WO2000018944A1 - Triacylglycerols enrichis en acides linoleiques conjugues (cla) - Google Patents

Triacylglycerols enrichis en acides linoleiques conjugues (cla) Download PDF

Info

Publication number
WO2000018944A1
WO2000018944A1 PCT/US1999/022126 US9922126W WO0018944A1 WO 2000018944 A1 WO2000018944 A1 WO 2000018944A1 US 9922126 W US9922126 W US 9922126W WO 0018944 A1 WO0018944 A1 WO 0018944A1
Authority
WO
WIPO (PCT)
Prior art keywords
octadecadienoic
percent
acid
lipase
acylglyceride
Prior art date
Application number
PCT/US1999/022126
Other languages
English (en)
Inventor
Gudmundur G. Haraldsson
Asgeir Saebo
Carl Skarie
Daria Jerome
Original Assignee
Conlinco, Inc.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Conlinco, Inc. filed Critical Conlinco, Inc.
Priority to AU63996/99A priority Critical patent/AU6399699A/en
Publication of WO2000018944A1 publication Critical patent/WO2000018944A1/fr

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/185—Acids; Anhydrides, halides or salts thereof, e.g. sulfur acids, imidic, hydrazonic or hydroximic acids
    • A61K31/19—Carboxylic acids, e.g. valproic acid
    • A61K31/20—Carboxylic acids, e.g. valproic acid having a carboxyl group bound to a chain of seven or more carbon atoms, e.g. stearic, palmitic, arachidic acids
    • A61K31/201—Carboxylic acids, e.g. valproic acid having a carboxyl group bound to a chain of seven or more carbon atoms, e.g. stearic, palmitic, arachidic acids having one or two double bonds, e.g. oleic, linoleic acids
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
    • A23L33/115—Fatty acids or derivatives thereof; Fats or oils
    • A23L33/12—Fatty acids or derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/50—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates
    • A61K47/51—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the non-active ingredient being a modifying agent
    • A61K47/54—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the non-active ingredient being a modifying agent the modifying agent being an organic compound
    • A61K47/542—Carboxylic acids, e.g. a fatty acid or an amino acid
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/50—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates
    • A61K47/51—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the non-active ingredient being a modifying agent
    • A61K47/54—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the non-active ingredient being a modifying agent the modifying agent being an organic compound
    • A61K47/543—Lipids, e.g. triglycerides; Polyamines, e.g. spermine or spermidine

