CN100556918C - A kind of preparation method of cyclodextrin-phthalocyanine binary combination - Google Patents
A kind of preparation method of cyclodextrin-phthalocyanine binary combination Download PDFInfo
- Publication number
- CN100556918C CN100556918C CNB2007101647057A CN200710164705A CN100556918C CN 100556918 C CN100556918 C CN 100556918C CN B2007101647057 A CNB2007101647057 A CN B2007101647057A CN 200710164705 A CN200710164705 A CN 200710164705A CN 100556918 C CN100556918 C CN 100556918C
- Authority
- CN
- China
- Prior art keywords
- cyclodextrin
- phthalocyanine
- add
- weight
- mol ratio
- 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
Abstract
That the present invention relates to is a kind of preparation method of cyclodextrin-phthalocyanine binary combination, and this method is that cyclodextrin and cobalt phthalocyanine are prepared cyclodextrin-phthalocyanine binary combination by synthesizing; Described cyclodextrin provides necessary hydrophobic space for analogue enztme, and the cobalt phthalocyanine provides effective reactive site for analogue enztme, and this is that other single cyclodextrin, phthalocyanine analogue enztme are unexistent; Cobalt phthalocyanine, cyclodextrin directly combine with covalent linkage, can be by concerted reaction etc. to substrate generation effect between cobalt phthalocyanine, the cyclodextrin; The present invention can be used for catalytic purification organic pollutant, cancer therapy etc.
Description
Technical field
That the present invention relates to is a kind of preparation method of cyclodextrin-phthalocyanine binary combination.
Background technology
Enzyme catalysis is compared with the general chemistry catalyzer, have advantages such as high efficiency, specificity and reaction conditions gentleness, and natural enzyme is too responsive to environment, operational condition is required harsh, easily inactivation costs an arm and a leg, so people attempt to keep the advantage of natural enzyme, change the shortcoming of its volatility inactivation, begin to carry out the modeling effort of enzyme function.This class enzyme model molecule that is used to make up analogue enztme at present has cyclodextrin, crown ether, cave ether, cage ether, porphyrin etc.Cyclodextrin is a more satisfactory enzyme model, and the catalytic characteristics of cyclodextrin are: the substrate molecule that participates in reaction is connect by the cyclodextrin molecular bag earlier, reacts with it again, and is quite similar with enzymatic reaction.Phthalocyanine is a plane macrocylc compound, one hole is arranged in the ring, can hold iron, copper, cobalt, aluminium, nickel, calcium, sodium, magnesium, zinc etc. are planted multiple metallic element, the metal phthalocyanine that contains metallic element has the structure similar to metalloporphyrin, studies show that, the many organic reactions of metal phthalocyanine energy catalysis, particularly can effectively activate oxygen molecule, and the autoxidation of catalyzing organic at ambient temperature, therefore metal phthalocyanine can be used as the model of simulation biological enzyme, tetracarboxylic cobalt phthalocyanine is one of them, studies have shown that tetracarboxylic cobalt phthalocyanine can catalyzed oxidation mercaptan etc. objectionable impurities.
As the existing many researchs of imitative enzyme catalyst, then belong to the problem of studying about cyclodextrin, metal phthalocyanine but utilize cyclodextrin and metal phthalocyanine to prepare cyclodextrin-phthalocyanine binary combination.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of cyclodextrin-phthalocyanine binary combination, it is that cyclodextrin and cobalt phthalocyanine are prepared cyclodextrin-phthalocyanine binary combination by synthesizing.The goods of this preparation gained can be used for the photodynamic therapy of catalytic purification organic pollutant, cancer etc.
