DESC:FIELD OF THE INVENTION

The present invention relates to process for preparation of a slow and sustained release pheromone which releases the desired pheromone substance into air for monitoring or mass trapping or mating disruption of pests. More particularly it discloses bio-degradable angstrom voids polymer (AVP) matrix and its formulation for a slow and sustained release of pheromone.

BACKGROUND OF THE INVENTION

A pheromone is a semio-chemical signalling compound naturally produced by many living organisms that send biological signals to other organisms of the same species or the different species. Pheromones are non-toxic, they have no adverse effects on non-target organisms, they do not kill parasitoids or other beneficial insects. All these features of the pheromones can be utilized for controlling the insect population. However, the same has not be done at larger scale. The biggest drawbacks of using pheromones to control insect populations is the cost of the pheromone. Most pheromone components vaporize quickly if not formulated in an appropriate sustain-release dispenser base. An insect pest generally emerges over a long period of time. So, it is a requirement of sustained release of a pheromone substance from the dispenser base to make the monitoring or mass trapping or mating disruption for the entire period of emergence. Also, the insect pheromones could be added to lure used in traps for population monitoring requires a very specific delivery rate. A too low delivery rate may be below the threshold of perceptions while too high delivery rate may confuse or repel the insect and prevent the insects from entering the trap.

The existing devices can be exemplified as follows, the material includes rubber, polyethylene, polypropylene, an ethylene-vinyl acetate copolymer containing 90% by weight or greater of ethylene repeating units, and polyvinyl chloride. The polyolefin-based plastics are also widely used so that they are inexpensive. Each of these devices and methods has certain advantages and drawbacks. The lures used in the above-mentioned devises are neither biodegradable nor release duration of the pheromone covers the entire crop cycle while being costly for mass use.

It is required for effective pest management to develop a control technology with pheromone to sustainably release a sufficient amount of pheromone from an attraction source to attract insect pests with respect to the monitoring or mass trapping or mating disruption and to maintain a sufficient amount of pheromone to cause mating disruption in an entire region to be controlled with respect to the mating disruption. Ideally, the release rate of the pheromone should be relatively constant and remain effective during the whole flight period of the pest. Therefore, there is an urgent need for the slow and sustain release dispersion medium along with devices which are eco-friendly and biodegradable.

SUMMARY OF THE INVENTION

The present disclosure provides for bio-degradable angstrom voids polymer (AVP) matrix and its formulation for a slow and sustained release of pheromone.

According to the present invention, the pheromone lure consists of pheromone impregnated in angstrom voids polymer (AVP) matrix as sustained release dispensing medium. Wherein which the pheromone retains their stability and the active ingredients are allowed to release at a continuous slow release rate for a prolonged period of time. However, it is necessary to instant release of high amount of pheromone substance in order to reach the pests which are far away. On the other hand, it is necessary to require extended release of a pheromone substance from the dispenser to make monitoring or mass trapping or the mating disruption for the entire period of pest emergence. Thus, the present invention AVP matrix consists together of pheromone impregnated bio-degradable polymer which gives instant release of pheromone as well as pheromone incorporated in angstrom voids polymer matrix extended release of the pheromone. In addition, the pheromone formulation is protected from the degradation of UV light, moisture, and high temperature by addition of anti-oxidants, pH stabilizers, moisture retainers, anti-microbial agent, surfactants and UV blockers.

In an embodiment, the present invention provides for a process for preparation of bio-degradable angstrom voids polymer (AVP) matrix for a slow and sustained release of one or more pheromones. The process, include steps of:
(a) mixing one or more pheromones and Zeolite in a container to get the one or more pheromones incorporated in angstrom voids spaces of zeolite, where the one or more pheromones being allowed to be completely intruded (absorbed) into the voids of Zeolite;
(b) preparing one or more pheromones gel matrix by
adding one or more gelling agents to water while mixture being continuously stirred, where the one or more gelling agents being added lot by lot and allowed to swell,
adding to the mixture obtained in previous step at least one of one or more preserving agents, one or more moisture retaining agents, one or more anti-microbial agents, one or more anti-oxidizing agents, and one or more UV-blockers, while continuously stirring,
adding one or more surfactants and one or more colouring agents to the mixture obtained in the previous step, and
adding the one or more pheromones dissolved in a suitable solvent to the mixture obtained in the previous step while being continuously stirred, thereby obtaining the one or more pheromones incorporated into the gel matrix;
(c) mixing the one or more pheromones incorporated in angstrom voids spaces of zeolite with the gel matrix incorporated with one or more pheromones thereby obtaining the bio-degradable angstrom voids polymer (AVP) matrix for a slow and sustained release of the one or more pheromones; and
(d) adding one or more organic pH modifiers to the bio-degradable angstrom voids polymer (AVP) matrix to adjust pH to 6.0 - 7.5., preferably in pH range 6.5-7.0.

In another embodiment, the present invention provides for a bio-degradable angstrom voids polymer (AVP) matrix for a slow and sustained release of pheromone, including one or more pheromones impregnated on Zeolite angstrom voids spaces, mixed with one or more pheromones gel matrix comprising at least one of one or more pheromones, one or more gelling agents, one or more preserving agents, one or more moisture retaining agents, one or more anti-microbial agents, one or more anti-oxidizing agents, and one or more UV-blockers, one or more surfactants. The pheromone impregnated in bio-degradable polymer matrix gives instant release of the pheromone as well as pheromone incorporated in angstrom voids spaces of zeolite gives slow and sustained release of the pheromone.

BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS

Figure 1 shows the graph plot depicting Methyl Eugenol Recovery with different concentrations in Bio-degradable Angstrom voids polymer (AVP) matrix formulation.
Figure 2 is a graph plot depicting the Cue lure - Recovery with Different Concentrations in Bio-degradable Angstrom voids polymer (AVP) matrix formulation.

DETAILED DESCRIPTION OF THE PRESENT INVENTION

The present invention provides for a process for preparation of bio-degradable angstrom voids polymer (AVP) matrix for a slow and sustained release of one more pheromones and product thereof.

In an embodiment, the present invention provides for a process for preparation of bio-degradable angstrom voids polymer (AVP) matrix for a slow and sustained release of one more pheromones. The process, include steps of:
(a) mixing one or more pheromones and Zeolite in a container to get the one or more pheromones incorporated in angstrom voids spaces of zeolite, where the one or more pheromones being allowed to be completely absorbed by Zeolite;
(b) preparing one or more pheromones gel matrix by
adding one or more gelling agents to water while mixture being continuously stirred, where the one or more gelling agents being added lot by lot and allowed to swell,
adding to the mixture obtained in previous step at least one of one or more preserving agents, one or more moisture retaining agents, one or more anti-microbial agents, one or more anti-oxidizing agents, and one or more UV-blockers, while continuously stirring,
adding one or more surfactants and one or more colouring agents to the mixture obtained in the previous step, and
adding the one or more pheromones dissolved in suitable eco-friendly organic solvent to the mixture obtained in the previous step while being continuously stirred, thereby obtaining the one or more pheromones gel matrix;
(c) mixing the one or more pheromones incorporated in angstrom voids spaces of zeolite with the one or more pheromones gel matrix thereby obtaining the bio-degradable angstrom voids polymer (AVP) matrix for a slow and sustained release of the one or more pheromones; and
(d) adding one or more organic pH modifiers to the bio-degradable angstrom voids polymer (AVP) matrix to adjust pH to 6.0 - 7.5., preferably in pH range 6.5-7.0.

The pheromones are either natural or synthetic which were selected from the group of molecules belonging to the class of acetate compounds, aldehyde compounds, carboxylic acid compounds, carboxylic acid esters, hydrocarbon compounds, keto compounds, alcohol and its derivate compounds, and other compounds.

Specifically, examples of acetate compounds not limited to, consists of (E)-2-Hexenyl acetate, (Z)-3-Hexenyl acetate, 1-Hexenyl acetate, (E)-2-Heptenyl acetate, 4-Methoxybenzyl acetate, Cyclohexyl 2-phenylacetate, Cyclohexyl acetate, (E)-2-Octenyl acetate, (Z)-3-Octenyl acetate, 2-Octenyl acetate, Ethyl 2-phenylacetate, Methyl 2-phenylacetate, Octyl acetate, 2-Nonenyl acetate, Nonyl acetate, (E)-2-Decenyl acetate, (Z)-3-Decenyl acetate, (Z)-4-Decenyl acetate, (Z)-5-Decenyl acetate, (Z)-7,9-Decadienyl acetate, (Z)-7-Decenyl acetate, 2-Decenyl acetate, Decyl acetate, (Z)-5-Undecenyl acetate, (Z)-7-Undecenyl acetate, (Z)-8-Undecenyl acetate, (Z)-9-Undecenyl acetate, 2-Undecenyl acetate, Undecyl acetate, (Z)-10-Dodecenyl acetate, (Z)-3-Dodecenyl acetate, (Z)-5-Dodecenyl acetate, (Z)-7-Dodecenyl acetate, (Z)-8-Dodecenyl acetate, (Z)-9,11-Dodecadienyl acetate, (Z)-9-Dodecenyl acetate, Dodecyl acetate, (Z)-4-Tridecenyl acetate, (Z)-8-Tridecenyl acetate, (Z)-9-Tridecenyl acetate, Tridecyl acetate, (Z)-10-Tetradecenyl acetate, (Z)-11-Tetradecenyl acetate, (Z)-12-Tetradecenyl acetate, (Z)-3-Tetradecenyl acetate, (Z)-5-Tetradecenyl acetate, (Z)-6-Tetradecenyl acetate, (Z)-7-Tetradecenyl acetate, (Z)-8-Tetradecenyl acetate, (Z)-9-Tetradecenyl acetate, Tetradecyl acetate, (Z)-10-Pentadecenyl acetate, (Z)-12-Pentadecenyl acetate, (Z)-8-Pentadecenyl acetate, (Z)-9-Pentadecenyl acetate, (Z)-10-Hexadecenyl acetate, (Z)-11-Hexadecenyl acetate, (Z)-12-Hexadecenyl acetate, (Z)-3-Hexadecenyl acetate, (Z)-5-Hexadecenyl acetate, (Z)-7-Hexadecenyl acetate, (Z)-9-Hexadecenyl acetate, Hexadecyl acetate, (Z)-11-Heptadecenyl acetate, (Z)-11-Octadecenyl acetate, (Z)-9-Octadecenyl acetate, Octadecyl acetate, and (Z)-11-Eicosenyl acetate.

Examples of aldehyde group comprising pheromone compounds not limited, consists of (E)-2-Hexenal, (Z)-3-Hexenal, (E)-2-Heptenal, (E)-2-Octenal, 2-Octenal, 2-Phenylacetaldehyde, 2-Phenylpropenal, (E)-2-Nonenal, (Z)-3-Nonenal, (Z)-4-Nonenal, (E)-2-Decenal, (Z)-4-Decenal, (Z)-5-Decenal, 1-Decenal, 2-Decenal, (E)-2-Undecenal, (Z)-5-Dodecenal, (Z)-7-Dodecenal, (Z)-9-Dodecenal, (Z)-4-Tridecenal, (Z)-5-Tetradecenal, (Z)-7-Tetradecenal, (Z)-9-Tetradecenal, (Z)-10-Pentadecenal, (Z)-10-Hexadecenal, (Z)-11-Hexadecenal, (Z)-7-Hexadecenal, (Z)-9-Hexadecenal, (Z)-9-Heptadecenal, (Z)-11-Octadecenal, (Z)-9-Octadecenal, and (Z)-11-Eicosenal.

