CN101544991B - Natural antioxidant of perilla flavone for cigarette and method for preparing same - Google Patents

Natural antioxidant of perilla flavone for cigarette and method for preparing same Download PDF

Info

Publication number
CN101544991B
CN101544991B CN2008100471748A CN200810047174A CN101544991B CN 101544991 B CN101544991 B CN 101544991B CN 2008100471748 A CN2008100471748 A CN 2008100471748A CN 200810047174 A CN200810047174 A CN 200810047174A CN 101544991 B CN101544991 B CN 101544991B
Authority
CN
China
Prior art keywords
perilla
cigarette
flavone
natural antioxidant
perilla flavone
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
Application number
CN2008100471748A
Other languages
Chinese (zh)
Other versions
CN101544991A (en
Inventor
魏敏
罗诚浩
蔡冰
王娟
张华�
郭国宁
熊宏春
韩旭
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Tobacco Hunan Industrial Co Ltd
Original Assignee
China Tobacco Hunan Industrial Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by China Tobacco Hunan Industrial Co Ltd filed Critical China Tobacco Hunan Industrial Co Ltd
Priority to CN2008100471748A priority Critical patent/CN101544991B/en
Publication of CN101544991A publication Critical patent/CN101544991A/en
Application granted granted Critical
Publication of CN101544991B publication Critical patent/CN101544991B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Manufacture Of Tobacco Products (AREA)
  • Pyrane Compounds (AREA)

Abstract

The invention discloses a natural antioxidant of perilla flavone for cigarette and a method for preparing the same, and relates to the technical field of additives for cigarettes. The natural antioxidant of perilla flavone for cigarette is prepared by the following steps that: the residue obtained after the naphtha is extracted from perilla leaves is dried, subjected to vacuum film breaking, soaking, compound enzyme-catalysis, namely ethanol refluxing extraction, pressure reduction suction filter and low-temperature high-speed centrifugation and refined to obtain an extracting solution of perilla flavone. The method for preparing the natural antioxidant of perilla flavone for cigarette comprises the following steps: (1) raw material processing, and vacuum film breaking; (2) soaking, and adding 0.1 to 1 percent compound enzyme; and (3) extraction and refining. When the extract of the invention is added to the cut tobacco, the quality of the cut tobacco is not changed. The raw material used by the invention is wide in source and low in cost and price; and the method has the advantages of simple technological process and simple equipment, and the extract can be used as a novel natural antioxidant for cigarette.

