CN100337114C - Mercapto-cotton fibre solid phase micro-column analyzing device and using method - Google Patents
Mercapto-cotton fibre solid phase micro-column analyzing device and using method Download PDFInfo
- Publication number
- CN100337114C CN100337114C CNB2004100037939A CN200410003793A CN100337114C CN 100337114 C CN100337114 C CN 100337114C CN B2004100037939 A CNB2004100037939 A CN B2004100037939A CN 200410003793 A CN200410003793 A CN 200410003793A CN 100337114 C CN100337114 C CN 100337114C
- Authority
- CN
- China
- Prior art keywords
- solid phase
- microtrabeculae
- cotton fiber
- sulfhydryl cotton
- fiber solid
- 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
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
The present invention relates to an automated device for separating and enriching heavy metal elements in sea water on site, which is used for separating and enriching a solid phase microcolumn based on sulfhydryl group cotton fibers. The present invention has the following main design ideas: (1) a liquid phase method is used for preparing sulfhydryl group chelate cotton fibers; (2) the sulfhydryl group chelate fibers obtained by preparation are developed into the solid phase microcolumn which is suitable for on-line separation, enrichment and real-time detection; (3) a system for samples, filtration, enrichment and measurement is controlled by a computer.
Description
Technical field
The present invention relates to a kind of analytical equipment of solid phase microtrabeculae, relate in particular to a kind of sulfhydryl cotton fiber solid phase micro pole analysis device.
The invention still further relates to the using method of above-mentioned analytical equipment.
Background technology
Contain a large amount of salinities in the seawater, matrix complexity, and the concentration of heavy metal element lower (being lower than the detection danger of many analytical instrument) as atomic absorption and plasma spectrometry, the heavy metal element of directly measuring in the seawater is very difficult.Therefore, in measuring seawater, during heavy metal element, need to separate in advance and enrichment.
Sulfydryl is a kind of good organic ligand, and application is early arranged in analytical chemistry.By chemical reaction, sulfydryl is connected on the skeleton of big molecule of natural fiber or resin, the sulfydryl type chelating ion exchange fiber of preparation or resin can be realized the quantitative absorption to contents of many kinds of heavy metal ion.Now, sulfhydryl cotton fiber separates and to be widely used in beneficiation technologies separating and measuring of trace heavy metal elements such as Co, Ni in all kinds of samples such as natural water, industrial waste water, soil, sediment, rock, mineral, animals and plants and food, Zn, Cd, Pb, Sn, Cu, Au, Ag, Hg, Pt.As far back as the seventies, sulfhydryl cotton fiber just is used for trace methyl mercury in the enrichment water by people such as the last heros in west.Nineteen ninety-five, people such as G ó mez are applied to measure Au and Ag in the Environmental Water sample with it.
The common feature of more than working is that the researcher generally adopts this extraordinary separation and concentration material of sulfydryl chelating cotton fiber, and it is applied to the analysis of actual environment sample.But their experiment is often based on single-element, and adopts the method for off-line (offline), needs the pre-treatment of sample and transfer, can bring the pollution or the loss of sample like this.
Summary of the invention
The purpose of this invention is to provide a kind of scene separation, enrichment automation equipment based on sulfhydryl cotton fiber.This apparatus structure is simple, and sample size is big, and sample introduction speed is fast, and enrichment multiple advantages of higher can reach the purpose that real-time online detects heavy metal in the seawater with the determining instrument coupling.
Compare with off-line method, online (online) separation and concentration has more advantage, good reproducibility, degree of accuracy height, and big sample size and low consumption amount, and can use robotization control.Sulfydryl chelating cotton fiber after the present invention will improve successfully is applied to heavy metal element Cu, Zn, Cd and the Pb in on-the-spot separation simultaneously, enrichment, the mensuration seawater.
For achieving the above object, the analytical equipment of sulfhydryl cotton fiber solid phase microtrabeculae provided by the invention comprises sulfhydryl cotton fiber solid phase microtrabeculae, flow circuit control valve, filtrator, peristaltic pump, two little threeways and plasma mass spectrograph;
Wherein, sulfhydryl cotton fiber solid phase microtrabeculae adopts the hollow polyfluortetraethylene pipe to make;
Flow circuit control valve is a six-way valve, is connected with two ends, eluant, eluent import, purified water inlet and a filtrator of sulfhydryl cotton fiber solid phase column respectively, and a waste liquid outlet is arranged;
A little threeway is connected between six-way valve and the purified water inlet, and as a sea intake, another little threeway is connected between sulfhydryl cotton fiber solid phase microtrabeculae and the peristaltic pump, as the waste liquid outlet of washing solid phase microtrabeculae;
Peristaltic pump is connected between sulfhydryl cotton fiber solid phase microtrabeculae and the pick-up unit.
Above-mentioned sulfhydryl cotton fiber solid phase microtrabeculae is will be filled into by the sulfhydryl cotton fiber of the present invention preparation in the polyfluortetraethylene pipe and obtain.
The synthetic method of sulfhydryl cotton fiber of the present invention is:
(1) by volume, thioacetic acid alcohol: acetic anhydride: acetate: sulfuric acid=1: 0.4-0.8: 0.2-0.6: 0.01-0.05, after shaking up and cooling off, add absorbent cotton, soak into evenly, being cooled to room temperature adds a cover, put into water-bath, bath temperature is controlled at 30-50 ℃, constant temperature 10-50 hour (this operation is preferably in the ventilating kitchen and carries out), take out and filter, and remaining thioglycolic acid is removed in washing.The sulfhydryl cotton fiber that makes is dried in 30-40 ℃ baking oven.Finished product is airtight, lucifuge, lower temperature are preserved down.
(2) sulfhydryl cotton fiber is filled in the teflon microtrabeculae, makes pre-separation enrichment microtrabeculae, be connected on the peristaltic pump, after the watery hydrochloric acid washing, re-use pure water and be washed till pH neutrality.
Analytical equipment method of operating of the present invention is:
With Sulfhydryl Cotton microtrabeculae, filtration unit, flow circuit control valve, peristaltic pump etc. and pick-up unit, connect such as plasma mass (ICP-MS), then:
The first step is with the flow velocity washing stream 1-2min of watery hydrochloric acid with 0.5-1.5ml/min;
Second step, neutral with the flow velocity washing stream of 8-12ml/min to the pH value with pure water;
The 3rd step, with seawater with the flow velocity of 10-20ml/min successively by filtrator, Sulfhydryl Cotton microtrabeculae, the metallic element of pre-separation can be combined on the sulfhydryl cotton fiber by huge legendary turtle, and the interference matrix in the seawater (as alkaline metal and earth alkali metal) promptly flows out with waste liquid;
In the 4th step, remove residual interference matrix sample with the flow velocity washing stream of 8-12ml/min with pure water;
In the 5th step, will be enriched in also online detection of heavy metal element wash-out on the microtrabeculae with the flow velocity of 0.5-1.5ml/min with watery hydrochloric acid.
If the pure water in the above-mentioned using method is used ultrapure water instead, effect is better.
The watery hydrochloric acid that the present invention is used, removing has special instruction, and its concentration is 0.5-1.5mol/l.
This scene based on Sulfhydryl Cotton solid phase microtrabeculae separate with enriching seawater in the good stability of heavy metal element, repeatability is high, simple in structure, sample size can reach 1500ml, the enrichment multiple can reach 1500 times.Use it for the heavy metal element in the separation and concentration seawater, and the analysis that the metallic element in the Canadian seawater standard reference materials is divided, measurement result conforms to standard value.
