CN1733793A - Process method for preparing sea cucumber saponin from sea cucumber processing waste liquid - Google Patents
Process method for preparing sea cucumber saponin from sea cucumber processing waste liquid Download PDFInfo
- Publication number
- CN1733793A CN1733793A CN 200510044122 CN200510044122A CN1733793A CN 1733793 A CN1733793 A CN 1733793A CN 200510044122 CN200510044122 CN 200510044122 CN 200510044122 A CN200510044122 A CN 200510044122A CN 1733793 A CN1733793 A CN 1733793A
- Authority
- CN
- China
- Prior art keywords
- sea cucumber
- ethanol
- saponin
- waste liquid
- liquid
- 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
- 241000251511 Holothuroidea Species 0.000 title claims abstract description 61
- 150000007949 saponins Chemical class 0.000 title claims abstract description 37
- 229930182490 saponin Natural products 0.000 title claims abstract description 36
- 239000001397 quillaja saponaria molina bark Substances 0.000 title claims abstract description 34
- 239000007788 liquid Substances 0.000 title claims abstract description 28
- 239000002699 waste material Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 10
- 238000012545 processing Methods 0.000 title description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000011347 resin Substances 0.000 claims abstract description 20
- 229920005989 resin Polymers 0.000 claims abstract description 20
- 239000006228 supernatant Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000706 filtrate Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 235000017709 saponins Nutrition 0.000 claims 3
- 239000012141 concentrate Substances 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 12
- 238000010828 elution Methods 0.000 abstract description 3
- 239000000049 pigment Substances 0.000 abstract description 3
- 238000004108 freeze drying Methods 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 239000003344 environmental pollutant Substances 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 231100000719 pollutant Toxicity 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 230000000274 adsorptive effect Effects 0.000 description 8
- 239000003463 adsorbent Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 230000004071 biological effect Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229920002683 Glycosaminoglycan Polymers 0.000 description 2
- 241000700605 Viruses Species 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 235000014633 carbohydrates Nutrition 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 241000965254 Apostichopus japonicus Species 0.000 description 1
- 208000005189 Embolism Diseases 0.000 description 1
- 208000010201 Exanthema Diseases 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241000700721 Hepatitis B virus Species 0.000 description 1
- 206010029113 Neovascularisation Diseases 0.000 description 1
- 206010039361 Sacroiliitis Diseases 0.000 description 1
- 208000002474 Tinea Diseases 0.000 description 1
- 241000130764 Tinea Species 0.000 description 1
- 206010047601 Vitamin B1 deficiency Diseases 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 230000010100 anticoagulation Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 208000002894 beriberi Diseases 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 201000005884 exanthem Diseases 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000020764 fibrinolysis Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000000762 glandular Effects 0.000 description 1
- 229930182478 glucoside Natural products 0.000 description 1
- 150000008131 glucosides Chemical class 0.000 description 1
- 241000411851 herbal medicine Species 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000003053 immunization Effects 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VYQNWZOUAUKGHI-UHFFFAOYSA-N monobenzone Chemical compound C1=CC(O)=CC=C1OCC1=CC=CC=C1 VYQNWZOUAUKGHI-UHFFFAOYSA-N 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 201000007094 prostatitis Diseases 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000026676 system process Effects 0.000 description 1
- -1 then Substances 0.000 description 1
- 210000001835 viscera Anatomy 0.000 description 1
Landscapes
- Extraction Or Liquid Replacement (AREA)
- Compounds Of Unknown Constitution (AREA)
Abstract
The technique to prepare saponin with sea-cucumber treatment waste liquid comprises, filtering the waste liquid to deposite with ethanol, placing, centrifuging; decompressing and condensing the supernatant to remove ethanol; forcing the condensed liquid to flow with velocity 1.5~2.0BV/h through macropore absorption resin; using water to elute and remove the salt, sugar and pigment with same flow velocity; using 60~70% ethanol elution liquid to elute the saponin absorbed on the resin; collecting the elution liquid to condense to extract shape; finally, freeze drying to obtain the product. this invention makes good use of the waste, has no pollutant to environment.