Examples of carboxylic group comprising pheromone compounds not limited, consists of (E)-2-Butenoic acid, (E)-2-Hexenoic acid, (Z)-2-Hexenoic acid, (Z)-3-Hexenoic acid, (E)-2-Octenoic acid, (Z)-5-Octenoic acid, 2-Octenoic acid, (Z)-6-Nonenoic acid, 9-Oxononanoic acid, (Z)-3-Decenoic acid, (Z)-4-Decenoic acid, (Z)-5-Undecenoic acid, (Z)-3-Dodecenoic acid, (Z)-5-Dodecenoic acid, (Z)-9-Dodecenoic acid, (Z)-5-Tetradecenoic acid, 7-Oxotetradecanoic acid, (Z)-11-Hexadecenoic acid, (Z)-9-Hexadecenoic acid, 9-Oxohexadecanoic acid, (Z)-11-Octadecenoic acid, (Z)-9-Octadecenoic acid, 9-Hydroxyoctadecanoic acid, and 9-Octadecenoic acid.

Examples of carboxylic esters group comprising pheromone compounds not limited, consists of (E)-2-Hexenyl butyrate, (E)-2-Hexenyl hexanoate, (E)-2-Hexyl hexenoate, (Z)-3-Hexenyl butyrate, (Z)-3-Hexenyl hexanoate, (Z)-3-Hexenyl isobutyrate, Butyl hexanoate, Hexyl butyrate, Hexyl hexanoate, Hexyl propionate, Methyl hexanoate, Pentyl hexanoate, Propyl hexanoate, (E)-2-Hexenyl benzoate, Benzyl acetate, Benzyl benzoate, Benzyl hexanoate, Ethyl 4-hydroxybenzoate, Ethyl 4-methylheptanoate, Heptyl butyrate, Pentyl benzoate, Phenyl propionate, Propyl 2-heptynoate, Propyl 4-hydroxybenzoate, (E)-2-Octenyl butyrate, (E)-2-Octenyl hexanoate, (Z)-4-Octenoic acid methyl ester, Ethyl (Z)-4-octenoate, Ethyl benzoate, Ethyl octanoate, Hexyl octanoate, Methyl benzoate, Methyl octanoate, Octyl butyrate, Octyl hexanoate, Octyl octanoate, (Z)-2-Nonenyl propionate, Nonyl butyrate, Decyl hexanoate, Decyl isobutyrate, Decyl octanoate, Decyl propionate, Ethyl decanoate, Hexyl decanoate, Methyl decanoate, Octyl decanoate, Hexyl undecanoate, Undecyl butyrate, Undecyl isobutyrate, (Z)-7-Dodecenyl butyrate, (Z)-7-Dodecenyl propionate, Dodecyl hexanoate, Dodecyl nonanoate, Dodecyl octanoate, Dodecyl undecanoate, Ethyl dodecanoate, Heptyl dodecanoate, Hexyl decanoate, Hexyl dodecanoate, Isopropyl (Z)-5-dodecenoate, Isopropyl (Z)-7-dodecenoate, Isopropyl (Z)-9-dodecenoate, Isopropyl dodecanoate, Methyl dodecanoate, Octyl dodecanoate, Pentyl dodecanoate, Propyl dodecanoate, sec-Butyl-(Z)-3-dodecenoate, Ethyl (Z)-9-tetradecenoate, Methyl tetradecanoate, Tetradecyl butyrate, Tetradecyl hexanoate, Tetradecyl isobutyrate, Tetradecyl octanoate, Tetradecyl propionate, Methyl (Z)-5-tetradecenoate, (Z)-11-Hexadecenyl trifluoroacetate, Ethyl (Z)-7-hexadecenoate, Ethyl (Z)-9-hexadecenoate, Isopropyl (Z)-9-hexadecenoate, Methyl (Z)-7-hexadecenoate, Methyl (Z)-8-hexadecenoate, Methyl (Z)-9-hexadecenoate, (Z)-3-Hexenyl octadecenoate, (Z)-7-Octadecenyl butyrate, (Z)-7-Octadecenyl isobutyrate, (Z)-9-Octadecenoic acid ethyl ester, (Z)-9-Octadecenoic acid methyl ester, and 1,2 –Dimethoxy-4-(prop-2-en-1-yl) benzene.

Examples of hydrocarbons comprising pheromone compounds not limited, consists of (Z)-4-Tridecene, (Z)-5-Tridecene, (Z)-6-Pentadecene, (Z)-7-Pentadecene, (Z)-7-Heptadecene, (Z)-8-Heptadecene, (Z)-7-Octadecene, (Z)-9-Octadecene, (Z)-9-Nonadecene, (Z)-9-Eicosene, (Z)-7-Heneicosene, (Z)-9-Heneicosene, (Z)-7-Docosene, (Z)-9-Docosene, (Z)-5-Tricosene, (Z)-7-Tricosene, (Z)-9-Tricosene, (Z)-7-Tetracosene, (Z)-9-Tetracosene, (Z)-10-Pentacosene, (Z)-11-Pentacosene, (Z)-5-Pentacosene, (Z)-7-Pentacosene, (Z)-9-Pentacosene, (Z)-8-Hexacosene, (Z)-9-Hexacosene, (Z)-11-Heptacosene, (Z)-12-Heptacosene, (Z)-7-Heptacosene, (Z)-9-Heptacosene, (Z)-11-Nonacosene, (Z)-12-Nonacosene, (Z)-7-Nonacosene, (Z)-9-Nonacosene, (Z)-11-Hentriacontene, and (Z)-9-Hentriacontene.