Description

Natural antioxidant of perilla flavone for cigarette and preparation method thereof
Technical field
The present invention relates to the cigarette additive technical field, specifically a kind of extraction preparation method of natural antioxidant of perilla flavone for cigarette.
Background technology
In tobacco product, should guarantee the flue gas quality, guarantee the low hazardness of cigarette again, in cigarette, add cigarette additive-inhibitor and more and more come into one's own.Extract natural antioxidants and carry out cigarette with being an important directions of lowering harm and decreasing coking, the applicant is exploring along this direction just.
Perilla Leaf is the leaf of labiate purple perilla Perilla frutescens (L.) Britt., claims Su Ye again, and tool is separated table function, is the annual herb plant.Originate in China, nowadays mainly be distributed in countries such as India, Burma, China, Japan, Korea, Korea S, Indonesia and Russia.All there are wild species and cultivar in China North China, Central China, south China, southwest and Taiwan Province.Purple perilla is used in China plantation has nearly 2000 history approximately, is mainly used in medicinal, oil usefulness, spices, aspect such as edible, its leaf (Su Ye), obstruct (caulis perllae), really (perillaseed) all can be used as medicine, soup can be eaten, done to tender leaf raw, cauline leaf can flood stain.In the last few years, purple perilla became a kind of multi-purpose plant of extremely World Focusing because of its distinctive active substance and nutritive ingredient, and economic worth is very high.States such as Russia, Japan, Korea S, the U.S., Canada have carried out a large amount of commerciality plantations to the Perilla plant, developed edible oil, medicine, flooded tens kinds of purple perilla products such as stain article, makeup.In the prior art; But Shang Weiyou extracts the precedent of cigarette additive from purple perilla, and, learn in the Perilla Leaf residue after aforementioned Perilla Leaf extracts sesame oil according to applicant research and to contain many useful components; All be used as waste disposal and fallen, do not obtain reasonable use as yet.
Summary of the invention
To the above-mentioned deficiency of prior art, the technical problem that the present invention will solve provides a kind of natural antioxidant of perilla flavone for cigarette and preparation method thereof, and perilla flavone is applied to obtain in the cigarette better antioxidation; The inventive method makes as the Perilla Leaf residue after the Perilla Leaf extraction sesame oil of waste material and obtains reasonable use, and it is higher to extract yield.
Technical scheme of the present invention is: natural antioxidant of perilla flavone for cigarette is by the preparation of following method and get: after Perilla Leaf is extracted the residue drying behind the volatile oil, and the perilla flavone extracting solution that must extract with vacuum rupture of membranes, immersion, compound enzymatic-alcohol reflux, decompress filter, centrifugal afterwards the making with extra care of low-temperature and high-speed.
Described prozyme is the combination enzyme of food grade solid powdery cellulase, polygalacturonase, proteolytic enzyme.
Described prozyme is made up of following component and umber: cellulase: polygalacturonase: proteolytic enzyme=0.5~2: 0.5~2: 0.5~2.
Described vacuum rupture of membranes is meant that the residue that Perilla Leaf is extracted behind the volatile oil places vacuum tightness 98% time, vacuumizes 2min, and all standing makes purple perilla cell walls rupture of membranes.
The preparation method of natural antioxidant of perilla flavone for cigarette carries out according to the following steps:
(1) raw material is handled: after will extracting Perilla Leaf residue behind the volatile oil and carrying out drying, the vacuum extractor of packing into vacuum tightness 98% time, vacuumizes 2min, and all standing carries out the vacuum rupture of membranes, makes purple perilla cell walls rupture of membranes, and pulverizing obtains Perilla Leaf residue meal then;
(2) immersion and enzyme are handled: get Perilla Leaf residue meal and put into container, add 0.1~1% prozyme, 5~10 times of water mixings, adjust pHs soak 1h~2h for 4.0~6.0,40 ℃-50 ℃;
(3) extraction is refining: add 3~5 times of 95% ethanol; 80 ℃~90 ℃ constant temperature water bath refluxing extraction 1~2h; Water pump vacuumizes decompress filter, be concentrated to original volume 1/4~1/5 after, separate with 8000~11000rpm high speed centrifugation, the gained supernatant is the perilla flavone extracting solution.
Described prozyme is food grade solid powdery cellulase, polygalacturonase, proteolytic enzyme.
Described prozyme is made up of following component and umber: cellulase: polygalacturonase: proteolytic enzyme=0.5~2: 0.5~2: 0.5~2.
