CN101282983A - Enzyme catalyzed de-acylation of chlorinated sugar derivatives - Google Patents
Enzyme catalyzed de-acylation of chlorinated sugar derivatives Download PDFInfo
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- CN101282983A CN101282983A CNA2006800346126A CN200680034612A CN101282983A CN 101282983 A CN101282983 A CN 101282983A CN A2006800346126 A CNA2006800346126 A CN A2006800346126A CN 200680034612 A CN200680034612 A CN 200680034612A CN 101282983 A CN101282983 A CN 101282983A
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- sucrose
- enzyme
- chlorinated
- reaction
- tgs
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
- C07H3/04—Disaccharides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
- C07H1/06—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H5/00—Compounds containing saccharide radicals in which the hetero bonds to oxygen have been replaced by the same number of hetero bonds to halogen, nitrogen, sulfur, selenium, or tellurium
- C07H5/02—Compounds containing saccharide radicals in which the hetero bonds to oxygen have been replaced by the same number of hetero bonds to halogen, nitrogen, sulfur, selenium, or tellurium to halogen
Abstract
A process of production of trichlorogalactosucrose is described in which deacylation of sucrose-6-ester is achieved by subjecting the reaction mixture after chlorination, neutralization and adjustment of pH to 6.5 to 7 to deacylation by using a lipase or a protease, in a free or in an immobilized form.
Description
Technical field
The present invention relates to be used to produce the novel method and the New Policy of 1-6-two chloro-1-6-dideoxy-β-fructofuranoses-4-chloro-4-deoxidation-galactopyranoside (TBS), be included in the enzymatic deacylation of the TGS of the 6-O-protection that obtains after the chlorination reaction.
Background technology
Art methods produces 4; 1 '; the strategy of 6 ' trichlorogalacto-sucrose (TGS) mainly comprises by the Vilsmeier-Haack reagent that uses self-forming chlorating sucrose-6-ester and comes chlorinated sucrose-6-ester to form 6-ethanoyl-4; 1 '; 6 '-trichlorogalacto-sucrose, described Vilsmeier-Haack reagent use such as the different chlorination reagents of phosphorus oxychloride, oxalyl chloride, phosphorus pentachloride etc. with such as three grades of acid amides (tertiary amide) of dimethyl formamide (DMF).After the described chlorination reaction, the alkaline hydrated oxide neutralization reaction material that uses suitable calcium, sodium etc. is to pH7.0～7.5.Use then the alkaline hydrated oxide of calcium, sodium, potassium etc. further make in and the pH of material rise to 9.5 or higher so that 6-ethanoyl-4,1 ', 6 '-trichlorogalacto-sucrose de-esterifying/deacetylation forms 4,1 ', 6 ' trichlorogalacto-sucrose.This alkali de-esterifying reaction/deacetylation comprises reactant is exposed among the harsh pH in the alkaline range that this has caused a large amount of DMF destroyed, and this is expensive input, influences it unfriendly in reacted recovery.
In art methods, this reaction mixture also is exposed to when deacetylation in the harsh temperatures, and this has caused the destruction of product TGS self.
Therefore, need a kind of method that does not expose DMF to the destructive deacetylation.
Developed a kind of method, it finishes enzymatic deacylation not exposing DMF to destructive pH.
Summary of the invention
Palmer etc. (1995) have reported the derivative of enzymatic deacylation with the partial acetylation of preparation sucrose at United States Patent (USP) no.5445951; it utilizes the enzymatic deacylation of sucrose ester; sucrose ester from no aqueous organic media; with can catalysis the combination of a kind of enzyme of described sucrose ester deacetylation or enzyme to be created in the sucrose derivative that pre-selected locations has the part deacetylation of free hydroxyl; and reclaim the sucrose derivative of the part deacetylation that is obtained, described sucrose ester is selected from by sucrose eight acyl esters (sucrose octaacylate); the group that sucrose seven acyl esters and sucrose six acyl esters are formed.
Enzymatic deacylation about sucrose ester or derivatives thereof/precursor does not have other known report.
