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WO2023043325A1 - Clivage lipidique en phase solide, et produits obtenus à partir de celui-ci - Google Patents

Clivage lipidique en phase solide, et produits obtenus à partir de celui-ci Download PDF

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Publication number
WO2023043325A1
WO2023043325A1 PCT/NZ2022/050123 NZ2022050123W WO2023043325A1 WO 2023043325 A1 WO2023043325 A1 WO 2023043325A1 NZ 2022050123 W NZ2022050123 W NZ 2022050123W WO 2023043325 A1 WO2023043325 A1 WO 2023043325A1
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Prior art keywords
solid phase
solution
phase material
ester
fatty acid
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English (en)
Inventor
Luke Valentine Schneider
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Natural Extraction Technologies Ltd
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Natural Extraction Technologies Ltd
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/04—Processes using organic exchangers
    • B01J41/05—Processes using organic exchangers in the strongly basic form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/04—Processes using organic exchangers
    • B01J41/07—Processes using organic exchangers in the weakly basic form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/20—Anion exchangers for chromatographic processes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
    • C11C1/02—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids from fats or fatty oils
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
    • C11C1/02—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids from fats or fatty oils
    • C11C1/025—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids from fats or fatty oils by saponification and release of fatty acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
    • C11C1/02—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids from fats or fatty oils
    • C11C1/04—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids from fats or fatty oils by hydrolysis
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
    • C11C1/08—Refining

Definitions

  • the present invention relates to methods for cleaving (e.g. saponifying and/or hydrolysing) a lipid ester so as to form a fatty acid (or salt thereof).
  • the present invention also relates to products (such as fatty acids and esters thereof; and alcohols derived from the lipid ester) produced by the method of the invention.
  • Lipids may be formed by plants and animals to create membranes and to chemically store energy reserves.
  • a lipid may be created by the esterification of a fatty acid carboxylic acid with an alcohol (such as a polyol, such as glycerol or a glycerol derivative), and hence may be referred to as a lipid ester.
  • Energy storage in the form of lipids is generally associated with the formation of triglycerides, which phase separate more effectively from the aqueous phase than those lipids that contain a water-soluble head group such as phosphoglycerides, the latter lipids being more often associated with biological membrane (lipid bilayer) formation.
  • the esterification reaction is only slightly endergonic.
  • Phase separation of the resulting lipid esters from the aqueous cellular environment drives the equilibrium towards lipid formation.
  • the equilibrium constant (K eq ) is directly related to the Gibb's free energy of the reaction ( lG r ) .
  • Vi stoichiometric coefficient associated with that component in the reaction.
  • T absolute reaction temperature
  • the alternative to drive this reaction is to selectively remove either the alcohol or the fatty acid from the reaction mixture as it is formed.
  • caustic sodium hydroxide
  • the rate of this reaction increases with temperature [Vidal et al. (2018)]. Whale oil was once produced by boiling whale blubber (mostly triglyceride lipids), skimming the resulting fatty acid oils produced by the hydrolysis reaction from the surface of the pot as they accumulated [Tower (1881)].
  • ester cleavage will typically occur under equilibrium conditions via nucleophilic substitution.
  • the basic salt is a hydroxide
  • the cleavage will generate a carboxylate anion.
  • the product may stay in the same phase, or may phase separate. The equilibrium may shift to favour the products, depending on whether phase separation occurs or not.
  • the pH of the aqueous solution determines the concentration of protons and hydroxyl ions and the resulting rate of the reaction [Murthy et al. (2012) and Yates and McClelland (1967)] at any given temperature. Independent of the catalysis mechanism, the reaction rate also increases with temperature [Vidal (2018)].
  • fatty acids While the cleavage rate at any pH increases with temperature, many fatty acids are not thermally stable and degrade at higher temperatures.
  • polyunsaturated fatty acids such as omega-3 and omega-6 fatty acids and lipid-soluble materials such as antho- and zeo-xanthins spontaneously decompose at temperatures above 45 °C.
  • omega-3 and omega-6 fatty acids and lipid-soluble materials such as antho- and zeo-xanthins spontaneously decompose at temperatures above 45 °C.
  • lipid-soluble materials such as antho- and zeo-xanthins spontaneously decompose at temperatures above 45 °C.
  • the analysis of the fatty acid composition of lipids requires that they be cleaved.
  • disease states e.g., Gaucher disease, Tay-Sachs disease, and Tangier's Disease
  • the fatty acid compositions of membrane lipids also change with growth temperature of coldblooded organisms [Marr and Ingraham (1962)], allowing the monitoring of the growth conditions under which the organism was produced, or localization of its point of harvest.
  • composition of the head groups of membrane glycerides can vary both by organism [Steger et al (2003)] and growth condition of that organism [Hood et al. (1986)] and once shed of the complexity presented by variable fatty acid compositions as lipids can be used for diagnostic purposes.
  • a lipid ester so as to form a fatty acid (or salt thereof) that substantially avoids one or more of the drawbacks of traditional cleavage techniques, including thermal degradation of one or more of the resultant fatty acids.
  • a second object of the invention is to drive the reaction by chelation of the fatty carboxylate. For example, by forming a contact ion pair with an anion exchange resin. Alternatively to release a cation from a cation exchange resin that will cause the fatty acid cation salt to precipitate or phase separate from the lipid soluble phase to a lipid insoluble phase.
  • a third object of the invention is to separate the glycerol from the free fatty acid by the selective chelation of the fatty acid to a resin by displacement chromatography.
  • the invention provides a method of cleaving a lipid ester so as to form a fatty acid (or salt thereof), the method comprising the steps of: i) dissolving a lipid ester in a solvent (such as an aprotic solvent) so as to form a solution;
  • lipid ester in the presence of water, contacting the solution with a functionalized solid phase material so that the lipid ester is cleaved so as to form a fatty acid or derivative thereof (such as an ester or contact ion pair) bound to the functionalized solid phase material and an alcohol derived from the lipid ester; ill) separating at least a portion of the solution from the fatty acid or derivative thereof (such as an ester or contact ion pair) bound to the functionalized solid phase material; and iv) displacing the fatty acid or derivative thereof from the functionalized solid phase material.
  • a functionalized solid phase material so that the lipid ester is cleaved so as to form a fatty acid or derivative thereof (such as an ester or contact ion pair) bound to the functionalized solid phase material and an alcohol derived from the lipid ester; ill) separating at least a portion of the solution from the fatty acid or derivative thereof (such as an ester or contact ion pair) bound to the functionalized solid
  • the invention provides a fatty acid or alcohol derived from the lipid ester produced by the method of the invention.
  • the solid phase surfaces can include weak or strong anion exchange resins and/or nucleophilic functional group(s).
  • the step of separating at least a portion of the solution from the fatty acid or derivative thereof (such as an ester) bound to the functionalized solid phase material allows for the facile separation and removal of components of the lipid ester such as glycerol.
  • Anion exchange resins may include an anion exchange functional group, such as: tertiary amino functional group (such as diethylaminoethyl (DEAE)); quaternary ammonium functional group; phosphonium functional group; sulfonium functional group; oxonium functional group; metal-cation based anion exchange functional group.
  • anion exchange functional group such as: tertiary amino functional group (such as diethylaminoethyl (DEAE)); quaternary ammonium functional group; phosphonium functional group; sulfonium functional group; oxonium functional group; metal-cation based anion exchange functional group.
  • nucleophilic functional groups are alcohol and thiol groups (e.g., phenolic, nitro-substituted phenolic polymer surfaces, or cysteine polyamides).
  • these solid phase surfaces sequester the carboxylic acids released from the esters, effectively removing them from the liquid phase onto the solid phase, thus driving the reactions further to completion, and so provide a high yield.
  • the residual alcohols can be removed by filtration before the fatty acids are displaced from the solid phase, thus also separating the glyceride and fatty acid components of the lipid, largely preventing lipid reformation.