Examples of keto group comprising pheromone compounds not limited, consists of Hexan-2-one, Hexan-3-one, Heptan-3-one, Heptan-4-one, 1-Octen-3-one, Octan-2-one, Octan-3-one, Nonan-3-one, Nonan-4-one, Methyldecan-2-one, Undecan-3-one, 1-Dodecen-3-one, Dodecan-3-one, Tridecan-3-one, Tetradecan-3-one, Hexadecan-3-one, 1-Heptadecen-3-one, and Heptadecan-9-one, 4-methyl-5-Nonanone, and 4-(4– Acetoxyphenyl)-2-Butanone.

Examples of alcohol and its derivatives group consisting pheromone compounds not limited, comprises of (Z)-2-Penten-1-ol, (E)-2-Hexen-1-ol, (Z)-2-Hexen-1-ol, (Z)-3-Hexen-1-ol, (E)-2-Octen-1-ol, (Z)-2-Octen-1-ol, (Z)-3-Octen-1-ol, (E)-2-Nonen-1-ol, (Z)-3-Nonen-1-ol, (Z)-6-Nonen-1-ol, (Z)-3-Decen-1-ol, (Z)-4-Decen-1-ol, (Z)-5-Decen-1-ol, (Z)-7,9-Decadien-1-ol, (Z)-10-Dodecen-1-ol, (Z)-3-Dodecen-1-ol, (Z)-5-Dodecen-1-ol, (Z)-7-Dodecen-1-ol, (Z)-8-Dodecen-1-ol, (Z)-9-Dodecen-1-ol, (Z)-3-Tetradecen-1-ol, (Z)-5-Tetradecen-1-ol, (Z)-7-Tetradecen-1-ol, (Z)-8-Tetradecen-1-ol, (Z)-9-Tetradecen-1-ol, (Z)-11-Hexadecen-1-ol, (Z)-7-Hexadecen-1-ol, (Z)-9-Hexadecen-1-ol, (Z)-11-Heptadecen-1-ol, (Z)-11-Octadecen-1-ol, (Z)-11-Eicosen-1-ol, and 4-Methyl-5-Nonan-1-ol and Methyl Eugenol.

In order to store pheromone lure for long term and to increase its effectiveness, it has to be protected from external environment stress, the abiotic and biotic stress factors like UV light, moisture, high temperature and micro-organisms is achieved by adding anti-oxidants, moisture retainers, anti-microbial agent, surfactants, UV blockers and preservatives.

The anti-oxidising agents are selected from a group consisting of Butylated Hydroxy Toluene (BHT), Butylated hydroxyl anisole (BHA), vitamin E, vitamin C, 2,6-di-tert-butyl-p-cresol, t-butyl hydroquinone(TBHQ), Lecithin soya 30%, 2,5-di-tert-butylhydroquinone. More preferably BHT, BHA and TBHQ. The stoichiometric ratio of the anti-oxidant agents in the gel matrix were added in the ratio about 0.1 to 3%, more preferably 0.5 to 1.5%.

The moisture retaining agents are selected from a group consisting of PEG (polyethylene glycol), PPG (polypropylene glycol), Glycerine. More preferably PEG and Glycerine. The stoichiometric ratio of the moisture retaining agents in the gel matrix were added in the ratio about 2 to 10%, more preferably 4 to 6%.

The anti-microbial agents are selected from a group consisting of sodium benzoate, sodium sorbate, potassium sorbate, propylene oxide, Benzalkonium chloride, Sorbic acid, Boric acid, Thiomersal, methyl-4-hydroxy benzoate. More preferably sodium benzoate, sodium sorbate. The stoichiometric ratio of the anti-microbial agents in the gel matrix were added in the ratio about 0.1 to 3%, more preferably 0.5 to 1.5%.

The UV-blockers are selected from a group consisting of Para-Amino benzoic acid, Zinc oxide, Benzophenone, Ethyl cinnamate. The stoichiometric ratio of the UV-blockers in the gel matrix were added in the ratio about 0.01 to 0.5%, more preferably 0.05 to 0.2%.

The preserving agents are selected from a group consisting of 2-chloroacetamide, Sodium sorbate, Potassium sorbate, Calcium sorbate, Benzoic acid, Sodium benzoate, Potassium benzoate, Calcium benzoate, Propylparaben or Propyl-p-hydroxy-benzoate, Methylparaben or Methyl-p-hydroxy-benzoate, Sulphur dioxide, Sodium sulphite, Sodium bisulphate, Sodium metabisulphite, Potassium metabisulphite, Potassium sulphite, Potassium bisulphate, Nisin, Natamycin or Pimaricin, Dimethyl dicarbonate, Potassium nitrite, Sodium nitrite, Sodium nitrate, Potassium nitrate, Propionic acid, Sodium propionate, Calcium propionate, Potassium propionate, Calcium disodium ethylenediaminetetraacetate or calcium disodium EDTA, Lysozyme. More preferably 2-chloroacetamide and benzyl alcohol. The stoichiometric ratio of the preserving agents in the gel matrix were added in the ratio about 0.1 to 3%, more preferably 0.5 to 1.5%.