Description of drawings
Fig. 1: the one-piece construction synoptic diagram of apparatus of the present invention
Fig. 2: the control principle synoptic diagram of flow circuit control valve of the present invention
Fig. 3: the sample size of seawater is to the influence of enrichment capacity
Fig. 4: the sample introduction flow velocity of seawater is to the influence of bioaccumulation efficiency
Fig. 5: the volume of eluant, eluent 1mol/l HCl is to the influence of bioaccumulation efficiency
Fig. 6: microtrabeculae of the present invention is reused 10 influences that metallic element is measured
Embodiment
Embodiment 1: see also Fig. 1 and Fig. 2, device of the present invention is to improve on existing analytical equipment on the whole, and its main improvements are to adopt sulfhydryl cotton fiber solid phase microtrabeculae.
Preparation sulfhydryl cotton fiber: in 500 milliliters reactor, add 100 milliliters of thioglycolic acids, 60 ml acetic anhydride, 40 milliliter 36% acetate, 3 milliliter 98% sulfuric acid.After shaking up and cooling off, add the absorbent cotton of 30 grams, soak into evenly, be cooled to room temperature and add a cover, put into water-bath, bath temperature is controlled at 40 ℃, and constant temperature is after 2 days, and this operation is preferably in the ventilating kitchen to be carried out.Take out afterwards, with acidproof filter funnel suction filtration, and fully remaining thioglycolic acid is removed in washing.The sulfhydryl cotton fiber that makes is dried in 30 ℃ baking oven.Finished product is airtight, lucifuge, lower temperature are preserved down.
Sulfhydryl cotton fiber is filled into pre-separation enrichment microtrabeculae: sulfydryl huge legendary turtle and cotton fiber with 0.1 gram, be loaded into 8 millimeters of internal diameters, length is in 5 centimetres the slight post of teflon, to be connected on the peristaltic pump.With 5 milliliters of 1.0mol l
-1HCl washing after, the ultrapure water that re-uses 18.3 Ω is washed till pH neutrality.Standby.
Sulfhydryl cotton fiber solid phase microtrabeculae, filtration unit, flow circuit control valve, peristaltic pump, the ICP-MS of above-mentioned preparation are connected, and its concrete annexation please refer to Fig. 1 and Fig. 2.Wherein:
Flow circuit control valve 2 is a six-way valve, respectively with 5 connections mutually of sulfhydryl cotton fiber solid phase microtrabeculae 1, eluant, eluent import 3, purified water inlet 4 and a filtrator, and a waste liquid outlet 10 is arranged.
Two 6,7, one of little threeways are connected between six-way valve 2 and the purified water inlet 4, with as a sea intake 8; One is connected between sulfhydryl cotton fiber solid phase microtrabeculae 1 and the peristaltic pump 9, with the waste liquid outlet 11 as washing solid phase microtrabeculae 1.Peristaltic pump 9 is connected between sulfhydryl cotton fiber solid phase microtrabeculae 1 and the ICP-MS.
The method of operating of heavy metal element in the mensuration seawater provided by the invention transfers to the state of representing as Fig. 2 solid line with flow circuit control valve 2 earlier, and little threeway 6 transfers to purified water inlet 4 and connects with operation valve 2, and little threeway 7 transfers to peristaltic pump 9 and connects with operation valve 2:
The first step is with the flow velocity washing stream 1min of 1mol/l HCl with 1ml/min.
Second step, neutral with the flow velocity washing stream of 10ml/min to the pH value with the 18.3 Ω ultrapure waters of 100ml.
Flow circuit control valve 2 is transferred to the state of being asked as Fig. 2 dotted line, little threeway 7 transfers to waste liquid outlet 11 and connects (peristaltic pump 9 disconnects with operation valve 2) with operation valve 2, carried out for the 4th step, remove residual interference matrix sample with the flow velocity washing stream of 10ml/min with the 18.3 Ω ultrapure waters of 10ml.
Again little threeway 7 is transferred to peristaltic pump 9 and connect (waste liquid outlet 11 disconnects with valve) with operation valve 2 and carried out for the 5th step, will be enriched in also online detection of heavy metal element wash-out on the microtrabeculae 1 with the flow velocity of 1ml/min with 1mol/l HCl.
Through following test case, can learn the performance of above-mentioned robotization seawater separation and concentration device.
Test case 1: according to the 3rd step of above-mentioned technology path.(200,400,600,800,1000, seawater sample 1500ml) is with the flow velocity inflow device of 15ml/min with different volumes.Measure the content of metallic element in the HCl eluent with plasma mass (ICP-MS).The results are shown in Figure 3.
Test case 2: according to the 3rd step of above-mentioned technology path.With the seawater sample of 1500ml with different flow velocitys (4,6,8,10,12,14,16,18,20ml/min) inflow device.With the content of metallic element in plasma mass (ICP-MS) the mensuration HCl eluent, calculate bioaccumulation efficiency.The results are shown in Figure 4.
Test case 3: according to the 3rd step of above-mentioned technology path.With the seawater sample of 1500ml flow velocity inflow device with 15ml/min.(0.25,0.5,0.75,1.0, the content of metallic element is calculated bioaccumulation efficiency in HCl eluent 1.5ml) to measure different volumes with plasma mass (ICP-MS).The results are shown in Figure 5.
Test case 4: according to the 3rd step of above-mentioned technology path.With the seawater sample of 1500ml flow velocity inflow device with 15ml/min.Measure the content of HCl eluent with plasma mass (ICP-MS).Same microtrabeculae is reused 10 times the results are shown in Figure 6.
5: four Sulfhydryl Cotton microtrabeculaes of test case use after the 4th step not wash-out immediately according to the 3rd step of technology path.In 4 ℃ of preservations 1 day, in 4 ℃ of preservations 5 days, in 4 ℃ of preservations 10 days, preserved 30 days in 4 ℃ after the separation and concentration use after a separation and concentration uses after the separation and concentration use in 4 ℃ of preservations 1 day a separation and concentration use back after the separation and concentration use.And then with the HCl wash-out of 1ml.Measure the content of metallic element in the eluent with plasma mass (ICP-MS).The results are shown in Table 1.
Test case 6: according to the 3rd step of above-mentioned technology path.The pH value of 1500ml Canada seawater standard model NASS-5 is transferred to 8.0, behind the device, measure the content of HCl eluent with plasma mass (ICP-MS) excessively.The results are shown in Table 2.
Test case 7: according to the 3rd step of above-mentioned technology path.The pH value of 1500ml Canada seawater standard model CASS-4 is transferred to 8.0, behind the device, measure the content of HCl eluent with plasma mass (ICP-MS) excessively.The results are shown in Table 3.
Table 1: after preserving different time, the wash-out microtubule is measured the content of metallic element in the seawater that obtains
| Time (my god) | Tenor (μ gl -1) | |||
| 1 5 10 30 | Cu 0.101 0.098 0.105 0.103 | Zn 0.175 0.183 0.168 0.163 | Cd 0.023 0.022 0.023 0.023 | Pb 0.044 0.042 0.042 0.041 |
Table 2: device is measured the metallic element (each sample determination 7 times) among the Canadian seawater standard model NASS-5
| Element | NASS-5 | |
| Measured value (μ gl -1) | Standard value (μ gl -1) | |
| Cu Zn Cd Pb | 0.312±0.015 0.091±0.007 0.021±0.002 0.010±0.001 | 0.297±0.046 0.102±0.039 0.023±0.003 0.008±0.005 |
Table 3: device is measured the metallic element (each sample determination 7 times) among the Canadian seawater standard model CASS-4
| Element | CASS-4 | |
| Measured value (μ gl -1) | Standard value (μ gl -1) | |
| Cu Zn Cd Pb | 0.623±0.031 0.375±0.014 0.028±0.002 0.011±0.001 | 0.592±0.055 0.381±0.057 0.026±0.003 0.0098±0.0036 |
Claims (1)
1. analytical equipment that adopts sulfhydryl cotton fiber solid phase microtrabeculae comprises sulfhydryl cotton fiber solid phase microtrabeculae, flow circuit control valve, filtrator, peristaltic pump, two little threeways and plasma mass spectrograph;
Wherein, sulfhydryl cotton fiber solid phase microtrabeculae adopts the hollow polyfluortetraethylene pipe to make;