The present invention and prior art relatively have the following advantages: pre-treatment of the present invention has adopted vacuum rupture of membranes and prozyme to handle; Destroyed cell wall structure to a greater degree; Effective constituent is come out more, reduce the water holdup of filter residue, improve productive rate and reduce extraction cost; And the vacuum rupture of membranes is that physical method, prozyme are treated to biological method, and is all safe, easy.Extract of the present invention does not change the flue gas quality after adding pipe tobacco.Its raw material source of the present invention is extensive, and cost is low, is worth cheap; Method technological process of the present invention is simple, and equipment is simple, and extract can be used as the new type natural cigarette and uses inhibitor.
Embodiment
Be described in further detail in the face of relevant technologies problem of the present invention down.The perilla flavone extracting solution that the applicant extracts the inventive method compares with the yield of handling directly the perilla flavone extracting solution that extracts with alcohol solvent without rupture of membranes, and the content of flavones is taked determined by ultraviolet spectrophotometry.
1, the preparation of typical curve
Accurately take by weighing rutin standard substance 0.0501g, use 30% dissolve with ethanol, and move into fully in the 500ml volumetric flask, with 30% ethanol constant volume.Get rutin standardized solution 0,1,2,4,6,8,10ml respectively in 7 25ml volumetric flasks, be supplemented to 15ml, add 5% Sodium Nitrite 0.7ml with 30% ethanol; Shake up, add 10% aluminum nitrate 0.7ml behind the placement 5min, add 4% sodium hydroxide 5ml behind the 6min again; Mixing; To scale, in wavelength 510nm place's colorimetric estimation, blank is a rutin 0ml reference liquid behind the 10min with 30% alcohol dilution.The typical curve regression equation that records absorbance A and concentration C mg/ml is: C=0.10016A, R2=0.99951.
2, the mensuration of flavones content
Spectrophotometry: adopt Sodium Nitrite-aluminum nitrate colourimetry.
Get each 0.2ml of extracting solution respectively in 5 25ml volumetric flasks, be supplemented to 15ml, add 5% Sodium Nitrite 0.7ml with 30% ethanol; Shake up, add 10% aluminum nitrate 0.7ml behind the placement 5min, add 4% sodium hydroxide 5ml behind the 6min again; Mixing; To scale, in wavelength 510nm place's colorimetric estimation, the record light absorption value is effective with at 0-1.0 behind the 10min with 30% alcohol dilution.
3, test-results
Record perilla flavone extracting solution through vacuum rupture of membranes of the present invention, compound enzymatic-solvent extraction, extract the perilla flavone extracting solution light absorption value of (contrast) with direct solvent after, promptly be the content of flavones by institute's value after the regression equation calculation.Raw material is the Perilla Leaf residue meal 10g behind the extraction volatile oil, and the extracting solution constant volume is to 500ml, and two kinds of method gained flavones contents are relatively seen table 1.
The flavones content contrast of table 1 extracting solution
Sample Concentration (mg/ml) Quality (g) Yield (%)
Through vacuum rupture of membranes, compound enzymatic-solvent extraction liquid 2.0052 1.0026 10.026%
The direct solvent extracting solution 1.1521 0.5761 5.761%
The raw material that the present invention adopted is the residue after Perilla Leaf extracts volatile oil, and is cheap.Process for extracting of the present invention is than without vacuum rupture of membranes, not enzyme-added direct solvent process for extracting, and the yield of the perilla flavone of gained obviously improves, and has improved extraction efficiency, has reduced production cost, and the vacuum rupture of membranes, to add composite enzyme method easy, easy to operate.
The applicant has also carried out the oxidation-resistance of perilla flavone extracting solution and has measured, and measures and takes phenanthroline system hydroxyl radical free radical to remove experiment.
1, get 1ml 0.75mmol/L phenanthroline ethanol solution adds 2ml, 0.15mol/L successively in test tube phosphate buffered saline buffer (PBS, pH=7.2) with 1ml zero(ppm) water, abundant mixing; The 0.75mmol/L copperas solution that adds the new preparation of 1ml; Behind the mixing, add 0.01% ydrogen peroxide 50 of the new preparation of 1ml, behind 37 ℃ of heating in water bath 1h; Survey light absorption value at 536nm, measured data are light absorption value A0.Replace 1ml 0.01% ydrogen peroxide 50 with 1ml zero(ppm) water, working method is same as described above, and the light absorption value A1 in the time of can recording 536nm is blank with A0.Replace 1ml 0.01% ydrogen peroxide 50 with the 1ml sample, working method is same as described above, and the light absorption value A2 in the time of can recording 536nm is blank with A0.
Clearance rate (%)=A2/A1 * 100%
2, perilla flavone extracting solution and xitix (Vc) solution of preparation 0.1,0.125,0.15,0.175,0.20mg/ml; Adding phenanthroline hydroxy radical qiao master gives birth in the system; Efficient to hydroxyl radical free radical in the perilla flavone extracting solution of different concns and xitix (Vc) the removing system detects, to the clearance rate of hydroxyl radical free radical relatively like table 2.
Table 2 different concns perilla flavone extracting solution and Vc contrast the free radical scavenging of phenanthroline system
Figure S2008100471748D00051
