CA2364245C - Water soluble group ia and iia double metal salt of(-)- hydroxycitric acid - Google Patents
Water soluble group ia and iia double metal salt of(-)- hydroxycitric acid Download PDFInfo
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- CA2364245C CA2364245C CA2364245A CA2364245A CA2364245C CA 2364245 C CA2364245 C CA 2364245C CA 2364245 A CA2364245 A CA 2364245A CA 2364245 A CA2364245 A CA 2364245A CA 2364245 C CA2364245 C CA 2364245C
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Abstract
This invention relates to a water soluble group IA and group IIA double metal salt of (-)-hydroxycitric acid having the general formula I: (see formula I) The present invention is also directed to a process for preparing the water soluble group IA and IIA double metal salt of (-)-hydroxycitric acid, and the use thereof in beverages and other food products.
Description
8991(PCT) Water Soluble Group IA and HA Double Metal Salt of (-)- Hydroxycitric Acid Technical field This invention relates to a new soluble double metal salt of group IA and II
A of (-) hydroxycitric acid. process of preparing the same and its use in beverages and other food products without effecting their flavor and properties. This product with >98% purity can be used safely not only as a food supplement in various nutriceutical formulations and beverages but also for effecting obesity control.
Background Art (-} Hydroxycitric acid (HCA) occurs in the fruit rind of Garcinia species (G.
to Cambogia, G. hidica and G. atrovh*iis). The first two species grow abundantly in India and the third occurs mostly in South East Asian countries. The success of this natural food product derived from Garcinia fruit has been documented and been in use since several centuries BC. Also known as "Kokum", the extracts of the fruit have been used, as a tart flavoring in meat and seafood dishes, turned into a refreshing beverage that serves as a unique flavor enhancer, gourmet spice and a digestive after aheavy meal. In Aynuveda, the traditional ancient system of herbal medicine in India, Garrcmia is also considered to be one of the prime herbs that are beneficial for the heart.
In more recent tines, Gannia has received worldwide attention as a 10 nutriceutical for.effective obesity control. Several scientists including at Hoffman-La Roche have established that HCA, the active ingredient in the fruit, prevents the conversion of excess carbohydrates to fat in animals. The energy released by the excess carbohydrate is converted into and stored as glycogen, a readily usable form of energy. Interestingly, it has been shown to inhibit ATP dependent citrate,-lyase, a key enzyme in' diverting carbohydrate to fatty acids and cholesterol synthesis.
(Sullivan et al. Lipids, 9:121 and 129 (1973). Sergio, W.. Medical Hypothesis :7:39 (1988).
The age-old practice of consuming Garcinia rind as a food additive by inhabitants of Malabar and Konkan coast of the Indian peninsula has established ..._._..._ ................... .... ..... -. ...... _......... ..... .
8991(PCT) the safety of HCA. The isolation and chemical nature of (-) hydroxycitric acic from Garcinia rind are described in the publication of Lewis Y.S., el aL
(Methods in Enzymology, 13:613 (1967) and in the patents (Indian patents 160753 &
and US patents 5536516 & 5656314).
s It is believed that consumption of HCA influences the body metabolism leading to the saturation of glycogen receptors in the liver and a consequent transmission of signals of satiation to brain. Even as a food supplement, (-) HCA
helps a person to loselcontrol weight in a natural way without affecting normal physical activities.
to In view of its unique property, several health care formulations incorporating HCA are being sold across the counter in the Western markets.
These include tablets, capsules, herbal teas, chocolate bars, milk shakes and other beverages. The active ingredient (HCA) from this insoluble HCA salt is released upon contact with hydrochloric and in the stomach and absorbed through the is intestine to exert its metabolic effect There is prior art on the preparation of a soluble tri-potassium- salt of (-) HCA (Lewis Y.S., et al (Methods in Enzymology, 13:613 (1967), International Patent application WO 96136585. However, its alkaline nature and risks associated with the consumption of high potassium (-36%) makes this io product unsuitable for HCA-based formulations.
In our earlier patents (Indian patent No. 178298 & US patents 5536516, 5656314) which describes preparation of a concentrate of (-) hydroxycitric acid and its lactone in liquid form, comprising of several steps like water extraction of Garcinia rind containing (-) hydroxycitric acid and its concentration, acetone ~s refinement of this concentrated water extract, evaporation of acetone.
loading thus obtained refined extract on ion-exchange columns containing an anion exchange resin followed by a cation exchange resin, and finally evaporation of the free acid liberated from the ion-exchange process to said concentration. This liquid fonn of (-) hvdroxycitric acid has problems of stability and half-life.
In addition, its highly acidic nature poses problems in formulating into beverage and various other food products without affecting their flavor and properties.
Disclosure of the Invention The object of this invention is to overcome the above drawbacks by developing a new soluble double metal salt of (-) hydroxycitric acid which will not pose any problem in formulating with beverages and various other food products without affecting their flavor and properties.
To achieve the.said objective, this invention provides a new soluble double to metal salt of group IA and 11 A of (-) hydroxycitric acid of general formula I
and more particularly formula 11 as given below:
H
H H-C-COO' 1Vb*
H-=
c-coo x+ HO- C-coo, HO-C-COO' HO-C-Coo I c~..
HO-C-coo- Y H
Formula I Formula 11 where X is IA group metal: Li or Na or K or Rb or Cs or Fr where Y is 1IA group meta(: Be or Mg or Ca or Sr or Ba or Ra where concentration of X in the salt varies from 1.5 - 5 1.0%, the concentration of Y in the salts varies from 2.0 - 50.9%, the concentration of (-)-hydroxycitric acid (HCA) in the salts varies from 31.0 -93. 0% depending on the nature of X and Y.
concentration of sodium in the salt: 8.58%, concentration of calcium in the salt: 14.92%
concentration of (-)-hydroxycitric acid: 76.50%, ENDED PAG
This invention further relates to a process for preparing the said soluble metal salt of group IA and IIA of (-) hydroxycitric acid of general formula I
or more particularly formula II comprising:
Step 1: preparing (-) hydroxycitric acid liquid concentrate/solid lactone of hydroxycitric acid from Garcinia extract, Step 2: neutralizing the free (-) hydroxycitric acid present in the said hydroxycitric acid liquid . concentrate/solid lactone present (-) io hydroxycitric acid with group IA metal hydroxides Step 3: displacing partially group IA metal ions in the above salt solutions by adding group IIA metal chlorides to form soluble double metal salt of group IA and RA of (-) hydroxycitric acid, Step 4: precipitating the said solubilised group IA and HA double metal salt of is (-) hydroxycitric acid by adding aqueous polar solvent to get soluble double metal salt of group IA and IIA of (-) hydroxycitric acid.
