CN101585787A - Benzenesulphonyl fluoride and its production and application - Google Patents
Benzenesulphonyl fluoride and its production and application Download PDFInfo
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- CN101585787A CN101585787A CNA2009100693076A CN200910069307A CN101585787A CN 101585787 A CN101585787 A CN 101585787A CN A2009100693076 A CNA2009100693076 A CN A2009100693076A CN 200910069307 A CN200910069307 A CN 200910069307A CN 101585787 A CN101585787 A CN 101585787A
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Abstract
The present invention relates to a kind of Benzenesulphonyl fluoride and preparation method thereof and and application.General formula is the compound of (I), and R is alkyl, alkoxyl group, acyl group, carboxylic acid group, cyano group, nitro, halogen or their mixing.With precursor compound benzene sulfonyl chloride and metal fluoride is that raw material carries out fluoro-reaction and is prepared in acetonitrile.With sulfonic acid fluoride (SO
2F) base is as reactive group, with parent benzene as chromophoric group, not only can be used for protein, peptide structure and amino acid whose mensuration, carry out protein or proteomics research as the novel Benzenesulphonyl fluoride (A NewKind of Benzenesulfonyl Fluoride) of auxiliary substituted radical with R, can also be used for the research and development of new drug, also can be used as medical and health organization diagnosis difficult and complicated illness, pharmacodynamic assessment, also can be used as the labelled reagent that national medicine inspection unit, quality inspection unit carry out quality monitoring.
Description
Technical field:
The present invention relates to a kind of Benzenesulphonyl fluoride and its production and application, be specially with the fluorine-based (SO of sulphonyl
2F) as reactive group, with parent benzene as chromophoric group, with R as the novel Benzenesulphonyl fluoride (A New Kind of Benzene Sulfonyl Fluoride) of auxiliary substituted radical and at amino acid and protein, peptide and contain one-level amino or secondary amino, hydroxyl, phenolic hydroxyl group, the compound of sulfydryl or the application in other chemical substance.Benzenesulphonyl fluoride not only can be used for protein, peptide structure and amino acid whose mensuration, carry out protein or proteomics research as derivatization reagent and labelled reagent, can also be used for the research and development of new drug, also can be used as medical and health organization diagnosis difficult and complicated illness, pharmacodynamic assessment, also can be used as the labelled reagent that national medicine inspection unit, quality inspection unit carry out quality monitoring.
Background technology:
At present in the applied labelled reagent of protein or proteomics research field, the derivative reaction temperature of many products is all about 60 ℃-70 ℃, lesser temps is also about 55 ℃, therefore the steric configuration of protein, peptide will be changed, cause protein, peptide to lose biological activity, thereby be difficult to measure proteinic secondary structure, tertiary structure.Specifically also show:
1) some labelled reagent can not be suitable fully for some amino acid of forming human body protein, for example, and to secondary amino acid, tryptophane, halfcystine, proline(Pro), oxyproline.
2) some labelled reagent with the functional group reactions of the chiral centre of a-amino acid after, can produce meso and turn usefulness into, cause part or all of stereochemistry information dropout.In peptide, can cause the part or all of epimerization of chiral centre to lose biological activity.
3) the existing labelled reagent of great majority is responsive to airborne psychromatic ratio, discharges corrosive gases, is easy to hydrolysis, thereby loses the reactive behavior of its derivatize.
4) the derivatize product stability that generated of some labelled reagent and amino acid reaction is low, and what influence that subsequent detection operates normally carries out severe patient even the detected result that can lead to errors.
5) some labelled reagent can't detect the known or unknown compound of ultramicron because detection sensitivity is not enough.
6) some labelled reagent causes fetch long price because synthesis procedure is complicated, can't popularize use.
Summary of the invention:
The object of the present invention is to provide a kind of novel Benzenesulphonyl fluoride and its production and application, to overcome the deficiency of prior art.Contain in the molecule of the present invention in visible region or the structure that can detect, and have and with protein, peptide, amino acid and to contain the compound of one-level amino, secondary amino, hydroxyl, phenolic hydroxyl group, sulfydryl or the active group that chemical substance is carried out derivative reaction in the near-ultraviolet light district.Have carry out derivative reaction under near body temperature (about 35 ℃-45 ℃, about pH8-10) condition, do not produce racemization role, product itself and derivatize product stability height, instrumental response value height, do not discharge corrosive gases, "dead", non-environmental-pollution, synthetic convenient, manufacturing cost is lower, be easy at room temperature preserve and transport characteristics.