Method of the present invention is: A) be that potassium hydroxide/cyclodextrin mixt of 1/25 is 1: 12～20 to add in the mixed solution that the volume ratio of componentss are tetrahydrofuran (THF)/water of 7/10 by weight with the weight ratio of components, after treating most of dissolving, by cyclodextrin and Tosyl chloride weight ratio is 1: 0.1～0.2 slowly to drip the tetrahydrofuran solution that weight percent concentration is 6% Tosyl chloride, vigorous stirring 2～6 hours, add acetone, separate out white solid, filter, with the ether washing, obtain 6 p-toluenesulfonyl modification cyclodextrins with the distilled water secondary recrystallization;
B) be 1: 10～17 to join in the new polyamine compounds that steamed by weight with 6 p-toluenesulfonyl modification cyclodextrins; Stir under nitrogen protection, after treating to dissolve fully, be warming up to 70～90 ℃, reacted 8-9 hour, underpressure distillation removes and desolvates, and the gained solid is dissolved in a small amount of hot water; Under agitation be added to an amount of volume ratio and be in 10/1 the acetone solution, collect white precipitate, repeat aforesaid operations 3～5 times,, after vacuum-drying, obtain 6 polyamines modification cyclodextrins with the mixed solvent recrystallization of alcohol-water 1-5 time;
C) be 1: 152: 2500 with mol ratio: 440 ammonium molybdate: cobalt chloride hexahydrate: urea: the mixture that the four class materials such as mixture of phthalic anhydride compounds are formed is transferred in the container after grinding evenly, is added a cover, be heated to 100～150 ℃ of insulations 1-60 minute, after treating bubble collapse, continue to be warming up to 170～200 ℃, react and obtain black-and-blue solid after 1～12 hour; Fragmentation is after hydrochloric acid/sodium chloride saturated solution is handled, and alkalization then, acidifying obtain carboxyl cobalt phthalocyanine for several times after centrifugation, collection, the drying;
D) be 1: 10～30 to join in the dimethyl formamide by weight with the polyamines modification cyclodextrin, temperature is controlled at-5～5 ℃, by being to add the carboxyl phthalocyanine at 0.5～1.5: 1 with polyamines modification cyclodextrin mol ratio; By being to add dicyclohexylcarbodiimide at 1.5～0.5: 1 with carboxyl phthalocyanine mol ratio, be to add I-hydroxybenzotriazole at 1.5～0.5: 1 with carboxyl phthalocyanine mol ratio, stir, in bathing, stirred 1～3 day-15～-5 ℃ of cryosels, at room temperature reacted then 3～5 days; Leave standstill, the elimination insolubles, filtrate splashes in the acetone, and collecting precipitation is with obtaining cyclodextrin-phthalocyanine binary combination behind the chromatogram purification.
Cyclodextrin of the present invention is alpha-cylodextrin or beta-cyclodextrin or γ-Huan Hujing.
The present invention compared with prior art has following outstanding advantage: 1) cyclodextrin provides necessary hydrophobic space for analogue enztme, and the cobalt phthalocyanine provides effective reactive site for analogue enztme, and this is that other single cyclodextrin, phthalocyanine analogue enztme are unexistent; 2) cobalt phthalocyanine, cyclodextrin directly combine with covalent linkage, can be by concerted reaction etc. to substrate generation effect between cobalt phthalocyanine, the cyclodextrin; 3) goods can be used for the photodynamic therapy of catalytic purification organic pollutant, cancer etc.
