic peak match | |
| CN104215705B (en) | A kind of method detecting Organochlorine Pesticides Residues In Agricultural Products | |
| CN105158189A (en) | Method for analyzing content of antioxidants in vegetable oil on basis of criterion of space angle | |
| Chang et al. | Evaluation of quality consistency of herbal preparations using five-wavelength fusion HPLC fingerprint combined with ATR-FT-IR spectral quantized fingerprint: Belamcandae rhizoma antiviral injection as an example | |
| CN104390926A (en) | Online rapid detection method of herba andrographis concentrated decolorization process | |
| CN105319296A (en) | Measuring method for methyl alcohol content | |
| CN203929720U (en) | A kind of finger-print pick-up unit that is applicable to essence spice for cigarette | |
| CN104569244B (en) | The construction method of the liquid-phase chromatograph finger print atlas of essence spice for cigarette | |
| CN102106950A (en) | Quality control method in NuJin capsule extraction and concentration process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |