WO2008030033A1 - Procédé de préparation de solutions supersaturées extrêmement stables de substrats hydrophiles dans des liquides ioniques - Google Patents

Procédé de préparation de solutions supersaturées extrêmement stables de substrats hydrophiles dans des liquides ioniques Download PDF

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Publication number
WO2008030033A1
WO2008030033A1 PCT/KR2007/004274 KR2007004274W WO2008030033A1 WO 2008030033 A1 WO2008030033 A1 WO 2008030033A1 KR 2007004274 W KR2007004274 W KR 2007004274W WO 2008030033 A1 WO2008030033 A1 WO 2008030033A1
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Prior art keywords
solution
hydrophilic substrate
water
supersaturated
ionic liquid
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PCT/KR2007/004274
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English (en)
Inventor
Yoon-Mo Koo
Sang Hyun Lee
Sung Ho Ha
Thanh Dang Dung
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Inha-Industry Partnership Institute
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Publication of WO2008030033A1 publication Critical patent/WO2008030033A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00—Processes for the preparation of sugar derivatives
    • 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

Definitions

  • the present invention relates to a method of preparing a highly stable supersaturated solution of a hydrophilic substrate in an ionic liquid. More particularly, the present invention relates to a method of preparing a supersaturated solution of a hydrophilic substrate, the method being capable of avoiding the problem of sugar solubility in various catalytic reactions .
  • Fatty acid sugar esters based on glucose, sucrose, etc.
  • sugars can be environment-friendly materials because they are cheap, recyclable and biodegradable biomaterials.
  • Most such sugar compounds can be synthesized using chemical or biological catalysts.
  • enzymatic preparation of sugar esters in nonaqueous media has the basic problem of low yield and low productivity due to the very low solubility of sugars in organic solvents .
  • Hydrophilic organic solvents must be used as reaction media in order to dissolve hydrophilic sugars such as glucose, sucrose and fructose.
  • hydrophilic organic solvents must be used as reaction media in order to dissolve hydrophilic sugars such as glucose, sucrose and fructose.
  • hydrophilic organic solvents must be used as reaction media in order to dissolve hydrophilic sugars such as glucose, sucrose and fructose.
  • hydrophilic organic solvents must be used as reaction media in order to dissolve hydrophilic sugars such as glucose, sucrose and fructose.
  • hydrophilic organic solvents must be used
  • hydrophilic substrates can be overcome using the following two methods.
  • an organic solvent that is less harmful to enzymes, such as acetonitrile, acetone, tert-butanol and 2-methyl-2-butanol
  • the other is based on the use of a room-temperature ionic liquid as a solvent for dissolving sugars.
  • ionic liquids are salts or salt compounds whose melting point is relatively low
  • salts that are liquid at room temperature are called room-temperature ionic liquids, and such ionic liquids are organic salts that consist of organic cations and anions.
  • the cations include dialkyl imidazolium, alkylpyridinium, quaternary ammonium and quaternary phosphonium.
  • the anions include NO 3 " , AlCl 4 " , Al 2 Cl 7 “ , AcO " , BF 4 (tetrafluoroborate) , PF 6 " (hexafluoromethane sulfonyl amide) , TFO “ (trifluoromethane sulfonate, CF 3 SOa “ ) i TF 2 N “ (trifluoromethane sulfonyl amide, (CF 3 SO 2 ) 2 N), CH 3 CH(OH)CO 2 " (L-lactate) , and SbF 6 " (hexafluoroantimonate) .
  • RTILs Room-temperature ionic liquids
  • RTILs Room-temperature ionic liquids
  • ionic liquids are non-volatile, nontoxic and non-inflammable, and have excellent thermal stability and ionic conductivity.
  • RTILs are also able to dissolve inorganic and organic metal compounds due to their high polarity, and exist in a liquid state over a wide temperature range. Due to their unique properties, RTILs have been suggested as potential green solvents.
  • ionic liquids such as melting point, viscosity, density, hydrophobicity and polarity, can be controlled by modifying the moieties of cations and anions constituting ionic liquids, ionic liquids suitable for desired purposes can be readily synthesized. Thus, ionic liquids are usually called "designer solvents".
  • Ionic liquids have been recently reported to have good potential as substitution reaction solvents for biocatalysts and in vivo changes. Ionic liquids have been also shown to enhance the reactivity, selectivity and stability of enzymes (Park et al. , Curr. Cpin. Biotechnol., 14, 432-437, 2003, Kragl et al., Curr. Opin. Biotechnol., 13, 565-571, 2002). In particular, ionic liquids containing dicyanamide (dca) as the anion have been reported to be good solvents for sugar dissolution and enzymatic reaction (Liu et al., Green Chem. , 7, 39-42, 2005).
  • the present invention provides a method of preparing a stable supersaturated solution of a hydrophilic substrate in an ionic liquid comprising the steps of (a) adding the hydrophilic substrate including carbohydrates to the ionic liquid to prepare a carbohydrate solution; (b) heating the carbohydrate solution to dissolve carbohydrate molecules that were not dissolved at step (a) ; and
  • step (c) slowly cooling the solution of step (b) to room temperature to obtain the supersaturated solution.
  • the present invention provides a method of preparing a stable supersaturated solution of a hydrophilic substrate in an ionic liquid comprising the steps of (a) dissolving an excessive amount of the hydrophilic substrate including carbohydrates in water to prepare a carbohydrate aqueous solution; (b) mixing the carbohydrate aqueous solution with the ionic liquid; and (c) removing water molecules contained in the mixture obtained at step (b) to obtain the supersaturated solution.
  • the supersaturated solutions of sugars which are prepared through an indirect water- mediated method using an ionic liquid, are stable and have constant sugar content one day later even though the solutions contain excess sugar molecules.
  • the supersaturated solutions of sugars are considered to overcome the problem of sugar solubility in various catalytic reactions.
  • FIG. 1 is a graph showing the glucose stability in a supersaturated solution prepared using a water-mediated method according to one embodiment of the present invention.
  • the term "supersaturated solution” refers to a solution in which a solute is dissolved in an amount greater than the solubility at a given temperature.
  • a supersaturated solution is conventionally prepared by slowly cooling a solution that has reached its solubility limit, or by slowing evaporating the solvent.
  • the introduction of a material enabling the crystallization or nucleation of solute molecules into the solution or gentle stirring results in the precipitation of the dissolved material as a solid, leading to a saturated state of the solution.
  • hydrophilic substrate includes carbohydrates, peptides, nucleic acids and water-soluble vitamins, and refers to a material that dissolves poorly in common organic solvents but dissolves well in water. Hydrophilic substrates are particularly exemplified by monosaccharides and a disaccharide, such as glucose, sucrose and fructose. Glucose is preferred.
  • the term "ionic liquid” refers to a salt or a salt compound that melts below 100 ° C, and particularly indicates a diimidazolium compound, which is exemplified by l-ethyl-3- methylimidazolium methylsulfate ( [Emim] [MS] ) , l-ethyl-3- methylimidazolium trifluoromethanesulfonate ( [Emim] [TfO] ) , 1-butyl- 3-methylimidazolium trifluoromethanesulfonate ( [Bmim] [TfO] ) , 1- ethyl-3-methylimidazolium tetrafluoroborate ( [Emim] [BF 4 ] ) , 1-butyl- 3-methylimidazolium tetrafluoroborate ( [Bmim] [BF 4 ] ) , l-methyl-3- octylimida
  • the present invention provides a direct method of preparing a stable supersaturated solution of a hydrophilic substrate in an ionic liquid.
  • the direct method comprises the steps of (a) adding the hydrophilic substrate, including carbohydrates, to the ionic liquid to prepare a carbohydrate solution; (b) heating the carbohydrate solution to dissolve carbohydrate molecules that were not dissolved at step (a) ; and (c) slowly cooling the solution of step (b) to room temperature to obtain the supersaturated solution.
  • the heating is preferably carried out between
  • the slow cooling is preferably carried out at a speed of 1°C to 10 ° C per minute in order to minimize the precipitation of the carbohydrate solute.
  • the present invention provides a indirect water-mediated method of preparing a very stable supersaturated solution of a hydrophilic substrate in an ionic liquid.
  • the indirect water-mediated method comprises the steps of (a) dissolving an excessive amount of the hydrophilic substrate including carbohydrates in water to prepare a carbohydrate aqueous solution; (b) mixing the carbohydrate aqueous solution with the ionic liquid; and (c) removing water molecules contained in the mixture obtained at step (b) to obtain the supersaturated solution.
  • a supersaturated solution of glucose in an ionic liquid is preferably prepared using the water-mediated indirect method, which includes dissolving excess glucose in water and then mixing the resulting solution with an ionic liquid.
