EP4077697A1 - Esters d'acide carboxylique de xylitol et procédé de préparation enzymatique de ceux-ci - Google Patents

Esters d'acide carboxylique de xylitol et procédé de préparation enzymatique de ceux-ci

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Publication number
EP4077697A1
EP4077697A1 EP20833825.1A EP20833825A EP4077697A1 EP 4077697 A1 EP4077697 A1 EP 4077697A1 EP 20833825 A EP20833825 A EP 20833825A EP 4077697 A1 EP4077697 A1 EP 4077697A1
Authority
EP
European Patent Office
Prior art keywords
xylitol
carboxylic acid
acid ester
weight
lipase
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.)
Pending
Application number
EP20833825.1A
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German (de)
English (en)
Inventor
Stefan Julian LIEBIG
Jan Marian Von Hof
Thomas Böhmer
Thomas THOMALLA
Kathrin Daniela Brandt
Christian Hartung
Hans Henning Wenk
Maxim YAVORSKY
Sunay Karacocuk
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Evonik Operations GmbH
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Evonik Operations GmbH
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Publication date
Application filed by Evonik Operations GmbH filed Critical Evonik Operations GmbH
Publication of EP4077697A1 publication Critical patent/EP4077697A1/fr
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
    • C12P7/6436—Fatty acid esters
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
    • C12N9/14—Hydrolases (3)
    • C12N9/16—Hydrolases (3) acting on ester bonds (3.1)
    • C12N9/18—Carboxylic ester hydrolases (3.1.1)
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
    • C12N9/14—Hydrolases (3)
    • C12N9/16—Hydrolases (3) acting on ester bonds (3.1)
    • C12N9/18—Carboxylic ester hydrolases (3.1.1)
    • C12N9/20—Triglyceride splitting, e.g. by means of lipase
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/02—Monosaccharides
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/04—Polysaccharides, i.e. compounds containing more than five saccharide radicals attached to each other by glycosidic bonds
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/44—Preparation of O-glycosides, e.g. glucosides
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/62—Carboxylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
    • C12P7/6436—Fatty acid esters
    • C12P7/6445—Glycerides
    • C12P7/6454—Glycerides by esterification
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

  • the invention relates to xylitol carboxylic acid esters and a process for the enzymatic production of xylitol carboxylic acid esters.
  • xylitol carboxylic acid esters are interesting products for the food and cosmetic industries.
  • EP2902009A1 describes the classic chemical esterification of xylitol with fatty acids in the absence of solvents in the presence of catalysts such as p-toluenesulfonic acid (pTSA) at temperatures of up to 200 ° C within 8 hours and the use of the xylitol carboxylic acid esters thus obtained as an active ingredient in cosmetic Formulations.
  • catalysts such as p-toluenesulfonic acid (pTSA) at temperatures of up to 200 ° C within 8 hours and the use of the xylitol carboxylic acid esters thus obtained as an active ingredient in cosmetic Formulations.
  • a disadvantage of the classic chemical esterification process is that under these conditions, at least partial dehydration or degradation of the xylitol always takes place (Biotechnol. Bioeng. 1995, 48, 214-221). Three degradation products of xylitol that frequently occur under such conditions are the anhydro-pentitols 1,4-anhydro-xylitol, 1,4-anhydro-arabinitol and 1,4-anhydro-ribitol (J. Carbohydr. Chem. 2004, 23, 4, 169-177 and Adv. Carbohydr. Chem. Biochem., 1983, 41, 27-66).
  • Another disadvantage of the process described in the prior art are additional process steps such as the use and subsequent separation of activated carbon and terra alba (calcium sulfate) in order to improve the color and smell of the products obtained.
  • Pedersen et al. (Enzyme Microb. Technol. 2007, 41, 3, 346-352) describe the enzymatic synthesis of xylitol carboxylic acid esters using solvents such as tert-butanol and pyridine at a temperature of 45 ° C.
  • solvents such as tert-butanol and pyridine at a temperature of 45 ° C.
  • a disadvantage of this process described in the prior art is that the use of solvents stands in the way of application in the food or cosmetics sector, and the necessary separation of the solvents also requires additional process steps such as crystallization, filtration or distillation.
  • Basri et al. (Carbohydr. Res. 2011, 346, 472-479) describe the solvent-free esterification of xylitol with both capric acid and caproic acid using a lipase from Candida antarctica at a maximum of 70 ° C and optimally at 60 ° C. This procedure leads to Product mixtures in which the ratio of esterified primary OH groups to esterified secondary OH groups is always greater than 80:20.
  • a disadvantage of this process described in the prior art is the use of molecular sieves, which makes it difficult to implement on an industrial scale.
  • Another disadvantage of this process described in the prior art is the use of solvents or solvent mixtures to terminate the reaction and to separate off the enzyme and the molecular sieve.
  • This procedure means an additional process step for the separation of the solvent used and takes the advantage of the solvent-free process.
  • a further disadvantage of this process described in the prior art is that tricarboxylic acid esters of xylitol are obtained as the main component in a relative proportion of more than 50% in the ester distribution.
  • Another disadvantage of this method described in the prior art is unclear enzyme loading.