The enzymatic deacylation of the TGS that the 6-O-that the present invention relates to obtain after chlorination reaction during the preparation artificial sweetening agent TGS protects.The embodiment that can carry out the chlorination reaction mixture of process of the present invention includes but not limited to, sucrose-6-ester mixes the process streams that the back is obtained with a kind of chlorination reagent, described chlorination reagent is described in (1983) United States Patent (USP) no 4380476 such as Mufti, Walkup etc. (1990No.4980463), Jenner etc. (1982) United States Patent (USP) no.4,362,869, Tulley etc. (1989) United States Patent (USP) no.4,801,700, Rathbone etc. (1989) United States Patent (USP) no.4,826,962, Bornemann etc. (1992) United States Patent (USP) no.5,141,860, Navia etc. (1996) United States Patent (USP) no.5,498,709, Simpson (1989) United States Patent (USP) no.4,889,928, Navia (1990) United States Patent (USP) no.4,950,746, Neiditch etc. (1991) United States Patent (USP) no.5,023,329, Walkup etc. (1992) 5, and 089,608, Dordick etc. (1992) United States Patent (USP) no.5,128,248, Khan etc. (1995) United States Patent (USP) no.5,440,026, Palmer etc. (1995) United States Patent (USP) no.5,445,951, Sankey etc. (1995) United States Patent (USP) no.5,449,772, Sankey etc. (1995) United States Patent (USP) no.5,470,969, Navia etc. (1996) United States Patent (USP) no.5,498,709, Navia etc. (1996) United States Patent (USP) no.5,530,106.
Separate the back or do not separate at the TGS intermediate product of 6-O-protection, in and after the chlorinated reaction mass, on the process streams that obtains in mode as mentioned above, carry out enzymatic deacylation.Because this enzymatic reaction, be present in three grades of acid amides of solvent in the neutral reaction mass and can not decompose and therefore cause described solvent recovering yield to improve.In the present invention, use in the suitable alkali and the chlorinated reaction mass after the chlorination reaction.In and the time, pH is controlled as and is lower than 6.0, the compound TGS of formation still has complete protected group at 6.Have or do not have separate carry out under the described compound this 6 go protection (deblocking).Some reference are in addition also pointed out and can be carried out this under three grades of acid amides and other solvent and the aqueous conditions and go protection being with or without.
The invention describes and use enzymatic means, wherein, when three grades of acid amides (comprising the DMF that is used for chlorination reaction) exist or do not exist, remove protected group enzyme selectivity 6 deacetylation.Method of the present invention is not to being that chlorination reaction result's the deacetylation effect of embodiment (the single solution of for example pure TGS-6-ester) is also fine.
The enzyme of catalyzed deacylation reaction is well-known, and esterase and proteolytic ferment carry out deacetylation and acetylization reaction and by Soedjak HS under the reaction conditions of gentleness, Spradlin JE (1994) .Biocatalysis 11:241-248; Therisod M, Klibanov AM (1986) J.Am.Chem.Soc.108:5638-5640; B.Cambou and A.M.Klibanov, J.Am.Chem.SOC., 106,2687 (1984); Kirpal S Bisht, Pure ﹠amp; Appl.Cbem., Vol.68, No.3, pp.749-752,1996; F.J.Plou1; _, M.A.Cruces1, Biotechnology Letters 21:635-639,1999 report widely.
In the present invention, in the reaction mass and after, use suitable alkali to regulate pH to 6.5.Under stirring at room, esterase is joined in the reaction mass lentamente then.Depend on enzymic activity and reaction conditions, the enzyme amount that is added in the reaction mass changes at 10%～40%w/v.Three grades of amide content about 10%～40% in neutral reaction mass.With the time that reaction mixture continues to stir 10～60h, preferred 16～20h.Monitor the transformation of the TGS of 6-O-protection by TLC to TGS.Thoroughly after the deacetylation, reaction mixture utilizes affinity chromatography to carry out the TGS separation.Utilize suitable this isolating TGS of method crystallization then.