The perilla flavone extracting solution that the inventive method obtains with the Perilla Leaf residue, the hydroxyl radical free radical that the phenanthroline system is produced has certain scavenging(action), and when 0.175mg/ml, clearance rate reaches 58.87%; Under same concentrations, perilla flavone extracting solution removing ability of the present invention is 5~10 times of natural antioxidants xitix (Vc), and within the specific limits, along with concentration increases, the removing ability also progressively strengthens.
With perilla flavone extracting solution of the present invention; Join in the pipe tobacco by 1%, 0.5%, 0.1% (mass percent); Dry and roll into cigarette and (smoke panel test by relevant regulations of the prior art; With Wuhan tobacco Group Co.,Ltd, red certain two types of cigarette of gold dragon are contrast, carry out sensory evaluating smoking and smoke gaseous phase free radical and measure.
1, sensory evaluating smoking
Smoke panel test through the military cigarette expert group of smokeing panel test, compare with blank, add Perilla Leaf residue flavone extractive in the pipe tobacco after, do not change the flue gas quality.
2, smoke gaseous phase free radical is measured
Make even each 20 of the cigarette of equal Dan Zhichong 0.920g ± 0.02g and average resistance to suction 1.065kPa ± 0.05kPa as test sample.The test cigarette of preparation is all put into the environment equilibrium water content 48h of climatic chamber in 22 ℃ ± 2 ℃ of temperature and relative humidity 60% ± 2%.Adopt electron spin resonance (ESR) to carry out smoke gaseous phase free radical and detect, the result sees table 3.
The experiment of flue gas radical is removed in the smoke adding of table 3 Perilla Leaf residue flavone extractive
Perilla flavone extracting solution consumption (%) Strength of signal (cm) Clearance rate (%)
0 21.8±3.2 /
0.1% 18.4±2.8 15.6%
0.5% 16.9±2.6 22.5%
1% 14.3±2.7 34.4%
Mensuration result shows, compares with contrast, and the cigarette smoke number of free radical that adds the perilla flavone extracting solution has certain reduction; And within the specific limits, along with the increase of perilla flavone extract concentration, clearance rate improves.
The applicant tests the stability of the perilla flavone extracting solution of the inventive method preparation.The experiment of first temperature stability.With content is perilla flavone extracting solution insulation 12h under 90 ℃ of 0.175mg/ml, or behind insulation 24h under 60 ℃, measures its flavones content and phenanthroline system hydroxyl radical free radical clearance rate, and the result sees table 4.
Table 4, temperature stability are measured
Figure S2008100471748D00071
Can know that by last table the perilla flavone extracting solution is better through 60 ℃ of insulation 24h rear stabilities, and compare flavones content before the heating and only slightly reduced 0.02mg/ml that its phenanthroline system hydroxyl radical free radical clearance rate has reduced by 12.66%; And that the sample result of 90 ℃ of insulation 12h is presented under this temperature thermostability is relatively poor, and it is half that flavones content has reduced, and phenanthroline system hydroxyl radical free radical clearance rate only has an appointment 5%.But in cigarette processing, after flavone extractive added pipe tobacco, the high temperature that runs into only maybe be in weather, room temperature influence scope, and also high temperature for a long time when the technology for making tobacco threds perfuming is so the cigarette of Perilla Leaf residue flavone extractive is used good thermal stability.It two is to have carried out pH value of solution gradient stability experiment.The perilla flavone extracting solution that with concentration is 0.175mg/ml is measured flavones content, phenanthroline system hydroxyl radical free radical clearance rate pH2,4,6,8, at 10 o'clock, and the result sees table 5.
Table 5, pH value of solution gradient stability
Can know by last table, the perilla flavone extracting solution, good at pH4~6 scope internal stabilities, its flavones content is constant basically, and phenanthroline system hydroxyl radical free radical clearance rate is constant basically.And also slant acidity of the pH value of pipe tobacco, about pH5~6, so the active pH value of perilla flavone extracting solution is fit to cigarette and uses.
The applicant has carried out smoke gaseous phase free radical mensuration
Make even each 20 of the cigarette of equal Dan Zhichong 0.920g ± 0.02g and average resistance to suction 1.065kPa ± 0.05kPa as test sample.The test cigarette of preparation is all put into the environment equilibrium water content 48h of climatic chamber in 22 ℃ ± 2 ℃ of temperature and relative humidity 60% ± 2%.Adopt electron spin resonance (ESR) to carry out smoke gaseous phase free radical and detect, the result sees table 6.
Table 6 adds perilla flavone extracting solution cigarette and removes the experiment of flue gas radical
Perilla flavone extracting solution consumption (%) Strength of signal (cm) Clearance rate (%)
0 21.8+3.2 /
0.05% 20.9+3.0 4.1
0.1% 18.4+2.8 15.6
0.5% 16.9+2.6 22.5
Last table is measured the result and is shown, compares with control samples, and the cigarette smoke number of free radical that adds the perilla flavone extracting solution has certain reduction; And within the specific limits, along with the increase of extract concentration, clearance rate improves.