Benzenesulphonyl fluoride provided by the invention has the compound of general formula for (I):
Wherein, R is alkyl, alkoxyl group, acyl group, carboxylic acid group, cyano group, nitro, halogen or their mixing.
The present invention has general formula and is selectable substituting group in the compound of (I):
R=4-ethyl, the 4-tertiary butyl, 4-halogen, 2-methoxyl group, 4-methoxyl group, 4-ethanoyl, 3-cyano group, 2-nitro, 3-nitro, 3-carboxylic acid group;
R=2,4-dimethyl, 3,5-dimethyl, 2-methyl-5-nitro, 4-methyl-3-nitro, 2-methoxyl group-4-methyl, 2-methyl-4-methoxyl group, 2,5-dimethoxy, 3,4-dimethoxy, 4-fluoro-3-nitro, 2-fluoro-5-nitro, 2-fluoro-4-methyl.
R=2,4, the 6-trimethylammonium;
The step that the preparation method of Benzenesulphonyl fluoride provided by the invention comprises: in the presence of phase-transfer catalyst poly(oxyethylene glycol) 400-800, with precursor compound benzene sulfonyl chloride of the present invention and metal fluoride is raw material, (with the acetonitrile is solvent in organic solvent, or dioxy land surround is a solvent), at least room temperature condition stirs down, carries out fluoro-reaction 1-2 hour, filters, remove with washing with alcohol and to desolvate drying.
Benzenesulphonyl fluoride provided by the invention is applied to protein, peptide or amino acid whose derivative reaction and detection thereof; Or carry out derivative reaction and detection thereof with the compound that contains one-level amino, secondary amino, hydroxyl, phenolic hydroxyl group, sulfydryl or other chemical substance.
Benzenesulphonyl fluoride provided by the invention is the labelled reagent with brand-new molecular structure, and it has lower molecular weight, and molecular weight ranges belongs to micromolecular compound between 178-239.6 dalton.Less molecule makes that Benzenesulphonyl fluoride is easier to permeate in the secondary of protein, peptide molecule or tertiary structure, carry out derivative reaction, reach trace, ultramicron qualitative and quantitative analysis purpose, promptly down can and contain one-level amino or the compound or the chemical substance of secondary amino, hydroxyl, phenolic hydroxyl group, sulfydryl are carried out derivative reaction with protein, peptide, amino acid at mild conditions (about 35 ℃-45 ℃, about pH8-10).Its derivatize product is stable, good reproducibility, and the instrumental response value height, detection sensitivity reaches the nmol-fmol level, makes the known or unknown compound of ultramicron reach the effect of chemical derivatization and instrument detecting.
The derivative reaction condition of Benzenesulphonyl fluoride gentleness can be carried out derivative reaction to protein, when peptide carries out derivative reaction about 35 ℃-45 ℃ under the condition of the denaturation temperature that is lower than protein and peptide.In derivative reaction, chiral centre functional group does not produce the racemization via oxazolone mechanism, make amino acid, peptide, protein and other contain the compound of chiral centre or unlikely the losing of stereochemistry breath of chemical substance, keep optical purity, the stereochemistry integrity, and their biological activity, make the Benzenesulphonyl fluoride can be at protein, peptide keeps inferring proteinic secondary structure on its bioactive basis, tertiary structure, thus make Benzenesulphonyl fluoride carry out mark to protein and peptide, demonstrate remarkable advantages when comparing with existing labelled reagent during qualitative and quantitative detection.
Benzenesulphonyl fluoride of the present invention has stability preferably, not only make itself to have stability (storage time is more than 18 months) preferably under room temperature and exsiccant environment, its derivatize product also has stability preferably in room temperature and wet environment.
Embodiment:
Embodiment 1:
4-anisole sulfonic acid fluoride CH
3O-C
6H
4-SO
2F's is synthetic:
To capacity is that 500ml has and adds Sodium Fluoride 10.5g, poly(oxyethylene glycol) 400 8g and acetonitrile 200ml in the four-hole round-bottomed flask of agitator, reflux exchanger, thermowell and charging opening.Stirred 60 minutes in 30 ℃ of water-baths, the Sodium Fluoride particle size is even until observing.The suspension that then in above-mentioned four-hole boiling flask, adds the 200ml acetonitrile that contains 20.6g 4-anisole SULPHURYL CHLORIDE.
Stopped reaction after continuing to stir 120 minutes under 30 ℃ of temperature.It is in the beaker of 1000ml that the outstanding mixed liquid of fluoro-reaction thing is poured into the capacity that fills 400ml distilled water under the whipped state, standing over night.
Filter out the fluoro product on B, remove acetonitrile with washing with alcohol, drying is weighed, and gets the crude product 14g of 4-anisole sulfonic acid fluoride.Recrystallization in ethanolic soln gets colourless crystallization product 4-anisole sulfonic acid fluoride, molecular weight 190.
4-anisole sulfonic acid fluoride is dissolved with acetonitrile, and being configured to concentration is 1 * 10
-6The solution of mol/L is determined at the ultraviolet-visible ultra-violet absorption spectrum under this concentration on UV 3150 uv-absorbing spectrophotometers.Record its maximum absorption wavelength λ max=270nm.
Embodiment 2:
2-methoxyl group 4-Methyl benzenesulfonyl fluorine 2-CH
3O4-CH
3-C
6H
4-SO
2F's is synthetic:
To capacity is that 500ml has and adds Sodium Fluoride 12.6g, Polyethylene Glycol-600 8g and acetonitrile 200ml in the four-hole boiling flask of agitator, reflux exchanger, thermowell and charging opening.Stirred 60 minutes in 30 ℃ of water-baths, the Sodium Fluoride particle size is even until observing.The suspension that then in above-mentioned four-hole boiling flask, adds the 200ml acetonitrile that contains 22g 2-methoxyl group 4-Methyl benzenesulfonyl chlorine.
Stopped reaction after continuing to stir 120 minutes under 30 ℃ of temperature.It is in the beaker of 1000ml that the outstanding mixed liquid of fluoro-reaction thing is poured into the capacity that fills 400ml distilled water under the whipped state, standing over night.
Filter out the fluoro product on B, remove acetonitrile with washing with alcohol, drying is weighed, and gets 2-methoxyl group 4-Methyl benzenesulfonyl fluorine crude product 14.2g.Recrystallization in ethanolic soln gets the colourless crystallization product, molecular weight 204.
2-methoxyl group 4-Methyl benzenesulfonyl fluorine is dissolved with acetonitrile, and being made into concentration is 1 * 10
-6The solution of mol/L is determined at the ultraviolet-visible ultra-violet absorption spectrum under this concentration on UV 3150 uv-absorbing spectrophotometers.Record its maximum absorption wavelength λ max=274nm.
Same experiment condition, at the phase-transfer catalyst polyoxyethylene glycol is (molecular mass of different reagent is got different phase-transfer catalyst polyoxyethylene glycol in the Benzenesulphonyl fluoride relatively) in the presence of the 400-800, corresponding precursor compound benzene sulfonyl chloride with Benzenesulphonyl fluoride product of the present invention is a raw material, with metal fluoride (Sodium Fluoride, or lithium fluoride, Potassium monofluoride, rubidium fluoride and cesium fluoride) be fluoro reagent, at acetonitrile (or dioxy land surround, 1,4-Dioxane) in the solvent, be at least under the room temperature condition, carried out fluoro-reaction 1-2 hour, and synthesized the various products in the Benzenesulphonyl fluoride series of the present invention.See Table 1-3.
Because the application of phase-transfer catalyst, make two kinds immiscible, in reaction medium, also be difficult to dissolved raw material-benzene sulfonyl chloride compound and metal fluoride is able to smooth reaction under the phase-transfer catalyst effect, thereby make the higher Benzenesulphonyl fluoride of productive rate.
Labelled reagent listed in the table 1,2,3 all can make with reference to the fluoro-reaction condition shown in embodiment 1 or the embodiment 2.
The group and the compound thereof of table 1:A series (SINORO-9AS) R representative
The group and the compound thereof of table 2:B series (SINORO-9BS) R representative
The group and the compound thereof of table 3:C series (SINORO-9CS) R representative
Embodiment 3:
Utilize the 4-anisole sulfonic acid fluoride reagent that serves as a mark to measure secondary amino acid: proline(Pro), oxyproline and Ethylglycocoll:
Instrument: U.S. Waters company high performance liquid chromatograph: 510 pumps, U6k sampler, 490E UV-detector, anti-phase C8 chromatographic column.
Reagent: proline(Pro), oxyproline, Ethylglycocoll (Aldrich product);
4-anisole sulfonic acid fluoride in the Benzenesulphonyl fluoride series (SINORO-9AS2, self-control);
Moving phase: accurately take by weighing the 6.8g sodium acetate, add about 850ml deionized water solution, transfer pH to 4.2 with 10% acetum, add deionized water to 1000ml, suction filtration is got this solution 770ml and is added trifluoroacetic acid aqueous solution 230ml mixing, and it is standby to outgas;
Method: 1. accurately compound concentration is the proline(Pro) aqueous solution, the oxyproline aqueous solution, the Ethylglycocoll aqueous solution, 3 of 2.5 μ mol/L, each 100 μ l of the 4 dehydroproline aqueous solution (interior mark), pH is Sodium Tetraborate-sodium hydroxide buffer solution 400 μ l of 9.3, and concentration is acetonitrile-water (volume ratio is 4: 1) the solution 100 μ l of the 4-anisole sulfonic acid fluoride of 400.0 μ mol/L.
2. accurately draw each 100 μ l and inner mark solution 100 μ l of proline(Pro), oxyproline and Ethylglycocoll solution, join 400 μ l pH and be in Sodium Tetraborate-sodium hydroxide buffer solution of 9.3, add distilled water to cubic capacity and reach 1000 μ l.
3. the acetonitrile-aqueous solution of getting above-mentioned mixed solution 500 μ l and 100 μ l concentration and be 400.0 μ mol/L 4-anisole sulfonic acid fluoride mixes, this mixed solution is injected the minisize reaction pipe, place 38 ℃ of waters bath with thermostatic control, insulation is rocked after 5 minutes and is taken out, adjust pH to 6-7 with dilute hydrochloric acid, stopped reaction.Take out, (general formula is: 4-CH to obtain the derivatize product of four seed amino acids and 4-anisole sulfonic acid fluoride
3O-C
6H
4-SO
2-NH-CHR-COOH) mixed solution.
4. the mixed solution of getting an amount of above-mentioned four kinds of derivatize products mixes with an amount of moving phase solution, carries out separation detection on high performance liquid chromatograph.
5. detect through UV-detector, behind the absorption peak of above-mentioned four kinds of derivatize products, be standard with the peak area of 3,4 dehydroprolines, record the quantitative data of proline(Pro), oxyproline and Ethylglycocoll.
6. its limit of detection reaches 10
-9-10
-12Mol.
Embodiment 4:
Utilize the 4-anisole sulfonic acid fluoride reagent that serves as a mark to measure secondary amino acid in one-level amino acid and the amino acid whose mixture of secondary:
Proline(Pro) in the secondary amino acid, oxyproline, Ethylglycocoll occur in urine unusually, are the objects of physiology, pathological research.Because they all are the residues in the oligopeptides molecule, therefore, at first will be hydrolyzed into amino acid to oligopeptides in testing process, just can carry out quantitative analysis.
Owing to coexist as the amino acid whose interference of one-level in the hydrolyzed solution, make testing process complicated.Complicated trace routine and the stability of operating for a long time tested test sample propose higher requirement, that is, need the derivatize product of proline(Pro), oxyproline and Ethylglycocoll to have advantages of higher stability in the process that its derivatize detects.
Utilize Benzenesulphonyl fluoride not only to avoid the amino acid whose interference of one-level, and improved the stability and the detection sensitivity of its derivatize product.
Instrument: U.S. Waters company high performance liquid chromatograph: 510 pumps, U6k sampler, 490E UV-detector, anti-phase C8 chromatographic column, Hettich whizzer Mikro200.
Reagent: 3, the 4 dehydroproline aqueous solution (interior mark),
4-anisole sulfonic acid fluoride in the Benzenesulphonyl fluoride series (SINORO-9AS2, self-control);
Method: 1. oligopeptides hydrolysis in the sample preparation-urine:
Adding concentration in the 1ml urine is the NaOH solution 1ml of 12N, imports in the heat resisting and pressure resisting Glass tubing, tight with the tetrafluoroethylene capping plug, is placed in the autoclave sterilizer, and at 121 ℃, 60 minutes postcooling of heating hydrolysis are to room temperature under the 1.034bar pressure condition.Be 1: 4 ratio by volume, in hydrolyzed solution, add the ultrapure water dilution.
2. in the 0.1ml hydrolyzed solution, add an amount of concentration and be 37% concentrated hydrochloric acid 0.1ml the hydrolyzed solution neutrality that neutralizes.Adding concentration again is the NaOH solution 0.8ml of 0.5mol, and concentration is the Na of 0.25mol
2CO
3Solution 0.8ml makes the pH that contains one-level amino acid and the amino acid whose hydrolyzed solution of secondary rise to 9.3.
3. o-phthalaldehyde(OPA) is sealed one-level amino acid, 4-anisole sulfonic acid fluoride mark secondary amino acid, ethyl acetate extraction;
Get 20 μ l urine peptide hydrolysate, with concentration be 3 of 0.1 μ mol/ml, 4-dehydrogenation-DL proline(Pro) (interior mark) 20 μ l mix.Is concentration that the o-phthalaldehyde(OPA) 20 μ l of 14.9mmol/ml join in the urine peptide hydrolysate that mixes, and at room temperature rocks 3 minutes, and the one-level amino acid in its hydrolyzed solution is carried out the derivatize sealing.Then adding concentration is the acetonitrile solution 20 μ l of the 4-anisole sulfonic acid fluoride of 0.285mg/100 μ l, at 37 ℃, rock reaction 5 minutes under pH 9.3 conditions, finish the amino acid whose derivatize capping of secondary in its hydrolyzed solution after, add acid and transfer pH to the 5-6 termination reaction.The mixed solution of 4-anisole sulfonic acid fluoride derivatize product of proline(Pro), oxyproline, the Ethylglycocoll in the secondary amino acid (its general formula is: 4-CH
3O-C
6H
4-SO
2-NH-CHR-COOH).
The adding volume ratio is 1: 1 acetonitrile and ultrapure water mixed solution 95 μ l in the derivative reaction mixed solution, mixes.Other gets 40 μ l ultrapure waters and injects derivative reaction mixed solution and acetonitrile and ultrapure water mixed solution, makes final water volume reach 100 μ l.Immediately to the ethyl acetate that wherein adds 0.5ml, and injecting centrifuge tube, is centrifugation 5 minutes on the whizzer of 8000RPM at rotating speed.Draw 25 μ l liquid from centrifuge tube bottom liquid phase and inject chromatographic column for further separation detection usefulness.
4. high performance liquid chromatography separation detection:
Chromatographic column moving phase is made up of solvent orange 2 A and solvent B.Wherein:
Solvent orange 2 A is: concentration is 150mmol, pH 3.0 biphosphate sodium water solutions; Solvent B is: by concentration is 4% N, and dinethylformamide (DMF) and volumetric ratio are that the mixed solution of 4: 1 acetonitriles and water is formed.
The pH of solvent orange 2 A regulates with phosphoric acid, wash-out under selected gradient condition.Single-column was finished in 10 minutes and is separated and ultraviolet detection, comprised and washing post time and column equilibration time.
5. at uv-absorbing wavelength 232nm place the derivatize product of proline(Pro), oxyproline and Ethylglycocoll and 4-anisole sulfonic acid fluoride being carried out qualitative, quantitative measures.Limit of detection reaches the pmol level.
Detect data and show and utilize the 4-anisole sulfonic acid fluoride reagent that serves as a mark to have very high sensitivity that chromatographic column can be finished separation detection in 10 minutes.Meet the requirement of clinical detection.
Claims (10)
1, a kind of Benzenesulphonyl fluoride is characterized in that it has the compound of general formula for (I):
Wherein, R is alkyl, alkoxyl group, acyl group, carboxylic acid group, cyano group, nitro, halogen or their mixing.
2, Benzenesulphonyl fluoride according to claim 1 is characterized in that:
R=4-ethyl, the 4-tertiary butyl, 4-halogen, 2-methoxyl group, 4-methoxyl group, 4-ethanoyl, 3-cyano group, 2-nitro, 3-nitro or 3-carboxylic acid group.
3, Benzenesulphonyl fluoride according to claim 2 is characterized in that: the R=4-methoxyl group.
4, Benzenesulphonyl fluoride according to claim 1 is characterized in that; R=2,4-dimethyl, 3,5-dimethyl, 2-methyl-5-nitro, 4-methyl-3-nitro, 2-methoxyl group-4-methyl, 2-methyl-4-methoxyl group, 2,5-dimethoxy, 3,4-dimethoxy, 4-fluoro-3-nitro, 2-fluoro-5-nitro or 2-fluoro-4-methyl.
5, Benzenesulphonyl fluoride according to claim 4 is characterized in that: R=2-methoxyl group 4-methyl.
6, Benzenesulphonyl fluoride according to claim 1 is characterized in that: R=2,4,6-trimethylammonium.
7, the preparation method of the described Benzenesulphonyl fluoride of claim 1 is characterized in that the step that comprises:
In the presence of phase-transfer catalyst poly(oxyethylene glycol) 400-800, be raw material with precursor compound benzene sulfonyl chloride and metal fluoride, in organic solvent, room temperature condition stirs at least, carries out fluoro-reaction 1-2 hour, filters, and removes with washing with alcohol and desolvates drying.
8, preparation method according to claim 7 is characterized in that described organic solvent is acetonitrile or dioxy land surround.
9, preparation method according to claim 7 is characterized in that described metal fluoride is lithium fluoride, Sodium Fluoride, Potassium monofluoride, rubidium fluoride or cesium fluoride.
10, the application of the described Benzenesulphonyl fluoride of claim 1 is characterized in that being applied to protein, peptide or amino acid whose derivative reaction and detection thereof; Or carry out derivative reaction and detection thereof with the compound that contains one-level amino, secondary amino, hydroxyl, phenolic hydroxyl group, sulfydryl or other chemical substance.
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105198683A (en) * | 2015-09-24 | 2015-12-30 | 信阳师范学院 | Preparation method of sulfuryl fluoride compound |
| CN109311786A (en) * | 2016-05-02 | 2019-02-05 | 陶氏环球技术有限责任公司 | The fluorinated method of aromatics |
| CN113620847A (en) * | 2021-08-11 | 2021-11-09 | 复旦大学 | Naphthalenesulfonyl compounds, preparation method and application thereof |
| CN114206822A (en) * | 2019-08-27 | 2022-03-18 | 关东电化工业株式会社 | Process for producing carboxylic acid fluoride |
-
2009
- 2009-06-18 CN CNA2009100693076A patent/CN101585787A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105198683A (en) * | 2015-09-24 | 2015-12-30 | 信阳师范学院 | Preparation method of sulfuryl fluoride compound |
| CN109311786A (en) * | 2016-05-02 | 2019-02-05 | 陶氏环球技术有限责任公司 | The fluorinated method of aromatics |
| CN109311786B (en) * | 2016-05-02 | 2021-12-03 | 陶氏环球技术有限责任公司 | Process for aromatic fluorination |
| CN114206822A (en) * | 2019-08-27 | 2022-03-18 | 关东电化工业株式会社 | Process for producing carboxylic acid fluoride |
| CN114206822B (en) * | 2019-08-27 | 2024-05-10 | 关东电化工业株式会社 | Process for producing carboxylic acid fluorides |
| CN113620847A (en) * | 2021-08-11 | 2021-11-09 | 复旦大学 | Naphthalenesulfonyl compounds, preparation method and application thereof |
| CN113620847B (en) * | 2021-08-11 | 2022-08-09 | 复旦大学 | Naphthalenesulfonyl compounds, preparation method and application thereof |
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Application publication date: 20091125 |