The TGS deacetylation of 6-O-protection is that employed esterase of TGS or proteolytic ferment can be its natural form or immobilization form.When using immobilized enzyme, this enzyme is filtered after finishing deacetylation.The enzyme of this recovery can also utilize again.This immobilized enzyme also can be filled in the post and reaction mass can be by this post and the TGS original position deacetylation that can carry out the 6-O-protection.These enzymes can be fixed in the synthetic polymer support or on it, and described carrier is such as but not limited to the carrier of polyacrylic acid or polystyrene or polyacrylamide, nylon based; Semi-synthetic or natural organic carrier is for example based on those carriers of saccharan (such as but not limited to Mierocrystalline cellulose, starch, dextran, agarose, chitosan, chitin etc.); Perhaps inorganic carrier is for example based on those carriers of carbon, silicon-dioxide, zirconium white, aluminum oxide, zirconium phosphate etc.
The source of esterase can be animal, plant or microbial source, preferred microorganism or bacterial origin, Bacillus thermocatenulatusis for example, Pseudomonas aeruginosa etc.; Fungic origin, Penicillium Roquefortii for example, Asperigillus niger, Asperigillus oryzae, Rhizopus niveus, Candida rugosa, Rhizomucor miheii, Candida antartctica etc.
During the process of described invention, the TGS product is not exposed among the pH or temperature condition as any harshness under the situation of the conventional deacylation process of using acid, alkali.This product minimization of loss of deacylation process than any other form.
During the process of described invention, three grades of acid amides are not exposed to pH or the temperature condition as any harshness under the situation of the conventional deacylation process of using acid, alkali.Therefore the decomposition of three grades of acid amides does not take place at all.Thereby the organic efficiency of three grades of acid amides is improved largely.
That describe below is embodiment, and it has illustrated work of the present invention and the scope that do not limit the present invention in any way.The scope of the ratio of the reactant of reactant, use, the reaction conditions of description, the enzyme of use etc. only are illustrative and scope extends to the reaction of its similar reactant, reaction conditions and the similar general character.Usually, the conspicuous any equivalent substitution of chlorinated sucrose production field technician is included in the scope of this specification sheets.Therefore, mention that acetic ester has comprised the ester group of any equivalence of the identical function that can carry out the present invention's discussion, can provide any of enzyme effect described herein or similar effect to substitute and use enzyme to comprise under similar reaction conditions.Many other changes of embodiment will be envisioned at an easy rate by those skilled in the art and they also are included in the scope of this specification sheets.Unless do not allow in the literary composition, mentioned odd number also is believed to comprise its plural form, that is, " a kind of organic solvent " that is used to extract comprises a kind of organic solvent of use or use multiple organic solvent continuously or be used in combination multiple organic solvent as mixture.
Embodiment
The chlorination reaction of embodiment 1, cane sugar-6-acetic ester
In the 5L reaction flask, add the 1280ml dimethyl formamide and be cooled to 0～5 ℃.Under agitation slowly add 635g phosphorus pentachloride (5.4mol) then, keep the temperature of reaction mass to be lower than 30 ℃.This material further is cooled to is lower than 0 ℃ and at-5 ℃ of DMF solution that slowly add cane sugar-6-acetic esters.Then reaction mass is heated to 80 ℃ and keep 1h, further is heated to 100 ℃ and keep 6h, finally reach 110～115 ℃ and keep 2～3h.Utilize HPLC to analyze the process of this reaction of monitoring.
Then, reaction mixture is cooled to-5～-8 ℃ and slowly add 20% sodium hydroxide solution so that the pH of material is raised to 5.5～6.5.The productive rate that utilizes this method to obtain is 55.4% sucrose input.
Embodiment 2, utilize esterase to carry out the enzymatic deacylation of 6-O-ethanoyl TGS
The calcium hydroxide slurry of use 50% is described reaction mass prepared, that contain 15g6-O-acetylize TGS with 1.5L according to embodiment 1 and is neutralized to pH7.5.Water neutral reaction mass is diluted to 6L.This DMF content in the neutral material be 33%.At ambient temperature, 84g is separated from Aspergillus oryzae ATCC 26850; The esterase of NCIM 1212 continues to join in the reaction mixture with stirring.Reaction continued several hours and monitored the generation of TGS and the disappearance of 6-O-acetylize TGS by TLC.Last at 42h, finish high to 98.4% deacetylation.