  • the process can be conducted in organic solvents that promote the solubility of the esters, particularly where the ester carboxylate is composed of long-chain fatty acids.
  • the process can be conducted in a batch process where the solid phase is mixed with the lipid solution, and the glyceride alcohols removed by filtration post-reaction.
  • the solid phase may be optionally rinsed.
  • the fatty acids may be subsequently released from the solid phase into a displacing solution and recovered separately by filtration.
  • the solid phase is packed into a chromatography column and the process is run as a displacement chromatography process.
  • the process can be used for biodiesel production, the recovery of food oils (including polyunsaturated fatty acids used as dietary supplements), and/or to prepare lipid samples for the analysis of the glyceride composition.
  • Figure 2. Solid phase cleavage process utilizing an alcohol functional surface.
  • Figure 3. Illustration of the basic steps in a displacement chromatography for ester cleavage by the solid support in the chromatography column. This process results in the separation of the ester alcohol and carboxylate moieties.
  • the ester is a lipid
  • the ester alcohol is a glyceride
  • the ester carboxylate is a fatty acid.
  • FIG. 4 Gas chromatogram of the fatty acids from duck fat samples.
  • Sample 1 corresponds to a sample of duck fat dissolved in chloroform (Example 1).
  • Samples 2 and 3 correspond to a replicate samples of the cleaved duck fat eluted from the Dianion WA30 ion exchange resin with 8% methanolic toluene methylation buffer (Example 5) after the overnight cleavage reaction.
  • anion exchange resins are used as the solid phase ( Figure 1).
  • the anion exchange solid surface functional group is optionally charged with hydroxyl ions in a basic solution.
  • a hydroxide base can be added to the ester solution to catalyze the reaction. Equilibration of the hydroxyl ion saturated solid phase with a lipid solution lowers the effective pH of the solution, catalyzing the ester cleavage.
  • the resulting fatty acids are ionized and freely ion exchange with other resin-bound hydroxyl ions freeing additional hydroxyl groups into the lipid solution, and removing the free fatty acids from the solution phase to the solid resin surface driving the reaction equilibrium.
  • the alkoxide ion produced from the ester cleavage consumes the proton liberated from ionization of the fatty acid to become neutralized, so the glycerides do not bind to the solid phase.
  • the effective solution pH is thus effectively maintained between the pK a of the ester carboxylate moiety (> 4) and the pK a of the ester alcohol moiety ( ⁇ 11). Since the ester alcohol is neutralized, it fails to bind to the anion exchange resin and stays in solution. Since the ester carboxylates are ionized at the solution pH, these bind to the anion exchange resin to maintain electroneutrality.
  • An advantage of this process is that it can be conducted in an organic solvent solution in which the esters are more soluble than in an aqueous solution (i.e., minimal to no water is needed to accomplish the cleavage). Furthermore it can be conducted without a solvent on liquid esters. Ion separation and kinetics are improved by using organic solvents with higher polarity or dielectric constants, but that maintain good solubility of the lipids and fatty acids.
  • suitable solid phases include crosslinked anion exchange resins, such as aminated styrene-divinylbenzene resin (e.g., Diaion WA30, Mitsubishi) or tetraakylammoniated polystyrenic resin (e.g., Amberlite IRA-900).
  • suitable solid phases include silicate or aluminate particle surfaces functionalized with pendant amine, alkylammonium, or tetraalkylphosphonium groups. The positively ionized or ionizable groups are covalently attached to the surface by an organic linker of variable length.
  • the solid surfaces may be porous. The solid surfaces may be formed into beads or presented as porous monoliths.
  • the surface is first treated with a hydroxide base in an aqueous solution (e.g., 1-10 M sodium hydroxide) or in an organic solvent in which the hydroxide salt is soluble (e.g., tetrabutylphosphonium or tetabutylammonium hydroxide in toluene).
  • a hydroxide base e.g., 1-10 M sodium hydroxide
  • organic solvent e.g., tetrabutylphosphonium or tetabutylammonium hydroxide in toluene.
  • This treatment displaces any anions ionically bound to the fixed cations on the surface and charges the surface with hydroxide ions.
  • the surface is then rinsed to remove the excess hydroxide and its counterion salt.
  • the hydroxy-charged resin is ready to use.
  • the surface may be first treated with a dilute aqueous acid solution in water with a pH below that of the pK a of the ionizable cation fixed to the surface. This will ionize the fixed surface charges and through mass action substitute hydroxyl ions at most of the fixed cation sites.
  • the surface can then be rinsed with deionized water to displace the remaining acid cations by mass action.
  • the surface may be optionally rinsed with a water-miscible, aprotic, organic solvent to remove the residual moisture. The resulting hydroxyl-charged surface is ready to use for ester cleavage.
  • the hydroxyl ion-charged anion exchange surface is then exposed to a solution containing the ester.
  • the ester may be dissolved in any deionized solvent in which it is soluble.
  • the ester need not be diluted, if presented to the solid surface in a liquid form.
  • Esters formed of longer chain, more hydrophobic, carboxylic acids typically require water-imiscible organic solvents, such as toluene or chloroform, to remain soluble.
  • Shorter chain esters e.g., ethylacetate, soluble to 8.3% in water
  • the ester-containing solution is contacted with the solid phase in a batch reaction. Mixing may be applied to speed diffusion to the surface where the reaction occurs.
  • the solid surface is contained in a chromatography column and the solution containing the ester is passed slowly through the chromatography column. In this preferred embodiment the reaction is complete when the original ester begins to elute from the back end of the column.
  • ester carboxylate anion formed can subsequently be displaced from the solid phase with a displacing agent.
  • a hydroxide salt solution e.g., NaOH, Mg(OH) 2 , or tetraalkylphosphonium hydroxide
  • the pH of the displacing solution is raised above the pK a of the positively-charged weak anions fixed to the solid surface, liberating the bound fatty acid carboxylates as salts of the conjugate hydroxide counterion.
  • the pH of the eluting solution is lowered below that of the pK a of the fatty acid to neutralize the fatty acids to force their displacement from the solid surface by the conjugate acid counterion, such as: Cl’, SO 4 2 ’, PO 4 3 ’, or acetate.
  • the ionically-bound ester carboxylate moieties are effectively displaced from the solid phase by the negatively-charged counter ion of the protic acid used.
  • the solid phase optionally can be recharged into the hydroxyl ion-charged form as described above and reused.
  • a solid phase including one or more nucleophilic functional groups can be used.
  • nucleophilic functional groups are alcohol and thiol groups.
  • an alcohol-functional solid phase can be used wherein the pK a of the alcohol group fixed to the resin is lower than that of the lipid glyceride alcohols (i.e., ⁇ 10).
  • Suitable examples for R in Figure 2 include aromatic or electron-withdrawing functionalized aromatic rings, such as phenolate and nitrophenolate moieties.
  • the solid phase fixed alcohol functional group performs a transesterification reaction with the esters displacing original alcohol moiety (pKa > 10) of the ester and forming a resinbound ester with the carboxylate moiety.
  • This reaction is kinetically faster when the fixed alcohol on the solid phase is first ionized under basic conditions to create an alcohol anion salt such as sodium or tetraalkylphosphonium phenoxide.
  • an alcohol anion salt such as sodium or tetraalkylphosphonium phenoxide.
  • the alcohol-functional solid phase is contacted with the ester solution.
  • a transesterification reaction naturally occurs, which can be catalyzed under either acidic or basic conditions.
  • no additional catalyst is necessary.
  • the carboxylate moiety of the ester will end up covalently attached through an ester linkage to the alcohol functional group of the solid support.
  • reaction solution containing the original ester alcohol group
  • the reaction solution, containing the original ester alcohol group can be separated from the solid phase containing the covalently-bound carboxylates to remove the unbound ester alcohols.
  • the solid phase can optionally, be rinsed.
  • the solid phase can then be treated with a hydroxide base solution with a pH above the pK a of the fixed alcohol functional group. This cleaves the solid phase-bound fatty acid esters regenerating the free alcohol anion salt.