The free (-) hydroxycitric acid present in the step 2 is neutralized by three equivalents of group IA metal hydroxides.
Partial displacement of group IA metal ion in step 3 is carried out with one 20 equivalent of group IIA metal chloride.
The soluble double metal salt of group I A and IIA of (-) hydroxycitric acid is obtained in powder from by spray drying prior to the solvent addition or spray drying water solubilised solvent precipitated material.
The said polar solvents are methanol, ethanol, propanol, isopropanol and 25 acetone.
The (-) hydroxycitric acid concentrate in step I is prepared from the Garcinia extract by:
i) treating the said Garcinia extract with group IA metal hydroxide to obtain soluble group IA metal salt of (-) hydroxycitric acid, 4.
8991(PCT) ii) displacing completely the said group IA metal ions with group IIA metal ion by adding group IIA metal chlorides solution to precipitate insoluble group IIA metal salts of (-) hydroxycitric acid.
iii) collecting the said precipitate of insoluble group IIA metal salt of (-) hydroxycitric acid and washing it with water, iv) adding a water soluble organic acid to the said precipitated insoluble group II A metal salt of HCA to form a stronger salt of group IIA metal and release (-) hydroxycitric acid, v) repeating the steps (iii) and (iv) to form concentrate of (-) hydroxycitric acid, to vi) decolorizing the said (-) hydroxycitric acid concentrate, if desired.
The water soluble organic acid used in step (iv) is an oxalic acid.
The (-) hydroxycitric acid concentrate in step 1 is also prepared from the Garcinia by:
i) extracting Garcinia rind with aqueous polar solvent and filtering, ii) heating the filtrate in vacuum at 50-80 C to evaporate the said polar solvent, iii) removing the water insoluble substances to get the (-) hydroxycitric acid concentrate, iv) decolorizing the said (-) hydroxycitric acid concentrate, if necessary.
The aqueous polar solvent used in step 1 is 80% acetone in water.
The (-) hydroxycitric acid concentrate in step I is also prepared from the Garcinia extract by:
i) loading the Garcinia extract containing free (-) hydroxycitric acid on anion exchange resin column, ii) washing the said column with group IA metal hydroxide solution to get group ,S IA metal salt of (-) hvdroxycitric acid, iii) loading the said group IA metal salt solution of (-) hydroxycitric acid on cation exchange resin to get tree (-) hvdroxvvcitric acid, iv) heating the said free (-) hvdroxvcitric acid in vacuum to evaporate water and get the (-) hvdroxycitric acid concentrate.
S
i) decolorizing the said (-) hydroxycitric acid concentrate, if necessary.
The said (-) hydroxycitric acid concentrate is decolorized by heating with 2-5% activated charcoal, if desired.
The said lactone of (-) hydroxycitric acid in step 1 is prepared by:
i) heating the (-) hydroxycitric acid concentrate at 67 C to form syrup of (-) hydroxycitric acid lactone, ii) drying and desiccating the said syrup to get solid mass of (-) hydroxycitric acid lactone.
A process for the preparation of soluble double metal salt of group IA and I1A
of (-) hydroxycitric acid comprising:
i) loading Garcinia extract containing free (-) hydroxycitric acid on an anion exchange resin column, ii) washing the said anion exchange resin column with Group IA metal hydroxide to obtain group IA metal salt of (-) hydroxycitric acid solution.
iii) treating the said group IA metal salt of (-) hydroxycitric acid partially with group HA metal chloride to get soluble double metal salt of group 1A and I1A
of (-) hydroxycitric acid.
Group IA metal hydroxides used are LiOH, NaOH, KOH, RbOH, CsOH and FrOH.
Group HA metal chlorides BeC12, MgCl2, CaC12, Sr(-'12, BaCl2 and RaC12.
The soluble double metal salt of group IA and IIA of (-) hydroxycitric acid is soluble sodium and calcium double metal salt of (-) hydroxycitric acid.
The process will now be described with reference to the following examples.
Example 1:
Water extract of Garcinia rind is obtained by counter current extraction, this is carried out in three vessels more specifically each time fresh Garcinia rind each time 1 Kg is loaded into vessel 3 and treated with 1.5 liters of water, the rind is moved from V3 to V2 then to V1. On the other hand the extract was moved from V1 to V2 then to V3. The extract obtained starting from 3Kgs of rind was 3.6 litres containing 620gms of acid along with the other water-soluble substances. The total soluble constituents in the extract i.e. brix was found to be 43 degrees. The extraction efficiency was found to be 90%. This acid was transferred to a vessel and neutralized by addition if 358 gm of sodium hydroxide. After cooling this solution to room temperature, 500 ml of solution containing 490 gin of calcium chloride was added to it and resultant insoluble calcium salt was centrifuged and washed thoroughly to removed the color and wo water soluble impurities. The salt obtained was dried and weight is found to be 693 gm.One hundred grams of this insoluble salt was taken in a one liter vessel to and 71.32 gin oxalic acid dihydrate dissolved in 350 ml of water was added and stirred at 150 RPM
on a shaker for 30 min, and the supernatant 210 ml of was collected. To this supernatant 71.32 gm of oxalic acid dihydrate was added and another 100 gm of calcium hydroxycitrate added and this procedure is followed until the hydroxycitric acid content in the extract reaches -45% detected by high performance liquid chromatography (HPLC). The traces of oxalic acid were also removed by finally adding excess calcium hydroxycitrate. This was monitored by HPLC by observing the total absence of oxalic acid peak. The solution of hydroxycitric acid thus obtained was found to contain 202 gm of acid in 450 ml of extract. This was neutralized by 117 gm of sodium hydroxide and the solution was cooled to room temperature. To this sodium salt solution of hydroxycitric acid, 200 ml of solution containing 81 gm of calcium chloride was added drop wise with vigorous stirring. The soluble sodium and calcium double metal salt of hydroxycitric acid was then precipitated by addition of ethanol. Then precipitated salt was filtered, washed with ethanol and dried to obtain 234 gin of the soluble sodium and calcium double metal salt of hydroxycitric acid (yield: 91.2%). In another experiment, the above procedure was repeated exactly after collecting the ethanol precipitated material. This was again dissolved in water ~AMENDED PAG IN 009900004 to 30% and the material thus obtained was spray dried to obtain 243 gm of the soluble salt of hydroxycitric acid (yield 95%).
EXAMPLE 2:
One hundred gm Garcinia Cambogia rind was extracted 4 times with 80%
acetone in water (250 ml each time) for 4 hours. The combined extract (830-ml) was concentrated to 300 ml by heating in vacuo at 56 C (500 millibar and filtered through cheese cloth to remove water insoluble non polar substances. The filtrate (260-m1) containing 18 gm of hydroxycitric acid decolorized by addition of 2.6 gm of activated io charcoal and filtered The resultant clear solution was concentrated to 50 ml, and the free acid was converted into the sodium salt of hydroxycitric acid by the addition of i l gm of sodium hydroxide pellets, were added. To this formed solution of sodium salt of (-) hydroxycitric acid 20 ml of solution containing 9 gm of calcium chloride was added drop wise with vigorous stirring. The soluble sodium and calcium double metal salt of hydroxycitric acid is then precipitated by addition of ethanol.
The precipitated soluble sodium and calcium double metal salt is filtered, washed with ethanol and dried to obtain 20.7 gm of the soluble sodium and calcium double metal salt of hydroxycitric acid (yield 89.84%).
EXAMPLE 3: An anion exchange resin (bed volume IL) was loaded onto a glass column and washed thoroughly with 10% aqueous sodium hydroxide to remove the chloride present in the resin. The column was then washed with water till the eluate pH was neutral. Three hundred milliliters of an aqueous solution containing 108 gm of (-) hydroxycitric acid was loaded onto the column and washed with water to remove the colored materials. The column was eluted with I liter of an aqueous solution containing 63 gm of sodium hydroxide followed by 0.5 L of water. The combined eluate (1.5 liters) containing sodium salt of hydroxycitric acid was divided into two parts (750 ml each) and the soluble sodium and calcium double metal salt was prepared as follows. A portion of the sodium salt of hydroxycitric acid (750 ml) was concentrated to 200 ml. Fifty milliliters of a solution containing 20.25 gm of calcium chloride was added drop wise with vigorous stirring. The soluble salt of hydroxycitric acid thus formed was precipitated by the addition of ethanol, collected by filtration, washed. with ethanol and dried to obtain 60.3 gm of the soluble calcium salt of hydroxycitric acid (yield: 91.8%).
b) The remaining portion of the eluate (750-m1) from the anion exchange column was passed through a column of cation exchange resin (bed volume 750ml). The column was washed with water until the pH of the eluent reached neutral. One liter of the flow through which contained 45 gm of free (-) hydroxycitric acid was collected, concentrated in Vacuo to 100 ml and.reneutralized by the addition of 27 gm of sodium hydroxide pellets. To the resultant solution of the sodium salt of (-) hydroxycitric acid, 50 ml of a solution containing 18 gm of calcium chloride was added drop wise with vigorous stirring. The resultant soluble calcium salt of hydroxycitric acid was precipitated by the addition of ethanol. The precipitated salt was filtered, washed with ethanol and dried to obtain 54 gm of the soluble calcium salt of (-) hydroxycitric acid (yield:
93.75%).
EXAMPLE 4:
One hundred milliliters of 48% enriched aqueous solution of hydroxycitric acid solution was evaporated 67 C in vacuo to remove water. The syrup thus formed was transferred into Petri dishes dried and desiccated under vacuum for 4-5 hours. The solid lactone of hydroxycitric acid weighing 30.6 gm was collected. To the said Lactone residue, 60 ml of a solution containing 18 gm of sodium hydroxide was added. To the resultant solution of the sodium salt of (-) hydroxycitric acid, 30 ml of a solution containing 12.6 gm of calcium chloride was added drop wise with vigorous stirring. The soluble salt of hydroxycitric acid is then precipitated by addition of ethanol. The precipitated salt was filtered, washed with ethanol and dried to obtain 36 gm of the soluble calcium salt of hydroxycitric acid (yield: 9.91%).
899 t(PCT) This invention also provides the use of the said soluble double metal salt of group IA and IIA of (-) hydroxycitric acid of formula I and particularly, formula 11 in beverages and other food products.
Beverages containing 0-15 weight % alcohol and syrups including soluble double metal salt of group IA and IIA of (-) hydroxycitric acid of formula I
or formula II in the proportion 0.01 -10 % w/v.
The said beverage is a Pilsner beer containing alcohol content 3.0-3.8 weight % or Dortmund beer containing alcohol content 2.5-4.0 weight % or Munich beer containing alcohol content 2.0-5.0 weight % or Munich Ale or io Porter beer containing alcohol contents 2.0-5.0 weight % or Stout beer containing alcohol content 5.0-6.5 weight %, each said beer includes the soluble double metal salt of group IA or IIA of formula I or 11 in the proportion 0.01-0.5 % w/v.
The said beverage is aerated or non-aerated beverage/colas and the syrups are either processed or naturally occurring like honey including soluble double metal salt of group IA and IIA of (-) hydroxycitric acid of formula I or II in the proportion 0.01-10 % w/v.
Soluble double metal salt of group IA and IIA of (-) hydroxycitric acid of formula I or formula II in the proportion 0.01-10 % w/v is added at any stage during the production of the beverage or processed syrups.
?S
A of (-) hydroxycitric acid. process of preparing the same and its use in beverages and other food products without effecting their flavor and properties. This product with >98% purity can be used safely not only as a food supplement in various nutriceutical formulations and beverages but also for effecting obesity control.
Background Art (-} Hydroxycitric acid (HCA) occurs in the fruit rind of Garcinia species (G.
to Cambogia, G. hidica and G. atrovh*iis). The first two species grow abundantly in India and the third occurs mostly in South East Asian countries. The success of this natural food product derived from Garcinia fruit has been documented and been in use since several centuries BC. Also known as "Kokum", the extracts of the fruit have been used, as a tart flavoring in meat and seafood dishes, turned into a refreshing beverage that serves as a unique flavor enhancer, gourmet spice and a digestive after aheavy meal. In Aynuveda, the traditional ancient system of herbal medicine in India, Garrcmia is also considered to be one of the prime herbs that are beneficial for the heart.
In more recent tines, Gannia has received worldwide attention as a 10 nutriceutical for.effective obesity control. Several scientists including at Hoffman-La Roche have established that HCA, the active ingredient in the fruit, prevents the conversion of excess carbohydrates to fat in animals. The energy released by the excess carbohydrate is converted into and stored as glycogen, a readily usable form of energy. Interestingly, it has been shown to inhibit ATP dependent citrate,-lyase, a key enzyme in' diverting carbohydrate to fatty acids and cholesterol synthesis.
(Sullivan et al. Lipids, 9:121 and 129 (1973). Sergio, W.. Medical Hypothesis :7:39 (1988).
The age-old practice of consuming Garcinia rind as a food additive by inhabitants of Malabar and Konkan coast of the Indian peninsula has established ..._._..._ ................... .... ..... -. ...... _......... ..... .
8991(PCT) the safety of HCA. The isolation and chemical nature of (-) hydroxycitric acic from Garcinia rind are described in the publication of Lewis Y.S., el aL
(Methods in Enzymology, 13:613 (1967) and in the patents (Indian patents 160753 &
and US patents 5536516 & 5656314).
s It is believed that consumption of HCA influences the body metabolism leading to the saturation of glycogen receptors in the liver and a consequent transmission of signals of satiation to brain. Even as a food supplement, (-) HCA
helps a person to loselcontrol weight in a natural way without affecting normal physical activities.
to In view of its unique property, several health care formulations incorporating HCA are being sold across the counter in the Western markets.
These include tablets, capsules, herbal teas, chocolate bars, milk shakes and other beverages. The active ingredient (HCA) from this insoluble HCA salt is released upon contact with hydrochloric and in the stomach and absorbed through the is intestine to exert its metabolic effect There is prior art on the preparation of a soluble tri-potassium- salt of (-) HCA (Lewis Y.S., et al (Methods in Enzymology, 13:613 (1967), International Patent application WO 96136585. However, its alkaline nature and risks associated with the consumption of high potassium (-36%) makes this io product unsuitable for HCA-based formulations.
In our earlier patents (Indian patent No. 178298 & US patents 5536516, 5656314) which describes preparation of a concentrate of (-) hydroxycitric acid and its lactone in liquid form, comprising of several steps like water extraction of Garcinia rind containing (-) hydroxycitric acid and its concentration, acetone ~s refinement of this concentrated water extract, evaporation of acetone.
loading thus obtained refined extract on ion-exchange columns containing an anion exchange resin followed by a cation exchange resin, and finally evaporation of the free acid liberated from the ion-exchange process to said concentration. This liquid fonn of (-) hvdroxycitric acid has problems of stability and half-life.
In addition, its highly acidic nature poses problems in formulating into beverage and various other food products without affecting their flavor and properties.
Disclosure of the Invention The object of this invention is to overcome the above drawbacks by developing a new soluble double metal salt of (-) hydroxycitric acid which will not pose any problem in formulating with beverages and various other food products without affecting their flavor and properties.
To achieve the.said objective, this invention provides a new soluble double to metal salt of group IA and 11 A of (-) hydroxycitric acid of general formula I
and more particularly formula 11 as given below:
H
H H-C-COO' 1Vb*
H-=
c-coo x+ HO- C-coo, HO-C-COO' HO-C-Coo I c~..
HO-C-coo- Y H
Formula I Formula 11 where X is IA group metal: Li or Na or K or Rb or Cs or Fr where Y is 1IA group meta(: Be or Mg or Ca or Sr or Ba or Ra where concentration of X in the salt varies from 1.5 - 5 1.0%, the concentration of Y in the salts varies from 2.0 - 50.9%, the concentration of (-)-hydroxycitric acid (HCA) in the salts varies from 31.0 -93. 0% depending on the nature of X and Y.
concentration of sodium in the salt: 8.58%, concentration of calcium in the salt: 14.92%
concentration of (-)-hydroxycitric acid: 76.50%, ENDED PAG
This invention further relates to a process for preparing the said soluble metal salt of group IA and IIA of (-) hydroxycitric acid of general formula I
or more particularly formula II comprising:
Step 1: preparing (-) hydroxycitric acid liquid concentrate/solid lactone of hydroxycitric acid from Garcinia extract, Step 2: neutralizing the free (-) hydroxycitric acid present in the said hydroxycitric acid liquid . concentrate/solid lactone present (-) io hydroxycitric acid with group IA metal hydroxides Step 3: displacing partially group IA metal ions in the above salt solutions by adding group IIA metal chlorides to form soluble double metal salt of group IA and RA of (-) hydroxycitric acid, Step 4: precipitating the said solubilised group IA and HA double metal salt of is (-) hydroxycitric acid by adding aqueous polar solvent to get soluble double metal salt of group IA and IIA of (-) hydroxycitric acid.
The free (-) hydroxycitric acid present in the step 2 is neutralized by three equivalents of group IA metal hydroxides.
Partial displacement of group IA metal ion in step 3 is carried out with one 20 equivalent of group IIA metal chloride.
The soluble double metal salt of group I A and IIA of (-) hydroxycitric acid is obtained in powder from by spray drying prior to the solvent addition or spray drying water solubilised solvent precipitated material.
The said polar solvents are methanol, ethanol, propanol, isopropanol and 25 acetone.
The (-) hydroxycitric acid concentrate in step I is prepared from the Garcinia extract by:
i) treating the said Garcinia extract with group IA metal hydroxide to obtain soluble group IA metal salt of (-) hydroxycitric acid, 4.
8991(PCT) ii) displacing completely the said group IA metal ions with group IIA metal ion by adding group IIA metal chlorides solution to precipitate insoluble group IIA metal salts of (-) hydroxycitric acid.
iii) collecting the said precipitate of insoluble group IIA metal salt of (-) hydroxycitric acid and washing it with water, iv) adding a water soluble organic acid to the said precipitated insoluble group II A metal salt of HCA to form a stronger salt of group IIA metal and release (-) hydroxycitric acid, v) repeating the steps (iii) and (iv) to form concentrate of (-) hydroxycitric acid, to vi) decolorizing the said (-) hydroxycitric acid concentrate, if desired.
The water soluble organic acid used in step (iv) is an oxalic acid.
The (-) hydroxycitric acid concentrate in step 1 is also prepared from the Garcinia by:
i) extracting Garcinia rind with aqueous polar solvent and filtering, ii) heating the filtrate in vacuum at 50-80 C to evaporate the said polar solvent, iii) removing the water insoluble substances to get the (-) hydroxycitric acid concentrate, iv) decolorizing the said (-) hydroxycitric acid concentrate, if necessary.
The aqueous polar solvent used in step 1 is 80% acetone in water.
The (-) hydroxycitric acid concentrate in step I is also prepared from the Garcinia extract by:
i) loading the Garcinia extract containing free (-) hydroxycitric acid on anion exchange resin column, ii) washing the said column with group IA metal hydroxide solution to get group ,S IA metal salt of (-) hvdroxycitric acid, iii) loading the said group IA metal salt solution of (-) hydroxycitric acid on cation exchange resin to get tree (-) hvdroxvvcitric acid, iv) heating the said free (-) hvdroxvcitric acid in vacuum to evaporate water and get the (-) hvdroxycitric acid concentrate.
S
i) decolorizing the said (-) hydroxycitric acid concentrate, if necessary.
The said (-) hydroxycitric acid concentrate is decolorized by heating with 2-5% activated charcoal, if desired.
The said lactone of (-) hydroxycitric acid in step 1 is prepared by:
i) heating the (-) hydroxycitric acid concentrate at 67 C to form syrup of (-) hydroxycitric acid lactone, ii) drying and desiccating the said syrup to get solid mass of (-) hydroxycitric acid lactone.
A process for the preparation of soluble double metal salt of group IA and I1A
of (-) hydroxycitric acid comprising:
i) loading Garcinia extract containing free (-) hydroxycitric acid on an anion exchange resin column, ii) washing the said anion exchange resin column with Group IA metal hydroxide to obtain group IA metal salt of (-) hydroxycitric acid solution.
iii) treating the said group IA metal salt of (-) hydroxycitric acid partially with group HA metal chloride to get soluble double metal salt of group 1A and I1A
of (-) hydroxycitric acid.
Group IA metal hydroxides used are LiOH, NaOH, KOH, RbOH, CsOH and FrOH.
Group HA metal chlorides BeC12, MgCl2, CaC12, Sr(-'12, BaCl2 and RaC12.
The soluble double metal salt of group IA and IIA of (-) hydroxycitric acid is soluble sodium and calcium double metal salt of (-) hydroxycitric acid.
The process will now be described with reference to the following examples.
Example 1:
Water extract of Garcinia rind is obtained by counter current extraction, this is carried out in three vessels more specifically each time fresh Garcinia rind each time 1 Kg is loaded into vessel 3 and treated with 1.5 liters of water, the rind is moved from V3 to V2 then to V1. On the other hand the extract was moved from V1 to V2 then to V3. The extract obtained starting from 3Kgs of rind was 3.6 litres containing 620gms of acid along with the other water-soluble substances. The total soluble constituents in the extract i.e. brix was found to be 43 degrees. The extraction efficiency was found to be 90%. This acid was transferred to a vessel and neutralized by addition if 358 gm of sodium hydroxide. After cooling this solution to room temperature, 500 ml of solution containing 490 gin of calcium chloride was added to it and resultant insoluble calcium salt was centrifuged and washed thoroughly to removed the color and wo water soluble impurities. The salt obtained was dried and weight is found to be 693 gm.One hundred grams of this insoluble salt was taken in a one liter vessel to and 71.32 gin oxalic acid dihydrate dissolved in 350 ml of water was added and stirred at 150 RPM
on a shaker for 30 min, and the supernatant 210 ml of was collected. To this supernatant 71.32 gm of oxalic acid dihydrate was added and another 100 gm of calcium hydroxycitrate added and this procedure is followed until the hydroxycitric acid content in the extract reaches -45% detected by high performance liquid chromatography (HPLC). The traces of oxalic acid were also removed by finally adding excess calcium hydroxycitrate. This was monitored by HPLC by observing the total absence of oxalic acid peak. The solution of hydroxycitric acid thus obtained was found to contain 202 gm of acid in 450 ml of extract. This was neutralized by 117 gm of sodium hydroxide and the solution was cooled to room temperature. To this sodium salt solution of hydroxycitric acid, 200 ml of solution containing 81 gm of calcium chloride was added drop wise with vigorous stirring. The soluble sodium and calcium double metal salt of hydroxycitric acid was then precipitated by addition of ethanol. Then precipitated salt was filtered, washed with ethanol and dried to obtain 234 gin of the soluble sodium and calcium double metal salt of hydroxycitric acid (yield: 91.2%). In another experiment, the above procedure was repeated exactly after collecting the ethanol precipitated material. This was again dissolved in water ~AMENDED PAG IN 009900004 to 30% and the material thus obtained was spray dried to obtain 243 gm of the soluble salt of hydroxycitric acid (yield 95%).
EXAMPLE 2:
One hundred gm Garcinia Cambogia rind was extracted 4 times with 80%
acetone in water (250 ml each time) for 4 hours. The combined extract (830-ml) was concentrated to 300 ml by heating in vacuo at 56 C (500 millibar and filtered through cheese cloth to remove water insoluble non polar substances. The filtrate (260-m1) containing 18 gm of hydroxycitric acid decolorized by addition of 2.6 gm of activated io charcoal and filtered The resultant clear solution was concentrated to 50 ml, and the free acid was converted into the sodium salt of hydroxycitric acid by the addition of i l gm of sodium hydroxide pellets, were added. To this formed solution of sodium salt of (-) hydroxycitric acid 20 ml of solution containing 9 gm of calcium chloride was added drop wise with vigorous stirring. The soluble sodium and calcium double metal salt of hydroxycitric acid is then precipitated by addition of ethanol.
The precipitated soluble sodium and calcium double metal salt is filtered, washed with ethanol and dried to obtain 20.7 gm of the soluble sodium and calcium double metal salt of hydroxycitric acid (yield 89.84%).
EXAMPLE 3: An anion exchange resin (bed volume IL) was loaded onto a glass column and washed thoroughly with 10% aqueous sodium hydroxide to remove the chloride present in the resin. The column was then washed with water till the eluate pH was neutral. Three hundred milliliters of an aqueous solution containing 108 gm of (-) hydroxycitric acid was loaded onto the column and washed with water to remove the colored materials. The column was eluted with I liter of an aqueous solution containing 63 gm of sodium hydroxide followed by 0.5 L of water. The combined eluate (1.5 liters) containing sodium salt of hydroxycitric acid was divided into two parts (750 ml each) and the soluble sodium and calcium double metal salt was prepared as follows. A portion of the sodium salt of hydroxycitric acid (750 ml) was concentrated to 200 ml. Fifty milliliters of a solution containing 20.25 gm of calcium chloride was added drop wise with vigorous stirring. The soluble salt of hydroxycitric acid thus formed was precipitated by the addition of ethanol, collected by filtration, washed. with ethanol and dried to obtain 60.3 gm of the soluble calcium salt of hydroxycitric acid (yield: 91.8%).
b) The remaining portion of the eluate (750-m1) from the anion exchange column was passed through a column of cation exchange resin (bed volume 750ml). The column was washed with water until the pH of the eluent reached neutral. One liter of the flow through which contained 45 gm of free (-) hydroxycitric acid was collected, concentrated in Vacuo to 100 ml and.reneutralized by the addition of 27 gm of sodium hydroxide pellets. To the resultant solution of the sodium salt of (-) hydroxycitric acid, 50 ml of a solution containing 18 gm of calcium chloride was added drop wise with vigorous stirring. The resultant soluble calcium salt of hydroxycitric acid was precipitated by the addition of ethanol. The precipitated salt was filtered, washed with ethanol and dried to obtain 54 gm of the soluble calcium salt of (-) hydroxycitric acid (yield:
93.75%).
EXAMPLE 4:
One hundred milliliters of 48% enriched aqueous solution of hydroxycitric acid solution was evaporated 67 C in vacuo to remove water. The syrup thus formed was transferred into Petri dishes dried and desiccated under vacuum for 4-5 hours. The solid lactone of hydroxycitric acid weighing 30.6 gm was collected. To the said Lactone residue, 60 ml of a solution containing 18 gm of sodium hydroxide was added. To the resultant solution of the sodium salt of (-) hydroxycitric acid, 30 ml of a solution containing 12.6 gm of calcium chloride was added drop wise with vigorous stirring. The soluble salt of hydroxycitric acid is then precipitated by addition of ethanol. The precipitated salt was filtered, washed with ethanol and dried to obtain 36 gm of the soluble calcium salt of hydroxycitric acid (yield: 9.91%).
899 t(PCT) This invention also provides the use of the said soluble double metal salt of group IA and IIA of (-) hydroxycitric acid of formula I and particularly, formula 11 in beverages and other food products.
Beverages containing 0-15 weight % alcohol and syrups including soluble double metal salt of group IA and IIA of (-) hydroxycitric acid of formula I
or formula II in the proportion 0.01 -10 % w/v.
The said beverage is a Pilsner beer containing alcohol content 3.0-3.8 weight % or Dortmund beer containing alcohol content 2.5-4.0 weight % or Munich beer containing alcohol content 2.0-5.0 weight % or Munich Ale or io Porter beer containing alcohol contents 2.0-5.0 weight % or Stout beer containing alcohol content 5.0-6.5 weight %, each said beer includes the soluble double metal salt of group IA or IIA of formula I or 11 in the proportion 0.01-0.5 % w/v.
The said beverage is aerated or non-aerated beverage/colas and the syrups are either processed or naturally occurring like honey including soluble double metal salt of group IA and IIA of (-) hydroxycitric acid of formula I or II in the proportion 0.01-10 % w/v.
Soluble double metal salt of group IA and IIA of (-) hydroxycitric acid of formula I or formula II in the proportion 0.01-10 % w/v is added at any stage during the production of the beverage or processed syrups.
?S
Claims (19)
1. A water soluble group IA and lIA double metal salt of (-)- hydroxycitric acid (HCA) of general formula I as given below:
where X+ is a IA group metal ion selected from the group consisting of Li+, Na+, K+, Rb+, Cs+, and Fr+;
where Y++ is IIA group metal selected from the group consisting of Be, Mg, Ca, Sr, Ba, and Ra;
where the concentration of X+ in the salt varies from 1.5-51.0% weight/weight, the concentration of Y++ in the salt varies from 2,0-50.9% weight/weight, and the concentration of HCA in the salt varies from 31.0-93.0% weight/weight depending on the nature of X+ and Y++.
where X+ is a IA group metal ion selected from the group consisting of Li+, Na+, K+, Rb+, Cs+, and Fr+;
where Y++ is IIA group metal selected from the group consisting of Be, Mg, Ca, Sr, Ba, and Ra;
where the concentration of X+ in the salt varies from 1.5-51.0% weight/weight, the concentration of Y++ in the salt varies from 2,0-50.9% weight/weight, and the concentration of HCA in the salt varies from 31.0-93.0% weight/weight depending on the nature of X+ and Y++.
2. The water soluble group IA and IlA double metal salt of (-)-hydroxycitric acid as claimed in claim 1, wherein X+ is Na+ and Y++ is Ca++;
the concentration of sodium in the salt is 8.58% weight/weight;
the concentration of calcium in the salt is 14.92% weight/weight; and the concentration of (-)-hydroxycitric acid is 76.50% weight/weight.
the concentration of sodium in the salt is 8.58% weight/weight;
the concentration of calcium in the salt is 14.92% weight/weight; and the concentration of (-)-hydroxycitric acid is 76.50% weight/weight.
3. A process of preparing the water soluble group IA and IIA double metal salt of (-)-hydroxycitric acid as defined in claim 1 characterized by:
(i) preparing (-)-hydroxycitric acid liquid concentrate and/or solid lactone of (-)-hydroxycitric acid from Garcinia extract;
(ii) neutralizing the free (-)-hydroxycitric acid present in said (-)-hydroxycitric acid liquid concentrate and/or solid lactone of (-)-hydroxycitric acid with group IA
metal hydroxides;
(iii) partially displacing the group IA metal ions by adding one equivalent of a group IIA metal chloride to form the water soluble group IA and IIA double metal salt of (-)-hydroxycitric acid; and (iv) precipitating said group IA and IIA double metal salt of (-)-hydroxycitric acid by adding an aqueous polar solvent to obtain the group IA and IIA double metal salt of (-)-hydroxycitric acid, wherein said aqueous polar solvent is methanol, ethanol, propanol, isopropanol, or acetone.
(i) preparing (-)-hydroxycitric acid liquid concentrate and/or solid lactone of (-)-hydroxycitric acid from Garcinia extract;
(ii) neutralizing the free (-)-hydroxycitric acid present in said (-)-hydroxycitric acid liquid concentrate and/or solid lactone of (-)-hydroxycitric acid with group IA
metal hydroxides;
(iii) partially displacing the group IA metal ions by adding one equivalent of a group IIA metal chloride to form the water soluble group IA and IIA double metal salt of (-)-hydroxycitric acid; and (iv) precipitating said group IA and IIA double metal salt of (-)-hydroxycitric acid by adding an aqueous polar solvent to obtain the group IA and IIA double metal salt of (-)-hydroxycitric acid, wherein said aqueous polar solvent is methanol, ethanol, propanol, isopropanol, or acetone.
4. The process as defined in claim 3 characterized in that the water soluble group IA and IIA double metal salt of (-)-hydroxycitric acid is obtained in powder form by spray drying prior to the solvent addition or spray drying the water solubilised solvent in the precipitate.
5. The process as defined in claim 3 characterized in that the preparation of (-)-hydroxycitric acid (HCA) concentrate from the Garcinia extract comprises:
(a) treating said Garcinia extract with a group IA metal hydroxide to obtain a water soluble group IA metal salt of (-)-hydroxycitric acid;
(b) displacing completely said group IA metal with group IIA metal by adding a group IIA metal chloride solution to precipitate a water insoluble group IIA metal salt of (-)-hydroxycitric acid;
(c) collecting said precipitate of group IIA metal salt of (-)-hydroxycitric acid and washing it with water;
(d) releasing (-)-hydroxycitric acid (HCA) by adding a water soluble organic acid to said precipitated group IIA metal salt of hydroxycitric acid (HCA) thereby forming a group IIA metal salt of said water soluble organic acid, wherein said water soluble organic acid is oxalic acid;
(e) repeating the steps (c) and (d) to form a concentrate of (-)-hydroxycitric acid; and (f) optionally, decolorizing said (-)-hydroxycitric acid concentrate.
(a) treating said Garcinia extract with a group IA metal hydroxide to obtain a water soluble group IA metal salt of (-)-hydroxycitric acid;
(b) displacing completely said group IA metal with group IIA metal by adding a group IIA metal chloride solution to precipitate a water insoluble group IIA metal salt of (-)-hydroxycitric acid;
(c) collecting said precipitate of group IIA metal salt of (-)-hydroxycitric acid and washing it with water;
(d) releasing (-)-hydroxycitric acid (HCA) by adding a water soluble organic acid to said precipitated group IIA metal salt of hydroxycitric acid (HCA) thereby forming a group IIA metal salt of said water soluble organic acid, wherein said water soluble organic acid is oxalic acid;
(e) repeating the steps (c) and (d) to form a concentrate of (-)-hydroxycitric acid; and (f) optionally, decolorizing said (-)-hydroxycitric acid concentrate.
6. The process as defined in claim 3 characterized in that the preparation of (-)-hydroxycitric acid concentrate from the Garcinia extract comprises:
(a) extracting Garcinia rind with an aqueous polar solvent and filtering, wherein said aqueous polar solvent is 80% acetone in water:
(b) heating the filtrate under vacuum at 50-90°C to evaporate said polar solvent;
(c) removing any water insoluble substances to get the (-)-hydroxycitric acid concentrate; and (d) optionally, decolorizing said (-)-hydroxycitric acid concentrate,
(a) extracting Garcinia rind with an aqueous polar solvent and filtering, wherein said aqueous polar solvent is 80% acetone in water:
(b) heating the filtrate under vacuum at 50-90°C to evaporate said polar solvent;
(c) removing any water insoluble substances to get the (-)-hydroxycitric acid concentrate; and (d) optionally, decolorizing said (-)-hydroxycitric acid concentrate,
7. The process as defined in claim 3 characterized in that the preparation of (-)-hydroxycitric acid concentrate from the Garcinia extract comprises:
(a) loading the Garcinia extract containing free (-)-hydroxycitric acid on an anion exchange resin column;
(b) washing said column with a group IA metal hydroxide solution to get a group IA
metal salt solution of (-)-hydroxycitric acid;
(c) loading said group IA metal salt solution of (-)-hydroxycitric acid on a cation exchange resin to get free (-)-hydroxycitric acid;
(d) heating said free (-)-hydroxycitric acid under vacuum to evaporate water and get (-)-hydroxycitric acid concentrate; and (e) optionally, decolorizing said (-)-hydroxycitric acid concentrate by heating with 2-5% activated charcoal.
(a) loading the Garcinia extract containing free (-)-hydroxycitric acid on an anion exchange resin column;
(b) washing said column with a group IA metal hydroxide solution to get a group IA
metal salt solution of (-)-hydroxycitric acid;
(c) loading said group IA metal salt solution of (-)-hydroxycitric acid on a cation exchange resin to get free (-)-hydroxycitric acid;
(d) heating said free (-)-hydroxycitric acid under vacuum to evaporate water and get (-)-hydroxycitric acid concentrate; and (e) optionally, decolorizing said (-)-hydroxycitric acid concentrate by heating with 2-5% activated charcoal.
8. The process as defined in claim 3 comprising:
(a) loading the Garcinia extract containing free (-)-hydroxycitric acid on an anion exchange resin column;
(b) washing said anion exchange resin column with a group IA metal hydroxide solution to obtain a group IA metal salt of (-)-hydroxycitric acid solution;
and (c) treating said solution of a group IA metal salt of (-)-hydroxycitric acid partially with group IlA metal chloride to get a soluble group IIA metal salt of hydroxycitric acid.
(a) loading the Garcinia extract containing free (-)-hydroxycitric acid on an anion exchange resin column;
(b) washing said anion exchange resin column with a group IA metal hydroxide solution to obtain a group IA metal salt of (-)-hydroxycitric acid solution;
and (c) treating said solution of a group IA metal salt of (-)-hydroxycitric acid partially with group IlA metal chloride to get a soluble group IIA metal salt of hydroxycitric acid.
9. The process as defined in claim 3 characterized in that the solid lactone of (-)-hydroxycitric acid is prepared by:
(a) heating the (-)-hydroxycitric acid concentrate at 67°C to form a syrup of (-)-hydroxycitric acid lactone; and (b) drying and desiccating said syrup to get a solid (-)-hydroxycitric acid lactone.
(a) heating the (-)-hydroxycitric acid concentrate at 67°C to form a syrup of (-)-hydroxycitric acid lactone; and (b) drying and desiccating said syrup to get a solid (-)-hydroxycitric acid lactone.