  • Another disadvantage of this process described in the prior art is the low conversion rate of only approx. 70% and thus the relatively large amount of remaining fatty acid of approx. 15% in the product mixture, which requires a subsequent separation of the fatty acid, possibly with prior neutralization to avoid unwanted by-products or, in the case of caproic, caprylic and capric acid, for example, an unpleasant odor.
  • Another disadvantage of this process described in the prior art is the selectivity for long-chain fatty acids.
  • Tan et al. J. Mol. Catal. B-Enzym 2013, 89, 61-66) describe the solvent-free esterification of xylitol with capric acid using a lipase (Candida sp 99-125) at a maximum of 50 ° C. From the analytical data given it can be deduced that the ratio of esterified primary OH groups to esterified secondary OH groups is always greater than 80:20.
  • a disadvantage of this process described in the prior art is the use of very finely ground xylitol (particle size ⁇ 0.2 mm), which means an additional process step and the use of special equipment (e.g. Dispermat or special mills) for a large-scale implementation.
  • Another disadvantage of this process described in the prior art are long reaction times (> 100 hours). Another disadvantage of this process described in the prior art is the separation of by-products at temperatures> 140 ° C., which has a negative effect on the color of the products. Another disadvantage of the process described in the prior art is the use of a commercially unavailable enzyme. Another disadvantage of the method described in the prior art is that the enzyme was not isolated from a wild type.
  • Another disadvantage of this process described in the prior art is the use of non-immobilized enzymes, which makes handling from a safety point of view and separation from the product more difficult. Another disadvantage of this process described in the prior art is the poor recyclability of the lipase used. Another disadvantage of this process described in the prior art is the use of a fed-batch process in order to avoid the high viscosity caused by an excess of xylitol or capric acid. Another disadvantage of this method described in the prior art is the use of a fed-batch method, which is a requires special measurement and control technology. Another disadvantage of this method described in the prior art is the addition of water, which has to be separated off again at the end of the process.
  • KR101939851 B1 describes esters of dehydrated xylitol, thus the by-products of the classic chemical esterification processes described above for the production of xylitol carboxylic acid esters, and the use of these carboxylic acid esters of anhydro-xylitol as a rheological additive / viscosity regulator in an emulsion.
  • a disadvantage of the anhydroxylitol carboxylic acid esters described in the prior art is their reduced hydrophilicity.
  • Another disadvantage of the anhydroxylitol carboxylic acid esters described in the prior art is their dark color.
  • Another disadvantage of such anhydroxylitol carboxylic acid esters is the poor thickening performance in aqueous surfactant systems.
  • the object of the invention was to provide a process for the production of sugar esters and / or sugar alcohol esters which is able to overcome at least one disadvantage of the prior art processes.
  • carboxylic acid esters represent excellent thickeners for aqueous surfactant systems.
  • xylitol carboxylic acid esters according to the invention also have an excellent color and a very good odor compared to the prior art.
  • One advantage of the present invention is that only very few degradation products of xylitol or esters of the degradation products are obtained as reaction products.
  • An advantage of the present invention is that the process according to the invention can be carried out in the absence of a solvent.
  • Another advantage of the present invention is that the xylitol carboxylic acid esters are obtained in a homogeneous reaction mixture, so that no additional process steps such as extraction, crystallization, filtration or distillation are required.
  • An advantage of the present invention is that the process can be carried out at elevated temperatures. This leads to better miscibility of the reactants while the recyclability of the enzyme used is surprisingly high.
  • Another advantage of the present invention is that the xylitol carboxylic acid esters obtained can be incorporated very easily into formulations, especially into cosmetic formulations. The present invention therefore relates to a xylitol carboxylic acid ester containing
  • Carboxylic acid ester of xylitol carboxylic acid ester of 1,4-anhydro-xylitol, carboxylic acid ester of 1,4-anhydro-arabinitol and carboxylic acid ester of 1,4-anhydro-ribitol, the weight ratio of the xylitol residues contained in the xylitol-carboxylic acid ester to the sum of all 1,4-anhydro-xylitol residues contained in the xylitol carboxylic acid ester, 1,4-anhydro-
  • Arabinitol residues and 1,4-anhydro-ribitol residues greater than or equal to 96: 4, preferably greater than 97: 3, particularly preferably greater than 98: 2, most preferably greater than 99: 1, is characterized in that the molar ratio of esterified primary hydroxyl groups to esterified secondary hydroxyl groups in the carboxylic acid esters of xylitol 80:20 to 20:80, preferably 75:25 to 25:75, even more preferably 70:30 to 30:70, even more preferably of
  • xylitol carboxylic acid ester in connection with the present invention comprises a composition which is at least 30% by weight, preferably at least 40% by weight, more preferably at least 50% by weight, particularly preferably at least 70% by weight. %, Carboxylic acid ester of xylitol based on the total composition.
  • by-products from the respective manufacturing process such as carboxylic acid esters of 1,4-anhydro-xylitol, carboxylic acid esters of 1,4-anhydro-arabinitol and carboxylic acid esters of 1,4-anhydro-ribitol, and unreacted starting materials may also be included.
  • carboxylic acid ester of xylitol in connection with the present invention denotes pure xylitol compounds.
  • carboxylic acid ester of 1,4-anhydro-xylitol in connection with the present invention denotes pure 1,4-anhydro-xylitol compounds.