Behind the deacetylation, utilize suitable method that this material is carried out TGS and separate.
Embodiment 3, the immobilization esterase of utilization on Eudragit RL100 carry out 6-O-ethanoyl TGS's
Enzymatic deacylation
In an experiment, use 50% calcium hydroxide slurry that the reaction mass that 2.5L contains 80g 6-O-acetylize TGS is neutralized to pH 5.5.Water neutral reaction mass is diluted to 6L.This in the neutral material content of DMF be 33%.In 25 ℃～30 ℃ temperature (normally envrionment temperature), the immobilization esterase of 120g on Eudragit RL100 continues to join in the reaction mixture with stirring.Reaction continued several hours and monitored the generation of TGS and the disappearance of 6-O-acetylize TGS by TLC.Last at 24h, finish high to 98.3% deacetylation.
Filter this material then and carry out the TGS separation.The enzyme water flushing that obtains from the strainer filter cake also stores to reuse.
The immobilization esterase that embodiment 4, utilization are filled in the post, on Eudragit RL100 carries out 6-O-second
The enzymatic deacylation of acyl group TGS
In an experiment, the 12g immobilized enzyme is filled into the glass column of diameter 2cm and high 8cm.The inlet of post is connected to wriggling delivery side of pump (delivery) and outlet and is connected to and contains the 500ml flask of neutral material (have 5g 6-O-ethanoyl-).The inlet of peristaltic pump also is connected to this neutral material.The neutral material circulated 6 hours by immobilized esterase bed with the flow velocity of 5ml/min.
Carried out TLC every one hour to observe the degree of the deacetylation that takes place in the flask.After 6 hours, observe and be higher than 98% deacetylation.
6-O-ethanoyl-TGS deacetylation is after TGS finishes, and the bed of immobilized enzyme stores up to reusing with deionized water rinsing and under 10% aqueous acetone solution.
Embodiment 5, the enzymatic that utilizes Alcalase-proteolytic ferment to carry out 6-O-ethanoyl TGS go second
Acylation reaction
With 1.0L contain 10g 6-O-acetylize TGS, after the chlorination in and material carry out enzymatic reaction.Water with this neutral reaction mass be diluted to 3.0L.Under 25～30 ℃ of temperature, will join the reactant from the 200ml Alclalase 2.4L enzyme derived from B.lichenformis of the commercially available acquisition of Novozymes.Reaction continued several hours and monitored the generation of TGS and the disappearance of 6-O-acetylize TGS by TLC.Last at 36h, finish high to 96.4% deacetylation.Behind the deacetylation, use suitable method that this material is carried out TGS and separate.
Claims (according to the modification of the 19th of treaty)
1, a kind of method of production chlorinated sucrose compound wherein utilizes the effect of the enzyme that can remove blocking group to make the chlorinated derivatives of the sucrose of the 6-O-protection in solution go protection.
2, method according to claim 1, wherein:
The sucrose of a, described 6-O-protection comprises one or more of cane sugar-6-acetic ester, sucrose-6-benzoic ether, sucrose-6-propionic ester, sucrose-6-laurate, sucrose-6-glutarate, sucrose-6-cetylate etc.,
B, described solution comprise the sucrose solution of pure chlorating 6-O-protection, or a (ii) process streams that obtains in the method for production chlorinated sucrose compound.
3, method according to claim 2, wherein:
A, described process streams comprise that one or more produce the method for chlorinated sucroses, comprise the method for chlorinated sucrose or chlorination 6-O-protection sucrose derivative method and
B, described chlorinated sucrose compound comprise one or more chlorinated sucrose, comprise trichlorogalacto-sucrose, dichlorogalactosucroand, tetrachloro sucralose etc.