Flow circuit control valve is a six-way valve, is connected with two ends, eluant, eluent import, purified water inlet and a filtrator of sulfhydryl cotton fiber solid phase column respectively, and a waste liquid outlet is arranged;
A little threeway is connected between six-way valve and the purified water inlet, and as a sea intake, another little threeway is connected between sulfhydryl cotton fiber solid phase microtrabeculae and the peristaltic pump, as the waste liquid outlet of washing solid phase microtrabeculae;
Peristaltic pump is connected between sulfhydryl cotton fiber solid phase microtrabeculae and the pick-up unit plasma mass spectrograph.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100037939A CN100337114C (en) | 2004-02-05 | 2004-02-05 | Mercapto-cotton fibre solid phase micro-column analyzing device and using method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100037939A CN100337114C (en) | 2004-02-05 | 2004-02-05 | Mercapto-cotton fibre solid phase micro-column analyzing device and using method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1651913A CN1651913A (en) | 2005-08-10 |
| CN100337114C true CN100337114C (en) | 2007-09-12 |
Family
ID=34867593
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100037939A Expired - Fee Related CN100337114C (en) | 2004-02-05 | 2004-02-05 | Mercapto-cotton fibre solid phase micro-column analyzing device and using method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100337114C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102262060A (en) * | 2010-05-27 | 2011-11-30 | 上海光谱仪器有限公司 | Method and device for analyzing heavy metal elements by on-line enrichment and atomic absorption spectrum |
| CN102967574A (en) * | 2012-12-11 | 2013-03-13 | 天津工业大学 | Method for fast enriching and detecting trace amount of As (V) and Cr (VI) contained in water by filling microcolumn by utilizing fiber |
| CN105527147B (en) * | 2015-11-23 | 2018-05-22 | 浙江省海洋水产研究所 | A kind of seawater sample Extraction of Heavy Metals device |
| CN114887605B (en) * | 2022-04-24 | 2023-10-03 | 中国农业科学院油料作物研究所 | Perfluoro cotton solid phase extraction material and application thereof in enrichment and detection of organic fluoride |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86100804A (en) * | 1986-02-03 | 1987-03-25 | 中国科学院长春地理研究所 | A kind of water sampling and mercapto-cotton enrichment tripping device |
| WO1988008977A1 (en) * | 1987-05-14 | 1988-11-17 | Nauchno-Tekhnicheskoe Obiedinenie Akademii Nauk Ss | Device for preparation of gradient solution for high-pressure liquid chromatograph |
| JPH03106406A (en) * | 1989-09-06 | 1991-05-07 | Hewlett Packard Co <Hp> | Automatic isolation extracting method wherein solid-phase sorbent is used, apparatus therefor, and cartridge type column used for its apparatus |
| US6080318A (en) * | 1996-09-25 | 2000-06-27 | Analyticon Ag Biotechnologie Pharmazie | HPLC-based device and method for separating high complex substance mixtures |
| CN1332364A (en) * | 2000-07-10 | 2002-01-23 | 中国科学院生态环境研究中心 | Methyl mercury analyzing process for battery |
| CN1419118A (en) * | 2002-12-12 | 2003-05-21 | 施文健 | Novel method for investigating cadmium and mercury |
| EP1316798A1 (en) * | 2001-11-27 | 2003-06-04 | Pascal Aznar | Prefilled columns for flash chromatography and for solid phase extraction with improved separation efficiency |
-
2004
- 2004-02-05 CN CNB2004100037939A patent/CN100337114C/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86100804A (en) * | 1986-02-03 | 1987-03-25 | 中国科学院长春地理研究所 | A kind of water sampling and mercapto-cotton enrichment tripping device |
| WO1988008977A1 (en) * | 1987-05-14 | 1988-11-17 | Nauchno-Tekhnicheskoe Obiedinenie Akademii Nauk Ss | Device for preparation of gradient solution for high-pressure liquid chromatograph |