Surfactants such as Triethanolamine, Triton x 100, Triethanolamine, Propylene glycol, Triton-X, Diethanolamine, sodium dodecyl sulphate, Poly ethylene glycol, Alkyl polyglycoside, Cetomacrogol 1000, Cetostearyl alcohol, Cetyl alcohol, Cocamide DEA, Cocamide MEA, Decyl glucoside, Decyl polyglucose, Disodium cocoamphodiacetate, Glycerol monostearate, IGEPAL CA-630, Isoceteth-20, Lauryl glucoside, Maltosides, Monolaurin, Mycosubtilin, Narrow-range ethoxylate, Nonidet P-40, Nonoxynol-9, Nonoxynols, NP-40, Octaethylene glycol monododecyl ether, N-Octyl beta-D-thioglucopyranoside, Octyl glucoside, Oleyl alcohol, PEG-10 sunflower glycerides, Pentaethylene glycol, monododecyl ether, Polidocanol, Poloxamer, Poloxamer 407, Polyethoxylated tallow amine, Polyglycerol polyricinoleate, Polysorbate, Polysorbate 20, Polysorbate 80, Sorbitan, Sorbitan monolaurate, Sorbitan, monostearate, Sorbitan tristearate, Stearyl alcohol, Surfactin and Tween 80. One or more of the surfactants were added in small amount which raises the pH and increases the swelling capacity of gelling agent.

The gelling agents are selected from a group consisting of Carbopol 940, Gelatine, Pluronic, sodium alginate, Beta cyclodextrin, Bentonite, Methyl cellulose, Carboxy methyl cellulose, chitosan, carboxy methyl chitosan, gellan gum, carrageenan, xanthan gum, silica, mannitol dioctanoate, PVA (poly vinyl alcohol), tragacanth, hydroxyethyl cellulose, hydroxypropyl cellulose, Locust bean gum, Pectin, Starch, agars, magnesium aluminium silicate. Preferred grades of polyacrylic acid are those referred to as Carbopol at concentrations of 0.5-10.0%. Higher concentrations of polyacrylic acid lower the release rate of the active components. Viscosities of polyacrylic acids are generally stable between pH 6.0 - 7.0, preferably in the pH range 6.5-7.0. The viscosity of the gels prepared ranged from about 0 to about 80,000 cps. The gelling agents are biodegradable.

The colouring agent used in one case is Tartrazine FD&C.

Procedure for preparation of 1000 grams of gel:
The procedure requires a wide mouthed container selected based on the amount of gel to be prepared. The container should be provided with a stirrer for the uniform mixing of the all the ingredients. For the 1000 gms of the gel preparation one can use about 2.0 L volume containers. 5.0-100.0 grams of carbopol (0.5 to 10%) was added to the solution and mixed slowly by stirring with the use of a mechanical stirrer. The carbopol was allowed to swell. Added other additives at the concentration of 0.1 - 5% by weight. Added pheromones dissolved in suitable eco-friendly organic solvent. Finally added zeolites (pore size - 400 Picometers) impregnated with 10.0 - 50.0% of pheromones and mixed well for uniform distribution. The final formulation solution was neutralized to pH 6.5 to 7.5 by the addition of organic pH modifiers.

In another embodiment, the present invention provides a bio-degradable angstrom voids polymer (AVP) matrix for a slow and sustained release of pheromones, including one or more pheromones impregnated on Zeolite angstrom voids spaces, mixed with one or more pheromones gel matrix comprising at least one of one or more pheromones, one or more gelling agents, one or more preserving agents, one or more moisture retaining agents, one or more anti-microbial agents, one or more anti-oxidizing agents, one or more UV-blockers, one or more surfactants and one or more organic pH modifiers. The pheromones impregnated in bio-degradable polymer matrix gives both instant release of the pheromone as well as pheromone incorporated in AVP matrix for extend release.

EXAMPLES

The present invention is explained further in the following specific examples which are only by way of illustration and are not to be construed as limiting the scope of the invention.

EXAMPLE-1
Procedure for preparation of AVP matrix of methyl eugenol for control of fruit fly:

STEP 1: Incorporation of methyl eugenol in AVP
A 50ml container was taken and 1.0 g of the methyl eugenol was added. To this 2.0g of Zeolite 4A was added and container was closed with lid and allowed for 10 minutes to complete absorption.

STEP 2: Preparation of methyl eugenol gel matrix
A 250ml beaker was taken and added 82 ml of water, with continuous stirring 2.0g of polyacrylate 940 (Carbopol 940) was added lot by lot and allowed to swell. To the mixture one after the other one, 1.0g of 2-chloroacetamide, 1.0g of sodium benzoate, 1.0g of BHT and 0.5g of p-amino benzoic acid were added with stirring. To this, 5.0g of glycerol (moisture retaining agent) and a pinch of tartrazine were added. To the mixture 1.0g of methyl eugenol dissolved in ethanol was added and continued stirring for 15 minutes.

STEP 3: Preparation of methyl eugenol impregnated AVP matrix
The methyl eugenol impregnated Zeolite was mixed with methyl eugenol impregnated gel matrix and the pH of AVP matrix is adjusted to 6.5 - 7.5 by the addition of triethanolamine.

The above procedure is applied for preparation of AVP matrix for the following pheromolecules for monitoring or mass trapping or the mating disruption of pests:

1. Melon fly – Cue lure.
2. House fly – Z-9 Tricosene.
3. Red palm weevil – 4-Methyl-5-Nonanol + 4-Methyl-5-Nonanol
4. Diamond back moth – Z-11Hexadecenol + Z-11Hexadecenal + Z-11Hexadecenyl-1-acetate.
5. Tea mosquito bug – Cis-3-Hexenyl acetate + Trans-2-Hexenol

A pheromone lure consists of Zeolite biodegradable polymer matrix, wherein which the pheromone present in a zeolite bio-degradable polymer matrix in an amount varying from about 0.5 % to 5.0 % by weight, more preferably 1%.