  • carboxylic acid ester of 1,4-anhydro-arabinitol in connection with the present invention denotes pure 1,4-anhydro-arabinitol compounds.
  • carboxylic acid ester of 1,4-anhydro-ribitol in connection with the present invention denotes pure 1,4-anhydro-ribitol compounds. This use of the term is based on the common nomenclature for polyol esters, which are known to have a tendency to dehydration in their synthesis and therefore the products represent mixed compositions.
  • sorbitan ester to mean a mixture comprising esters of 1,4-sorbitan (1,4-anhydro-sorbitol), esters of 1,5-sorbitan (1,5-anhydro-sorbitol), but also esters des isosorbides and esters of sorbitol, as well as free sorbitol, cf. for example Food emulsifiers and their applications, 1997, page 26.
  • xylitol carboxylic acid ester containing carboxylic acid ester of xylitol, carboxylic acid ester of 1,4-anhydro-xylitol, carboxylic acid ester of 1,4-anhydro-arabinitol and carboxylic acid ester of 1,4-anhydro-ribitol, where the weight ratio of the carboxylic acid esters xylitol residues contained in the total of all 1,4-anhydro-xylitol residues, 1,4-anhydro-arabinitol residues and 1,4-anhydro-ribitol residues contained in the carboxylic acid esters is greater than or equal to 96: 4 ” clearly and unambiguously that in the xylitol carboxylic acid ester according to the invention the content of at least one selected from carboxylic acid ester of 1,4-anhydro-xylitol, carboxylic acid ester of 1,4-anhydro-arabinitol and carboxy
  • This method includes the alkaline hydrolysis of the xylitol carboxylic acid ester to be analyzed, separation of the carboxylic acids and analysis of the xylitol and its breakdown products 1,4-anhydro-xylitol, 1,4-anhydro-arabinitol and 1,4-anhydro-ribitol.
  • 150 mg of the xylitol carboxylic acid ester to be analyzed are placed in 2.00 mL of an aqueous 1 M KOH solution and hydrolyzed at 95 ° C. for 30 min with stirring.
  • the reaction solution is then cooled to room temperature and adjusted to pH 2-3 with a 2 M aqueous HCl solution.
  • the resulting carboxylic acids are then extracted with diethyl ether (3 c 3.00 mL), the organic supernatant being pipetted off after each extraction.
  • the aqueous solution is heated to 50 ° C. for 20 minutes while stirring, whereby the remaining ether is removed (boiling point diethyl ether: 34.6 ° C.).
  • Measurement time 30.0 min Xylitol and its degradation products are separated by means of ion exchange processes.
  • the peak area of xylitol is related to the sum of the peak areas of 1,4-anhydro-xylitol, 1,4-anhydro-arabinitol and 1,4-anhydro-ribitol.
  • Reference substances for the breakdown products of xylitol are commercially available or, alternatively, they can be obtained by heating xylitol in bulk in the presence of acidic (> 140 ° C) or basic (> 180 ° C) catalysts.
  • the molar ratio of esterified primary hydroxyl groups to esterified secondary hydroxyl groups in the carboxylic acid esters of xylitol is determined by 13 C-NMR spectroscopy.
  • a deuterated solvent mixed with a relaxation accelerator (chromium (III) acetylacetonate; 1%).
  • DMSO-d6, CDCh and methanol-d4 have proven to be suitable solvents. If the sample is not completely soluble in one of the solvents, a solvent mixture must be found.
  • the prepared sample solution is transferred to a 5 mm NMR tube and introduced into the NMR spectrometer.
  • the NMR spectroscopic investigations can in principle be carried out with any commercially available NMR device.
  • a device of the Avance 400 type from Bruker was used for the present NMR spectroscopic investigations.
  • the spectra were recorded with the following parameters:
  • the integration was investigated using the TOPSPIN software (version 3.0).
  • a DEPT spectrum is recorded in advance to precisely identify the esterified primary and the esterified secondary hydroxyl groups.
  • the molar ratio of esterified primary to esterified secondary hydroxyl groups is determined by subtracting the integral value P (signal group of esterified primary hydroxyl groups) from the integral value C (signal group of the ester carbonyl groups).
  • An integral value S is thus obtained for the signal group of the esterified secondary hydroxyl groups, which cannot be determined directly due to superposition with other signals.
  • xylitol carboxylic acid esters are preferred, which are characterized in that the carboxylic acid content is derived from a carboxylic acid containing 2 to 34, preferably 4 to 24, particularly preferably 6 to 22, carbon atoms. According to the invention, the carboxylic acid content is preferably derived from a natural fatty acid or mixtures thereof.
  • Natural fatty acids can be prepared on the basis of naturally occurring vegetable or animal oils and preferably have 6 to 30 carbon atoms, in particular 8 to 22 carbon atoms. Natural fatty acids are usually unbranched and usually consist of an even number of carbon atoms. Any double bonds have a cis configuration.
  • caproic acid caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, pelargonic acid (obtainable for example from ozonolysis or oxidative cleavage of oleic acid), isostearic acid, stearic acid, 12-hydroxystearic acid, dihydroxystearic acid, undecylenic acid) (obtainable from ricinoleic acid) , Oleic acid, linoleic acid, linolenic acid, petroleic acid, elaidic acid, arachidic acid, behenic acid, erucic acid, gadoleic acid, linolenic acid, eicosapentaenoic acid, docosahexaenoic acid and arachidonic acid.