  • the indirect water-mediated method involves preparing a supersaturated solution by dissolving an excess sugar in water using the high water solubility of sugars, mixing the resulting solution with an ionic liquid, and removing water contained in the mixture through distillation under reduced pressure.
  • the amount of water contained in the supersaturated solution obtained at step (c) is preferably less than 0.1%. In this case, the supersaturated glucose solution is very stable because glucose is not crystallized even when it exists in an excessive amount in the solution.
  • Glucose (50 mg) and sucrose (50 mg) were individually added to a glass vial containing 1 ml of an ionic liquid. Each suspension was stirred at 60 ° C for 12 hrs. The supersaturated solution containing excess sugar was slowly cooled to 25 ° C and allowed to stand at 25 ° C for 2 hrs. After the solution was centrifuged, the clear supernatant was recovered and diluted in deionized water. Then, the sugar content was determined using a dinitrosalicylic acid (DNS) method. When the interference of the ionic liquid was investigated during the analysis process, the ionic liquid was observed not to affect the analysis using the DNS method in the measured concentration range (0.1 g/L to 1.0 g/L) .
  • DNS dinitrosalicylic acid
  • Glucose (50 mg) and sucrose (50 mg) were individually dissolved in water (0.3 ml) and then mixed with 1 ml of an ionic liquid. Water contained in the mixture was removed through distillation under reduced pressure at 60 ° C for 12 hrs. The amount of water was increased in order to increase the glucose content. The concentration of glucose in the aqueous solution was maintained at 167 g/L. The content of water remaining in the mixture was calculated based on the weight difference before and after evaporation. The residual water content in ionic liquid was less than 0.1% and confirmed through Karl-Fischer titration. The supersaturated sugar solution was slowly cooled to 25°C and allowed to stand at 25 ° C for 2 hrs. After the solution was centrifuged, the clear supernatant was recovered and diluted in deionized water. Then, the sugar content was determined using a DNS method.
  • the amount of sugars dissolved in the supersaturated solutions, prepared in Examples 1 and 2 was measured as follows.
  • the glucose concentration was determined through a DNS method using a glucose standard.
  • the sucrose concentration was measured through a DNS method using a sucrose standard after sucrose was hydrolyzed with HCL.
  • the solubility of sugars in ionic liquids was measured as follows . Glucose (50 mg) and sucrose (50 mg) were individually added to a glass vial containing 1 ml of an ionic liquid. Each suspension was stirred for 24 hrs at 25 ° C and 60 ° C. After the solution was centrifuged, the clear supernatant was recovered and diluted in deionized water. Then, the sugar content was determined using a DNS method.
  • the solubility of D- (+) -glucose in water-miscible ionic liquids at 25 ° C and 60 ° C and the glucose concentrations of the supersaturated solutions prepared in Examples 1 and 2 are given in Table 1, below.
  • an ionic liquid contained an [Emim] cation the glucose solubility was greatly affected by the structure of an anion of the ionic liquid.
  • the solubility of glucose in ionic liquids containing [TfO] and [BF 4 ] was greatly affected by temperature.
  • the solubility of glucose in these ionic liquids increased with increasing temperature from 25 ° C to 60°C.
  • ionic liquid [Bmim] [TfO] has been reported to be a good reaction medium for lipase-catalyzed reactions
  • ionic liquids containing a [TfO] anion are useful in enzymatic reactions using hydrophilic substrates such as sugars.
  • sucrose in ionic liquids at 25°C and 60°C and the sucrose concentrations of the supersaturated solutions prepared in Examples 1 and 2 are given in Table 2, below.
  • the solubility of sucrose in ionic liquids was much lower than that of glucose.
  • the solubility of sucrose in ionic liquids containing a [TfO] anion increased with increasing temperature.
  • sucrose in [Emim] [MS] was incubated at 60 ° C for 12 hrs, the solution turned into a viscous brown liquid, but no sugar crystals were observed.
  • the supersaturated sucrose solution prepared using the indirect water-mediated method was stable, whereas a supersaturated sucrose solution prepared using the direct method was unstable and thus easily crystallized.
  • the supersaturated solutions of sucrose in all tested ionic liquids showed about 5 times higher sucrose than the solubility of at 25 ° C.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Biotechnology (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Molecular Biology (AREA)
  • Saccharide Compounds (AREA)
  • Medicinal Preparation (AREA)