Definitions

  • This invention relates to novel triacylglycerols containing greater than 50 percent conjugated linoleic acids, upwardly in excess of 80 percent of the c9,tll- octadecadienoic and tl0,cl2 octadecadienoic isomers in a mixture, with less than five percent each of 8,10- octadecadienoic acyl-, 11, 13 -octadecadienoic acyl- glycerol isomers, and various trans, trans- octadecadienoic acyl isomers.
  • essential fatty acids In animal lipid metabolism, there are certain fatty acids, termed "essential" fatty acids, which must be supplied from vegetable sources.
  • the essential fatty acids are required as structural components for the lipid content of cell membranes but cannot be synthesized by the animal, as summarized in Ohlrogge, et al., The Plant Cell 7: 957 (1895). This includes the essential fatty acid c9 , cl2-linoleic acid.
  • Structural variants of 9 , 12-linoleic acid, some of which are naturally occurring, include the conjugated isomers .
  • CLA conjugated linoleic acids
  • CLA has also been identified as a strong cytotoxic agent against target human melanoma, colorectal and breast cancer cells in vitro.
  • a recent major review article confirms the conclusions drawn from individual studies. See Ip, Am. J. Clin. Nutr., 66 (6 Supp) : 1523s (1997).
  • U.S. Patent No. 5,585,400 discloses a method for attenuating allergic reactions in animals mediated by type I or TgE hypersensitivity by administering a diet containing CLA.
  • CLA in concentrations of about 0.1 to 1.0 percent was also shown to be an effective adjuvant in preserving white blood cells.
  • U.S. Patent No. 5,674,901 (Cook, et al . ) disclosed that oral or parenteral administration of CLA in either free acid or salt form resulted in elevation in CD-4 and CD-8 lymphocyte subpopulations associated with cell-mediated immunity.
  • fatty acids are not provided in free fatty acid form, but rather in phosph- or acyl-glyceride form.
  • the general type and distribution of fatty acid containing lipid components in plant tissue is described in detail in Ohlrogge, et al . , supra .
  • the uptake and metabolism pathways and kinetics differ from the acylglyceride and free acid forms.
  • the binding, rheology, and palatability properties of these respective compounds differs.
  • True triacylglycerols are considerably more palatable, with markedly reduced aftertaste .
  • WO 91/16443 discloses a method utilizing C. antarctica lipase, C. fugosa lipase, and other enzymes to catalyze formation of triacylglycerides from free polyunsaturated fatty acids or their esters and glycerol. Conversion to glycerides is essentially complete at 98 percent when the resulting water or lower polyhydric alcohol byproducts are continuously removed. Maintenance of isomer distribution is also reported in Haraldsson, et al . , Tetrahedron 51: 941 (1995). Again, these results are applicable only to the higher polyunsaturated fatty acids and esters. The degree of reaction, and the influence of chain length and double bond portions on enzyme specificity is discussed in detail in Macrae,
  • a preferred form of CLA incorporates free fatty acids of the derived conjugated linoleic fatty acids or their corresponding esters into acylglycerols of either mono-, di-, or triacylglycerol structure.
  • CLA glycerides may conveniently be provided in conjunction with CLA glycerides to achieve the derived nutritive benefits of the CLA together with a balanced ration. These rations may be compounded as premixes .
  • linoleic acid or its corresponding ester are converted primarily to the conjugated c9,tll and tl0,cl2 isomers in a carefully controlled reaction yielding greater than 90 percent of these isomers, so that less than a combined 1 percent of the 11,13 isomers, less than 1 percent of the 8,10 isomers, less than 1 percent of the double trans species (the t9,tll and tl0,tl2 isomers), and less than 1 percent total unidentified linoleic acid species, in the aggregate less than five percent, is present in contrast to conventional compositions. In many individual product runs, the final composition has levels of these species virtually undetectable by GC analysis.
  • the 1 percent limit in concentration of the 11,13 and 8,10 isomers serves as a convenient and practical quality assurance standard of purity for a commercial scale manufactured food grade product.
  • CLA or esters thereof such defined composition are then reacted with glycerol in the process of lipase, preferably C. antarctica lipase, to produce acylglycerol derivatives.
  • the percentage of mono-, di-, and tri-glycerides is dependent upon the time of reaction.
  • a triacylglyeride is provided having a biological effect, and comprising the structure
  • R x , R 2 and R 3 are selected from a hydroxyl group and a C18:2 fatty acid in which the C18:2 fatty acid is characterized in the content of c9 , tll-octodecadienoic acid; and tlO, cl2-octodecadienoic acid.
  • There conjugated fatty acids are present in greater than 50 percent, with a content of 8 , 10-octodecanoic acid and 11, 13-octodecanoic acid isomers of less than 5 percent in the aggregate.
  • the content of trans, trans isomers is also typically less than 5 percent .
  • the acylglycerides may be used either in triglyceride form or as mono- or di- glyceride intermediates in animal feed or food at a level of about 0.05 to about 3.0 percent by weight .
  • the present invention also provides a new process for making novel conjugated linoleic acid-containing compositions from free fatty acids of the requisite purity and defined composition.
  • the process comprises the steps of dissolving in the specific non-aqueous solvent propylene glycol, an alkali compatible with a non-aqueous medium such as potassium hydroxide, cesium hydroxide, cesium carbonate, or an organic alkali such as tetraethyl ammonium hydroxide, in the absence of metallic-based isomerization catalyst systems, blending into the alkaline propylene glycol a seed oil, heating under an inert gas atmosphere and at ambient pressures to a temperature in the range of 130-165 degrees C, preferably about 150 degrees C.
  • a non-aqueous medium such as potassium hydroxide, cesium hydroxide, cesium carbonate, or an organic alkali such as tetraethyl ammonium hydroxide
  • the process stream may be interrupted after the reaction mix is prepared, either prior to or after the heat step.
  • the mix may then be stored for further processing in continuous acidification and distillation steps and/or be further processed at another location.
  • the isomerized blended reaction mix contains 30-60 percent processed seed oil, 10-40 percent alkali, and 30-60 percent propylene glycol. In this process it is important to utilize propylene glycol because of its heating properties and the patterns of isomerization obtained.
  • the components of the dissolved fatty acid reaction mix are present, as follows : 30-60 percent seed oil
  • the process comprises forming a blended reaction mix containing linoleic acid-containing seed oil, propylene glycol, and an alkali compatible with a nonaqueous medium, isomerizing said linoleic acid contained in said seed oil by heating to form conjugated linoleic acids, aquefying to release glycerol. Toxicity is avoided, as will be posed if other, undesirable organic solvents such as ethylene glycol are used. Under the nonreflux conditions, it is possible to vary the processing temperature over a range to obtain the desired result with oils of differing fatty acid composition.
  • the temperature is critical, as the percentage of trans, trans species, as well as other undesired and unidentified species increases as temperature rises.
  • the processing time requires about 2 to 6.5 hours and gives isomerized yields of greater than 90 percent, frequently as high as 99.5 percent.
  • use of sunflower and safflower oil is essential because of its high native 9,12 linoleic acid content, but also because of low levels of sterols, contaminating phospholipids, and other residues that tend to foul the processing equipment and result in a less pure final product. This makes it possible to prepare on an industrial scale, a product of controlled isomer content without a subsequent distillation step to ensure sufficient product purity.
  • the fatty acid esters may be prepared by conventional techniques, and then isomerized in a monohydric alcohol solvent in the presence of an alkali metal oxide, sodium ethoxide being preferred, according to the method more fully disclosed in co-pending application No. 09/132,593.
  • the isomer distribution of CLA is essentially the same as with propylene glycol.
  • the glycerol acylating step is then carried out as before.
  • Figure 1 is a rectilinear plot showing incorporation of CLA into various glycerides direct progress of the direct esterification reaction.
  • Figure 2 is a molecular diagram of the c9,tll- octadecadienoic acid and tlO , cl2-octadecadienoic acid isomers .
  • composition of the present invention results from a highly controlled isomerization process, under nonaqueous conditions (propylene glycol solvent for free fatty acid, and monohydric alcohol for the corresponding esters) , and from using the preferred starting material of sunflower or safflower oil.
  • This composition has not heretofore been obtained, for application to an industrial scale, because the conventional processes historically produce conjugated linoleic acids for entirely different purposes, namely, as drying oils in the paint industry. Also, there has not been an appreciation of the implications of the isomer content of the final product, because the analytical methods for characterizing the fatty acids has not been widely available.
  • Patent No. 4,381,264 teaches a process where a low water content reaction zone (0.5% water) contains stoichiometric base in the presence of S0 2 to obtain conjugation of the double bonds of various polyunsaturated fatty acids.
  • the aqueous alkali process was adapted in U.S. Patent No. 4,164,505 to a continuous flow process in which an alkali metal hydroxide and water are continuously charged in a flow zone maintained at between 200 and 370 degrees C. At these temperatures, the time of reaction should be greatly foreshortened, but there is relatively little control over the isomerization. At the higher end of the temperature range, one would predict almost complete conversion to double trans species .
  • Baltes et al . (U.S. Patent 3,162,658) disclose the use of nonaqueous solvents and various metallic bases as catalysts for the conjugation of fatty acids .
  • the various reaction parameters of the methods described by Baltes et al . are summarized in Table 2.
  • Baltes et al . also disclose the use various low boiling point solvents. As most of these reactions were conducted at temperatures above the boiling point of the solvent employed, it is apparent that the reactions were conducted under pressure, which is an independent factor influencing the formation of octadecadienoic acid isomers . The product derived from these reactions will thus contain undesirable isomers.
  • the CLA of the present invention lacks isomers such as the 8,10 isomer, the 11,13 isomer, and the various trans-trans isomers.
  • This composition was produced by a tightly controlled nonaqueous alkali isomerization process. Sunflower oil or safflower oil are reacted at an ambient pressure under an inert gas atmosphere with an excess of alkali in a high-boiling point solvent, namely propylene glycol at a temperature below the boiling point of the solvent. These reaction conditions allow for precise control of the temperature (and constant ambient pressure) of the conjugation process.
  • the alkali is an inorganic alkali such as potassium hydroxide, cesium hydroxide, cesium carbonate or an organic alkali such as tetraethyl ammonium hydroxide.
  • the catalyst is preferably provided in a molar excess as compared to the fatty acid content of oil.
  • the solvent is propylene glycol.
  • the reaction is conducted within a temperature range 130 to 165°C, most preferably at about 150°C.
  • the time of the reaction may vary, however, there is an increased likelihood of the formation of undesirable isomers when the reaction is conducted for long periods of time. A relatively short reaction time of 2.0 to 6.5 hours has proved satisfactory for excellent yields.
  • the essential oils for conjugation are sunflower and safflower oil. As compared to soybean oil, these oils have lower concentrations of undesirable components such as phosphatides and sterols. These undesirable components may contribute to the formation of gums which foul the conjugation equipment and other undesirable polymers.
  • undesirable components such as phosphatides and sterols. These undesirable components may contribute to the formation of gums which foul the conjugation equipment and other undesirable polymers.
  • esterification of fatty acids to the alkyl esters methanol or ethanol are preferred, although other branched or straight chain monohydric alcohols may be used.
  • product of varying viscosity can be used to obtain the desired flow or compounding characteristics without affecting the therapeutic or nutritional properties arising from the CLA moieties.
  • the theory and practice of esterification are conventional. A basic explanation of the most common methods is set forth in the McCraw-Hill Encyclopedia of Science & Technology, McGraw-Hill Book Co., N.Y.: 1996 (5th ed.). The animal and human body has a variety of esterases, so that the CLA-ester is cleaved to release the free fatty acids readily. Tissue uptake may have a different kinetics depending on the tissue involved and the benefit sought .
  • Crude sunflower or safflower oil is the essential fatty acid source for producing CLA.
  • Sunflower oil contains a high amount of linoleic acid (about 65% on average) .
  • Safflower oil typically contains even higher amounts (greater than 70%) .
  • a hexane extract of crude, non-degummed oil is the starting substrate for CFAP production. This extract is commercially available and is the same quality as the oil used as the starting point for edible products. The ability to use raw sunflower or safflower oil as the starting substrate provides an important economic advantage because it is less expensive than refined sunflower oil .
  • a novel triacylglycerol is synthesized comprising the novel CLA isomer mixture disclosed hereinafter for non-aqueous isomerization of linoleic acid from sunflower and/or safflower oils.
  • the pure triacylglycerols highly enriched for CLA may be confirmed by H NMR. Esterification proceeds using immobilized Candida antarctica Lipase.
  • the CLA will contain at least 40 and upwardly 45-48 percent of c9,tll- octadecadienoic and tlO , cl2 -octadecadienoic acids, and mixtures thereof.
  • esters 8,10; 11,13; and trans, trans isomers There will be less than one percent esters 8,10; 11,13; and trans, trans isomers or less than five percent in the aggregate .
  • the resultant triacylglycerol is not purified further to remove all levels of phosphatidyl and sterol residues. But those levels remaining from isomerization of sunflower and safflower oils will be adequate for commercial applications involving safe, edible products in feed and food .
  • the immobilized Candida antarctica lipase is to be employed in a manner similar to that described for n-3 type polyunsaturated fatty acids, in Harraldson et al .
  • the esterification reaction is conducted at 50°-75° C, preferably 65 ° C, in the absence of any solvent and a vacuum employed in order to remove the co-produced water or alcohols (from esters) upon formation. This shifts the triacylglycerol production to completion and ensures a highly pure product virtually free of any mono- and diacylglycerols in essentially quantitative yields. Stoichiometric amounts of free fatty acids may be used, i.e.
  • R is hydrogen or an alkyl radical such as an ethyl, methyl, butyl, isopropyl, isobutyl or the like.
  • the 1- or 3- mono-acyglyeride is formed first, followed by the 1, 3 diacylglyeride, and finally the triglyceride at the more extended reaction times.
  • the mono- and diacylglyerides are useful intermediates in that they manifest biological activity, but have greater soluability in aqueous cellular environments and can participate in alternative molecular synthetic pathways such as synthesis of phospholipids or other funtional lipids.
  • triglycerides are frequently deposited intact in cell membranes or storage vesicles.
  • the administration of CLA in mono-, di- or triglycerol form may influence the mode and distribution of uptake, metabolic rate and structural or physiological role of the CLA component.
  • EXAMPLE 1 General. H nuclear magnetic resonance spectra were recorded on a Bruker AC 250 NMR spectrometer in deuterated chloroform as a solvent . HPLC separations were carried out by a PrepLCTM System 500A instrument from Waters using the PrepPak ® 500/Silica Cartridge column from Millipore, eluting with 10% diethyl ether in petroleum ether. Analytical GLC was conducted on a Perkin-Elmer 8140 Gas Chromatograph according to a previously described procedure, as described in Haraldsson, et al . , Acta Chem Scanned 45: 723 (1991). The immobilized Candida antarctica lipase was provided by Novo Nordisk in Denmark as NovozymeTM.
  • TonalinTM Its purity was confirmed by analytical GLC and high-field NMR spectroscopy which revealed some glyceride impurities.
  • the CLA concentrate was found to contain 43.3% 9-cis, 11-trans-linoleic acid, 44.5% 10- trans, 12-cis-linoleic acid, 5.4% of other CLA isomers, 5.6% oleic acid and 0.6% each of palmitic and stearic acid as determined by GLC at the Science Institute.
  • Immobilized Candida antarctica lipase (1.25 g) was added to a mixture of glycerol (1.22 g. 13.3 mmol) and CLA as free fatty acid (M.wt.280.3 g/mol; 11.6 g, 41.5 mmol) .
  • the mixture was gently stirred on a magnetic stirrer hot plate at 65° C under continuous vacuum of 0.01-0.5 Torr .
  • the volatile water produced during the progress of the reaction was continuously condensed into liquid nitrogen cooled traps. After 48 h the reaction was discontinued, n-hexane added and the enzyme separated off by filtration.
  • the organic phase was treated with an alkaline aqueous solution of sodium carbonate to remove excessive free fatty acids (when required) .

