WO2013008172A1 - Zwitterionic liquid as co-catalyst for the enzymatic esterification - Google Patents

Zwitterionic liquid as co-catalyst for the enzymatic esterification Download PDF

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Publication number
WO2013008172A1
WO2013008172A1 PCT/IB2012/053503 IB2012053503W WO2013008172A1 WO 2013008172 A1 WO2013008172 A1 WO 2013008172A1 IB 2012053503 W IB2012053503 W IB 2012053503W WO 2013008172 A1 WO2013008172 A1 WO 2013008172A1
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Prior art keywords
ionic liquid
zwitterion
enzyme
carbon atoms
solvent
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PCT/IB2012/053503
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French (fr)
Inventor
Roger Marti
Ennio Vanoli
Sandrine AEBY
Fabian FISCHER
Manuel HAPPE
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Ecole D'ingenieurs Et D'architectes De Fribourg
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Publication of WO2013008172A1 publication Critical patent/WO2013008172A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
    • 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
    • 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
    • C12N9/96—Stabilising an enzyme by forming an adduct or a composition; Forming enzyme conjugates
    • 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
    • C12P7/6436—Fatty acid esters
    • 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

  • This invention relates to novel zwitterion ionic liquids (zIL) and their production. This invention also relates to the use of zwitterion ionic liquids as co-catalyst for enzymatic esterification reactions.
  • the present invention is directed to use this type of zwitterionic liquid to optimize the catalytic effect of the enzyme that means conversion rate, selectivity and overall yield.
  • Example of the invention use is the production of bio lubricant from oleic acid and glycerol derivatives.
  • Document WO2007012825A1 discloses a process for producing an olefin and/or an ether, which comprises heating an alcohol in the presence of an acidic ionic compound which exists in a liquid state at a temperature of below 150°C.
  • Document WO2010066330A2 disclose an enzyme-catalyzed method in the presence of at least one ionic liquid as solvent, to a composition containing at least one ionic liquid and at least one enzyme.
  • Document CN101376818A discloses a method for preparing diesel oil through cavitation effect cooperated with ionic liquid activating.
  • Document CN101451072A discloses a method for preparing biodiesel through catalysis of sulfonic acid-type ionic liquid.
  • the first object of the present invention is to provide a novel zwitterionic ionic liquid according to the general formula (I)
  • R1 represents a hydrogen atom, an alkyl chain having 1 to 16 carbon atoms, or a perfluoroalkyl chain having 4 to 12 carbon atoms,
  • R2 represents a methyl or a benzyl group
  • n an integer of 3 to 4.
  • Another object of the present invention is to provide a process for the preparation of the zwitterionic ionic liquid described above comprising the following steps:
  • Another object of the present invention is the use of the zwitterion ionic liquid as defined above as a co-catalyst for an enzymatic esterification reaction.
  • Another object of the present invention is to provide a zwitterion ionic liquid- coated enzyme, wherein the zwitterionic ionic liquid is represented by the following formula (I)
  • R1 represents a hydrogen atom, an alkyl chain having 1 to 16 carbon atoms, or a perfluoroalkyl chain having 4 to 12 carbon atoms
  • R2 represents a hydrogen atom, a methyl or a benzyl group
  • n represents an integer of 3 to 4
  • the enzyme is a lipase
  • Another of the present invention is the process for preparation of the zwitterion ionic liquid-coated enzyme according to the invention comprising the following steps:
  • step (ii) mixing the solution of step (i) with the enzyme for coating the enzyme; (iii) adding a volume of a solvent and shacking the suspension at room temperature;
  • Another object of the present invention is the use of the zwitterion ionic coated enzyme as defined above in an enzymatic esterification reaction.
  • the present invention relates to the synthesis of ionic liquids and their applications: the coating of the enzyme used for the biotransformation that improves enzyme functions.
  • the synthesis of the zwitterion ionic liquids is a one-step reaction.
  • imidazolium salts are used with a long alkyl chain as the principal compound.
  • Their properties are close to the desired reaction conditions which are a melting point below 70°C and hydrophobic structure.
  • the chemical structure (I) of zIL's is shown below:
  • R1 represents a hydrogen atom or an alkyl group having 1 to 16 carbon atoms
  • R2 represents a methyl or a benzyl rest
  • n is a chain with 3 or 4 CH 2 - groups.
  • Each ionic liquid is characterized by its polarity (Nile Red method), melting point, NMR, IR, and hydrophobicity.
  • a stock solutions of ionic liquid 100 mg/mL and 10 mg/mL in acetonitrile were prepared.
  • 50 U ( ⁇ 30 mg) lipase from Candida antarctica was placed 50 U ( ⁇ 30 mg) lipase from Candida antarctica.
  • the lipase was coated 50 % w/w by the enzyme weight.
  • the volume of the needed stock solution was calculated by the needed mass of ionic liquid.
  • the ester was formed as verified by H-NMR, conversions and selectivity shown in

Abstract

The present invention concerns a zwitterion ionic liquid-coated enzyme, wherein the ionic liquid is an organic salt. The zwitterion ionic liquid improves the enzyme functions, such as the yield, selectivity and the conversion rate. The coated enzyme is used for the synthesis of the natural lubricant (biodiesel).