Description
Technical field
The present invention relates to a kind of processing method of utilizing the sea cucumber processing-waste to prepare the sea cucumber saponin.
Background technology
Since ancient times, sea cucumber is exactly one of precious eight product in sea, and it is under the jurisdiction of the Echinodermata Holothuroidea.In Ming Dynasty's " food book on Chinese herbal medicine ", point out that already sea cucumber has main invigorating premordial QI, grows the beneficial vital organs of the human body and dispels many health-preserving functions such as deficient.Along with the raising of living standards of the people and the enhancing of health care consciousness, the medical care effect of sea cucumber has obtained approval and application more and more widely, having formed with countries and regions such as China, Singapore, Hong Kong, Japan, Korea S, the U.S., Indonesia, Philippines simultaneously is the trade and the consumption market at center, some are the product consequentiality that starting material are developed with the sea cucumber, as holothurian oral liquid, sea cucumber peptide nourishing capsule, sea cucumber wine, freeze-drying sea cucumber etc.
Recent study finds that the main active ingredient in the sea cucumber is its secondary metabolite---the sea cucumber saponin, the sea cucumber saponin all has distribution in sea cucumber body wall corium reticular tissue, body cavity, interior glandular tube and internal organ, has multiple pharmacologically active activity, as antitumor action, raising immunizing power, anti-neovascularization, anticoagulation, promotion fibrinolysis, the formation of inhibition embolism, anti-inflammatory action (as sacroiliitis) and anti-radioactivity, and suppress hiv virus, hepatitis B virus, simple scar exanthema virus etc.; In addition, research finds that also the sea cucumber saponin has the antifungal efficacy of wide spectrum.At present, the scientific research institution of existing a lot of countries is devoted to the research and development based on the product of sea cucumber saponin.Japan has been walked in the prostatitis in the world in this field, and Japanese Bei Chuanshi utilizes the stichopus japonicus soap. and glucoside has been developed the product of treatment beriberi and tinea alba fungi resisting infection.Usually the method for extracting the sea cucumber saponin from sea cucumber is to adopt traditional organic solvent extractionprocess, these class methods are produced not only complex operation of sea cucumber saponin, to the equipment requirements height, use a large amount of organic solvents (as methyl alcohol) in the production process, contaminate environment, and the sea cucumber overall utilization rate is not high, after having extracted the sea cucumber saponin, other nutritional activities composition can not effectively utilize, and the sea cucumber resource has been caused serious waste.Because the restriction of above various reasons, at present, China is relatively backward in the research in this field, institute's development product only is confined to the processing of the thick product of sea cucumber, and saponin component residues in the processing-waste more in the course of processing, waste liquid can not get effective utilization, has caused the significant wastage of resource.
Summary of the invention
The present invention seeks to make full use of the waste liquid in the sea cucumber course of processing, a kind of processing method for preparing the sea cucumber saponin with the sea cucumber waste liquid is provided.
Present method is to utilize sea cucumber to send out the system waste liquid as extracting material, at first, the sea cucumber waste liquid is filtered, remove insoluble composition, then, filtrate is used ethanol sedimentation, leave standstill, centrifugal to remove the albumen in the filtrate, compositions such as mucopolysaccharide, again with centrifuged supernatant with common concentrating under reduced pressure technology concentrating under reduced pressure to remove alcohol component wherein, the gained concentrated solution, with the flow velocity of 1.5～2.0 times of column volumes (BV)/h by macroporous adsorptive resins, then water with same flow velocity wash-out to remove salinity wherein, carbohydrate, impurity components such as pigment are that 60～70% ethanol elutions are attracted to the sea cucumber saponin component on the macroporous adsorbent resin with concentration then, collect elutriant and be evaporated to the medicinal extract shape, lyophilize becomes sea cucumber saponin dry product.