Embodiment
The present invention will be described in detail below in conjunction with embodiment:
Embodiment 1:A) be that potassium hydroxide/alpha-cylodextrin mixture of 1/25 is to add at 1: 12 in the mixed solution that the volume ratio of components is tetrahydrofuran (THF)/water of 7/10 by weight with the weight ratio of components, after treating most of dissolving, by alpha-cylodextrin and Tosyl chloride weight ratio is slowly to drip the tetrahydrofuran solution that weight percent concentration is 6% Tosyl chloride at 1: 0.1, vigorous stirring 2 hours, add acetone, separate out white solid, filter, with the ether washing, obtain 6 p-toluenesulfonyl modification cyclodextrins with the distilled water secondary recrystallization;
B) be to join in the new polyamine compounds that steamed at 1: 10 by weight with 6 p-toluenesulfonyl modification cyclodextrins; Stir under nitrogen protection, after treating to dissolve fully, be warming up to 70 ℃, reacted 8 hours, underpressure distillation removes and desolvates, and the gained solid is dissolved in a small amount of hot water; Under agitation be added to an amount of volume ratio and be in 10/1 the acetone solution, collect white precipitate, repeat aforesaid operations 3 times,, after vacuum-drying, obtain 6 polyamines modification cyclodextrins with the mixed solvent recrystallization of alcohol-water 1 time;
C) be 1: 152: 2500 with mol ratio: 440 ammonium molybdate: cobalt chloride hexahydrate: urea: the mixture that the four class materials such as mixture of phthalic anhydride compounds are formed is transferred in the container after grinding evenly, is added a cover, be heated to 100 ℃ of insulations 1 minute, after treating bubble collapse, continue to be warming up to 170 ℃, react and obtain black-and-blue solid after 1 hour; Fragmentation is after hydrochloric acid/sodium chloride saturated solution is handled, and alkalization then, acidifying obtain carboxyl cobalt phthalocyanine for several times after centrifugation, collection, the drying;
D) be to join in dimethyl formamide at 1: 10 by weight with the polyamines modification cyclodextrin, temperature is controlled at-5 ℃, by being to add the carboxyl phthalocyanine at 0.5: 1 with polyamines modification cyclodextrin mol ratio; By being to add dicyclohexylcarbodiimide at 1.5: 1 with carboxyl phthalocyanine mol ratio, be to add I-hydroxybenzotriazole at 1.5: 1 with carboxyl phthalocyanine mol ratio, stir, in bathing, stirred 1 day-15 ℃ of cryosels, at room temperature reacted then 3 days; Leave standstill, the elimination insolubles, filtrate splashes in the acetone, and collecting precipitation is with obtaining cyclodextrin-phthalocyanine binary combination behind the chromatogram purification.
Embodiment 2, A) be that potassium hydroxide/beta-cyclodextrin mixture of 1/25 is to add at 1: 20 in the mixed solution that the volume ratio of components is tetrahydrofuran (THF)/water of 7/10 by weight with the weight ratio of components, after treating most of dissolving, by beta-cyclodextrin and Tosyl chloride weight ratio is slowly to drip the tetrahydrofuran solution that weight percent concentration is 6% Tosyl chloride at 1: 0.2, vigorous stirring 6 hours, add acetone, separate out white solid, filter, with the ether washing, obtain 6 p-toluenesulfonyl modification cyclodextrins with the distilled water secondary recrystallization;
B) be to join in the new polyamine compounds that steamed at 1: 17 by weight with 6 p-toluenesulfonyl modification cyclodextrins; Stir under nitrogen protection, after treating to dissolve fully, be warming up to 90 ℃, reacted 9 hours, underpressure distillation removes and desolvates, and the gained solid is dissolved in a small amount of hot water; Under agitation be added to an amount of volume ratio and be in 10/1 the acetone solution, collect white precipitate, repeat aforesaid operations 5 times,, after vacuum-drying, obtain 6 polyamines modification cyclodextrins with the mixed solvent recrystallization of alcohol-water 5 times;
C) be 1: 152: 2500 with mol ratio: 440 ammonium molybdate: cobalt chloride hexahydrate: urea: the mixture that the four class materials such as mixture of phthalic anhydride compounds are formed is transferred in the container after grinding evenly, is added a cover, be heated to 150 ℃ of insulations 60 minutes, after treating bubble collapse, continue to be warming up to 200 ℃, react and obtain black-and-blue solid after 12 hours; Fragmentation is after hydrochloric acid/sodium chloride saturated solution is handled, and alkalization then, acidifying obtain carboxyl cobalt phthalocyanine for several times after centrifugation, collection, the drying;
D) be to join in dimethyl formamide at 1: 30 by weight with the polyamines modification cyclodextrin, temperature is controlled at 5 ℃, by being to add the carboxyl phthalocyanine at 1.5: 1 with polyamines modification cyclodextrin mol ratio; By being to add dicyclohexylcarbodiimide at 0.5: 1 with carboxyl phthalocyanine mol ratio, be to add I-hydroxybenzotriazole at 0.5: 1 with carboxyl phthalocyanine mol ratio, stir, in bathing, stirred 3 days-5 ℃ of cryosels, at room temperature reacted then 5 days; Leave standstill, the elimination insolubles, filtrate splashes in the acetone, and collecting precipitation is with obtaining cyclodextrin-phthalocyanine binary combination behind the chromatogram purification.