  • xylitol carboxylic acid esters are particularly preferred, which are characterized in that the carboxylic acid portion is derived from fatty acid mixtures selected from at least two selected from the group caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, pelargonic acid (obtainable for example from ozonolysis or oxidative cleavage of oleic acid), isostearic acid, stearic acid, 12-hydroxystearic acid, dihydroxystearic acid, undecylenic acid (obtainable for example from the pyrolysis of ricinoleic acid), oleic acid, linoleic acid, linolenic acid, petroleic acid, elaidic acid, arachidic acid, behenic acid, linoleic acid, gosaadoleic acid and arachidonic acid.
  • the carboxylic acid portion is derived from fatty acid mixtures selected from at least two
  • xylitol carboxylic acid esters are preferred, which are characterized in that the mean degree of esterification of the carboxylic acid esters of xylitol contained is from 1.0 to 4.0, preferably from 1.0 to 3.0, particularly preferably from 1.1 to 2.7 , particularly preferably from 1.3 to 2.6.
  • xylitol carboxylic acid esters which are characterized in that the average degree of esterification of the carboxylic acid esters of xylitol present is from 2.7 to 4.0.
  • the mean degree of esterification of the xylitol carboxylic acid esters contained in the xylitol carboxylic acid ester according to the invention is determined, for example, by first determining the content of free xylitol and its Degradation products 1,4-anhydro-xylitol, 1,4-anhydro-arabinitol and 1,4-anhydro-ribitol is determined via GC or HPLC.
  • the saponification number, the acid number and the content of free and neutralized fatty acids (for example via GC as described below under "Determination of the content of free carboxylic acid") must be determined.
  • the determination of the carboxylic acid composition after alkaline saponification gives an average molar mass of the carboxylic acid residues contained in the xylitol carboxylic acid ester.
  • the mean degree of esterification can then be calculated from this.
  • a xylitol carboxylic acid ester is preferred, which is characterized in that the contained carboxylic acid esters of xylitol contain monoesters of xylitol, diesters of xylitol and triesters of xylitol, the triesters of xylitol preferably in an amount based on all carboxylic acid esters of xylitol contained of 10 to 50% by weight, preferably from 15% by weight to 45% by weight, particularly preferably from 20% by weight to 40% by weight.
  • the carboxylic acid esters of xylitol contained contain monoesters of xylitol, diesters of xylitol, triesters of xylitol, and tetraesters of xylitol.
  • a xylitol carboxylic acid ester which is characterized in that it contains 0.05% by weight to 40% by weight, preferably 0.2% by weight to 25% by weight, particularly preferably 0.5% by weight .-% to 10% by weight, contains free xylitol, the percentages by weight being based on the total xylitol carboxylic acid ester.
  • the alcohols are quantitatively converted into their trimethylsilyl ethers by reaction at 80 ° C. (30 minutes) and then examined by means of GC / FID.
  • Carrier gas hydrogen, constant flow, 2 mL / min
  • Temperature program 100 ° C - 140 ° C with 10 ° C / min, then 140 ° C - 300 ° C with 5 ° C / min, then Condition at 300 ° C for 5 minutes.
  • the xylitol is separated off and its mass fraction is determined using an internal standard method.
  • the GC system is calibrated by measuring mixtures of xylitol and the internal standard with a known composition.
  • a xylitol carboxylic acid ester which is characterized in that it contains less than 25% by weight, preferably from 0.01% by weight to 20% by weight, particularly preferably from 0.05% by weight to Contains 10% by weight, at least one free carboxylic acid, the percentages by weight being based on the total xylitol carboxylic acid ester.
  • the at least one free carboxylic acid can be present in protonated or neutralized form.
  • the acid number is first determined.
  • the weight fraction can be determined via the acid number and the molecular weight of the fatty acid in question.
  • Suitable methods for determining the acid number are in particular those in accordance with DGF C-V 2, DIN EN ISO 2114, Ph.Eur. 2.5.1, ISO 3682 and ASTM D 974.
  • 0.6 g of the xylitol carboxylic acid ester according to the invention are boiled under reflux for 4 hours in 25 ml of an ethanolic 0.5 M KOH solution. Then the pH is adjusted to pH 2-3 with sulfuric acid, and the released carboxylic acids are separated off by three extractions with one volume of petroleum ether each time. The combined extracts are concentrated to approx. 10 mL by evaporation.
  • Suitable determination methods for determining the fatty acid distribution are in particular those according to DGF C VI 11a, DGF C-VI 10a and GAT - Ringtest 7/99.
  • a 0.5 mL aliquot of the petroleum ether extract obtained as described above is mixed with 0.5 mL MTBE and 1 mL trimethylanilinium hydroxide (0.2 M in methanol) in an autosampler vessel and analyzed by GC. This is carried out in a gas chromatograph, which is equipped with a split / splitless injector, a capillary column and a flame ionization detector, under the following conditions: Injector: 290 ° C., split 30 mL Injection volume: 1 mI_
  • Carrier gas helium, head pressure 70 kPa
  • the carboxylic acids are separated as their methyl esters according to their carbon chain length. By evaluating the peak areas, the mass ratio of these methyl carboxylic acid esters to one another and, by means of their respective molecular weights, their molar ratio can be determined therefrom, which corresponds to the molar ratio of the associated carboxylic acids. In addition, an average molecular weight of this fatty acid mixture can be determined:
  • a with a normalized mass fraction of the methyl carboxylate / in the mixture of all methyl carboxylates [%].
  • Ai peak area of the methyl carboxylate / in the GC chromatogram [%].
  • n with n, amount of substance [mol] of the carboxylic acid methyl ester / in 100 g, a ,
  • n, amount of substance [mol] of the methyl carboxylate / in 100 g Carboxylic acid methyl ester mixture.
  • Mi molecular weight of the carboxylic acid / [g / mol].
  • a xylitol carboxylic acid ester is preferred, which is characterized in that in the total monoester content of the carboxylic acid ester of xylitol, from 5% by weight to 25% by weight, preferably from 7% by weight to 15% by weight, is particularly preferred from 9 wt% to 13 wt%, secondary ester regioisomer is included.
  • a xylitol carboxylic acid ester is preferred according to the invention, which is characterized in that at least two regioisomers are contained in the total monoester portion of the carboxylic acid ester of xylitol and in the total diester portion of the carboxylic acid ester of xylitol.
  • a xylitol carboxylic acid ester is preferred, which is characterized in that in the total diester content of the carboxylic acid ester of xylitol, from 25% by weight to 45% by weight, preferably from 28% by weight to 39% by weight, is particularly preferred from 30% by weight to 37% by weight, regioisomers in which at least one secondary hydroxyl group is esterified.
  • the determination of the content of secondary ester regioisomer in the total monoester portion of the carboxylic acid ester of xylitol according to the invention and the determination of the content of triester species based on the sum of all carboxylic acid esters of xylitol and the determination of the content of regioisomers in the total diester portion, for the at least one secondary hydroxyl group is esterified can be carried out by means of gas chromatography, if necessary coupled with mass spectrometry (GC-FID and GC-MS):
  • the esters contained in the sample are separated according to their total chain length.
  • the ratios of the individual ester species to one another are determined via the respective area percentages of the GC-FID peaks.
  • the identification / assignment of the peaks to the individual ester species takes place via GC-MS, if necessary also via a retention time comparison of separately produced and isolated standards, eg for the mono- and diesters esterified exclusively on primary hydroxyl groups.
  • This method can also be used to determine the content of free protonated and free neutralized carboxylic acids, as these are also derivatized.
  • the invention also relates to a process for the enzymatic production of a xylitol carboxylic acid ester, preferably a xylitol carboxylic acid ester according to the invention, comprising the process steps
  • acyl group donors can be used according to the invention.
  • Such are, for example, carboxylic acid esters or carboxylic acids themselves, as well as mixtures thereof.
  • Carboxylic acid esters preferably used as acyl group donors according to the invention are selected from esters based on alkanols and polyols with up to 6 carbon atoms, particularly preferably with up to 3 carbon atoms, very particularly preferably glycerol esters.
  • carboxylic acid esters used as acyl group donors according to the invention are selected from triglycerides, in particular natural fats and oils, particularly preferably selected from the group comprising, preferably consisting of, coconut fat, palm kernel oil, olive oil, palm oil, argan oil, castor oil, linseed oil, babassu oil, rapeseed oil, algae oils, Sesame oil, soybean oil, avocado oil, jojoba oil, diestel oil, almond oil, cottonseed oil, shea butter, sunflower oil, cupuaccu butter and oils with a high proportion of polyunsaturated fatty acids (PUFAS) are used.
  • Sorbitan esters, monoglycerides and diglycerides, in particular with the acyl groups described below, can also be used with preference.
  • the acyl group donor is particularly preferably selected from fatty acid acyl group donors which, in particular, provide an acyl group selected from the group of acyl groups of natural fatty acids.
  • Preferred fatty acids in this context are the fatty acids mentioned above in connection with the xylitol carboxylic acid ester according to the invention, preferably forming the carboxylic acid portion, with an identical degree of preference.
  • carboxylic acids in particular fatty acids
  • fatty acids are preferably used as acyl group donors, the fatty acids specifically mentioned in connection with the xylitol carboxylic acid ester according to the invention being preferably used with an identical degree of preference.
  • mixtures of fatty acids with glycerol fatty acid esters are alternatively preferably used as acyl group donors, those in connection with the invention
  • Xylitol carboxylic acid esters specifically the aforementioned fatty acids are preferably used both in the fatty acids and in the glycerol fatty acid components with an identical degree of preference.
  • the mixture of fatty acid with glycerol fatty acid ester used preferably has a weight ratio of fatty acid to glycerol fatty acid ester of 80:20 to 99: 1, preferably 90:10 to 99: 1, particularly preferably 95: 5 to 99: 1.
  • a method preferred according to the invention is characterized in that the xylitol and the at least one acyl group donor at least 80% by weight, preferably at least 90% by weight, particularly preferably at least 95% by weight, based on the total reaction mixture at the beginning of process step B. ) turn off.
  • the entire reaction mixture consists largely of the starting materials, thus xylitol and acyl group donor, the entire reaction mixture can contain very little solvent, if at all.
  • the acyl group donor does not fall under the term “solvent” in the process according to the invention.