10. The process as defined in claim 3 characterized in that the free (-)-hydroxycitric acid present in step (ii) is neutralized by three equivalents of group IA
metal hydroxides
metal hydroxides
11. The process as defined in any one of claims 3 to 9 characterized in that the (-)-hydroxycitric acid concentrate is decolorized by heating with 2-5% activated charcoal.
12, The process as defined in claim 3 characterized in that the group IIA
metal chloride of step (iii) is calcium chloride.
metal chloride of step (iii) is calcium chloride.
13. The process as defined in any one of claims 3 to 9 characterized in that the group IA
metal hydroxides are selected from the group consisting of LiOH, NaOH, RbOH, CsOH, and FrOH, and the group IIA metal chlorides are selected from the group consisting of BeCl2, MgCl2, CaCl2, SrCl2, BaCl2, and RaCl2.
metal hydroxides are selected from the group consisting of LiOH, NaOH, RbOH, CsOH, and FrOH, and the group IIA metal chlorides are selected from the group consisting of BeCl2, MgCl2, CaCl2, SrCl2, BaCl2, and RaCl2.
14. The process as defined in claim 3 characterized in that the polar solvent of step (iv) is ethanol.
15. The process as defined in any one of claims 3 to 14 characterized in that the soluble group IA and IIA metal salt of (-)-hydroxycitric acid is the soluble sodium and calcium double salt of (-)-hydroxycitric acid.
16. A beverage containing 0-15 weight % alcohol and a syrup comprising a water soluble group IA and IIA double metal salt of (-)-hydroxycitric acid, as defined in claim 1, in the proportion 0.01% w/v -10 % w/v.
17. The beverage as defined in claim 16 characterized in that said beverage is a beer selected from the group consisting of a Pilsner beer having an alcohol content of 3.0 weight %-3.9 weight %, a Dortmund beer having an alcohol content of 2.5 weight %-4.0 weight %, a Munich beer having an alcohol content of 2.5 weight %-5.0 weight %, a Munich Ale having an alcohol content of 5.0 weight %-6.5 weight %, and a Porter beer having an alcohol content of 5.0 weight %-6.5 weight %, wherein the beer comprises the soluble double metal salt of group IA and IIA in the proportion 0,01%o w/v-0.5 % w/v.
18. The beverage as defined in claim 16 characterized in that said beverage is an aerated or non-aerated beverage or cola, and the syrup is either processed or naturally occurring.
19. The beverage according to claim 18 wherein the syrup is honey.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/IN1999/000004 WO2000048983A1 (en) | 1999-02-18 | 1999-02-18 | Soluble double metal salt of group ia and iia of (-) hydroxycitric acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2364245A1 CA2364245A1 (en) | 2000-08-24 |
| CA2364245C true CA2364245C (en) | 2010-10-05 |
Family
ID=11076651
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2364245A Expired - Fee Related CA2364245C (en) | 1999-02-18 | 1999-02-18 | Water soluble group ia and iia double metal salt of(-)- hydroxycitric acid |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP1154978A1 (en) |
| JP (1) | JP2002542152A (en) |
| AU (1) | AU2851799A (en) |
| CA (1) | CA2364245C (en) |
| IL (1) | IL144827A0 (en) |
| WO (1) | WO2000048983A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7927636B1 (en) | 1997-07-14 | 2011-04-19 | Interhealth Nutraceuticals, Inc. | Hydroxycitric acid compositions, pharmaceutical and dietary supplements and food products made therefrom, and methods for their use in reducing body weight |
| US7119110B2 (en) | 2001-10-05 | 2006-10-10 | Interhealth Nutraceuticals Incorporated | Method and composition for preventing or reducing the symptoms of insulin resistance syndrome |
| US20030119913A1 (en) | 2001-12-20 | 2003-06-26 | Ohia Sunny E. | Method for increasing serotonin levels in a person by administration of a composition incorporating (-)-hydroxycitric acid, and related compositions thereof |
| US6875891B2 (en) * | 2003-05-12 | 2005-04-05 | Laila Impex | Process for preparing highly water soluble double salts of hydroxycitric acid particularly alkali and alkaline earth metal double salts |
| JP2007505129A (en) * | 2003-09-11 | 2007-03-08 | グリュコン テクノロジーズ グループ エルエルシー | Enteric delivery product of (-)-hydroxycitric acid |
| US20100152488A1 (en) * | 2007-02-16 | 2010-06-17 | Vittal Mallya Scientific Research Foundation | High Purity (-) Hydroxycitric Acid Metal Salt Derivatives and Method of Preparation of the Same |
| JP2011079752A (en) * | 2009-10-05 | 2011-04-21 | Kracie Home Products Ltd | Pancreatic lipase inhibitor, food and beverage composition containing the same and pharmaceutical composition |
| EP3509578B1 (en) * | 2016-09-08 | 2022-12-21 | Glykon Technologies Group, LLC | Monomeric bimetal hydroxycitric acid compounds and methods of making and using the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3536630A (en) * | 1968-05-21 | 1970-10-27 | Us Agriculture | Calcium sequestration in highly alkaline medium |
| US5536516A (en) * | 1994-08-24 | 1996-07-16 | Renaissance Herbs, Inc. | Hydroxycitric acid concentrate and food products prepared therefrom |
| WO1996036585A1 (en) * | 1995-05-15 | 1996-11-21 | Sabinsa Corporation | A new process for the production of potassium hydroxy citric acid, and compositions containing the potassium hydroxy citric acid |
-
1999
- 1999-02-18 AU AU28517/99A patent/AU2851799A/en not_active Abandoned
- 1999-02-18 JP JP2000599724A patent/JP2002542152A/en not_active Withdrawn
- 1999-02-18 EP EP99909175A patent/EP1154978A1/en not_active Withdrawn
- 1999-02-18 WO PCT/IN1999/000004 patent/WO2000048983A1/en not_active Application Discontinuation
- 1999-02-18 IL IL14482799A patent/IL144827A0/en unknown
- 1999-02-18 CA CA2364245A patent/CA2364245C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| IL144827A0 (en) | 2002-06-30 |
| JP2002542152A (en) | 2002-12-10 |
| WO2000048983A1 (en) | 2000-08-24 |
| CA2364245A1 (en) | 2000-08-24 |
| EP1154978A1 (en) | 2001-11-21 |
| AU2851799A (en) | 2000-09-04 |
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