Embodiment 3, A) be that potassium hydroxide/γ-Huan Hujing mixture of 1/25 is to add at 1: 16 in the mixed solution that the volume ratio of components is tetrahydrofuran (THF)/water of 7/10 by weight with the weight ratio of components, after treating most of dissolving, by γ-Huan Hujing and Tosyl chloride weight ratio is slowly to drip the tetrahydrofuran solution that weight percent concentration is 6% Tosyl chloride at 1: 0.17, vigorous stirring 3 hours, add acetone, separate out white solid, filter, with the ether washing, obtain 6 p-toluenesulfonyl modification cyclodextrins with the distilled water secondary recrystallization;
B) be to join in the new polyamine compounds that steamed at 1: 14 by weight with 6 p-toluenesulfonyl modification cyclodextrins; Stir under nitrogen protection, after treating to dissolve fully, be warming up to 80 ℃, reacted 7 hours, underpressure distillation removes and desolvates, and the gained solid is dissolved in a small amount of hot water; Under agitation be added to an amount of volume ratio and be in 10/1 the acetone solution, collect white precipitate, repeat aforesaid operations 4 times,, after vacuum-drying, obtain 6 polyamines modification cyclodextrins with the mixed solvent recrystallization of alcohol-water 3 times;
C) be 1: 152: 2500 with mol ratio: 440 ammonium molybdate: cobalt chloride hexahydrate: urea: the mixture that the four class materials such as mixture of phthalic anhydride compounds are formed is transferred in the container after grinding evenly, is added a cover, be heated to 130 ℃ of insulations 1-60 minute, after treating bubble collapse, continue to be warming up to 185 ℃, react and obtain black-and-blue solid after 6 hours; Fragmentation is after hydrochloric acid/sodium chloride saturated solution is handled, and alkalization then, acidifying obtain carboxyl cobalt phthalocyanine for several times after centrifugation, collection, the drying;
D) be to join in dimethyl formamide at 1: 14 by weight with the polyamines modification cyclodextrin, temperature is controlled at 0 ℃, by being to add the carboxyl phthalocyanine at 1: 1 with polyamines modification cyclodextrin mol ratio; By being to add dicyclohexylcarbodiimide at 1: 1 with carboxyl phthalocyanine mol ratio, be to add I-hydroxybenzotriazole at 1: 1 with carboxyl phthalocyanine mol ratio, stir, in bathing, stirred 2 days-10 ℃ of cryosels, at room temperature reacted then 4 days; Leave standstill, the elimination insolubles, filtrate splashes in the acetone, and collecting precipitation is with obtaining cyclodextrin-phthalocyanine binary combination behind the chromatogram purification.