4, method according to claim 3, wherein said chlorating method comprise utilizes following one or more method reactions with sucrose derivative and one or more chlorination reagents, comprising:
A, the sucrose that is dissolved in the 6-O-protection in the pyridine and the reaction of SULPHURYL CHLORIDE, or
B, in the presence of triphenylphosphine and vinyl trichloride, the sucrose of 6-O-protection and the reaction of thionyl chloride, or
C, comprise that it is [HClC=N that sucrose-6-ester divides the sucrose-6-ester and the general formula of 6-O-protection
+R
2] Cl
-Or [HPOCl
2OC
+=N
+R
2] Cl
-The Vilsmeier reagent react, wherein R represents alkyl, preferable methyl or ethyl.
5, method according to claim 4, the effect that wherein can remove the enzyme of blocking group are to obtain from esterase or proteolytic enzyme.
6, according to the described method of claim 5, wherein said esterase or proteolytic enzyme are freely or immobilized enzyme.
7, method according to claim 6 comprises step:
A, will be at (i) solution or (ii) one produce the cane sugar-6-acetic ester chlorination reagent chlorination that contains in the process streams that obtains in the reaction of chlorinated sucrose, described chlorination reagent is selected from the group of being made up of Vilsmeier reagent, SULPHURYL CHLORIDE or thionyl chloride,
B, regulate this claim step (a) the pH of process streams to about 6.5～7,
The TGS deacetylation of the 6-O-protection that forms in c, the process streams with step (a); its (i) by with its with freely or immobilized esterase or freely or immobilized proteolytic enzyme contact; preferably be accompanied by in reaction vessel concussion or utilize by being filled into the enzyme bed recirculation in the post; preferably the enough time of about 25～30 ℃ envrionment temperature to finish the deacetylation of maximum possible about 95%
D, from the process streams of this claim step (c)-kind or multiple undesired component separate TGS.
Claims (7)
1. a method of producing chlorinated sucrose compound wherein utilizes the effect of the enzyme that can remove blocking group to make the sucrose of the 6-O-protection in solution go protection.
2. method according to claim 1, wherein:
The sucrose of a, described 6-O-protection comprises one or more of cane sugar-6-acetic ester, sucrose-6-benzoic ether, sucrose-6-propionic ester, sucrose-6-laurate, sucrose-6-glutarate, sucrose-6-cetylate etc.,
B, described solution comprise the sucrose solution of pure 6-O-protection, or a (ii) process streams that obtains in the method for production chlorinated sucrose compound.
3. method according to claim 2, wherein:
A, described process streams comprise that one or more produce the method for chlorinated sucroses, comprise chlorinated sucrose or sucrose derivative method and
B, described chlorinated sucrose compound comprise one or more chlorinated sucrose, comprise trichlorogalacto-sucrose, dichlorogalactosucroand, tetrachloro sucralose etc.
4. method according to claim 3, wherein said chlorating method comprise utilizes following one or more methods reactions with sucrose or sucrose derivative and one or more chlorination reagents, comprising:
A, be dissolved in the sucrose in the pyridine and the reaction of SULPHURYL CHLORIDE, or
B, in the presence of triphenylphosphine and vinyl trichloride, the reaction of sucrose and thionyl chloride, or
C, sucrose-6-ester and general formula are [HClC=N
+R
2] Cl
-Or [HPOCl
2OC
+=N
+R
2] Cl
-The Vilsmeier reagent react, wherein R represents alkyl, preferable methyl or ethyl.
5. method according to claim 4, the effect that wherein can remove the enzyme of blocking group are to obtain from esterase or proteolytic enzyme.
6. according to the described method of claim 5, wherein said esterase or proteolytic enzyme are freely or immobilized enzyme.