Abstract

L'invention a pour objet un procédé de préparation d'une solution supersaturée extrêmement stable d'un substrat hydrophile dans un liquide ionique. Lorsqu'on prépare une solution de sucres supersaturée en utilisant un procédé employant indirectement de l'eau et un liquide ionique, la solution est stable, bien qu'elle contienne un excès de molécules de sucre, et on ne peut guère modifier sa teneur en sucres un jour après. De ce fait, on peut envisager que ce procédé permet de surmonter le problème de la solubilité de sucres dans diverses réactions catalytiques impliquant des sucres en tant que substrat.
PCT/KR2007/004274 2006-09-06 2007-09-05 Procédé de préparation de solutions supersaturées extrêmement stables de substrats hydrophiles dans des liquides ioniques WO2008030033A1 (fr)

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KR1020060085769A KR100791848B1 (ko) 2006-09-06 2006-09-06 이온성 액체에서 매우 안정한 친수성 물질의 과포화용액제조 방법
KR10-2006-0085769 2006-09-06

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9172274B2 (en) 2011-06-16 2015-10-27 General Electric Company System, method, and apparatus for operating a power distribution system

Citations (2)

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Publication number Priority date Publication date Assignee Title
US6020367A (en) * 1997-12-02 2000-02-01 Avon Products, Inc. Supersaturated ascorbic acid solutions
EP1466894A1 (fr) * 2003-04-09 2004-10-13 Reis de Aguiar Navarro y Rosa, Joao Miguel Sels de tétraalkyle-diméthylguanidinium et leur utilisation comme liquides ioniques

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US4853457A (en) * 1987-10-26 1989-08-01 General Electric Company Preparation of spirobiindane polyarylates, and spirobiindane polyarylate-polyethylene terephthalate copolymers, via melt polymerization

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6020367A (en) * 1997-12-02 2000-02-01 Avon Products, Inc. Supersaturated ascorbic acid solutions
EP1466894A1 (fr) * 2003-04-09 2004-10-13 Reis de Aguiar Navarro y Rosa, Joao Miguel Sels de tétraalkyle-diméthylguanidinium et leur utilisation comme liquides ioniques

Non-Patent Citations (2)

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Title
KRAGL ET AL.: "Enzyme catalysis in ionic liquids", CURR. OP. IN BIOTECHNOLOGY, vol. 13, 2002, pages 565 - 571, XP002267363, DOI: doi:10.1016/S0958-1669(02)00353-1 *
LIU ET AL.: "Room-temperature ionic liquids that dissolve carbohydrates in hgh concentrations", GREEN CHEM., vol. 7, 2005, pages 39 - 42 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9172274B2 (en) 2011-06-16 2015-10-27 General Electric Company System, method, and apparatus for operating a power distribution system

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