The present invention makes full use of sea cucumber and sends out the waste liquid that is produced in the system process, utilize macroporous adsorbent resin to send out the system waste liquid and extract the sea cucumber saponin from sea cucumber, can make in the sea cucumber waste liquid 95% saponin obtain enrichment, make intact structure of isolating saponin and effective biological activity, experiment shows, separates the saponin component that obtains and have good biological effect from the sea cucumber waste liquid.The principal feature of this technology is the discarded liquid that can make full use of after sea cucumber sends out system, and simple to operate, with short production cycle, with high content of technology, production cost is low, and environmentally safe, product have high utility value.
Embodiment
1, sea cucumber sends out discarded liquid after the system and filters (perhaps centrifugal) and remove insoluble composition;
2, ethanol is added in the filtrate, and to make alcohol concn wherein be 20～25%, leave standstill more than 10 hours; If the alcohol concn in the filtrate surpasses 25%, will influence sea cucumber saponin extraction yield; If concentration is lower than 20%, albumen, mucopolysaccharide composition are removed not exclusively in the filtrate, stop up macroporous adsorptive resins easily.
3, ethanol sedimentation liquid is centrifugal, and 2500～3000r/min more than the 30min, collects supernatant liquor;
4, with the supernatant liquor concentrating under reduced pressure, temperature is controlled at 45～50 ℃ (in case saponin pyrohydrolysises), and the alcohol component of removing in the supernatant liquor gets concentrated solution; The strong and weak length that is connected the sugar chain on the main chain backbone with it of biological activity of discovering the sea cucumber saponin has confidential relation, during concentrating under reduced pressure such as temperature too high, can make part sugar chain hydrolytic cleavage, and the biologic activity of influence extraction gained saponin; Therefore, temperature remains on 45～50 ℃ of concentrating under reduced pressure the saponin structure in the supernatant liquor is remained intact.
5, the concentrated solution behind the concentrating under reduced pressure, by macroporous adsorptive resins, the sea cucumber saponin is adsorbed on the macroporous adsorbent resin with the flow velocity of 1.5～2.0BV/h; Flow velocity is too high, and sea cucumber saponin adsorption rate will be reduced; Flow velocity is low excessively, will increase extraction time.
6, then wash above-mentioned macroporous adsorptive resins with same flow velocity, to remove impurity components such as salinity residual in the macroporous adsorbent resin, carbohydrate, pigment with 4～6BV water;
7, then be 60～70% ethanol, the sea cucumber saponin component that is adsorbed on the macroporous resin eluted that collection elutriant concentrating under reduced pressure (temperature is controlled at 45～50 ℃) promptly gets medicinal extract shape sea cucumber saponin with concentration;
8, above-mentioned medicinal extract lyophilize is got sea cucumber saponin dry product.
Embodiment 1
The discarded liquid 5L centrifugal (rotating speed is at 2500r/min) that sea cucumber sends out after the system removes insolubles, supernatant liquor is with ethanol sedimentation and to make alcohol concn wherein be 25%, left standstill 10 hours, centrifugal above-mentioned precipitated liquid, rotating speed is at 2500r/min, centrifugal 45min, collect supernatant liquor, the supernatant liquor concentrating under reduced pressure is removed alcohol component, temperature is controlled at 45 ℃ during concentrating under reduced pressure, liquid 2L behind the concentrating under reduced pressure, with the flow velocity of 2BV/h by AB-8 type macroporous adsorptive resins (R35mm * H90mm), then wash above-mentioned macroporous adsorptive resins with the flow velocity of 2BV/h with 6BV water, then, the sea cucumber saponin component that is adsorbed on the macroporous adsorbent resin is eluted, collect elutriant concentrating under reduced pressure (temperature is controlled at 45 ℃) to the medicinal extract shape with 70% ethanol of 5BV, with medicinal extract-20 ℃ freezing, get sea cucumber saponin dry product with freeze drier-54 ℃ of following lyophilizes then.
Embodiment 2
Sea cucumber sends out the discarded liquid 5L multilayer filtered through gauze after the system, filtrate is with ethanol sedimentation and to make alcohol concn wherein be 25%, left standstill 12 hours, centrifugal above-mentioned precipitated liquid, rotating speed is at 3000r/min, centrifugal 30min, collect supernatant liquor, the supernatant liquor concentrating under reduced pressure is removed alcohol component, temperature is controlled at 50 ℃ during concentrating under reduced pressure, the liquid 1.5L behind the concentrating under reduced pressure, with the flow velocity of 1.5BV/h by D101 type macroporous adsorptive resins (R30mm * H100mm), then wash above-mentioned macroporous adsorptive resins with same flow velocity with 6BV water, then, the sea cucumber saponin component that is adsorbed on the macroporous adsorbent resin is eluted, collect elutriant concentrating under reduced pressure (temperature is controlled at 50 ℃) to the medicinal extract shape with 60% ethanol of 6BV, with medicinal extract-20 ℃ freezing, get sea cucumber saponin dry product with freeze drier-54 ℃ of following lyophilizes then.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100441221A CN1313479C (en) | 2005-07-17 | 2005-07-17 | Method for preparing holothurin from waste solution of sea cucumber processing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100441221A CN1313479C (en) | 2005-07-17 | 2005-07-17 | Method for preparing holothurin from waste solution of sea cucumber processing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1733793A true CN1733793A (en) | 2006-02-15 |
| CN1313479C CN1313479C (en) | 2007-05-02 |
Family
ID=36076435
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100441221A Expired - Fee Related CN1313479C (en) | 2005-07-17 | 2005-07-17 | Method for preparing holothurin from waste solution of sea cucumber processing |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1313479C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060905A (en) * | 2010-11-12 | 2011-05-18 | 山东省科学院生物研究所 | Process method for preparing sea cucumber saponin Holotoxin A1 reference substance by using fresh sea cucumber processing waste liquid |
| CN102406048A (en) * | 2011-11-29 | 2012-04-11 | 山东好当家海洋发展股份有限公司 | Method for preparing sea cucumber glycoprotein by using sea cucumber blanching liquid |
| CN102512452A (en) * | 2011-11-29 | 2012-06-27 | 山东好当家海洋发展股份有限公司 | Process method for preparing sea cucumber glycosides by using sea cucumber coelomic fluid |
| CN101375863B (en) * | 2008-09-17 | 2013-07-31 | 青岛佳日隆海洋食品有限公司 | Method for extracting polysaccharide and other multiple active components in boiling juice of trepang |
| CN104262451A (en) * | 2014-10-24 | 2015-01-07 | 威海芝恩药业股份有限公司 | Method for extracting holothurin from sea cucumber processing waste fluid |
| CN104739868A (en) * | 2015-02-15 | 2015-07-01 | 大连工业大学 | Comprehensive Utilization Method of Sea Ginseng Processing Waste Liquid |
| CN110590967A (en) * | 2019-08-27 | 2019-12-20 | 中国海洋大学 | A method for recovering organic matter rich in sea cucumber polysaccharides from sea cucumber blanching liquid |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101585873B (en) * | 2009-07-09 | 2012-10-03 | 大连水产学院 | Method for reclaiming protein and crude polysaccharide from waste sea cucumber processing liquid |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005063789A1 (en) * | 2003-12-31 | 2005-07-14 | Council Of Scientific & Industrial Research | Isolation of bivittoside d from sea cucumber and activity thereof |
-
2005
- 2005-07-17 CN CNB2005100441221A patent/CN1313479C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101375863B (en) * | 2008-09-17 | 2013-07-31 | 青岛佳日隆海洋食品有限公司 | Method for extracting polysaccharide and other multiple active components in boiling juice of trepang |
| CN102060905A (en) * | 2010-11-12 | 2011-05-18 | 山东省科学院生物研究所 | Process method for preparing sea cucumber saponin Holotoxin A1 reference substance by using fresh sea cucumber processing waste liquid |
| CN102406048A (en) * | 2011-11-29 | 2012-04-11 | 山东好当家海洋发展股份有限公司 | Method for preparing sea cucumber glycoprotein by using sea cucumber blanching liquid |
| CN102512452A (en) * | 2011-11-29 | 2012-06-27 | 山东好当家海洋发展股份有限公司 | Process method for preparing sea cucumber glycosides by using sea cucumber coelomic fluid |
| CN102406048B (en) * | 2011-11-29 | 2013-04-17 | 山东好当家海洋发展股份有限公司 | Method for preparing sea cucumber glycoprotein by using sea cucumber blanching solution |
| CN102512452B (en) * | 2011-11-29 | 2013-08-28 | 山东好当家海洋发展股份有限公司 | Process method for preparing sea cucumber glycosides by using sea cucumber coelomic fluid |
| CN104262451A (en) * | 2014-10-24 | 2015-01-07 | 威海芝恩药业股份有限公司 | Method for extracting holothurin from sea cucumber processing waste fluid |
| CN104262451B (en) * | 2014-10-24 | 2016-04-13 | 威海芝恩药业股份有限公司 | A kind of method extracting selenka from Holothurian machining waste liquid |
| CN104739868A (en) * | 2015-02-15 | 2015-07-01 | 大连工业大学 | Comprehensive Utilization Method of Sea Ginseng Processing Waste Liquid |
| CN110590967A (en) * | 2019-08-27 | 2019-12-20 | 中国海洋大学 | A method for recovering organic matter rich in sea cucumber polysaccharides from sea cucumber blanching liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1313479C (en) | 2007-05-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100590109C (en) | Extraction Technology of Active Components of Herb Cistanche | |
| CN108619202A (en) | The method that a kind of extraction of eutectic solvent, macroporous absorbent resin isolate and purify burdock leaf flavonoids | |
| CN101402627A (en) | Synchronous separation, extraction and purification method for flavone, alkaloid and polysaccharide in lotus leaf | |
| CN112870236B (en) | Flavone effective part of abelmoschus manihot and preparation method and application thereof | |
| CN105622776A (en) | Flos farfarae polysaccharide extraction and purification method | |
| CN103694364A (en) | Method for synchronously extracting, separating and purifying polysaccharides and flavones of cyclocarya paliurus | |
| CN103435486A (en) | Novel method for preparing high-purity chlorogenic acid in honeysuckle | |
| CN103860631A (en) | Method for preparing liquorice active substances | |
| CN103467617A (en) | Method for continuous counter-current ultrasonic extraction of high-purity astragalus polysaccharide | |
| CN103044566A (en) | Method for preparing antioxidant polysaccharide from dictyophora indusiata aqueous extract residues | |
| CN101709094A (en) | Method for separating sweet tea polysaccharide by ultrafiltration membranes | |
| CN1313479C (en) | Method for preparing holothurin from waste solution of sea cucumber processing | |
| CN107693559A (en) | The preparation method of Notogineng Extract | |
| CN107126452A (en) | Gypenosides and preparation method thereof | |
| CN102579516A (en) | Method for separating purified seabuckthorn flavonoid from large berry seabuckthorn marc | |
| CN106883306A (en) | A kind of extraction separation method of the sunflower stem core polysaccharide with antitumor activity | |
| CN101121118B (en) | Modified macroporous polyvinyl alcohol resin and method for separating and purifying Chinese medicinal herb polysaccharide | |
| CN104926767A (en) | Method of purification preparation of citrus flavones by adopting macroporous adsorption resin | |
| CN102218087B (en) | Method for preparing total flavone extracts of pagoda flower | |
| CN107903328A (en) | A kind of wrinkled papaya seed polysaccharide and preparation method thereof | |
| CN104892719A (en) | Novel efficient preparation method for asiaticoside | |
| CN108164611A (en) | A kind of method of garlic synthesis extraction and application | |
| CN106119429A (en) | A kind of production method of Radix Notoginseng sugar | |
| CN110423262A (en) | A kind of Astragalus Root P.E preparation method rich in Astragaloside IV | |
| CN102836201B (en) | Preparation method of abrus herb total flavonoids |
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: 20070502 Termination date: 20110717 |