CN100509103C - Method for producing solid-phase microextraction capillaries - Google Patents
Method for producing solid-phase microextraction capillaries Download PDFInfo
- Publication number
- CN100509103C CN100509103C CNB2007100518078A CN200710051807A CN100509103C CN 100509103 C CN100509103 C CN 100509103C CN B2007100518078 A CNB2007100518078 A CN B2007100518078A CN 200710051807 A CN200710051807 A CN 200710051807A CN 100509103 C CN100509103 C CN 100509103C
- Authority
- CN
- China
- Prior art keywords
- capillary
- gma
- ethylene glycol
- glycol dimethacrylate
- crosslinking agent
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Treatment Of Liquids With Adsorbents In General (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention is concerned with the prepare method of capillary for solid phase microextraction. The methacrylic acid glycidyl is function monomer, the ethyleneglycol dimethacrylate is vulcanizing agent, toluene and dodecyl are mixed pore-causing agent, and 2,2'-azobisisobutyronitrile is initiator. Mix and mill the stuff and pour into quartz capillary disposed with ethylene, close and heat to polymerization. After the reaction, use solvent to clean capillary and remove the rudimental monomer, vulcanizing agent and pore-causing agent to get whole capillary with the polymer of methacrylic acid glycidyl and ethyleneglycol dimethacrylate. Use vitriol to clear the whole capillary to get hydroxylation, or clear the capillary with diethylamine and close to heat at 65 to 75 degree to get the capillary with the polymer of methacrylic acid glycidyl and ethyleneglycol dimethacrylate derived from diethylamine. The method is easy and low cost and the extraction agency stuff is fit to set up a credible and high sensitive analysis method.
Description
Technical field
The present invention relates to a kind of method for producing solid-phase microextraction capillaries, refer in particular to the GMA-ethylene glycol dimethacrylate polyalcohol integral column extracting preparation method capillaceous that can in SPME, use, belong to the analytical chemistry field.
Background technology
At present, the analytic target that analytical chemistry is faced becomes increasingly complex, the coexistence chaff interference is formed complicated and may be interacted with the object analysis deposits yields, the concentration of object analysis thing often is trace or ultra trace level, thereby a kind of effective sample pre-treatments technology plays a part very crucial setting up of analytical method in the process.Up to now, tens kinds of sample-pretreating methods have been arranged, its purpose all is to remove to greatest extent the sample substrate interference and analysans in the sample is carried out enrichment farthest.
The SPME a kind of solvent-free extracting process that to be earlier 1990s proposed and grown up by professor Pawliszyn of Canadian Waterloo university.Its centralized procurement sample, extraction, enrichment and sample introduction be in one, and be simple to operate, expense is cheap, favorable reproducibility, therefore obtained in environmental monitoring, Pharmaceutical Analysis and food security field using widely.SPME because energy and high performance liquid chromatography realize the automatic online coupling, thereby has obtained increasing concern as a kind of new model of SPME in the pipe.This seminar is first with in the solid phase micro-extraction technique in the organic polymer integral post material introduction tube, successively prepared based on poly-(methacrylic acid-ethylene glycol dimethacrylate) integral post extraction capillary of the hydrophobic effect and the cation exchange mechanism of action with based on poly-(acrylamide-vinylpyridine) integral post extraction capillary of the hydrophobic effect and the anion exchange mechanism of action.But the solid-phase microextraction extraction capillary with GMA-ethylene glycol dimethacrylate polymer manufacture does not also appear at present.
Summary of the invention
The purpose of this invention is to provide a kind of method for producing solid-phase microextraction capillaries, refer in particular to the GMA-ethylene glycol dimethacrylate polyalcohol integral column extracting preparation method capillaceous that can in SPME, use, in the SPME of polar substances, use with the hydroxylated GMA-ethylene glycol dimethacrylate polyalcohol integral column extracting capillary energy of this method preparation; GMA-ethylene glycol dimethacrylate polyalcohol integral column extracting the capillary energy of the diethylamine derivatization of preparation is used in the SPME of acidic materials.