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Epidemiology (AREA)
  • Animal Behavior & Ethology (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Molecular Biology (AREA)
  • Biophysics (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Mycology (AREA)
  • Nutrition Science (AREA)
  • Food Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Fats And Perfumes (AREA)

Abstract

L'invention concerne de nouveaux acylglycérides renfermant des mono-, di- et triacylglycérides, caractérisés par le fait qu'ils renferment principalement comme acides linoléiques conjugués les acides octadécadiénoïques t9,c11- et c10,t12, à l'exception des isomères 11,13-, 8,10- et trans,trans.
PCT/US1999/022126 1998-09-25 1999-09-23 Triacylglycerols enrichis en acides linoleiques conjugues (cla) WO2000018944A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU63996/99A AU6399699A (en) 1998-09-25 1999-09-23 Triacylglycerols of enriched cla content

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US16041698A 1998-09-25 1998-09-25
US09/160,416 1998-09-25

Publications (1)

Publication Number Publication Date
WO2000018944A1 true WO2000018944A1 (fr) 2000-04-06

Family

ID=22576819

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1999/022126 WO2000018944A1 (fr) 1998-09-25 1999-09-23 Triacylglycerols enrichis en acides linoleiques conjugues (cla)

Country Status (2)

Country Link
AU (1) AU6399699A (fr)
WO (1) WO2000018944A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002041706A2 (fr) * 2000-11-21 2002-05-30 Alpha Foods Ingredients, Inc. Glycerides bioactifs d'acide linoleique conjugue et procede d'utilisation
EP1281750A2 (fr) * 2001-08-02 2003-02-05 Rinoru Oil Mills Co., Ltd. Monoglycérides contenant des acides gras conjugués et leur procédé de production
EP1354934A1 (fr) 2002-04-12 2003-10-22 Loders Croklaan B.V. Procédé de préparation de triglycerides d'acide linoléique conjugué (ALC)
US7759096B2 (en) 2004-01-29 2010-07-20 Stepan Company Process for enzymatic production of triglycerides
US20120076906A1 (en) * 2009-06-25 2012-03-29 Kasia Aeberhardt Flavouring ingredient
CN109655536A (zh) * 2018-11-21 2019-04-19 广州白云山汉方现代药业有限公司 一种中链甘油三酯中辛酸甘油二酯和癸酸甘油二酯的含量检测方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5208356A (en) * 1989-02-17 1993-05-04 Wisconsin Alumni Research Foundation Octadecadienoic phospholipic esters, antioxidant and mold inhibiting compositions
EP0779033A1 (fr) * 1995-11-14 1997-06-18 Unilever N.V. Produit à tartiner comestible
US5851572A (en) * 1997-04-25 1998-12-22 Wisconsin Alumni Research Foundation Method of increasing fat firmness and improving meat quality in animals with conjugated linolenic acid