Description

Zwitterionic liquid as co-catalyst for the enzymatic esterification
Cross-reference to related application
The present application claims the benefit of the priority of European patent application Number 11173686.4, filed on July 12, 2011 in the name of Ecole d'ingenieurs et d'architectes de Fribourg, the entire disclosure of which is incorporated herein by reference.
Field of invention
This invention relates to novel zwitterion ionic liquids (zIL) and their production. This invention also relates to the use of zwitterion ionic liquids as co-catalyst for enzymatic esterification reactions.
More particularly, the present invention is directed to use this type of zwitterionic liquid to optimize the catalytic effect of the enzyme that means conversion rate, selectivity and overall yield.
Example of the invention use is the production of bio lubricant from oleic acid and glycerol derivatives.
State of the art
The catalysis by ionic liquid for bioesterification is already known. However, the zIL which are described in the invention, provide a much better influence on enzyme activity if we compare the reaction yield, reaction time, and selectivity. There are already a number of patents about ionic liquids used in bioesterification. The zwitterion ionic liquids are known in literature, but not for the applications mentioned in this application.
Document US2004087462A1 discloses an ionic liquid-coated enzyme, which presents as a liquid phase at a temperature of about 150°C or below. This ionic liquid-coated enzyme improves enzyme functions.
Document WO2007012825A1 discloses a process for producing an olefin and/or an ether, which comprises heating an alcohol in the presence of an acidic ionic compound which exists in a liquid state at a temperature of below 150°C. Document WO2010066330A2 disclose an enzyme-catalyzed method in the presence of at least one ionic liquid as solvent, to a composition containing at least one ionic liquid and at least one enzyme.
Document CN101376818A discloses a method for preparing diesel oil through cavitation effect cooperated with ionic liquid activating.
Document CN101451072A discloses a method for preparing biodiesel through catalysis of sulfonic acid-type ionic liquid.
Document WO 2010013822A discloses a nanoparticle/dispersant complex, nanoparticle dispersion liquid, and nanoparticle matrix-material complex.
Some publications discuss about zwitterionic liquids:
- Langmuir 2010, 26 (20), 15754-15760, 'Synthesis of a new zwitterionic surfactant containing an imidazolium ring. Evaluating the chameleon-like behavior of zwitterionic micelles'
- Journal of Materials Chemistry 2006, 16, 1475-1482, 'Structural factors to improve physic-chemical properties of zwitterions as ion conductive matrices'
- Beilstein Journal of Organic Chemistry 2010, 6, No 31 , 'Comparison of zwitterionic N-alkylaminomethanesulfonic acids related compounds in the good buffer series' General description of the invention
We have found that the use of a zwitterion ionic liquid unexpectedly improves the activity of an enzyme catalysing a bioesterification reaction.
The first object of the present invention is to provide a novel zwitterionic ionic liquid according to the general formula (I)
Figure imgf000003_0001
(I)
wherein R1 represents a hydrogen atom, an alkyl chain having 1 to 16 carbon atoms, or a perfluoroalkyl chain having 4 to 12 carbon atoms,
R2 represents a methyl or a benzyl group,
n represents an integer of 3 to 4.
Another object of the present invention is to provide a process for the preparation of the zwitterionic ionic liquid described above comprising the following steps:
(i) Reacting a substituted imidazole derivative (R1 = hydrogen atom, an alkyl chain having 1 to 16 carbon atoms, or a perfluoroalkyl chain having 4 to 12 carbon atoms, R2 = methyl or a benzyl group) with propanesultone or butanesultone in toluene as solvent
(ii) Purification by dissolution in polar solvents like acetone or ethanol and precipitation with non-polar solvents like heptane or cyclohexane. Purification by re-crystallization from acetonitrile or toluene.
Another object of the present invention is the use of the zwitterion ionic liquid as defined above as a co-catalyst for an enzymatic esterification reaction.
Another object of the present invention is to provide a zwitterion ionic liquid- coated enzyme, wherein the zwitterionic ionic liquid is represented by the following formula (I)
Figure imgf000004_0001
(I)
wherein
R1 represents a hydrogen atom, an alkyl chain having 1 to 16 carbon atoms, or a perfluoroalkyl chain having 4 to 12 carbon atoms, R2 represents a hydrogen atom, a methyl or a benzyl group, n represents an integer of 3 to 4, and
wherein the enzyme is a lipase.
Another of the present invention is the process for preparation of the zwitterion ionic liquid-coated enzyme according to the invention comprising the following steps:
(i) preparing a solution of the zwitterion ionic liquid by dissolving the zwitterion ionic liquid in a solvent;
(ii) mixing the solution of step (i) with the enzyme for coating the enzyme; (iii) adding a volume of a solvent and shacking the suspension at room temperature;
(iv) removing the solvent in order to obtain the zwitterion ionic liquid- coated enzyme.
Another object of the present invention is the use of the zwitterion ionic coated enzyme as defined above in an enzymatic esterification reaction.
Detailed description of the invention
The invention is discussed below in a more detailed way with examples :
The present invention relates to the synthesis of ionic liquids and their applications: the coating of the enzyme used for the biotransformation that improves enzyme functions.
The synthesis of the zwitterion ionic liquids is a one-step reaction. Usually the imidazolium salts are used with a long alkyl chain as the principal compound. Their properties are close to the desired reaction conditions which are a melting point below 70°C and hydrophobic structure. The chemical structure (I) of zIL's is shown below:
Figure imgf000006_0001
(I)
wherein R1 represents a hydrogen atom or an alkyl group having 1 to 16 carbon atoms, R2 represents a methyl or a benzyl rest, n is a chain with 3 or 4 CH2- groups.
Each ionic liquid is characterized by its polarity (Nile Red method), melting point, NMR, IR, and hydrophobicity.
Ex is of a 1-butyl-2-methyl-3(propyl-3-sulfonyl) imidazolium
Figure imgf000006_0002
Chemical Formula: C8H14N2 Chemical Formula: C-1 -1 H20 2O3S
Molecular Weight: 138.21 Molecular Weight: 260.35
1-Butyl-2-methylimidazol (710 mg, 0.9 mmol, 1 equivalent) was dissolved in 10 ml toluene and propanesultone (610 mg, 0.9 mmol, 1 equivalent) was added. The clear solution was heated at reflux temperature for 3h at which time a some withe precipitate was formed. The reaction mixture was cooled to room temperature and the white suspension was then filtered and washed with 5 ml toluene. The white solid was dried under high vacuum at 60°C for 4 h, yielding the desired product (89 mg, 38% yield). H NMR analysis confirms the structure and a purity of >98 %. Melting point by DSC: 160 °C. The application for the zwitterion ionic liquid is the coating of the enzyme for the bioesterification, as shown in example 2. Example 2: Esterification reaction with zIL-coated enzyme as shown below
Figure imgf000007_0001
Synthesis of 1-octyl-3(propyl-3-sulfonyl) imidazolium
1 equivalent of 1 -octyl-imidazole was reacted with 1 equivalent of propanesultone at reflux temperature in 10% toluene as solvent. After 10 hours, the mixture was cooled down at room temperature and then filtrated. The cake was washed with 3 portions of toluene before drying under high vacuum at 60°C. The reaction is resumed below:
Figure imgf000007_0002
Coating of free enzymes with ionic liquid:
For the coating a stock solutions of ionic liquid 100 mg/mL and 10 mg/mL in acetonitrile were prepared. In a sealed vial with a volume of 5 imL was placed 50 U (~ 30 mg) lipase from Candida antarctica. The lipase was coated 50 % w/w by the enzyme weight. The volume of the needed stock solution was calculated by the needed mass of ionic liquid.
To the enzyme and ionic liquid 500 uL acetonitrile was added and the suspension was shacked 20 min at room-temperature and acetonitrile was removed under vacuum oven 50 mbar and room-temperature. Finally the coated lipase was stored at 0 mbar and room-temperature for one night.
Synthesis of trimethylolpropanesters with ionic liquid coated lipase:
In a sealed glass of 5 ml_ 2 mmol (0.2682 g) trimethylolpropan (TMP); 2 mmol (0.5649 g) oleic acid, 50 U coated lipase from Candida antartica and 100 mg molecular sieve 0.3 nm dry were added. The vial was placed for the reaction in a hybridization oven at 70°C for 3 days. For the purification the reaction mixtures were dissolved in acetone and filtered through a G3-filter. The acetone was removed in an evaporation unit at 60°C under nitrogen gas flow. The pale yellow oil was analyzed by 1 H-NMR (400 MHz) in THF-d8 for oleic acid and TMP conversion, and mono-, di- and triester selectivity.
Results
The ester was formed as verified by H-NMR, conversions and selectivity shown in
Table 1.
Table 1 Conversions of oleic acid and TMP with selectivity from the reaction mixture 1/1 oleic acid/TMP
Figure imgf000008_0001