  • the carboxylates form salts with the counterion of the hydroxide solution.
  • the carboxylate salts can be recovered by separating the ester carboxylate salts from the solid surface.
  • the solid phase can be treated with an acid solution with a pH below the pK a of the ester carboxylates. This catalyzes the cleavage of the esters regenerating the free alcohol.
  • the carboxylates are released from the surface as neutral carboxylic acids in solution and can be separated from the solid phase.
  • the solid phase is composed of thiol functional groups. Both aromatic and aliphatic thiols have pK a 's below those of aliphatic alcohols and will form thioesters with the ester carboxylates.
  • the fixed thiol group can be ionized before reaction with the ester by incubating the solid phase with a hydroxide base prior to exposure.
  • the solid phase can be exposed to an acidic solution of the ester.
  • the solid phase can be exposed to a basic solution containing the ester. Both the acidic and basic solutions catalyzing the transesterification reaction.
  • the carboxylate moiety of the ester is retained on the solid surface.
  • the alcoholic moiety of the ester remains in the solution so that it can be separated from the carboxylate moiety.
  • the carboxylate moiety is then released from the solid phase into solution and the solution containing the dissolved carboxylate moiety separated from the solid phase.
  • the solid phase can optionally be regenerated and re-used.
  • the process can be conducted in a batch process where the resin is mixed with the lipid solution.
  • the solid phase is packed into a chromatography column and the process is run as a chromatography process.
  • Displacement chromatography [Gu (2012)] is the preferred embodiment as this uses the least reagents and produces the most concentrated form of both the ester alcohol and carboxylate ( Figure 3).
  • the lipids can be dissolved in a substantially organic phase with sufficient small amount of water present in this phase to drive the reaction. If necessary, water can be drawn into the organic phase through the addition of a polar, jointly-miscible, aprototic, cosolvent (e.g., acetonitrile).
  • a polar, jointly-miscible, aprototic, cosolvent e.g., acetonitrile
  • a biphasic water in oil emulsion can be used such that water reacted in the continuous organic phase is replenished from the included aqueous phase.
  • the water can be suspended in the pores of the solid phase resin with a pure oil phase contacted with the outer surface of the resin.
  • a pure organic solvent can be used. Said organic solvents chosen such that they do not form anions that will complete with the carboxylates for the solid phase.
  • a sample of 5 g of commercial duck fat was dissolved in 50 mL of chloroform.
  • a 0.1 mL sample of this lipid solution was taken and diluted into 1 mL of a 30% methanol/70% toluene mixture.
  • a 0.25 mL sample of this dilution was then transferred into 1.13 mL of methylation buffer (Example 2).
  • the sample was capped, mixed, and incubated for 16 hours at 45 °C in a heating block.
  • the samples were centrifuged to remove any particulates transferred to a glass gas chromatography vial and capped with a rubber gasket.
  • An 8% methanolic HCI solution was prepared by mixing 362.5 mL of methanol (Sigma, technical grade) with 100 mL of 37% HCI in water (Sigma) to make 462.5 mL in a glass bottle.
  • Methylation buffer was prepared by mixing 230 mL of this 8% methanolic HCI solution with 600 mL of methanol and 300 mL of toluene (Sigma).
  • a 10 g sample of a weak anion exchange resin (Diaion WA90) was added to a 25 mL solution of 1.0 M NaOH and equilibrated overnight to charge the resin with hydroxide ions. The charged resin was then rinsed with deionized water and dried.
  • Example 3 The dried and hydroxyl-charged Diaion WA90 resin (Example 3) was added to a 50 mL polypropylene centrifuge tube.
  • the 25 mL sample of duck fat in chloroform (Example 1) was added to the tube along with 2.5 mL of deionized water, which created a second phase.
  • the tube was sealed and rotated overnight end-over-end on a rotary mixer at room temperature.