The technical scheme that realizes the object of the invention is: be function monomer with the GMA, ethylene glycol dimethacrylate is a crosslinking agent, toluene and lauryl alcohol are for mixing pore-foaming agent, azodiisobutyronitrile is an initator, with function monomer, crosslinking agent, toluene and lauryl alcohol by volume 1～2: 13～25: 2～4: 36～42 ratio, the initator quality is 1～2% of function monomer and a crosslinking agent quality summation, mixing and stirring under room temperature, pour in the quartz capillary of vinyl modification, seal, be heated to 55～70 ℃ of initiated polymerizations, after polymerisation is finished, fully clean capillary with solvent and remove unreacted monomer, crosslinking agent and pore-foaming agent, obtain GMA-ethylene glycol dimethacrylate polymer integral column capillary tube, be used for cleaning capillary and remove unreacted monomer, the solvent of crosslinking agent and pore-foaming agent is an acetonitrile, methyl alcohol or oxolane.
Fully wash resulting GMA-ethylene glycol dimethacrylate polymer integral column capillary tube with 0.1～0.5mol/L sulfuric acid, obtain hydroxylated GMA-ethylene glycol dimethacrylate polymer integral column capillary tube after reaction is finished.
Fully wash resulting GMA-ethylene glycol dimethacrylate polymer integral column capillary tube with diethylamine, seal, in 70 ± 5 ℃ of fully reactions, obtain the GMA-ethylene glycol dimethacrylate polymer integral column capillary tube of diethylamine derivatization.
And, when preparation GMA-ethylene glycol dimethacrylate polymer integral column capillary tube, can pour into again in the quartz capillary of vinyl modification after sonic oscillation was removed bubble in 5～10 minutes after function monomer, crosslinking agent, mixing pore-foaming agent and the initator mixing and stirring.
Hydroxylated GMA-ethylene glycol dimethacrylate polymer integral column capillary tube that the present invention makes, because the glycol group that its polymer backbone surface has polarity, therefore can produce specific adsorption effects such as dipole-dipole and hydrogen bond, polar substances is had very high selectivity and extracting power.The GMA of the diethylamine derivatization that the present invention makes-ethylene glycol dimethacrylate polymer integral column capillary tube is because its polymer backbone surface has the anion exchange site, so can carry out enrichment, extraction to acidic materials.
Not only method is simple, with low cost but also the polymeric material long service life that makes for this method for preparing the polymeric material spe medium provided by the invention, loading capacity is big, enrichment multiple height, favorable reproducibility, can be used for setting up reliable high-sensitivity analysis method.
Description of drawings
Fig. 1 is used for managing five kinds of polar contaminants chromatograms of interior SPME and high performance liquid chromatography on-line coupling analysis environments water sample for the hydroxylated GMA-ethylene glycol dimethacrylate polymer integral column capillary tube of embodiment 1 preparation.
Fig. 2 is used for managing interior SPME and high performance liquid chromatography on-line coupling analysis urine methylene-dioxy amphetamine chromatogram for the hydroxylated GMA-ethylene glycol dimethacrylate polymer integral column capillary tube of embodiment 2 preparations.
Fig. 3 is used for managing interior SPME and high performance liquid chromatography on-line coupling detection soy sauce preservative benzoic acid and sorbic acid chromatogram for the GMA-ethylene glycol dimethacrylate polymer integral column capillary tube of the diethylamine derivatization of embodiment 3 preparations.
Fig. 4 is used for managing interior SPME and high performance liquid chromatography on-line coupling detection soda preservative benzoic acid and sorbic acid chromatogram for the GMA-ethylene glycol dimethacrylate polymer integral column capillary tube of the diethylamine derivatization of embodiment 3 preparations.
Fig. 5 is used for managing interior SPME and high performance liquid chromatography on-line coupling detection jam preservative benzoic acid and sorbic acid chromatogram for the GMA-ethylene glycol dimethacrylate polymer integral column capillary tube of the diethylamine derivatization of embodiment 3 preparations.
Fig. 6 is used for managing interior SPME and high performance liquid chromatography on-line coupling detection preserved fruit preservative benzoic acid and sorbic acid chromatogram for the GMA-ethylene glycol dimethacrylate polymer integral column capillary tube of the diethylamine derivatization of embodiment 3 preparations.