Claims (2)
1, a kind of preparation method of cyclodextrin-phthalocyanine binary combination, this method is: A) be that potassium hydroxide/cyclodextrin mixt of 1/25 is 1: 12～20 to add in the mixed solution that the volume ratio of componentss are tetrahydrofuran (THF)/water of 7/10 by weight with the weight ratio of components, after treating most of dissolving, by cyclodextrin and Tosyl chloride weight ratio is 1: 0.1～0.2 slowly to drip the tetrahydrofuran solution that weight percent concentration is 6% Tosyl chloride, vigorous stirring 2～6 hours, add acetone, separate out white solid, filter, with the ether washing, obtain 6 p-toluenesulfonyl modification cyclodextrins with the distilled water secondary recrystallization;
B) be 1: 10～17 to join in the new polyamine compounds that steamed by weight with 6 p-toluenesulfonyl modification cyclodextrins; Stir under nitrogen protection, after treating to dissolve fully, be warming up to 70～90 ℃, reacted 8-9 hour, underpressure distillation removes and desolvates, and the gained solid is dissolved in a small amount of hot water; Under agitation be added to an amount of volume ratio and be in 10/1 the acetone solution, collect white precipitate, repeat aforesaid operations 3～5 times,, after vacuum-drying, obtain 6 polyamines modification cyclodextrins with the mixed solvent recrystallization of alcohol-water 1-5 time;
C) be 1: 152: 2500 with mol ratio: 440 ammonium molybdate: cobalt chloride hexahydrate: urea: the mixture that the four class materials such as mixture of phthalic anhydride compounds are formed is transferred in the container after grinding evenly, is added a cover, be heated to 100～150 ℃ of insulations 1-60 minute, after treating bubble collapse, continue to be warming up to 170～200 ℃, react and obtain black-and-blue solid after 1～12 hour; Fragmentation is after hydrochloric acid/sodium chloride saturated solution is handled, and alkalization then, acidifying obtain carboxyl cobalt phthalocyanine for several times after centrifugation, collection, the drying;
D) be 1: 10～30 to join in the dimethyl formamide by weight with the polyamines modification cyclodextrin, temperature is controlled at-5～5 ℃, by being to add carboxyl cobalt phthalocyanine at 0.5～1.5: 1 with polyamines modification cyclodextrin mol ratio; By being to add dicyclohexylcarbodiimide at 1.5～0.5: 1 with carboxyl cobalt phthalocyanine mol ratio, with carboxyl cobalt phthalocyanine mol ratio is to add I-hydroxybenzotriazole at 1.5～0.5: 1, stir, in-15～-5 ℃ of cryosels are bathed, stirred 1～3 day, at room temperature reacted then 3～5 days; Leave standstill, the elimination insolubles, filtrate splashes in the acetone, and collecting precipitation is with obtaining cyclodextrin-phthalocyanine binary combination behind the chromatogram purification.
The preparation method of 2 cyclodextrin-phthalocyanine binary combinations according to claim 1 is characterized in that described cyclodextrin is alpha-cylodextrin or beta-cyclodextrin or γ-Huan Hujing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101647057A CN100556918C (en) | 2007-12-06 | 2007-12-06 | A kind of preparation method of cyclodextrin-phthalocyanine binary combination |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101647057A CN100556918C (en) | 2007-12-06 | 2007-12-06 | A kind of preparation method of cyclodextrin-phthalocyanine binary combination |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101182362A CN101182362A (en) | 2008-05-21 |
| CN100556918C true CN100556918C (en) | 2009-11-04 |
Family
ID=39447801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007101647057A Expired - Fee Related CN100556918C (en) | 2007-12-06 | 2007-12-06 | A kind of preparation method of cyclodextrin-phthalocyanine binary combination |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100556918C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103446969B (en) * | 2013-06-07 | 2015-02-11 | 南开大学 | Micro-nano reactor based on phthalocyanine bridging methylation cyclodextrin and preparation of micro-nano reactor |
| CN111943989B (en) * | 2020-07-20 | 2023-08-01 | 青岛职业技术学院 | Cluster-phthalocyanine binary molecule photosensitizer and preparation method and application thereof |
| CN115140788A (en) * | 2022-08-02 | 2022-10-04 | 王兵雷 | Processing method of water pollution control agent |