Claims (2)

1. the preparation method of a natural antioxidant of perilla flavone for cigarette is characterized in that described method carries out according to the following steps:
(1) raw material is handled: after will extracting Perilla Leaf residue behind the volatile oil and carrying out drying, the vacuum extractor of packing into vacuum tightness 98% time, vacuumizes 2min, and all standing carries out the vacuum rupture of membranes, makes purple perilla cell walls rupture of membranes, and pulverizing obtains Perilla Leaf residue meal then;
(2) immersion and enzyme are handled: get Perilla Leaf residue meal and put into container, add 0.1~1% prozyme, 5~10 times of water mixings, adjust pHs soak 1h~2h for 4.0~6.0,40 ℃-50 ℃; Described prozyme is food grade solid powdery cellulase, polygalacturonase, proteolytic enzyme;
(3) extraction is refining: add 3~5 times of 95% ethanol; 80 ℃~90 ℃ constant temperature water bath refluxing extraction 1~2h; Water pump vacuumizes decompress filter, be concentrated to original volume 1/4~1/5 after, separate with 8000~11000rpm high speed centrifugation, the gained supernatant is the perilla flavone solution of extraction.
2. the preparation method of natural antioxidant of perilla flavone for cigarette according to claim 1 is characterized in that described prozyme is made up of following component and umber: cellulase: polygalacturonase: proteolytic enzyme=0.5~2: 0.5~2: 0.5~2.
CN2008100471748A 2008-03-28 2008-03-28 Natural antioxidant of perilla flavone for cigarette and method for preparing same Expired - Fee Related CN101544991B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2008100471748A CN101544991B (en) 2008-03-28 2008-03-28 Natural antioxidant of perilla flavone for cigarette and method for preparing same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2008100471748A CN101544991B (en) 2008-03-28 2008-03-28 Natural antioxidant of perilla flavone for cigarette and method for preparing same

Publications (2)

Publication Number Publication Date
CN101544991A CN101544991A (en) 2009-09-30
CN101544991B true CN101544991B (en) 2012-03-07

Family

ID=41192369

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2008100471748A Expired - Fee Related CN101544991B (en) 2008-03-28 2008-03-28 Natural antioxidant of perilla flavone for cigarette and method for preparing same

Country Status (1)

Country Link
CN (1) CN101544991B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101843363B (en) * 2010-05-13 2013-05-22 云南烟草科学研究院 Application of seabuckthorn in preparing cigarette and application method
CN101953510B (en) * 2010-07-07 2013-09-11 澳华达香料科技(广州)有限公司 Method for extracting antioxidant from smashed tobacco powder
CN103601711B (en) * 2013-11-04 2016-09-07 广东中烟工业有限责任公司 A kind of coumarin derivative and its preparation method and application
CN105267299A (en) * 2015-09-22 2016-01-27 盐城工学院 Perilla flavone and perilla flavone derivative extraction method
CN110664638A (en) * 2019-09-24 2020-01-10 中北大学 Perilla frutescens essence mask and preparation method thereof
CN114774198A (en) * 2022-04-22 2022-07-22 珠海安生凤凰制药有限公司 Based on CO2Method for extracting radix Angelicae sinensis extract by supercritical extraction

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1329103A (en) * 2001-08-07 2002-01-02 姜浩奎 Method for extracting protein, short peptide, nucleic acid, isoflavone, saponin and oligosaccharide by using high and low temperature soybean cake
CN1687029A (en) * 2005-03-28 2005-10-26 武汉工业学院 Method for extracting compound of carotenoid and flavonoid from leaves of purple operilla

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1329103A (en) * 2001-08-07 2002-01-02 姜浩奎 Method for extracting protein, short peptide, nucleic acid, isoflavone, saponin and oligosaccharide by using high and low temperature soybean cake
CN1687029A (en) * 2005-03-28 2005-10-26 武汉工业学院 Method for extracting compound of carotenoid and flavonoid from leaves of purple operilla

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
刘宁等.超声辅助提取紫苏叶黄酮及其清除自由基作用研究.《西北林学院学报》.2008,第23卷(第1期),158-161. *
胡浩斌等.正交试验法优选东紫苏中黄酮类化合物的提取工艺.《中药材》.2006,第29卷(第3期),296-298. *
魏敏等.酶促提取紫苏残渣黄酮加速氧化试验及稳定性分析.《食品研究与开发》.2009,第30卷(第8 期),26-30. *

Also Published As

Publication number Publication date
CN101544991A (en) 2009-09-30

Similar Documents

Publication Publication Date Title
CN101544991B (en) Natural antioxidant of perilla flavone for cigarette and method for preparing same
CN103965369B (en) Ganoderan, method for extraction and purification and the application as tobacco humectant thereof
CN101538509B (en) Method and application for extracting tobacco use spice from corn cob
CN102993328B (en) Method for comprehensively extracting polysaccharides, polyphenol and saponin from camellia oleifera abel defatted cakes
Pan et al. Ultrasound-assisted deep eutectic solvents extraction of polysaccharides from Morchella importuna: optimization, physicochemical properties, and bioactivities
CN103804507A (en) Maryland tobacco polysaccharide, extracting and purifying method and application thereof as antioxidant
CN101693745A (en) Lucid ganoderma polysaccharide and extraction method thereof as well as cigarette containing lucid ganoderma polysaccharide and preparation method thereof
He et al. Characteristics and antioxidant capacities of five hawthorn wines fermented by different wine yeasts
CN105686069A (en) Tobacco extract and preparation method and application thereof
CN106957373A (en) A kind of Chinese yam polysaccharide extracting method
CN103304677B (en) A kind of method of separation and purification Rhizoma amorphophalli glucomannan
CN104957761B (en) Free state and the application in Medicated cigarette of the bound form aroma material in fruit
CN103705647A (en) Process method for extracting general flavone of golden camellia leaves by CO2 supercritical method
CN105131140A (en) Trigonella foenum-graecum polysaccharide extraction purification method and applications of trigonella foenum-graecum polysaccharide as humectant in cigarettes
CN103910808A (en) Spice tobacco bud polysaccharide, as well as preparation method and application thereof as antioxidant
CN103965370B (en) Jujube polysaccharide, method for extraction and purification and the application as tobacco humectant thereof
CN111184682A (en) Preparation method of hypecoum vulgare cell extract with whitening and antioxidant effects
CN101606751A (en) One tobacco articles free radical scavenger
Shlini et al. Extraction of phenolics, proteins and antioxidant activity from defatted tamarind kernel powder
CN103980374B (en) Polysaccharides from morinda officinalis how, method for extraction and purification and the application as tobacco humectant thereof
CN104031161B (en) Herba Lysimachiae polysaccharide, method for extraction and purification and the application as tobacco humectant thereof
CN110624088B (en) Extraction process of ginger flavone and research on antioxidant performance
CN113512021A (en) Method for simultaneously extracting procyanidine and polysaccharide from rosa davurica pall seeds
CN103980378B (en) Agaricus Blazei Murrill polysaccharide, method for extraction and purification and the application as tobacco humectant thereof
CN105732839A (en) Preparation method of high-activity tricholoma matsutake polysaccharide

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
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20120307

Termination date: 20170328