Claims

Claims
1. A zwitterion ionic liquid according to the general formula (I)
Figure imgf000009_0001
(l)
wherein
R1 represents a hydrogen atom, an alkyl chain having 1 to 16 carbon atoms, or a perfluoroalkyl chain having 4 to 12 carbon atoms,
R2 represents a methyl or a benzyl group,
n represents an integer of 3 to 4.
2. A process for preparation of the zwitterionic ionic liquid according to claim 1 comprising the following steps:
(i) Reacting a substituted imidazole derivative (R1 = hydrogen atom, an alkyl chain having 1 to 16 carbon atoms, or a perfluoroalkyl chain having 4 to 12 carbon atoms, R2 = methyl or a benzyl group) with propanesultone or butanesultone in toluene as solvent.
(ii) Purification by dissolution in polar solvents like acetone or ethanol and precipitation with non-polar solvents like heptanes or cyclohexane.
Purification by re-crystallization from acetonitrile or toluene.
3. Use of the zwitterion ionic liquid according to claim 1 as a co-catalyst for an enzymatic esterification reaction.
4. Use according to claim 3, wherein the zwitterionic ionic liquid coats the enzyme. A zwitterion ionic liquid-coated enzyme, wherein the zwitterionic ionic liquid is represented by the following formula (I)
Figure imgf000010_0001
(I)
wherein
R1 represents a hydrogen atom, an alkyl chain having 1 to 16 carbon atoms, or a perfluoroalkyl chain having 4 to 12 carbon atoms,
R2 represents a hydrogen atom, a methyl or a benzyl group,
n represents an integer of 3 to 4, and
wherein the enzyme is a lipase.
A process for preparation of the zwitterion ionic liquid-coated enzyme according to claim 5 comprising the following steps:
(i) preparing a solution of the zwitterion ionic liquid by dissolving the zwitterion ionic liquid in a solvent;
(ii) mixing the solution of step (i) with the enzyme for coating the enzyme;
(iii) adding a volume of a solvent and shacking the suspension at room temperature;
(iv) removing the solvent in order to obtain the zwitterion ionic liquid- coated enzyme.
Use of the zwitterion ionic liquid-coated enzyme according to claim 5 in an enzymatic esterification reaction.
PCT/IB2012/053503 2011-07-12 2012-07-09 Zwitterionic liquid as co-catalyst for the enzymatic esterification WO2013008172A1 (en)

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EP11173686 2011-07-12

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103254070A (en) * 2013-02-03 2013-08-21 青岛科技大学 Method for preparing 2-(4-isobutylphenyl)propionate from 1-(4-isobutylphenyl)ethanol
JP2018191623A (en) * 2017-05-22 2018-12-06 国立大学法人金沢大学 Zwitterion, and additive for culture medium containing zwitterion and poorly-soluble material dissolving agent
CN110860311A (en) * 2018-08-27 2020-03-06 东北林业大学 Sulfonated cellulose-based ionic liquid catalyst and preparation method thereof
CN110878018A (en) * 2019-11-19 2020-03-13 陕西科技大学 Method for preparing nipagin ester
WO2023189293A1 (en) * 2022-03-31 2023-10-05 Ｅｎｅｏｓ株式会社 Base oil for lubricating oil, lubricating oil and working fluid

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103254070A (en) * 2013-02-03 2013-08-21 青岛科技大学 Method for preparing 2-(4-isobutylphenyl)propionate from 1-(4-isobutylphenyl)ethanol
JP2018191623A (en) * 2017-05-22 2018-12-06 国立大学法人金沢大学 Zwitterion, and additive for culture medium containing zwitterion and poorly-soluble material dissolving agent
JP7233669B2 (en) 2017-05-22 2023-03-07 国立大学法人金沢大学 Poorly soluble substance solubilizer containing zwitterion
CN110860311A (en) * 2018-08-27 2020-03-06 东北林业大学 Sulfonated cellulose-based ionic liquid catalyst and preparation method thereof
CN110878018A (en) * 2019-11-19 2020-03-13 陕西科技大学 Method for preparing nipagin ester
WO2023189293A1 (en) * 2022-03-31 2023-10-05 Ｅｎｅｏｓ株式会社 Base oil for lubricating oil, lubricating oil and working fluid

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