| CN115322340B (en) * | 2022-08-17 | 2023-06-20 | 四川大学 | Conjugated polymer biocatalysis material and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1940170A (en) * | 2006-09-21 | 2007-04-04 | 浙江理工大学 | Production of cyclodextrin-phthalocyanine double analog enzyme functional fibre |
-
2007
- 2007-12-06 CN CNB2007101647057A patent/CN100556918C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1940170A (en) * | 2006-09-21 | 2007-04-04 | 浙江理工大学 | Production of cyclodextrin-phthalocyanine double analog enzyme functional fibre |
Non-Patent Citations (1)
| Title |
|---|
| "过氧化物模拟酶的研究--四磺基铁酞菁与β-CD的包合物的分析应用". 郑琦等.江汉大学学报（自然科学版），第32卷第1期. 2004 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101182362A (en) | 2008-05-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Noveron et al. | A synthetic analogue of the active site of Fe-containing nitrile hydratase with carboxamido N and thiolato S as donors: synthesis, structure, and reactivities | |
| Kovacs | Tuning the relative stability and reactivity of manganese dioxygen and peroxo intermediates via systematic ligand modification | |
| Justice et al. | Unsaturated, Mixed‐Valence Diiron Dithiolate Model for the Hox State of the [FeFe] Hydrogenase | |
| Hikichi et al. | Synthesis and characterization of the benzoylformato ferrous complexes with the hindered tris (pyrazolyl) borate ligand as a structural model for mononuclear non-heme iron enzymes | |
| Oppelt et al. | Photocatalytic reduction of artificial and natural nucleotide co-factors with a chlorophyll-like tin-dihydroporphyrin sensitizer | |
| CN100556918C (en) | A kind of preparation method of cyclodextrin-phthalocyanine binary combination | |
| Zhang et al. | Metal hydride-embedded titania coating to coordinate electron transfer and enzyme protection in photo-enzymatic catalysis | |
| Guha et al. | Bio-relevant manganese (II) compartmental ligand complexes: Syntheses, crystal structures and studies of catalytic activities | |
| Huang et al. | Deciphering the Fenton-reaction-aid lignocellulose degradation pattern by Phanerochaete chrysosporium with ferroferric oxide nanomaterials: Enzyme secretion, straw humification and structural alteration | |
| Sui et al. | Syntheses, structure, redox and catalytic epoxidation properties of dioxomolybdenum (VI) complexes with Schiff base ligands derived from tris (hydroxymethyl) amino methane | |
| Kim et al. | Photochemical production of NADH using cobaloxime catalysts and visible-light energy | |
| Saha et al. | An amino acid coordinated vanadium (IV) complex: Synthesis, structure, DFT calculations and VHPO mimicking catalytic bromoperoxidation of organic substrates | |
| Song et al. | Novel ruthenium phthalocyanine-containing model complex for the active site of [FeFe]-hydrogenases: synthesis, structural characterization, and catalytic H2 evolution | |
| Martins et al. | Nanostructured binuclear Fe (III) and Mn (III) porphyrin materials: Tuning the mimics of catalase and peroxidase activity | |
| Laskar et al. | Cellulose as recyclable organocatalyst for ipso-hydroxylation of arylboronic acids | |
| Yan Poon et al. | How metal ion lewis acidity and steric properties influence the barrier to dioxygen binding, peroxo O–O bond cleavage, and reactivity | |
| Maurya | Structural models of vanadate-dependent haloperoxidases, their reactivity, immobilization on polymer support and catalytic activities | |
| Qiu et al. | Efficient catalytic oxidation of benzyl alcohol by tetrasubstituted cobalt phthalocyanine-MWCNTs composites | |
| Cuetos et al. | Immobilized redox enzymatic catalysts: Baeyer–Villiger monooxygenases supported on polyphosphazenes | |
| Slama et al. | Semisynthetic enzymes: Synthesis of a new flavopapain with high catalytic efficiency | |
| CN109912002A (en) | A kind of method of organic pollutant in processing waste water from dyestuff | |
| CN106636056A (en) | System for co-immobilizing laccase and mediator on amino silanized magnetic oxidized graphene nano particles and preparation method thereof | |
| Hou et al. | Recent Advances in Visible Light‐induced Asymmetric Transformations of Carbonyl Compounds into Chiral Alcohols | |
| Özkan et al. | Influence of load on the recycling stability of nanospheres attached platinium ion for determination of glucose | |
| Amao et al. | Visible-light induced hydrogen and formic acid production from biomass and carbon dioxide with enzymatic and artificial photosynthesis 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: 20091104 Termination date: 20121206 |