EP1940232A1 - Verfahren und zusammensetzung auf basis von quinoa-saponinen (chenopodium quinoa) für die bekämpfung von aquatischen süsswasserschnecken - Google Patents

Verfahren und zusammensetzung auf basis von quinoa-saponinen (chenopodium quinoa) für die bekämpfung von aquatischen süsswasserschnecken

Info

Publication number
EP1940232A1
EP1940232A1 EP06750486A EP06750486A EP1940232A1 EP 1940232 A1 EP1940232 A1 EP 1940232A1 EP 06750486 A EP06750486 A EP 06750486A EP 06750486 A EP06750486 A EP 06750486A EP 1940232 A1 EP1940232 A1 EP 1940232A1
Authority
EP
European Patent Office
Prior art keywords
quinoa
saponins
phase
husk
extract
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP06750486A
Other languages
English (en)
French (fr)
Inventor
Ricardo San Martin Gamboa
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dictuc SA
Hiley Paul
Original Assignee
Dictuc SA
Hiley Paul
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 Dictuc SA, Hiley Paul filed Critical Dictuc SA
Publication of EP1940232A1 publication Critical patent/EP1940232A1/de
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/08—Magnoliopsida [dicotyledons]
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/40—Liliopsida [monocotyledons]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Definitions

  • the present invention relates to a method and a composition based on quinoa saponins ⁇ Chenopodium quinoa) intended for the control of aquatic fresh water snails such as Pomacea spp., Isidorella spp., Biomphalaria spp, Lymnaea spp., etc..
  • the method of the invention considers that the saponins are obtained from quinoa husk and are partially hydrolyzed in basic medium or with enzymes, increasing significantly their molluscicidal activity.
  • the invention also considers a method for the control of fresh water snails, which comprises the application of a composition based on quinoa saponins partially hydrolyzed, in which the dose results in the death of the snails but not in the death non-target organism, such as fish, frogs, etc., allowing the safe application of the method on flooded plantations such as rice fields, as well as in rivers and lakes.
  • the composition comprises liquid and powders which does not attack beneficial forms of aquatic life like fishes Prior Art
  • niclosamide a widely recommended compound for the control of the golden apple snail in rice fields (Pomacea spp), is effective at doses from 0.5 - 1.0 mg/L (Bayer, 2005).
  • the product kills 50% of tropical fish (LC 5 o) as carps with only 0.14 mg/L (World Health Organization, WHO 2002. WHO Specifications and Evaluations for Public Health pesticides, Niclosamide).
  • WHO 2002. WHO Specifications and Evaluations for Public Health pesticides, Niclosamide This means that no fish must be in the rice fields while the product is applied nor must the water be discharged into the rivers or lakes nearby.
  • the cost of niclosamide is US $ 80-100/hectare, which is unaffordable for many farmers.
  • saponins from the Andean quinoa cereal (Chenopodium quinoa) is intended for the control of fresh water snails.
  • Saponins are natural tensoactives present in many plants. One of its main properties is that they foam abundantly in aqueous solutions. They are also capable of permeating plant walls and microorganisms due to their association with sterols that are present in the cell membranes. Their chemical structure consists in a hydrophobic nucleus (sapogenin), to which sugar chains of hydrophilic nature are bound.
  • saponins There are two main types of saponins depending on the chemical structure of sapogenin: triterpenic saponins (where the sapogenin is a triterpene) and steroidal saponins (where the sapogenin is a steroid).
  • the major industrial sources of steroidal and triterpenic saponins are Yucca shidigera and Quillaja saponaria Molina extracts, respectively.
  • the biological and chemical activities of the saponins are directly related to the number of sugar chains bound to the sapogenin. Saponins with sapogenins that have two sugar chains are called bi-desmosidic saponins; those that have one sugar chain attached to the sapogenin are called mono-desmosidic saponins.
  • bi-desmosidic saponins have much lower activities.
  • bi-desmosidic saponins have good tensoactive properties and produce abundant foam.
  • Quinoa saponins are mainly bi-desmosidic, with sugar chains attached at C-3 and C-28. They concentrate in the outer husk of the grain, which is removed prior to consumption, and is a sub- product without commercial value.
  • the quinoa husk has the following advantages: 1) low cost (it is a by product); 2) abundant (it is found in Venezuela and Peru, and more recently in Chile); 3) high saponin content (25-30%); 4) Quinoa saponins have recently been approved by the US Environmental Protection Agency for its use against pathogenic fungi, bacteria, and viral plant diseases (Saponins of Chenopodium quinoa. Biopesticides Registration Action Document PC Code 097094. U.S. Environmental Protection Agency. Office of Pesticide Programs. Biopesticides and Pollution Prevention Division, 2005). This facilitates registration of the product in other countries.
  • the method considers that the quinoa soponins are partially hydrolyzed in basic medium or with enzymes. This eliminates sugar in C-28, turning the saponins into mono- desmosidic, increasing thus their molluscicidal activity in a significant way.
  • a major advantage of the present invention is that the mono-desmosidic quinoa saponins have a moderate toxicity to non-target organisms such as fish. This means that the lethal concentrations for snails are not lethal for fish. Thus the product is safe for its use in fresh water systems that have fish and other forms of beneficial aquatic life.
  • quinoa has at least 16 types of triterpenic saponins, within which the bidesmosidic saponins prevail (Woldemichael, G. and Wink, M. 2001. Identification and biological activities of triterpenoid saponins from Chenopodium quinoa. J. Agric. Food Chem. 49: 2327-2332.), that are mainly concentrated in the husk, with a high content of the molluscicidal triterpenes oleanolic acid and hederagenin.
  • the most important works relates to the use of Phytolacca dodecandra extracts in Africa (particularly Ethiopia), for the control of snails of Biomphalaria, Bulinus and Oncomelania genus, which transmit the schistosomiasis disease. This is the second most important disease in tropical countries, which affects over 200 million people.
  • the P. dodecandra plant contains fruits (berry type) with 25% of saponins.
  • the molluscicidal saponins are oleanolic acid glycosides and are active from 1.5 to 3 ppm. These saponins have been used for the control of snails that transmit schistosomiasis, but only in rural areas and in a craft way.
  • molluscicidal saponins also are very toxic to non-target organisms such as fish.
  • tea seed cake a by product of tea seed oil production in China
  • This product is very economical (US $ 0.35/kg, US $ 16-27/hectare), but like the synthetic chemical products, its use is restricted because it is extremely toxic for fish and the environment at low doses (1-2 mg saponin/L).
  • the USP Patent 6,649,182 describes a method to protect plantules of rice against golden apple snails. To this purpose the roots of the plantules are impregnated with chemical molluscicides, as well as saponins extracted from the tea seed cake.
  • the patent do no relates to the direct control of snails by the addition of saponins to the rice field water nor to the use of partially hydrolyzed saponins as it is in the invention.
  • the present invention allows for the production of highly molluscicidal saponins from an abundant and low cost row material. Furthermore, the product is safe for human beings and the environment. Detailed Description of the Invention
  • the method of the invention considers the production of a composition based on partially hydrolyzed quinoa saponins which does not attack beneficial forms of aquatic life like fishes.
  • the preparation of a liquid formulation considers a first phase of extraction with water. For this, the quinoa husk is contacted with water by stirring at a temperature from 20 to 90° C for 0.1 to 3 h. Once the initial extraction is finished, the husk is separated from the liquid extract by different alternate forms such as decantation, filtration with the help of diatomaceous earth or centrifugation. The husk already extracted is contacted with water again in similar conditions as in the initial extraction in order to maximize the recovery of the saponins.
  • the husk extract is separated in the same way as in the initial extraction. If desired, more than two extractions can be performed to maximize saponin recovery.
  • the extracts are combined and treated with base at pH from 8 to 12 and heat (50-100° C) for 1-3 h, to give partially hydrolyzed saponins, which have mono-desmosidic features.
  • the extract is cooled at room temperature and concentrated acid is added to bring the extract to pH 3-7.5.
  • the extract is then concentrated by evaporation at atmospheric pressure or vacuum until the desired concentration of solids is reached in the final product, which can be from 5 to 50% of solids.
  • the final extract can be filtrated with the help of diatomeaceous earth or by centrifugation or decantation to eliminate impurities before packing. In this phase, excipients or preservatives can also be added to improve its stability.
  • hydrolytic enzymes that allow the conversion of bi-desmosidic saponins into mono-desmosidic saponins can be used.
  • beta-glucosidase enzymes can be used, which hydrolyze the glucose group present in C-28.
  • the husk is extracted with water as described above, and the liquid extract is recovered, to which enzymes in optimal conditions of temperature, time and pH are added.
  • the degree of hydrolysis can be determined by saponins analysis by reverse phase HPLC or another analytical method. Once the hydrolysis is finished, the extract is subjected to the concentration, filtration and addition of excipients and preservatives phases already described.
  • liquid composition that comprises such aqueous quinoa extract with a concentration from 1 to 40% partially hydrolyzed quinoa saponins and an excipient.
  • This composition is applied in effective amounts in order to control fresh water snails.
  • the effective amount should range from 4 to 200/kg/hectare.
  • the preparation of a solid formulation comprises contacting the quinoa husk with water in a ratio of 1 part by weight of husk with 1-10 parts by weight of water, at a temperature from 20 to 90° C and 0.1-3 h, with stirring.
  • the mixture is then treated with base at pH from 8 to 12 with the addition of NaOH or another basic agent and heat from 50 to 100° C for 0.1-3 h, to obtain partially hydrolyzed saponins with mono-desmosidic features.
  • the partial hydrolysis is finished, the mixture is cooled at room temperature, and concentrated acid is added to bring it to pH 3-7.5.
  • the mixture is then dried at a temperature that may range from 20 to 80° C.
  • hydrolytic enzymes that allow the conversion of bi-desmosidic saponins into mono-desmosidic saponins can be used.
  • beta-glucosidase enzymes can be used, which hydrolyzes the glucose group present in C-28.
  • the husk is extracted with water as it has been described, and the enzymes in optimal conditions of temperature, time and pH are added.
  • the degree of hydrolysis can be determined by saponins analysis by reverse phase HPLC or another analytical method. Once the hydrolysis is finished, the mixture is dried at a temperature that may range from 20 to 80° C.
  • compositions that comprises a solid quinoa formulation with a concentration from 1 to 40% of partially hydrolyzed quinoa saponins and an excipient.
  • This composition is applied in effective amounts in order to control fresh water snails.
  • the effective amount should range from 4 to 200/kg/hectare.
  • any of the two formulations liquid or dry under any of their preferred modalities of extraction should be added at saponin concentration from 5 to 20 ppm to the water to be treated.
  • the example of the invention consisted in the application of different compositions based on quinoa saponins for the control of golden apple snail (Pomacea canaliculata), to measure then their effect on both snails and fish.
  • the objective of the example was to determine the product concentrations that kill 100% of snails in 24 h: LCi 00 (24 h), and 50% of fish in 24, 48, and 96 h: LC 50 (24 h), LC 50 (48 h), and LC 50 (96
  • the saponin toxicology in snails was assessed with golden apple snails (Pomacea canaliculata). For this purpose, 20 to 35 mm adult snails, collected in a nursery located in IsIa de Maipo (Chile) were used. The snails were maintained in 25 x 20 x 15 cm. glass aquaria with lids, 7,5 liters of capacity each, and water was treated with a chlorine neutralizing product, 2 drops every liter of water. This product is harmless for fish, snails and plants. Each aquarium was filled with 2.5 L of tap water. The snails were kept at 20-22°C using electrical heaters (3 Watt resistance), while checking the water temperature every 12h with a mercury thermometer for aquaria. The water pH was checked every 24 h with a pH-meter (Orion, model 420A) keeping the parameter considered appropriate for the snails (pH 7-8).
  • snails were acclimatized to lab conditions for a week, receiving food every 12 h, with Nutrafin Max complete food in flakes. They were exposed to a 6 h cycle con artificial light (25 W) every 24 h. Four snails were placed in each aquarium and each experiment was carried out three times. In order to determine LCio O (24h), the snails were observed at 24 h, recording the eventual clinical signs y mortalities, assessed by stimuli with a stainless steal needle and detection or lack of movement. After 24 h, snails classified as dead were placed in a separate container with fresh water and checked for recovery. Only those snails that did not recover within additional 24 h in fresh water were reported dead.
  • the saponin toxicology in fish was assessed in 2-3 g goldfish (Carassius auratus auratus) using the products and the aquarium system previously described. This time 5 liters of water per aquarium were used, temperature 16-18 0 C. Four fish were used in each aquarium and each experiment was carried out three times. In some experiments 7-8 g tilapias were used, kept al 21- 22 0 C. Every 24 h during 96 h, the number of dead fish per aquarium was recorded.
  • Table 1 shows the results of the experiments for the different product concentrations.
  • Table 2 summarizes lethal concentrations for snails and fish. Tea seed cake, in 24 h and at very low doses of saponins (1.5 ppm of saponins) kills 100% of fish, and only 66% of snails. This makes it impossible to use this product in rice fields, rivers and lakes nearby, because the doses and periods to kill snails is more lethal for fish. This is similar to niclosamide behavior, which kills fish at lower concentrations than snails.
  • quinoa husk the concentration of 40 ppm of saponin (the biggest essayed) does not cause the death neither in snails nor in fish.
  • goldfish and tilapia do not die in 96h, which makes it safe to use it.
  • Liquid composition without partial hydrolysis of the saponins does not kill neither snails nor fish at 40 ppm of saponins in 24 h, but it does in 48 h.
  • composition based on partially hydrolyzed quinoa saponins is lethal for snails at lower dosages than for fish. This makes it possible for use it safely in flooded rice fields, and it is also safe for rivers and lakes.
  • the composition and method to treat fresh water snails have the advantage of being of natural origins and economical, because it is an industrial by product derivative.
  • Table 1 Quinoa saponin toxicology in snails and fish.

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
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EP06750486A 2005-07-13 2006-04-18 Verfahren und zusammensetzung auf basis von quinoa-saponinen (chenopodium quinoa) für die bekämpfung von aquatischen süsswasserschnecken Withdrawn EP1940232A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CL200501745 2005-07-13
PCT/US2006/014458 WO2007008268A1 (en) 2005-07-13 2006-04-18 Method and a composition based on quinoa saponins (chenopodium quinoa) intended for the control of aquatic fresh water snails

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EP1940232A1 true EP1940232A1 (de) 2008-07-09

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EP06750486A Withdrawn EP1940232A1 (de) 2005-07-13 2006-04-18 Verfahren und zusammensetzung auf basis von quinoa-saponinen (chenopodium quinoa) für die bekämpfung von aquatischen süsswasserschnecken

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EP (1) EP1940232A1 (de)
WO (1) WO2007008268A1 (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114885963A (zh) * 2022-06-09 2022-08-12 广西墨匠生物制药有限公司 以茶麸为原料的生物农药及其制备方法和应用

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Publication number Priority date Publication date Assignee Title
GB1277417A (en) * 1968-06-21 1972-06-14 Nat Res Dev Improvements relating to molluscicides
US6355249B2 (en) * 1998-04-17 2002-03-12 Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of Agriculture And Agri-Food Canada Process for recovery and purification of saponins and sapogenins from quinoa (Chenopodium quinoa)

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2007008268A1 *

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