The specific embodiment
Embodiment 1:
With function monomer: GMA 5 μ L, crosslinking agent: ethylene glycol dimethacrylate 65 μ L, pore-foaming agent: toluene 10 μ L and lauryl alcohol 180 μ L, initator: azodiisobutyronitrile 0.8mg is mixing and stirring at room temperature, pour in the quartz capillary of vinyl modification, seal, 60 ℃ of initiated polymerization 20h, after polymerisation is finished, fully clean capillary with methyl alcohol and remove unreacted monomer, crosslinking agent and pore-foaming agent.Wash resulting integral column capillary tube 3h with 0.1mol/L sulfuric acid, obtain hydroxylated GMA-ethylene glycol dimethacrylate polymer integral column capillary tube.
Hydroxylated GMA-ethylene glycol dimethacrylate polymer integral column capillary tube with preparation is a spe medium, with interior SPME of pipe and high performance liquid chromatography combined instrument apparatus that patent No. ZL03254844.3 provides environmental water sample is analyzed.
Extraction and chromatographiccondition: the extraction flow velocity is 0.03mL/min, and the extraction time is 10min.Analytical column is Thermo Hypersil ODS post (250mm * 4.6mm i.d., 5 μ m), and flowing is that 0.02mol/L phosphate buffer (pH3.9) mixes flow velocity 1mL/min with acetonitrile with 50: 50 (v/v) mutually.Testing conditions is a UV-detector, and the detection wavelength is 280nm.
Environmental water sample is analyzed: gather East Lake, Wuhan City water sample, and centrifugal, get supernatant, regulating sample solution pH value is 8.0.Behind 0.45 μ m nylon leaching film, but just direct injected extraction.Through the extraction after, with peak area with concentration secondary water sample direct injected peak area ratio, the analyte in the environmental water sample obtains tangible enrichment.Fig. 1 is 1 μ g/mL extraction and direct injected contrastive colours spectrogram.The result shows that use extraction material provided by the invention carries out this sample analysis, and concentration effect is obvious, and the rate of recovery is higher than 88%, and the relative standard deviation that extraction is analyzed illustrates that less than 10% this solid-phase micro-extracting device is applicable to the environmental water sample analysis.
Direct injected among Fig. 1 (A) and extraction sample introduction (B) chromatographic curve.Peak 1: phenol; Peak 2:2-nitrophenol; Peak 3:3-nitrophenol; 4: repefral; 5: diethyl phthalate.
Embodiment 2:
With function monomer: GMA 10 μ L, crosslinking agent: ethylene glycol dimethacrylate 70 μ L, pore-foaming agent: toluene 15 μ L and lauryl alcohol 210 μ L, initator: azodiisobutyronitrile 1.2mg is mixing and stirring at room temperature, ultrasonic 10min is to remove bubble, pour in the quartz capillary of vinyl modification, seal, 65 ℃ of initiated polymerization 16h.After polymerisation is finished, fully clean capillary with acetonitrile and remove unreacted monomer, crosslinking agent and pore-foaming agent.Wash resulting integral column capillary tube 3h with 0.5mol/L sulfuric acid, obtain hydroxylated GMA-ethylene glycol dimethacrylate polymer integral column capillary tube.
Hydroxylated GMA-ethylene glycol dimethacrylate polymer integral column capillary tube with preparation is a spe medium, with interior SPME of pipe and high performance liquid chromatography combined instrument apparatus that patent No. ZL 03 254844.3 provides urine sample is analyzed.
Extraction and chromatographiccondition: the extraction flow velocity is 0.03mL/min, and the extraction time is 20min.Analytical column is Kromasil ODS post (150mm * 4.6mm i.d., 5 μ m).Flowing is that 0.02mol/L phosphate buffer (pH3.9) mixes flow velocity 1mL/min with methyl alcohol with 30: 70 (v/v) mutually.Testing conditions is a UV-detector, and the detection wavelength is 210nm.