7. method according to claim 6 comprises step:
A, will be at (i) solution or (ii) one produce the cane sugar-6-acetic ester chlorination reagent chlorination that contains in the process streams that obtains in the reaction of chlorinated sucrose, described chlorination reagent is selected from the group of being made up of Vilsmeier reagent, SULPHURYL CHLORIDE or thionyl chloride,
B, regulate this claim step (a) the pH of process streams to about 6.5～7,
The TGS deacetylation of the 6-O-protection that forms in c, the process streams with step (a); its (i) by with its with freely or immobilized esterase or freely or immobilized proteolytic enzyme contact; preferably be accompanied by in reaction vessel concussion or utilize by being filled into the enzyme bed recirculation in the post; preferably the enough time of about 25～30 ℃ envrionment temperature to finish the deacetylation of maximum possible about 95%
D, from a kind of undesired component of the process streams of this claim step (c), separate TGS.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IN1175MU2005 | 2005-09-22 | ||
| IN1175/MUM/2005 | 2005-09-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101282983A true CN101282983A (en) | 2008-10-08 |
Family
ID=38023686
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800346126A Pending CN101282983A (en) | 2005-09-22 | 2006-09-21 | Enzyme catalyzed de-acylation of chlorinated sugar derivatives |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP1940858A4 (en) |
| JP (1) | JP2009508519A (en) |
| KR (1) | KR20080056187A (en) |
| CN (1) | CN101282983A (en) |
| AU (1) | AU2006313335A1 (en) |
| BR (1) | BRPI0617599A2 (en) |
| CA (1) | CA2623246A1 (en) |
| EA (1) | EA200800654A1 (en) |
| IL (1) | IL190251A0 (en) |
| LV (1) | LV13762B (en) |
| NO (1) | NO20081899L (en) |
| WO (1) | WO2007054973A2 (en) |
| ZA (1) | ZA200802518B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181494A (en) * | 2011-03-21 | 2011-09-14 | 盐城捷康三氯蔗糖制造有限公司 | Synthesis of sucrose-6-fatty acid ester through selective catalysis of immobilized aspergillus oryzae lipase |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8822674D0 (en) * | 1988-09-27 | 1988-11-02 | Tate & Lyle Plc | Preparation of acylated sucrose derivatives |
| US5445951A (en) * | 1993-02-02 | 1995-08-29 | Mcneil-Ppc, Inc. | Regioselective enzymatic deacylation of sucrose esters in anhydrous organic media |
-
2006
- 2006-09-21 BR BRPI0617599-6A patent/BRPI0617599A2/en not_active Application Discontinuation
- 2006-09-21 KR KR1020087008005A patent/KR20080056187A/en not_active Application Discontinuation
- 2006-09-21 CA CA002623246A patent/CA2623246A1/en not_active Abandoned
- 2006-09-21 EP EP06842764A patent/EP1940858A4/en not_active Withdrawn
- 2006-09-21 JP JP2008531892A patent/JP2009508519A/en active Pending
- 2006-09-21 AU AU2006313335A patent/AU2006313335A1/en not_active Abandoned
- 2006-09-21 CN CNA2006800346126A patent/CN101282983A/en active Pending
- 2006-09-21 WO PCT/IN2006/000385 patent/WO2007054973A2/en active Application Filing
- 2006-09-21 EA EA200800654A patent/EA200800654A1/en unknown
-
2008
- 2008-03-18 ZA ZA200802518A patent/ZA200802518B/en unknown
- 2008-03-18 IL IL190251A patent/IL190251A0/en unknown
- 2008-04-09 LV LVP-08-59A patent/LV13762B/en unknown
- 2008-04-22 NO NO20081899A patent/NO20081899L/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| BRPI0617599A2 (en) | 2011-08-02 |
| WO2007054973A2 (en) | 2007-05-18 |
| NO20081899L (en) | 2008-06-23 |
| ZA200802518B (en) | 2009-06-24 |
| EP1940858A2 (en) | 2008-07-09 |
| JP2009508519A (en) | 2009-03-05 |
| IL190251A0 (en) | 2008-11-03 |
| EP1940858A4 (en) | 2009-06-17 |
| AU2006313335A1 (en) | 2007-05-18 |
| KR20080056187A (en) | 2008-06-20 |
| CA2623246A1 (en) | 2007-05-18 |
| EA200800654A1 (en) | 2009-02-27 |
| LV13762B (en) | 2009-01-20 |
| WO2007054973B1 (en) | 2007-08-23 |
| WO2007054973A3 (en) | 2007-07-12 |
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