| JPH03106406A (en) * | 1989-09-06 | 1991-05-07 | Hewlett Packard Co <Hp> | Automatic isolation extracting method wherein solid-phase sorbent is used, apparatus therefor, and cartridge type column used for its apparatus |
| US6080318A (en) * | 1996-09-25 | 2000-06-27 | Analyticon Ag Biotechnologie Pharmazie | HPLC-based device and method for separating high complex substance mixtures |
| CN1332364A (en) * | 2000-07-10 | 2002-01-23 | 中国科学院生态环境研究中心 | Methyl mercury analyzing process for battery |
| EP1316798A1 (en) * | 2001-11-27 | 2003-06-04 | Pascal Aznar | Prefilled columns for flash chromatography and for solid phase extraction with improved separation efficiency |
| CN1419118A (en) * | 2002-12-12 | 2003-05-21 | 施文健 | Novel method for investigating cadmium and mercury |
Non-Patent Citations (3)
| Title |
|---|
| "微柱固相萃取-电感耦合等离子体质谱联用技术用于测定高盐样品中痕量的铅" 杨朝勇等，厦门大学学报(自然科学版)，第40卷第5期 2001 * |
| "微柱在线预富集FI-ICP-AES测定痕量La和Gd" 刘怀志等，武汉大学学报(自然科学版)，第43卷第2期 1997 * |
| "流动注射无机偶合化学发光测定水样中痕量锑" 范顺利等，分析试验室，第20卷第6期 2001 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1651913A (en) | 2005-08-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1888850A (en) | Apparatus for double-channel simultaneously separating and enriching heavy metal elements in seawater | |
| CN102262060A (en) | Method and device for analyzing heavy metal elements by on-line enrichment and atomic absorption spectrum | |
| CN109444070A (en) | Oil content all automatic measurement instrument in water | |
| CN105510483B (en) | The system of perfluor and multi-fluorinated compounds in a kind of full-automatic on-line checking serum | |
| CN109521160A (en) | Heavy metal quick screening method in a kind of solid waste Leaching | |
| CN102062711A (en) | Organic pollutant enriching device and method for pretreatment of water sample with bulk mass | |
| CN109061016A (en) | A kind of preparation method and application of the solid-phase extraction column of enriched biological amine | |
| CN108732000A (en) | A kind of heavy metal in sea water pretreatment unit | |
| CN100337114C (en) | Mercapto-cotton fibre solid phase micro-column analyzing device and using method | |
| CN220584136U (en) | Multidimensional multichannel liquid chromatographic separation system | |
| CN214622475U (en) | Preprocessing device based on ion chromatography survey soluble salt composition | |
| CN212159315U (en) | Device for automatically enriching red tide toxins in concentrated seawater | |
| CN103185756B (en) | Sample pretreatment method for analysis of anions in alcohol amine solution | |
| CN113341030B (en) | High-flux liquid chromatography-mass spectrometry system and separation and analysis method | |
| CN102980789B (en) | Water petroleum pollutant on-line enrichment device | |
| CN201697826U (en) | Heavy metal element orderly flowing injection on-line enrichment device | |
| CN205981835U (en) | Processor before chemical analysis sample is synthesized | |
| CN113030347B (en) | Pretreatment device and method for determining soluble salt components based on ion chromatography | |
| CN101358946B (en) | Anionic polymer grafting coatings capillary pipe and analytical method for on-line enrichment for protein | |
| CN104849341B (en) | The measuring method of mercury element content in a kind of gangue or flyash | |
| CN114018678A (en) | Device and method for purifying and separating copper isotopes in soil | |
| CN203370327U (en) | Automatically dynamic hollow fiber membrane liquid-liquid-liquid microextraction device | |
| CN104133022B (en) | Trace oxygen Flucloxacillin extracting and enriching and quantitative method on suspended particulate substance in water | |
| CN106950301B (en) | Determination method of dioxin in sediment and rapid pretreatment method of sediment | |
| CN206504931U (en) | One heavy metal species on-line preconcentration system |
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: 20070912 |