  • Possible solvents would be, for example, ketones such as methyl isobutyl ketone or cyclohexanone, sterically hindered secondary alcohols such as 2-butyl-1-octanol, methylcyclohexanols, 1-methoxy-2-propanol, 2,3-butanediol, 2-octanol, diacetone alcohol, 2-methyl -2-butanol, and ethers such as 1,4-dioxane, tetrahydrofuran and Varonic APM.
  • ketones such as methyl isobutyl ketone or cyclohexanone
  • sterically hindered secondary alcohols such as 2-butyl-1-octanol, methylcyclohexanols, 1-methoxy-2-propanol, 2,3-butanediol, 2-octanol, diacetone alcohol, 2-methyl -2-butanol
  • ethers such as
  • Solvents based on the total reaction mixture, are present in total at a maximum of less than 20% by weight, preferably less than 10% by weight, in particular less than 5% by weight.
  • the term “at most less than X% by weight” is to be equated with “a content of less than X% by weight”.
  • the process according to the invention is particularly preferably carried out without a solvent.
  • a preferred method according to the invention is characterized in that the molar
  • a method preferred according to the invention is characterized in that method step A)
  • Mixing the xylitol and the at least one acyl group donor for at least ten minutes, preferably 30 minutes, even more preferably 60 minutes, comprises, the mixing preferably in a temperature range from 80 ° C to 120 ° C, preferably from 90 ° C to 120 ° C, even more preferably from 95 ° C to 120 ° C, even more preferably from 100 ° C to 120 ° C, is performed.
  • lipases preferably used in process step B) are immobilized on a solid support.
  • Lipases preferably used according to the invention in process step B) are lipases selected from the group comprising the lipase from Thermomyces lanuginosus (accession number 059952), the lipases A and B (accession number P41365) from Candida antarctica and the lipase from Mucor miehei (accession number P19515), the Lipase from Humicola sp.
  • the lipases A and B (accessionnumber Candida) from Candida in particular P41365 are preferred, as are in each case at least 60%, preferably at least 80%, preferably at least 90%, particularly preferably at least 95%, 98% or
  • accession numbers listed in connection with the present invention correspond to the ProteinBank database entries of the NCBI dated 01/01/2017; As a rule, the version number of the entry is indicated by a ". digit” such as ".1".
  • the enzymes homologous at the amino acid level preferably have, compared to the reference sequence, at least 50%, in particular at least 90%, enzyme activity in propyl laurate units defined in connection with the present invention.
  • PLU propyl laurate unit
  • 1-propanol and lauric acid are mixed homogeneously in an equimolar ratio at 60 ° C.
  • the reaction is started with the addition of enzyme and the reaction time is stopped.
  • Samples are taken from the reaction mixture at intervals and the content of converted lauric acid is determined by means of titration with potassium hydroxide solution.
  • the enzyme activity in PLU results from the rate at which 1 g of the enzyme under consideration synthesizes 1 pmol propyl laurate per min at 60 ° C., cf.
  • “Homology at the amino acid level” in the context of the present invention is understood to mean the “amino acid identity”, which can be determined with the aid of known methods.
  • special computer programs with algorithms are used, taking special requirements into account. Preferred methods for determining the identity initially produce the greatest correspondence between the sequences to be compared.
  • Computer programs used to determine identity include, but are not limited to, the GCG program package, including
  • BLASTP BLASTN
  • FASTA Altschul, S. et al., Journal of Molecular Biology 215 (1990), pp. 403-410.
  • the BLAST program can be obtained from the National Center For
  • NCBI Biotechnology Information
  • the person skilled in the art is aware that various computer programs are available for calculating the similarity or identity between two nucleotide or amino acid sequences.
  • the percentage identity between two amino acid sequences can be determined by the Needleman and Wunsch (J. Mol. Biol. (48): 444-453 (1970)) algorithm, which is available in the GAP program in the GCG software package ( via http://www.gcg.com) using either a Blossom 62 matrix or a PAM250 matrix, a gap weight of 16, 14, 12, 10, 8, 6, or 4 and one length weight of 1, 2, 3, 4, 5, or 6.
  • Those skilled in the art will recognize that using different parameters will lead to slightly different results, but that the percent identity between two amino acid sequences will not be significantly different overall.
  • the Blossom 62 matrix is usually used with the default settings (gap weight: 12, length weight: 1).
  • An identity of 60% according to the above algorithm means 60% homology in connection with the present invention. The same goes for higher identities.
  • per gram of xylitol to be converted preferably 500 PLU to 2000 PLU, preferably from 200 PLU to 1500 PLU, particularly preferably from 25 PLU to 1250 PLU, lipase are used.
  • process step B) is preferably carried out at a pressure of less than 1 bar, preferably less than 0.5 bar and particularly preferably less than 0.1 bar.
  • process step B) is alternatively preferably carried out in a bubble column reactor, with at least one inert gas flowing through the reaction mixture; this is preferably selected from the group comprising, preferably consisting of, nitrogen and argon.
  • the gas flow is 1 to 60 kg / h, preferably 5 to 25 kg / h, even more preferably 10 to 14 kg / h.
  • process step B) is preferably characterized in that process step B) is ended at the latest 180 hours, preferably 120 hours, particularly preferably 100 hours, after the addition of the lipase.