Quantification of Methyl Eugenol in Bio-degradable Angstrom voids polymer (AVP) matrix formulation: validation of the method
Standard dilution: 62.1 mg diluted to 10 ml with diluent Potency of Standard (%) 99.0
Bracketing standard
Sl. No RT Area RT Area % agreement
1 6.315 3400.053 Std 01 6.315 3489.487 101.56
2 6.315 3572.603 Std 02 6.315 3438.966 98.55
3 6.315 3485.312
4 6.315 3439.262
5 6.315 3487.757
6 6.315 3435.988
Average 3470.163
SD 60.1185648
RSD 1.73

Methyl Eugenol Recovery with Different Concentrations in Bio-degradable Angstrom voids polymer (AVP) matrix formulation

AVP Zeolites spiked with Methyl eugenol Methyl eugenol spiked in ppm Area Average Assay % Recovery
20% 4.94 2680.62 2668.189 96.47 19.29
2655.757
50% 12.36 3844.345 3820.769 109.28 54.64
3797.192
80% 19.776 3624.845 3620.415 107.77 86.22
3615.985
100% 24.72 2808.600 2791.970 96.76 96.76
2775.340
120% 29.66 3244.396 3238.604 96.72 116.07
3232.812

Figure 1 shows the graph plot depicting Methyl Eugenol Recovery with different concentrations in Bio-degradable Angstrom voids polymer (AVP) matrix formulation.
Quantification of Cue lure in Bio-degradable Angstrom voids polymer (AVP) matrix formulation: validation of the method
Standard dilution: 62.3 mg diluted to 10 ml with diluent Potency of Standard (%) 98.0
Bracketing standard
Sl. No RT Area RT Area % agreement
1 9.889 3388.650 Std 01 9.880 3125.557 97.19
2 9.888 3263.807 Std 02 9.880 3122.590 99.91
3 9.887 3042.210
4 9.887 2995.560
5 9.885 3082.363
6 9.885 3215.825
Average 3164.736
SD 150.3203773
RSD 4.75

Cue lure - Recovery with Different Concentrations in Bio-degradable Angstrom voids polymer (AVP) matrix formulation
AVP Zeolites spiked with Cue lure Cue lure spiked in ppm Area Average Assay % Recovery
20% 4.9 2533.63 2545.295 99.89 19.98
2556.96
50% 12.388 3144.345 3170.769 98.44 49.22
3197.192
80% 19.838 3124.845 3170.415 102.44 81.95
3215.985
100% 25.561 2658.600 2669.470 100.41 100.41
2680.340
120% 28.16 2944.396 2938.604 100.34 120.40
2932.812

Figure 2 is a graph plot depicting the Cue lure - Recovery with Different Concentrations in Bio-degradable Angstrom voids polymer (AVP) matrix formulation.
Table 1 to 6; Statistical analysis (ANOVA) for the various responses (contact, approach, flight) of Melon fly (Bactrocera cucurbitae) and fruit fly (Bactrocera dorsalis) towards pheromone impregnated Bio-degradable AVP matrix formulation and control in wind tunnel assay.
Table 1: Response of CONTACT of Melon fly (Bactrocera cucurbitae)
Treatments
1 2 Total
N 15 15 30
?X 234 31 265
Mean 15.6 2.0667 8.8333
?X2 3754 75 3829
SD 2.7203 0.8837 7.1635

Result Details
Source SS df MS
Between-treatments 1373.6333 1 1373.6333 F = 335.81257
Within-treatments 114.5333 28 4.0905
Total 1488.1667 29

F- ratio value is 335.81257. The P-value is <0.00001. The result is significant at P<0.05 level
Table 2: Response of APPROACH of Melon fly (Bactrocera cucurbitae)
Treatments
1 2 Total
N 15 15 30
?X 251 53 304
Mean 16.7333 3.5333 10.1333
?X2 4261 219 4480
SD 2.0862 1.5055 6.9468

Result Details
Source SS df MS
Between-treatments 1306.8 1 1306.8 F = 394.86043
Within-treatments 92.6667 28 3.3095
Total 1399.4667 29

F- ratio value is 394.86043. The P-value is <0.00001. The result is significant at P<0.05 level

Table 3: Response of FLIGHT of Melon fly (Bactrocera cucurbitae)
Treatments
1 2 Total
N 15 15 30
?X 279 139 418
Mean 18.6 9.2667 13.933
?X2 5209 1313 6522
SD 1.1932 1.3345 4.9055

Result Details
Source SS df MS
Between-treatments 653.3333 1 653.3333 F = 330.60241
Within-treatments 44.5333 28 1.5905
Total 27.6667 14 1.9762

F- ratio value is 330.60241. The P-value is <0.00001. The result is significant at P<0.05 level

Table 4: Response of CONTACT of fruit fly (Bactrocera dorsalis)
Treatments
1 2 Total
N 15 15 30
?X 235 14 249
Mean 15.6667 0.9333 8.3
?X2 3723 22 3745
SD 1.7182 0.7988 7.6074

Result Details
Source SS df MS
Between-treatments 1628.0333 1 1628.0333 F = 829.82282
Within-treatments 50.2667 28 1.7952
Total 27.4667 14 1.9619

F- ratio value is 829.82282. The P-value is <0.00001. The result is significant at P<0.05 level
Table 5: Response of APPROACH fruit fly (Bactrocera dorsalis)
Treatments
1 2 Total
N 15 15 30
?X 255 55 310
Mean 17 3.6667 10.333
?X2 4375 239 4614
SD 1.6903 1.633 6.9745

Result Details
Source SS df MS
Between-treatments 1333.3333 1 1333.3333 F = 427.48092
Within-treatments 77.3333 28 2.7619
Total 43.6667 14 3.119

F- ratio value is 427.48092. The P-value is <0.00001. The result is significant at P<0.05 level
Table 6: Response of FLIGHT of fruit fly (Bactrocera dorsalis)
Treatments
1 2 Total
N 15 15 30
?X 278 170 448
Mean 18.5333 11.3333 14.933
?X2 5174 2046 7220
Std.Dev. 1.2459 2.9196 4.2745

Result Details
Source SS df MS
Between-treatments 388.8 1 388.8 F = 75.39058
Within-treatments 141.0667 28 5.0381
Total 72.2 14 5.1571

F- ratio value is 75.39058. The P-value is <0.00001. The result is significant at P<0.05 level
Table 7 to 9; Statistical analysis (ANOVA) for the various responses (contact, approach, flight) of RPW (Rhynchophorus ferrugineus) towards pheromone impregnated Bio-degradable AVP matrix formulation and control in wind tunnel assay.
Table 7: Response of CONTACT of RPW (Rhynchophorus ferrugineus)
Groups Count Sum Average Variance
Pheromone 10 56 5.6 1.15556
control 10 9 0.9 0.76667

Source of Variation SS df MS F P-value F critical
Between Groups 110.5 1 110.45 114.919 3E-09 4.4139
Within Groups 17.3 18 0.961111111

Total 127.8 19
F- ratio value is 114.919 The P-value is <0.00001. The result is significant at P<0.05 level

Table 8: Response of approach of RPW (Rhynchophorus ferrugineus)
Groups Count Sum Average Variance
Treatment 10 83 8.3 0.6777778
Control 10 65 6.5 0.7222222

Source of Variation SS df MS F P-value F crit
Between Groups 16.2 1 16.2 23.142857 0.0001 4.41387
Within Groups 12.6 18 0.7

Total 28.8 19
F- ratio value is 23.142 The P-value is <0.00001. The result is significant at P<0.05 level

Table 9: Response of flight of RPW (Rhynchophorus ferrugineus)
Groups Count Sum Average Variance
Treatment 10 83 8.3 0.6777778
Control 10 65 6.5 0.7222222

Source of Variation SS df MS F P-value F crit
Between Groups 16.2 1 16.2 23.142857 0.0001 4.41387
Within Groups 12.6 18 0.7

Total 28.8 19
F- ratio value is 23.1428 The P-value is <0.00001. The result is significant at P<0.05 level

There may be minor variations not departing from the scope of the invention for different types of pheromones to be impregnated.

The present invention provides for a process for preparation of novel, cost effective, slow and extended release of impregnated pheromone in angstrom voids polymer (AVP) matrix as well the product by the process. The AVP matrix with the pheromolecules serves both purposes of instant release of high amount of pheromone substance in order to reach the pests which are far away and extended release of the pheromone substance. These two features make the AVP matrix with the pheromolecules a suitable candidate to be used in insect trapping devices to enable monitoring or mass trapping or the mating disruption for the entire period of pest emergence.

Further the angstrom voids polymer (AVP) matrix and its formulations are bio-degradable, cost effective and efficacious.
,CLAIMS:We Claim:

1. A process for preparation of bio-degradable angstrom voids polymer (AVP) matrix for a slow and sustained release of one more pheromones, comprising steps of:
(a) mixing one or more pheromones and Zeolite in a container to get the one or more pheromones incorporated in angstrom voids spaces of the zeolite, where the one or more pheromones being allowed to be completely absorbed by Zeolite;
(b) preparing one or more pheromones gel matrix by
adding one or more gelling agents to water while mixture being continuously stirred, where the one or more gelling agents being added lot by lot and allowed to swell,
adding to the mixture obtained in previous step at least one of one or more preserving agents, one or more moisture retaining agents, one or more anti-microbial agents, one or more anti-oxidizing agents, and one or more UV-blockers, while continuously stirring,
adding one or more surfactants and colouring agent to the mixture obtained in the previous step, and
adding the one or more pheromones dissolved in ethanol to the mixture obtained in the previous step while being continuously stirred, thereby obtaining the one or more pheromones gel matrix;
(c) mixing the one or more pheromones incorporated in angstrom voids spaces of zeolite with the one or more pheromones in gel matrix thereby obtaining the bio-degradable angstrom voids polymer (AVP) matrix for a slow and sustained release of the one or more pheromones; and
(d) adding one or more organic pH modifiers to the bio-degradable angstrom voids polymer (AVP) matrix to adjust pH to 6.0 - 7.5., preferably in pH range 6.5-7.0

2. The process as claimed in claim 1, wherein viscosity of the bio-degradable angstrom voids polymer (AVP) matrix ranges from 0 to about 80,000 cps.

3. The process as claimed in claim 1, wherein the one or more pheromones are selected from the group consist of acetate compounds, aldehyde compounds, carboxylic acid compounds, carboxylic acid esters, hydrocarbon compounds, keto compounds, alcohol and its derivates compounds and other compounds.

4. The process as claimed in claim 1, wherein the one or more gelling agents are selected from a group consisting of Carbopol 940, Gelatin, Pluronic, sodium alginate, Beta cyclo dextrin, Bentonite, Methyl cellulose, Carboxy methyl cellulose, chitosan, carboxy methyl chitosan, gellan gum, carrageenan, xanthan gum, silica, mannitol dioctanoate, PVA (poly vinyl alcohol), tragacanth, hydroxyethyl cellulose, hydroxypropyl cellulose, Locust bean gum, Pectin, Starch, agars, magnesium aluminium silicate.

5. The process as claimed in claim 1, wherein one or more gelling agents are in concentrations of 0.5-10.0%.

6. The process as claimed in claim 1, wherein the one or more anti-oxidizing agents are selected from a group consisting Butylated Hydroxy Toluene (BHT), Butylated hydroxyl anisole (BHA), vitamin E, vitamin C, 2,6-di-tert-butyl-p-cresol, Tert-Butylhydroquinone, Lecithin soya 30%, and 2,5-di-tert-butylhydroquinone.

7. The process as claimed in claim 1, wherein the one or more anti-oxidant agents being added in the one or more pheromones gel matrix in the stoichiometric ratio of 0.1 to 3%, preferably 0.5 to 1.5%.

8. The process as claimed in claim 1, wherein the one or more moisture retaining agents are selected from a group consisting of PEG (polyethylene glycol), PPG (polypropylene glycol), and Glycerine.

9. The process as claimed in claim 1, wherein the one or more moisture retaining agents being added in the one or more pheromones gel matrix in stoichiometric ratio of 2 to 10%, preferably 4 to 6%.

10. The process as claimed in claim 1, wherein the one or more anti-microbial agents are selected from a group consisting of sodium benzoate, sodium sorbate, potassium sorbate, propylene oxide, Benzalkonium chloride, Sorbic acid, Boric acid, Thiomersal, and methyl-4-hydroxy benzoate.

11. The process as claimed in claim 1, wherein the one or more anti-microbial agents being added in the one or more pheromones gel matrix in stoichiometric ratio of 0.1 to 3%, preferably 0.5 to 1.5%.

12. The process as claimed in claim 1, wherein the one or more UV-blockers are selected from a group consisting of Para-Amino benzoic acid, Zinc oxide, Benzophenone, and Ethyl cinnamate.

13. The process as claimed in claim 1, wherein the one or more UV-blockers being added in the one or more pheromones gel matrix in stoichiometric ratio of 0.01 to 0.5%, preferably 0.05 to 0.2%.

14. The process as claimed in claim 1, wherein the one or more preserving agents are selected from a group consisting of 2-chloroacetamide, Sodium sorbate, Potassium sorbate, Calcium sorbate, Benzoic acid, Sodium benzoate, Potassium benzoate, Calcium benzoate, Propylparaben or Propyl-p-hydroxy-benzoate, Methylparaben or Methyl-p-hydroxy-benzoate, Sulphur dioxide, Sodium sulphite, Sodium bisulphate, Sodium metabisulphite, Potassium metabisulphite, Potassium sulphite, Potassium bisulphate, Nisin, Natamycin or Pimaricin, Dimethyl dicarbonate, Potassium nitrite, Sodium nitrite, Sodium nitrate, Potassium nitrate, Propionic acid, Sodium propionate, Calcium propionate, Potassium propionate, Calcium disodium ethylenediaminetetraacetate or calcium disodium EDTA and Lysozyme.

15. The process as claimed in claim 1, wherein the one or more preserving agents being added in the one or more pheromones gel matrix in stoichiometric ratio of 0.1 to 3%, preferably 0.5 to 1.5%.

16. The process as claimed in claim 1, wherein the surfactants are selected from a group consisting Triethanolamine, Triton-X 100, Triethanol amine, Propylene glycone, Triton-X, Diethanol amine, sodium dodecyl sulphate, Poly ethylene glycol, Alkyl polyglycoside, Cetomacrogol 1000, Cetostearyl alcohol, Cetyl alcohol, Cocamide DEA, Cocamide MEA, Decyl glucoside, Decyl polyglucose, Disodium cocoamphodiacetate, Glycerol monostearate, IGEPAL CA-630, Isoceteth-20, Lauryl glucoside, Maltosides, Monolaurin, Mycosubtilin, Narrow-range ethoxylate, Nonidet P-40, Nonoxynol-9, Nonoxynols, NP-40, Octaethylene glycol monododecyl ether, N-Octyl beta-D-thioglucopyranoside, Octyl glucoside, Oleyl alcohol, PEG-10 sunflower glycerides, Pentaethylene glycol, monododecyl ether, Polidocanol, Poloxamer, Poloxamer 407, Polyethoxylated tallow amine, Polyglycerol polyricinoleate, Polysorbate, Polysorbate 20, Polysorbate 80, Sorbitan, Sorbitan monolaurate, Sorbitan, monostearate, Sorbitan tristearate, Stearyl alcohol, Surfactin and Tween 80.

17. The process as claimed in claim 1, wherein the one or more organic pH modifiers being added to the bio-degradable angstrom voids polymer (AVP) matrix in small amount in order to adjust the pH and increase the swelling capacity of the gelling agent.

18. A bio-degradable angstrom voids polymer (AVP) matrix for a slow and sustained release of pheromone, comprising:

one or more pheromones impregnated on to Zeolite angstrom voids spaces is mixed with

one or more pheromones gel matrix comprising at least one of one or more pheromones, one or more bio-degradable gelling agents, one or more preserving agents, one or more moisture retaining agents, one or more anti-microbial agents, one or more anti-oxidizing agents, one or more UV-blockers, one or more surfactants and one or more organic pH modifiers where

pheromone impregnated in the bio-degradable gelling agent gives instant release of the pheromone as well as pheromone incorporated in angstrom void spaces of zeolite gives extended release of the pheromone.

19. The bio-degradable AVP matrix as claimed in claim 1, wherein the one more pheromones retain its stability and are allowed to release at a continuous slow release rate for a prolonged period of time.