  • Example 4 After the solid phase cleavage reaction (Example 4) was allowed to progress overnight, the solution was filtered off the resin. The resin was rinsed with a 70% toluene/30% methanol solution to remove any residual lipids and residual glyceride alcohols. The fatty acid carboxylates were then eluted by adding 25 mL of the methanolic HCI toluene solution (Example 2), incubating for 15 min, and separating the methanolic HCI toluene solution from the resin by filtration. The filtrate was collected and heated at 45 °C overnight [method of Ichihara and Fukubayashi (2010)] to convert the fatty acids to their corresponding methyl esters.
  • the methylated fatty acids obtained from Examples 1 and 5 were analyzed on a Shimadzu GC-2014 gas chromatograph equipped with a 30 m Restek Stabiwax capillary column (0.25 mm ID, 0.25 micron film thickness) using a flame ionization detector (FID).
  • the injection volume was 1 pL using a split injector at 220 °C with a split ratio of 1:186 using hydrogen at 50 cm/s as the carrier gas.
  • the FID was operated at 250 °C.
  • the column was operated with a temperature gradient consisting of 160 °C for 1 min. The temperature was increased to 185 °C at 5 °C/min then increased to 240 °C at 8 °C/min.
  • salt refers to a compound prepared by the reaction of an organic acid (typically a carboxylic acid herein) with a pharmaceutically acceptable mineral or organic base; as used herein, “salt” also includes hydrates and solvates of salts made in accordance with this invention. Exemplary mineral or organic acids or bases are as listed in Tables 1-8 in Handbook of Pharmaceutical Salts, P.H.
  • salts include, but are not limited to salts formed from a carboxylate and a Group I alkali or Group II alkaline earth metal cation, such as potassium, sodium, lithium, magnesium, calcium.

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Abstract

La présente invention concerne des procédés pour cliver (par exemple saponifier et/ou hydrolyser) un ester lipidique de façon à former un acide gras ou un sel de celui-ci. La présente invention concerne également des produits (tels que des acides gras et des esters de ceux-ci) produits selon le procédé de l'invention.
PCT/NZ2022/050123 2021-09-15 2022-09-08 Clivage lipidique en phase solide, et produits obtenus à partir de celui-ci Ceased WO2023043325A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2771480A (en) * 1953-07-29 1956-11-20 Benjamin Clayton Purification of glyceride oils by means of ion-exchange resins
JPS60163832A (ja) * 1984-02-03 1985-08-26 Nisshin Oil Mills Ltd:The グリセリドの加水分解法
WO2003087027A1 (fr) * 2002-04-12 2003-10-23 Oleon Procede d'hydrolyse directe d'esters d'acides gras en acides gras correspondants
WO2010005391A1 (fr) * 2008-07-08 2010-01-14 Agency For Science, Technology And Research Production de biodiesel par une hydrolyse enzymatique suivie d’une estérification chimique/enzymatique

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2771480A (en) * 1953-07-29 1956-11-20 Benjamin Clayton Purification of glyceride oils by means of ion-exchange resins
JPS60163832A (ja) * 1984-02-03 1985-08-26 Nisshin Oil Mills Ltd:The グリセリドの加水分解法
WO2003087027A1 (fr) * 2002-04-12 2003-10-23 Oleon Procede d'hydrolyse directe d'esters d'acides gras en acides gras correspondants
WO2010005391A1 (fr) * 2008-07-08 2010-01-14 Agency For Science, Technology And Research Production de biodiesel par une hydrolyse enzymatique suivie d’une estérification chimique/enzymatique

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* Cited by examiner, † Cited by third party
Title
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SCARPA ALFONSO; CASSANDRO CLAUDIA; DE LUCA PIETRO; GRECO ANTONIO; CHIARELLA GIUSEPPE; DE VINCENTIIS MARCO; CASSANDRO ETTORE; RALLI: "Therapeutic role of intravenous glycerol for Meniere’s disease. Preliminary results", AMERICAN JOURNAL OF OTOLARYNGOLOGY., W.B. SAUNDERS, PHILADELPHIA, PA., US, vol. 41, no. 4, 21 April 2020 (2020-04-21), US , XP086200430, ISSN: 0196-0709, DOI: 10.1016/j.amjoto.2020.102498 *
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