  • a method preferred according to the invention is characterized in that by-products formed in method step B), for example in the case that the acyl group donor used is an acid, water, in the case that the acyl group donor used is an ester, the corresponding alcohol, are removed.
  • Process step C) of the process according to the invention comprises the purification of the xylitol carboxylic acid ester.
  • the process according to the invention preferably comprises in process step C) separating off the lipase used in the process according to the invention.
  • the lipase is immobilized on a carrier
  • a filter in particular a bag filter
  • the method of the present invention is preferably characterized in that no molecular sieve is used in it.
  • the method of the present invention is preferably characterized in that the substrates are not used in the present immobilized form on solid supports, such as, for example, silica.
  • the present invention also provides the xylitol carboxylic acid ester obtainable by the process according to the invention.
  • Another object of the present invention is the use of the xylitol carboxylic acid esters according to the invention and / or the xylitol carboxylic acid esters obtainable by the process according to the invention as a viscosity regulator, care active ingredient, foam booster or solubilizer, antimicrobial agent, antistatic agent, binder, corrosion inhibitor, dispersant, emulsifier, Film formers, humectants, opacifiers, oral care products, preservatives, skin care products, hydrophilic emollients, foam stabilizers and nonionic surfactants, preferably as viscosity regulators, emulsifiers, antimicrobial agents and hydrophilic emollients, particularly preferably as viscosity regulators, in particular as thickeners, in particular in cleaning or care formulations.
  • Example 1 Enzymatic esterification of xylitol with 2.00 eq.
  • Carylic acid accordinging to the invention
  • a mixture of xylitol (60.0 g, 0.394 mol, 1.00 eq.)
  • Candida antarctica lipase B (5.21 g; Purolite D5619, corresponds to 45110 PLU) was added. The mixture was stirred at 80 ° C. and 15 mbar for 24 h and the water formed was continuously distilled off during this time. The mixture was then filtered through a Buchner funnel with a Schwarzband filter at 80 ° C. in order to remove the enzyme. The product obtained was homogeneous in the melt, colorless and had an acid number of 1.2 mg KOH / g. The content of triesters based on the sum of all the carboxylic acid esters of xylitol contained was 27% by weight, determined from the area percentages of the GC-FID peaks.
  • Example 2 Enzymatic esterification of xylitol with 2.00 eq. Caprylic / capric acid (according to the invention)
  • the mixture was then filtered through a Buchner funnel with a Schwarzband filter at 80 ° C. in order to remove the enzyme.
  • the product obtained was homogeneous in the melt, colorless and had an acid number of 2.7 mg KOH / g.
  • the content of triesters based on the sum of all the carboxylic acid esters of xylitol contained was 26% by weight, determined from the area percentages of the GC-FID peaks.
  • Example 3 Enzymatic esterification of xylitol with 1.80 eq.
  • Candida antarctica lipase B (6.48 g; Purolite D5619, corresponds to 56106 PLU
  • the mixture was stirred at 85 ° C. and 50 mbar for 24 h and the water formed was continuously distilled off during this time.
  • the mixture was then filtered through a Buchner funnel with a Schwarzband filter at 80 ° C. in order to remove the enzyme.
  • the product obtained was homogeneous in the melt, colorless and had an acid number of 1.5 mg KOH / g.
  • the content of triesters based on the sum of all the carboxylic acid esters of xylitol contained was 25% by weight, determined from the area percentages of the GC-FID peaks.
  • Example 4 Enzymatic esterification of xylitol with 2.00 eq.
  • the product obtained was homogeneous, clear, light yellow in the melt and had an acid number of 1.3 mg KOH / g.
  • the content of triesters based on the sum of all the carboxylic acid esters of xylitol contained was 35% by weight, determined from the area percentages of the GC-FID peaks.
  • Example 5 Enzymatic esterification of xylitol with 2.00 eq. Oleic acid (according to the invention)
  • Example 8 Enzymatic esterification of xylitol with 2.00 eq. Caprylic acid at low temperature (not according to the invention)
  • Table 1 compares the parameters determined for the examples according to the invention and those not according to the invention.
  • Example 9 Thickening performance in a cosmetic formulation
  • a cosmetic formulation consisting of 9% SLES, 3% cocamidopropyl betaine and 0.7% NaCl in water was produced. The pH of this formulation was adjusted to 5.2 with citric acid.
  • 1.1% of the above-mentioned example substances were incorporated at 60 ° C. with stirring for 30 min, and the viscosities were measured at 22 ° C. with the aid of a Brookfield viscometer (spindle 62, 30 rpm revolutions). The results of the viscosity measurements are shown in Table 2.
  • Table 2 Viscosity of the example formulation with 1.1% thickener
  • Recipes 1a, 1b and 1c AP / deodorant formulations containing aluminum salts
  • Formulations 2a, 2b and 2c Aluminum-free deodorant formulation without AP active ingredients
  • Formulations 3a, 3b and 3c ON deodorant emulsion containing potassium alum Recipe 4a and 4b: AP / Deodorant Lotion
  • Recipes 5a, 5b and 5c AP / deodorant creams Recipe 6a and 6b: Sun Care Spray SPF 30
  • Formulations 11a, 11b and 11c Sun protection lotion SPF 50, high UVA protection
  • Formulations 17a and 17b O / W Foundation
  • Formulations 18a, 18b, 18c and 18d Lotions with cosmetic active ingredients
  • Formulations 19a, 19b and 19c Lotion with low oil phase content
  • Formulations 21a, 21b and 21c O / W Blemish Balm Lotion
  • Formulations 22a, 22b, 22c and 22d Lotion for sensitive skin
  • Formulations 24a, 24b and 24c Preservative-Free Lotions 1
  • Formulations 24d, 24e and 24f preservative-free lotions 2
  • Formulations 25a and 25b W / O lotion
  • Formulations 29a, 29b and 29c W / O cream based on natural ingredients
  • Formulations 30a, 30b, and 30c Cold Manufacture Lotion
  • Formulations 31a, 31b and 31c Moisturizing lotion with urea
  • Formulations 32a, 32b, 32c and 32d W / O lotion with a silky, light skin feel
  • Formulations 35a and 35b Sun protection lotion SPF 30 UVA with insect repellent
  • Formulations 37a, 37b, 37c and 37d Sun protection spray SPF 30 UVA
  • Formulations 38a, 38b, 38c and 38d Sun protection lotion SPF 50 UVA
  • Recipes 42a, 42b, 42c, 42d and 42e AP / deodorant spray or aerosol spray

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Abstract

L'invention concerne des esters d'acide carboxylique de xylitol et un procédé de préparation enzymatique d'esters d'acide carboxylique de xylitol.
EP20833825.1A 2019-12-20 2020-12-17 Esters d'acide carboxylique de xylitol et procédé de préparation enzymatique de ceux-ci Pending EP4077697A1 (fr)

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EP19218421.6A EP3839052A1 (fr) 2019-12-20 2019-12-20 Procédé de fabrication enzymatique d'esters de sucre et/ou d'esters d'alcool de sucre
PCT/EP2020/086737 WO2021122972A1 (fr) 2019-12-20 2020-12-17 Esters d'acide carboxylique de xylitol et procédé de préparation enzymatique de ceux-ci

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EP19218421.6A Withdrawn EP3839052A1 (fr) 2019-12-20 2019-12-20 Procédé de fabrication enzymatique d'esters de sucre et/ou d'esters d'alcool de sucre
EP20833826.9A Pending EP4077698A1 (fr) 2019-12-20 2020-12-17 Esters de sorbitane et procédé de préparation enzymatique de ceux-ci
EP20833824.4A Pending EP4077696A1 (fr) 2019-12-20 2020-12-17 Procédé de préparation enzymatique d'esters de sucre et/ou d'esters d'alcool de sucre
EP20833825.1A Pending EP4077697A1 (fr) 2019-12-20 2020-12-17 Esters d'acide carboxylique de xylitol et procédé de préparation enzymatique de ceux-ci

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EP20833826.9A Pending EP4077698A1 (fr) 2019-12-20 2020-12-17 Esters de sorbitane et procédé de préparation enzymatique de ceux-ci
EP20833824.4A Pending EP4077696A1 (fr) 2019-12-20 2020-12-17 Procédé de préparation enzymatique d'esters de sucre et/ou d'esters d'alcool de sucre

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BR112023026502A2 (pt) 2021-06-18 2024-03-05 Evonik Operations Gmbh Composição de éster do ácido n-nonanoico de álcool do açúcar anidro, seu método de produção e uso, e formulação

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GB1016885A (en) * 1962-10-16 1966-01-12 Ledoga Spa Xylitol esters
BE623684A (fr) * 1962-10-19
GB1025028A (en) * 1962-12-28 1966-04-06 Ledoga Spa Xylitol esters
JPS58116688A (ja) * 1981-12-28 1983-07-11 Asahi Denka Kogyo Kk 油脂類のエステル基交換反応方法
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WO2007036235A1 (fr) 2005-09-30 2007-04-05 Novozymes A/S Immobilisation d'enzymes
DE102009001748A1 (de) * 2009-03-23 2010-09-30 Evonik Goldschmidt Gmbh Formulierungen enthaltend Sorbitancarbonsäureester
KR101452769B1 (ko) * 2012-09-25 2014-10-21 지준홍 지속성 냉감 효과를 갖는 자일리톨 지방산 에스테르를 유효성분으로 함유하는 화장료 조성물
KR101939851B1 (ko) 2013-10-01 2019-01-17 켐유니온 키미카 엘티디에이 화장품, 약제학 및 수의학 적용분야를 위한 항미생물, 공-유화제 및 증점제 특성을 가지는 자일리틸 에스테르 함유 조성물
KR20150057589A (ko) * 2013-11-20 2015-05-28 지준홍 자일리톨 지방산 에스테르를 유효성분으로 포함하는 방부제 조성물
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KR101823324B1 (ko) * 2016-07-12 2018-03-14 주식회사 일신웰스 당 지방산 에스테르 제조방법

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US20230033620A1 (en) 2023-02-02
EP4077698A1 (fr) 2022-10-26
JP2023507446A (ja) 2023-02-22
WO2021122971A1 (fr) 2021-06-24
JP2023507448A (ja) 2023-02-22
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WO2021122972A1 (fr) 2021-06-24
EP3839052A1 (fr) 2021-06-23
BR112022011457A2 (pt) 2022-08-23
US20230023141A1 (en) 2023-01-26
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BR112022011988A2 (pt) 2022-08-30

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