Urine sample is analyzed: gather healthy human urine's sample, and centrifugal, get supernatant.With the secondary water dilution with volume, regulating sample solution pH value is 8.0, behind 0.45 μ m nylon leaching film, and the direct injected extraction.Fig. 2 is for adding the urine sample extraction-chromatography figure of 100ng/mL standard specimen.The result shows that use extraction material provided by the invention carries out this sample analysis, highly sensitive (detect and be limited to 12ng/mL), the rate of recovery is higher than 80%, and the relative standard deviation that extraction is analyzed illustrates that less than 10% this solid-phase micro-extracting device is applicable to the urine sample analysis.
(A) is blank urine sample extraction curve among Fig. 2, is to add 100ng/mL standard specimen extraction curve in the urine sample (B).
Embodiment 3:
With function monomer: GMA 5 μ L, crosslinking agent: ethylene glycol dimethacrylate 70 μ L, pore-foaming agent: toluene 20 μ L and lauryl alcohol 180 μ L, initator: azodiisobutyronitrile 1.0mg is mixing and stirring at room temperature, ultrasonic 5min is to remove bubble, pour in the quartz capillary of vinyl modification, seal, 55 ℃ of initiated polymerization 24h.After polymerisation is finished, fully clean capillary with acetonitrile, methyl alcohol or oxolane and remove unreacted monomer, crosslinking agent and pore-foaming agent.Wash resulting GMA-ethylene glycol dimethacrylate polymer integral column capillary tube 2h with diethylamine then, seal, in 70 ℃ of reaction 5h, obtain the GMA-ethylene glycol dimethacrylate polymer integral column capillary tube of diethylamine derivatization.
GMA-ethylene glycol dimethacrylate polymer integral column capillary tube with the diethylamine derivatization is a spe medium, with interior SPME of pipe and high performance liquid chromatography combined instrument apparatus that patent No. ZL03254844.3 provides food samples is analyzed.
Extraction and chromatographiccondition: the extraction flow velocity is 0.03mL/min, and the extraction time is 5min.Analytical column is Kromasil ODS post (150mm * 4.6mm i.d., 5 μ m), and flowing is that the 0.02mo1/L ammonium acetate solution mixes flow velocity 0.8mL/min with methyl alcohol with 70: 30 (v/v) mutually.Testing conditions is a UV-detector, and the detection wavelength is 230nm.
Food samples is analyzed: soy sample: take by weighing 10 ± 0.5mg sample, (20mM pH4.0) is diluted to 10mL, and behind 0.45 μ m nylon leaching film, sample introduction extracts with PBS.The soda sample: take by weighing 20 ± 1.0mg sample, (20mM pH4.0) is diluted to 10mL, and behind 0.45 μ m nylon leaching film, sample introduction extracts with PBS.Jam sample: take by weighing 10 ± 0.5mg sample, with an amount of PBS (20mM, pH4.0) dilution, ultrasonic 10min.Be settled to 10mL at last, behind 0.45 μ m nylon leaching film, the sample introduction extraction.Preserved fruit sample: take by weighing 10 ± 0.5mg sample, add the 0.3mL acetonitrile, ultrasonic 10min.(20mM pH4.0) is settled to 10mL, and behind 0.45 μ m nylon leaching film, direct injected extracts with PBS at last.Fig. 3 analyzes chromatogram for the actual sample extraction.The result shows that use extraction material provided by the invention carries out the actual sample analysis, simple to operate, quick, the rate of recovery is higher than 85%, and the relative standard deviation that extraction is analyzed is less than 9%, illustrates that this solid-phase micro-extracting device is highly suitable for the assay determination of benzoic acid and sorbic acid in the food.
Fig. 3 is soy sauce extraction curve, and Fig. 4 is soda extraction curve, and Fig. 5 is jam extraction curve, and Fig. 6 is preserved fruit extraction curve.The peak 1 among each figure: benzoic acid; Peak 2: sorbic acid.
Claims (4)
1, a kind of method for producing solid-phase microextraction capillaries, it is characterized in that: be function monomer with the GMA, ethylene glycol dimethacrylate is a crosslinking agent, toluene and lauryl alcohol are for mixing pore-foaming agent, azodiisobutyronitrile is an initator, with function monomer, crosslinking agent, toluene and lauryl alcohol be the ratio of 1～2:13～25:2～4:36～42 by volume, the initator quality is 1～2% of function monomer and a crosslinking agent quality summation, mixing and stirring under room temperature, pour in the quartz capillary of vinyl modification, seal, be heated to 55～70 ℃ of initiated polymerizations, after polymerisation is finished, fully clean capillary with solvent and remove unreacted monomer, crosslinking agent and pore-foaming agent, obtain GMA-ethylene glycol dimethacrylate polymer integral column capillary tube, be used for cleaning capillary and remove unreacted monomer, the solvent of crosslinking agent and pore-foaming agent is an acetonitrile, methyl alcohol or oxolane.
2, according to the described method for producing solid-phase microextraction capillaries of claim 1, it is characterized in that: fully wash resulting GMA-ethylene glycol dimethacrylate polymer integral column capillary tube with 0.1～0.5mol/L sulfuric acid, obtain hydroxylated GMA-ethylene glycol dimethacrylate polymer integral column capillary tube after reaction is finished.
3, according to the described method for producing solid-phase microextraction capillaries of claim 1, it is characterized in that: fully wash resulting GMA-ethylene glycol dimethacrylate polymer integral column capillary tube with diethylamine, seal, in 70 ± 5 ℃ of fully reactions, obtain the GMA-ethylene glycol dimethacrylate polymer integral column capillary tube of diethylamine derivatization.
4, according to the described method for producing solid-phase microextraction capillaries of claim 1, it is characterized in that: after sonic oscillation was removed bubble in 5～10 minutes after function monomer, crosslinking agent, mixing pore-foaming agent and the initator mixing and stirring, pour into again in the quartz capillary of vinyl modification.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100518078A CN100509103C (en) | 2007-04-06 | 2007-04-06 | Method for producing solid-phase microextraction capillaries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100518078A CN100509103C (en) | 2007-04-06 | 2007-04-06 | Method for producing solid-phase microextraction capillaries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101073714A CN101073714A (en) | 2007-11-21 |
| CN100509103C true CN100509103C (en) | 2009-07-08 |
Family
ID=38975083
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100518078A Expired - Fee Related CN100509103C (en) | 2007-04-06 | 2007-04-06 | Method for producing solid-phase microextraction capillaries |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100509103C (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101279145B (en) * | 2008-05-27 | 2010-06-09 | 厦门大学 | Methacrylate polymer solid-phase micro-extraction fibre and method of producing the same |
| CN101858898B (en) * | 2010-05-18 | 2012-08-29 | 华中师范大学 | Monolithic column solid phase extraction sample pretreatment method |
| CN102225249B (en) * | 2011-04-06 | 2013-04-17 | 福州大学 | Preparation method of organic-inorganic hybrid monolithic capillary column |
| CN102500344B (en) * | 2011-10-27 | 2013-10-09 | 西北工业大学 | Preparation method for non-polar polymer monolithic columns |
| CN102600641B (en) * | 2012-03-27 | 2013-12-04 | 福州大学 | Multi-action mode hydrophilic organic polymer monolithic column |
| CN103877954A (en) * | 2012-12-20 | 2014-06-25 | 中国科学院大连化学物理研究所 | Preparation of methacrylic acid-ethylene glycol dimethacrylate polymer monolithic column |
| CN103263900A (en) * | 2013-06-07 | 2013-08-28 | 吉林大学 | Method for preparing nano aluminum oxide material modified polymer integral column |
| CN103908935B (en) * | 2014-03-21 | 2016-02-10 | 中国科学院长春应用化学研究所 | A kind of capillary glass tube microfluidic devices and use this device to prepare there is the method for the polymer microballoon of multi-stage artery structure |
| CN104107687B (en) * | 2014-07-08 | 2016-06-22 | 广东药学院 | A kind of polyalcohol integral pole and its preparation method and application |
| CN104458972B (en) * | 2014-09-16 | 2016-08-24 | 吉林出入境检验检疫局检验检疫技术中心 | Indium sesquioxide. modification integral post and preparation method thereof |
| CN107649105A (en) * | 2017-09-19 | 2018-02-02 | 福州大学 | A kind of quinine immobilization ionic liquid multi-mode capillary integral post and preparation method thereof |
| CN108421542B (en) * | 2018-03-22 | 2020-08-07 | 河南科技学院 | Application of liquid metal microspheres as pore-forming agent in preparation of monolithic column |
| CN114904499B (en) * | 2022-05-26 | 2024-03-12 | 闽江学院 | Chiral Co-L-GG doped organic polymer capillary monolithic column |
| CN115301216B (en) * | 2022-08-04 | 2024-04-05 | 武汉大学 | High internal phase emulsion polymerization grading porous capillary monolithic column and preparation method and application thereof |
| CN117388422B (en) * | 2023-12-13 | 2024-03-08 | 广东省农业科学院农业生物基因研究中心 | Automatic aflatoxin on-line enrichment analysis device and analysis method |
-
2007
- 2007-04-06 CN CNB2007100518078A patent/CN100509103C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101073714A (en) | 2007-11-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100509103C (en) | Method for producing solid-phase microextraction capillaries | |
| Zhang et al. | Sensitive detection of bisphenol A in complex samples by in-column molecularly imprinted solid-phase extraction coupled with capillary electrophoresis | |
| Masque et al. | Molecularly imprinted polymers: new tailor-made materials for selective solid-phase extraction | |
| Mei et al. | Determination of trace bisphenol A in complex samples using selective molecularly imprinted solid-phase extraction coupled with capillary electrophoresis | |
| CN100595225C (en) | Method for producing molecular engram polyalcohol microsphere and method for separating enrofloxacin thereof | |
| CN102068968B (en) | Lead ion imprinting integral column and preparation method thereof | |
| Valcárcel et al. | Coupling continuous separation techniques to capillary electrophoresis | |
| CN105056913B (en) | A kind of preparation method of the In-tube SPME compound post for phosphoric acid extraction peptide | |
| CN105548392B (en) | The method for detecting Multiple Classes of Antibiotics in feces of livestock and poultry simultaneously using high performance liquid chromatography | |
| CN104341552A (en) | Fluoroquinolone substitute template molecularly imprinted polymer and application thereof | |
| CN102604008B (en) | Preparation method of pefloxacin surface molecular imprinting polymer and application thereof | |
| Wei et al. | Methods of sample preparation for determination of veterinary residues in food matrices by porous monolith microextraction-based techniques | |
| CN101612555A (en) | A kind of stirring rod for whole molecularly imprinted polymer and preparation method thereof | |
| CN107868181B (en) | Climbazole substituted template molecularly imprinted polymer and preparation method and application thereof | |
| Fan et al. | On-line selective solid-phase extraction of 4-nitrophenol with β-cyclodextrin bonded silica | |
| JPS5866835A (en) | System and method of mixing reagent | |
| Rocha et al. | Solid-phase extractions in flow analysis | |
| Carrasco-Correa et al. | Evaluation of 2, 3-epoxypropyl groups and functionalization yield in glycidyl methacrylate monoliths using gas chromatography | |
| CN101507885A (en) | Hydrophile solid-phase extraction muddler and preparation method thereof | |
| CN105964310B (en) | The preparation method and purposes of anion exchange in-line purification Solid Phase Extraction integral post | |
| CN106018596A (en) | Online microwave-assisted chiral derivatization-LC/MS (liquid chromatography/mass spectrometry) analysis system and method | |
| CN105879851B (en) | Graphite oxide ene-type in-line purification Solid Phase Extraction integral post and preparation method and purposes | |
| CN101249314A (en) | Solid phase extraction muddler taking polyvinyl alcohol integral material as coating and preparation thereof | |
| CN109621889A (en) | The preparation method of mesoporous magnetism silicon substrate Microcystin adsorbent | |
| CN108927113A (en) | A kind of nanometer hydroxyapatite functionalization Solid Phase Extraction integral post |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090708 Termination date: 20100406 |