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5208356A (en) * 1989-02-17 1993-05-04 Wisconsin Alumni Research Foundation Octadecadienoic phospholipic esters, antioxidant and mold inhibiting compositions
EP0779033A1 (fr) * 1995-11-14 1997-06-18 Unilever N.V. Produit à tartiner comestible
US5851572A (en) * 1997-04-25 1998-12-22 Wisconsin Alumni Research Foundation Method of increasing fat firmness and improving meat quality in animals with conjugated linolenic acid

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
GARCIA ET AL.: "Enrichment of Butteroil with Conjugated Linoleic Acid via Enzymatic Interesterification (Acidolysis) Reactions", BIOTECHNOLOGY LETTERS,, vol. 20, no. 4, April 1998 (1998-04-01), pages 393 - 395, XP002925354 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002041706A2 (fr) * 2000-11-21 2002-05-30 Alpha Foods Ingredients, Inc. Glycerides bioactifs d'acide linoleique conjugue et procede d'utilisation
WO2002041706A3 (fr) * 2000-11-21 2003-01-03 Alpha Foods Ingredients Inc Glycerides bioactifs d'acide linoleique conjugue et procede d'utilisation
EP1281750A2 (fr) * 2001-08-02 2003-02-05 Rinoru Oil Mills Co., Ltd. Monoglycérides contenant des acides gras conjugués et leur procédé de production
EP1281750A3 (fr) * 2001-08-02 2003-03-12 Rinoru Oil Mills Co., Ltd. Monoglycérides contenant des acides gras conjugués et leur procédé de production
US7220873B2 (en) 2001-08-02 2007-05-22 The Nisshin Oillio Group, Ltd. Conjugated fatty acid containing monoglycerides and process for producing them
EP1354934A1 (fr) 2002-04-12 2003-10-22 Loders Croklaan B.V. Procédé de préparation de triglycerides d'acide linoléique conjugué (ALC)
US7759096B2 (en) 2004-01-29 2010-07-20 Stepan Company Process for enzymatic production of triglycerides
US20120076906A1 (en) * 2009-06-25 2012-03-29 Kasia Aeberhardt Flavouring ingredient
CN109655536A (zh) * 2018-11-21 2019-04-19 广州白云山汉方现代药业有限公司 一种中链甘油三酯中辛酸甘油二酯和癸酸甘油二酯的含量检测方法
CN109655536B (zh) * 2018-11-21 2021-11-12 广州白云山汉方现代药业有限公司 一种中链甘油三酯中辛酸甘油二酯和癸酸甘油二酯的含量检测方法

Also Published As

Publication number Publication date
AU6399699A (en) 2000-04-17

Similar Documents

Publication Publication Date Title
US7514096B2 (en) Triacylglycerols of enriched CLA content
EP1456330B1 (fr) Acylglycerides fonctionnels
US8207225B2 (en) Conjugated linoleic acid compositions
AU2003274548B2 (en) Conjugated linoleic acid compositions
EP1276709B1 (fr) Procedes de preparation d'isomeres d'acide linoleique conjugue (alc)
AU2001251449A1 (en) Conjugated linoleic acid compositions
AU2001257627A1 (en) Methods for preparing CLA isomers
WO2000018944A1 (fr) Triacylglycerols enrichis en acides linoleiques conjugues (cla)
JP2015129136A (ja) 共役リノール酸組成物
US7776353B1 (en) Conjugated linoleic acid compositions

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref country code: AU

Ref document number: 1999 63996

Kind code of ref document: A

Format of ref document f/p: F

AK Designated states

Kind code of ref document: A1

Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ DE DK DM EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase