WO2006017310A1 - Methods and reagents for treating honeybees for parasitic mites - Google Patents
Methods and reagents for treating honeybees for parasitic mites Download PDFInfo
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- WO2006017310A1 WO2006017310A1 PCT/US2005/024738 US2005024738W WO2006017310A1 WO 2006017310 A1 WO2006017310 A1 WO 2006017310A1 US 2005024738 W US2005024738 W US 2005024738W WO 2006017310 A1 WO2006017310 A1 WO 2006017310A1
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- formic acid
- acid
- controlled release
- release composition
- polymer gel
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- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/02—Saturated carboxylic acids or thio analogues thereof; Derivatives thereof
Definitions
- the invention relates to compositions and methods for controlling infestations of honeybee colonies. More particularly, the invention relates to compositions and methods for treating honeybees for parasitic infestations, such as mite infestations.
- Parasitic mites have caused serious problems both for the beekeeping industry and more broadly in agriculture, since honeybees are important for pollination of many important crops.
- honeybees are important for pollination of many important crops.
- parasitic mites that cause problems for honeybees.
- Varroa jacobsoni and the tracheal mite Acarapis woodi cause infestations that have resulted in extensive reductions in honeybee populations.
- the successful management of honeybees in the face of these pests requires multiple approaches for control, including breeding of resistant strains and various treatments and control measures.
- Formic acid has been used quite effectively in much of the world to control mite infestation, but it is not currently registered for use in the United States. Formic acid vapors are known to be effective for controlling parasitic mites in honeybees. However, formic acid is corrosive and toxic; thus, using it can be hazardous for the user. Methods and compositions for application of formic acid have taken a variety of forms, including liquid, support materials soaked in liquid formic acid, strips of formic acid, and menthol-paste. Formic acid has been used in liquid form in Europe and Canada and has been shown to control parasitic mites of honeybees in a wide variety of situations.
- Another approach that has been developed for dispensing formic acid involves mixing either polyacrylic acid or fumed silica with a formic acid solution to make a gel.
- formic acid is a strong acid, it can destroy gelling agents and/or prevent adequate gel stability (thus resulting in failure to form a stable gel, leakiness of the resulting gel, and other similar stability problems).
- Formic acid can be difficult to mix with other reagents as well, which can also contribute to instability problems of resulting gels.
- current methods can require handling liquid formic acid, frequent applications and/or extensive hive manipulation.
- the invention relates generally to compositions and methods for treating honeybees for infestations.
- the invention can provide one or more advantages when used to treat honeybees for infestations, particularly mite infestations.
- the invention provides a controlled release composition for treatment of parasitic mites in honeybees, the composition comprising a covalently crosslinked polymer gel and an active agent comprising a salt of formic acid.
- the active agent can comprise free formic acid, or a combination of a salt of formic acid and formic acid.
- the invention provides methods for controlling parasitic mites in honeybees, the methods comprising treating the honeybees with a controlled release composition comprising a covalently crosslinked polymer gel and an active agent comprising a salt of formic acid.
- the active agent can comprise free formic acid, or a combination of a salt of formic acid and formic acid.
- the invention provides a packaged product for treating honeybees for infestations. According to these aspects, the invention provides a controlled release composition for treatment of parasitic mites in honeybees in a stable packaging.
- the inventive compositions and methods provide less hazardous and more convenient techniques for treating honeybees, as well as greater control of the rate of release of the active agent.
- the rate of release of the active agent is at least partly controlled by the polymer gel composition itself. This is in contrast to prior methods and compositions that rely upon packaging of a pest control composition to control release of the active agent.
- the invention allows the option of formulating gels having different release rates for use under different conditions of weather and hive conditions, such as levels of mite infestation.
- the active agent is incorporated into a covalently crosslinked polymer gel.
- the resulting gel can be cast into any desirable shape, for example, by polymerizing appropriate monomers in a solution containing the active ingredient and optional additives.
- the active ingredient is provided in a mechanically stable, firm, and/or non-flowing state. This is in contrast to prior compositions that are provided in the form of a paste-like gel that is capable of flowing (and are thus more hazardous for the user and for shipping and handling).
- the covalently crosslinked polymer gel formulation of the invention can, in preferred embodiments, allow greater control over rates of release of the active agent compared with liquid formic acid.
- the inventive covalently crosslinked polymeric gel compositions do not require manipulation by the user to change physical or chemical characteristics of the composition, such as dilution of the composition prior to application to a hive (as can be required when liquid formic acid is used).
- the covalently crosslinked polymer gel also provides an advantageously stable polymeric matrix for delivery of the active agent.
- a polymer gel is formulated to include a high concentration of ionic species, the stability of the polymer gel can be difficult to maintain.
- the polymer gels of the invention include high concentrations of ionic species (acid ions).
- the covalent crosslinking creates a polymeric matrix that maintains the acid ions in a stable, non-flowable format.
- the inventive polymer gels provide a more stable matrix than gels that are formed using ionic associations or ionic crosslinking.
- the framework of the polymer gel that is formed by ionic associations or crosslinking may be susceptible to attack by ionic species (for example, acid ions) causing a breakdown of the polymer gel (which, in turn, can result in a flowable gel).
- ionic species for example, acid ions
- the components of the inventive compositions are easily combined to provide a well-dispersed mixture containing active agent that can be subsequently polymerized to provide a stable polymer gel.
- the active agent can be dissolved in the other components of the polymer gel, and the mixture can be polymerized to form a uniform distribution of active agent within the polymer gel.
- the resulting covalently crosslinked polymer gel provides a mechanically stable product that does not readily flow and/or release liquid formic acid.
- the invention can provide polymeric materials wherein stability of the polymeric material is independent of any packaging considerations and/or characteristics.
- the mechanically stable polymer gel provides a matrix that releases formic acid vapors only, and not liquid formic acid.
- the packaging materials and conditions for the inventive compositions can be much more flexible than prior formulations that rely upon liquid formic acid or formic acid compositions that are flowable.
- the active agent can include a salt of formic acid, either as the sole active agent, or in combination with formic acid.
- the active ingredient can be provided in a partially neutralized form that can advantageously reduce hazards associated with handling the composition.
- the inventive compositions and methods provide controlled release of vapors from an active agent contained within a covalently crosslinked polymer gel for treatment of honeybees.
- the controlled release compositions are formulated to behave in a desired manner under defined conditions, characterized by a controlled administration of vapors from the active agent over a given time frame in comparison to raw active material.
- the inventive formulations described herein are capable of maintaining a desired vapor concentration of formic acid in the atmosphere of a defined volume of a bee environment, such as a beehive.
- the controlled release composition is capable of releasing a regulated dose of vapors from the active agent at a desired rate, preferably releasing a defined quantity of formic acid vapors into a beehive over a chosen period of time, such as the reproductive cycle of the targeted honeybee population.
- controlled delivery of the vapors from the active agent is accomplished over a period of about 2-3 weeks, as this period constitutes at least one honeybee brood cycle.
- the controlled release thus provides a desired concentration of formic acid vapors within the bee environment by including an effective amount of the active agent in the polymeric gel.
- the effective amount of the active agent is the amount an active agent alone, or together with other substances (as described herein), that produces the desired effect (such as reduction in mite population) in a bee colony. During treatment, such amounts can depend upon such factors as the size of the beehive (in terms of bee population as well as physical volume), the particular pest targeted by the inventive methods and formulations, environmental conditions (such as temperature, humidity and the like), infestation level, and like factors within the knowledge and expertise of a bee keeper.
- the effective amount of the active agent provides a sufficient concentration of formic acid vapors to achieve at least 70%, or at least 75%, or at least 80% infestation control of the parasite without effecting significant mortality of the honeybee population.
- One preferred vapor concentration for controlling mites is in the range of about 0.08 to about 0.16 mg/L (or about 40 - 80 ppm), ( Exp Appl Acarol. 2003;29(3-4):303-13.)
- One of skill in the art, given the present description, can readily determine the effective amount of the active agent required to treat a honeybee population for mite infestation.
- the inventive compositions and methods can be applied over a treatment course.
- the treatment course refers to the dosage rate of one or more active agents over time, to provide a desired concentration of formic acid vapors to a bee population.
- factors of a treatment course include dosage rate and time course of treatment (total time during which the active agent(s) is administered).
- the inventive methods provide formic acid vapors that can penetrate the brood cells or comb (and thereby reach pests affecting bee larvae in the brood).
- the time course of treatment is in the range of about 2 to about 3 weeks (although treatment for periods longer than 3 weeks is certainly possible as well).
- the present invention is directed to methods and apparatuses for effectively controlling parasitic mites in honeybees, and in particular for delivering active agents to a bee population in a controllable manner.
- compositions in accordance with the present invention can advantageously be used to provide flexibility in treatment duration and conditions.
- the present invention has been developed for controllably providing one or more active agents to a bee population for a desired treatment course.
- the present description often refers to the administration of a single active agent for treatment of mite infestations.
- the inventive composition and methods can include more than one active agent, for example, when a combination of formic acid and a salt of formic acid is used.
- the invention provides controlled release compositions for treatment of parasitic mites in honeybees, the composition comprising a covalently crosslinked polymer gel and an active agent comprising a salt of formic acid.
- the active agent can comprise free formic acid, or a combination of a salt of formic acid and formic acid.
- the active agent is transported from the controlled release polymer gel composition via the vapor phase onto the target pest.
- the active agent evaporates or sublimates from the controlled release polymer gel in a regulated concentration into the atmosphere of the bee environment (such as a bee hive) and maintains a preselected concentration range for at least a 2 week treatment course, or a 2-3 week treatment course.
- effective control of infestations can be achieved such that the infestation is reduced to a level of 30% or less, or 25% or less, or 20% or less of a starting infestation level, wherein the starting infestation level is the infestation level prior to treatment initiation.
- the reduction in infestation levels to 20% is accomplished within a typical honeybee brood cycle, for example, the 2-3 week brood cycle of honeybees.
- the invention provides controlled release of an active agent from a covalently crosslinked polymer gel.
- the covalently crosslinked polymer gel can be formed by polymerization of acidic monomers.
- the acidic monomers are selected to have a pKa similar to or lower than formic acid (lower than 3.75 at 20°C), such as, for example, acrylic acid, maleic acid, or 2- acrylamido-2-methyl-l-propanesulfonic acid (AMPS).
- comonomers such as methacrylic acid, maleic acid (or maleic anhydride), acrylamide and N,N-dimethylacrylamide, N,N-dimethylacrylic acid, hydroxyethylmethacrylate, hydroxyethylacrylate.
- polymerization can be initiated by free radical generators such as ammonium persulfate or 4,4'-azobis(4-cyanovaleric acid).
- the amount of monomers used to form the polymer gel is not critical, so long as the desired consistency (for example, mechanical stability, firmness) of the resulting polymer gel is achieved.
- the polymer gel can be crosslinked using bifunctional monomers, such as for example N,N-methylene-bis-acrylamide (BIS), N,N'-(1,2- dihydroxyethylene)bisacrylamide, 3-(acryloyloxy)-2-hydroxypropyl methacrylate, ethylene glycol dimethacrylate, or ethylene glycol diacrylate.
- bifunctional monomers such as for example N,N-methylene-bis-acrylamide (BIS), N,N'-(1,2- dihydroxyethylene)bisacrylamide, 3-(acryloyloxy)-2-hydroxypropyl methacrylate, ethylene glycol dimethacrylate, or ethylene glycol diacrylate.
- the inventive methods comprise the application of a single active agent.
- a salt of formic acid can be incorporated into the crosslinked polymer gel and formic acid released therefrom.
- the methods entail application of a combination of free formic acid and a salt of formic acid.
- exemplary salts of formic acid include, without limitation, sodium formate, potassium formate, lithium formate, ammonium formate, and tetramethylammonium formate.
- a preferred salt is sodium formate.
- the methods entail application of free formic acid as the active agent.
- the covalently crosslinked polymer gel provides an improved stable delivery vehicle for the formic acid.
- the covalently crosslinked polymer gel includes a salt of formic acid
- one or more releasing agents is also included with the polymer gel composition.
- the releasing agent is a nonvolatile acid that acts to release formic acid from the salt.
- Exemplary nonvolatile acids that can be used according to these embodiments include malic acid, oxalic acid, citric acid, lactic acid, phosphoric acid, and sulfuric acid.
- a releasing agent need not be added as a separate component to the polymer gel composition, particularly in situations when other components of the polymer gel composition can provide the function of assisting release of the formic acid from the salt.
- nonvolatile acids when utilized as monomers in the polymeric gel (such as acrylic acid, methacrylic acid, maleic acid), these acids can function to assist release of the formic acid from the salt.
- an additional releasing agent need not be provided.
- the concentration of the releasing agent is not particularly critical to the invention, but the releasing agent is preferably present in excess of the concentration of formic acid salt. In some embodiments, for example, the releasing agent is present in an amount of 2- fold molar excess relative to the concentration of the formic acid salt.
- the active agent is present in the covalently crosslinked polymer gel in an amount sufficient to provide a desired vapor concentration of formic acid within the bee environment.
- the formic acid is present in an amount up to about 70% by weight of the crosslinked polymer gel, or up to about 65% by weight, or in the range of about 1% to about 70%, or about 10% to about 60%.
- the salt of formic acid is present in an amount up to about 50% by weight of the crosslinked polymer gel, or in the range of about 1% to about 50%, or about 10% to about 40% (all percentages by weight, based upon the total weight of the crosslinked polymer gel composition).
- the active agent comprises a combination of free formic acid and salt of formic acid
- the free formic acid can be present in an amount up to about 70% by weight, or up to about 65% by weight, or in the range of about 1% to about 70%, or about 10% to about 60%
- the formic acid salt can be present in an amount up to about 50% by weight of the crosslinked polymer gel, or in the range of about 1 % to about 50%, or about 10% to about 40%.
- the invention further includes an acceptable support material associated with the crosslinked polymer gel.
- the support material can be fabricated of any material that does not significantly negatively impact the bee population to be treated.
- the support material does not adversely affect the release of active agent from the polymer gel composition.
- suitable support material can include fibrous material, such as paper-based materials, or polymeric-based materials (for example, high density polyethylene fibrous materials such as TyvekTM (DuPont)), or other nonwovens.
- Exemplary support materials can provide such characteristics as durability, permeability, absorbance, and lightweight.
- the support material can be associated with the polymer gel to form a polymer gel product.
- the resulting polymer gel product can be held together in any suitable manner, for example, utilizing suitable fixtures such as adhesive, binders (such as fibers, cords, threads, and the like), staples, and the like.
- suitable fixtures such as adhesive, binders (such as fibers, cords, threads, and the like), staples, and the like.
- the support material can provide a gel composition that is more easily handled by the user.
- the inventive polymer gels are preferably sufficiently firm and mechanically stable, such that they can be used without any further physical or chemical manipulation by the end user (for example, diluting, drying, or the like).
- the crosslmked polymer gel can be used in combination with various types of dispensing systems that allow emission of formic acid vapor.
- Perforated containers can be useful, whether pre-perforated with some mechanism for uncovering the perforations or perforated by various means just prior to use.
- a shallow plastic tray dispenser can be utilized. Any type of dispensing system can be utilized according to the invention.
- the dispensers can be placed in several locations within the bee environment such that the vapors are distributed in the bee hive.
- a typical preparation of a controlled release composition appropriate monomers are polymerized in a solution containing the selected active agent (salt of formic acid, or a combination of free formic acid and a salt of formic acid) and a crosslinking agent.
- a polymerization initiator and/or catalyst are also present in the solution.
- a chain reaction is initiated in which monomers are polymerized into long chains.
- a crosslinking agent is included in the polymerization reaction, the chains become crosslmked to form a gel, whose porosity is determined by the length of the chains and the degree of crosslinking.
- the crosslinking of the monomers gives the obtained polymer gel a mechanically stable matrix structure.
- polymerization can be accomplished by dissolving the monomers, crosslinkers, and active agent in solvent (such as distilled water).
- An polymerization initiator such as an initiator peroxide (for example, ammonium persulfate) can be added to the solution.
- polymerization catalysts such as a quaternary amine (for example, N,N,N',N'-tetramethylenediamine, TEMED) can be added to the solution as well.
- the reagents are thoroughly mixed and allowed to stand until the crosslinked polymer gel is formed (the desired gel firmness is achieved).
- the solution can be poured into a casting container before significant polymerization has taken place.
- an inert gas such as nitrogen, argon, helium, and the like
- atmospheric oxygen is a free radical scavenger that can inhibit polymerization.
- Such preparative steps can include, for example, cutting the polymer gel to a desired size, providing a support material on one or more surfaces of the polymer gel, and/or packaging the polymer gel in a suitable package until use. For example, if the polymer gel is not intended to be used immediately, it can be desirable to package the polymer gel in a sealed container until use.
- the invention provides means of dispensing formic acid vapors without the need to handle liquid formic acid, which is caustic and toxic, and thus is hazardous to work with.
- the invention forms a covalently crosslinked polymer gel by polymerizing appropriate monomers in a solution containing a salt of formic acid, or some combination of free acid and a salt of formic acid, as well as crosslinking agents, to form a crosslinked gel.
- One advantage of this invention is that the gel containing active agent does not flow or leak liquid from the gel.
- the gel is also sufficiently strong to make it easy to handle without exposure to liquid formic acid.
- the rate and duration of release of formic acid vapors can be adjusted to obtain optimal control of the release of formic acid vapor.
- the extent of crosslinking of the gel can affect the release of formic acid vapor from the gel, as described herein.
- the strength and concentration of the nonvolatile acid can also affect the rate and duration of release of formic acid vapors, for example, by releasing the formic acid from its salt form.
- One exemplary embodiment of the invention is a gel slab of approximately 12 cm x 12 cm by approximately 5 mm thick.
- the gel slab can be overlaid on each side with a fibrous or absorbent material, such as pieces of TyvekTM or paper towel, cut to the appropriate size for ease of handling and to prevent the gel from sticking to the packaging or other surfaces.
- the fibrous material can extend beyond the gel or be configured to enclose the gel (as in an envelope), to allow handling without contacting the gel.
- the gel slabs can simply be removed from packaging and placed into a bee environment (such as a hive).
- one gel slab can be placed in the top of the hive and another gel slab placed in the bottom of the hive, either onto the bottom board through the entrance, or under a bottom screen as part of an integrated pest management system. See Vet Parasitol 2003 Feb 13;l l l(2-3):241-5.
- the compositions can be suitably processed and packaged for use by a consumer.
- the polymer gel compositions are shelf stable.
- shelf stable refers to the compositions of the invention being suitable for storage at ambient temperatures (such as room temperature) without the polymer gel composition substantially breaking down by, for example, hydrolysis of linkages forming the polymeric matrix and the like, and becoming unsuitable for use to treat honeybees.
- the compositions are stable for a period of several months, or six months or more, or a year or more.
- the stability of the inventive compositions is independent of the type of packaging utilized in connection with the compositions.
- inventive covalently crosslinked polymer gels provide a mechanically stable gel that retains the active agent (formic acid salt and/or formic acid) and thus reduces the risk of release of liquid formic acid. Therefore, the inventive compositions can be packaged in any material that is stable when exposed to formic acid vapors.
- such stable packaging can be formed from materials that are resistant to degradation by acid (acid-stable), including, but not limited to, such metallic materials as foil, and/or polymeric materials such as polyolefm materials. It can be desirable to minimize or prevent the release of formic acid vapors from the product. In part, this can be accomplished by virtue of the stability of the gel itself- the covalently crosslinked polymer gel maintains the active agent within the polymeric gel and allows release of the formic acid vapors.
- a gas-impermeable packaging can be utilized with the product.
- the packaging can be heat-sealed or can comprise a container that is suitably sealed such that gas is not able to escape the packaging.
- Suitable packaging can include pouches, bags, box containers, and the like.
- the controlled release composition is placed within an envelope of material.
- the envelope is configured to encase the composition and permit release of acid vapors during use of the article.
- the envelope is provided as a component of the article to be used by the end user (such as a bee keeper).
- Use of an envelope to enclose the material can provide several advantages, such as allowing the user to handle the article without contacting the polymeric gel material and/or the acid components of the article.
- the envelope can provide a convenient format for use of the controlled release product, since the product can be easily handled, placed within the hive environment, and moved (if necessary) during use of the product.
- the envelope can be fabricated from any suitable material that is vapor- permeable yet impermeable to polar liquids.
- Exemplary materials for the envelope include hydrophobic porous materials that are woven or nonwoven.
- the hydrophobic material can be fibrous material provided in the form of fabric, sheets, or the like.
- Exemplary nonwoven materials are polyolef ⁇ ns, such as polypropylene, polyethylene, and the like.
- One preferred nonwoven polyolef ⁇ n is a high-density polyethylene material (such as commercially available from DuPontTM under the product name TyvekTM).
- the envelope can be utilized as the sole packaging of the polymer gel material or can be used in combination with another form of packaging.
- the envelope is provided as an inner packaging of the final controlled release product.
- the final controlled release product includes a combination packaging composed of the inner envelope (that encloses the polymer gel) and an outer packaging (that encloses the envelope-containing polymer gel).
- the controlled release polymer composition is provided within the envelope, which is in turn provided within an outer packaging as described above.
- This type of combination packaging can be advantageous in several aspects.
- the combination packaging can allow the end user to select the number of enveloped compositions to utilize at a time, while leaving the remaining enveloped compositions in the outer packaging for later use. Further, such combination packaging provides a format that is safely handled by the end user, since exposure to liquid acid components is minimized. Still further, such combination packaging can enhance the self-life of the products.
- the envelope can be used as a replacement for, or in addition to, a support material associated with the polymer gel.
- Support materials are described elsewhere herein. The following examples illustrate the present invention without, however, limiting the same thereto.
- Example 1 Synthesis of a gel containing formic acid and a salt of formic acid
- Nitrogen was bubbled through the solution, then the box covered tightly and put into an oven at about 5O 0 C overnight to polymerize into a gel.
- the gel was removed from the box and overlaid on each side with pieces of paper towel cut to approximately the size of the gel and stored in a sealed container until used.
- Example 2 Testing of formic acid/sodium formate gels in active beehives Two gel slabs prepared by the procedure of Example 1 were placed in a beehive, consisting of three hive bodies, one at the top under an inner cover and one under a screen at the bottom of the hive.
- the formic acid vapor concentration was measured by inserting a tube into a hole drilled in the bottom hive body using a Draeger tube (Fisher, Cat. No. 17- 985-234) and an Accuro Draeger pump Fisher, Cat. No. 17-986-70A) following the manufacturer's instructions. After 24 hours, the concentration was 23 ppm. The temperature was 68 0 F. After seven days, the concentration was 40 ppm. The temperature was 7O 0 F. After 11 days, the concentration was 12 ppm when the temperature was 52 0 F. Two other hives were treated similarly with similar results.
- Example 3 Synthesis of a gel containing formic acid and sodium formate in crosslinked polyacrylic acid for laboratory comparison Methylene-bis-acrylamide (25 mg) was dissolved in 4.0 ml of formic acid. To that solution was added 2.0 ml of acrylic acid (29.2 mmole). In a separate solution, 1.0 gm of sodium formate and 125 mg of ammonium persulfate were dissolved in 1.0 ml of distilled water. The solutions were combined to achieve a final volume of 8.5 ml. The combined solution was poured into a plastic box. Nitrogen was bubbled through the solution, then the box covered tightly and put into an oven at about 5O 0 C - 60° C overnight to polymerize into a gel. After overnight in the oven, the gel was removed and covered on each side with paper towel pieces cut to approximately the dimensions of the gel and stored in a zip lock plastic bag until used.
- Example 4 Synthesis of a gel containing formic acid and sodium formate in crosslinked polyfaerylic/maleic acid) for laboratory comparisons
- Maleic anhydride 2.0 gm, 20.4 mmole
- methylene-bis-acrylamide 25 mg
- Maleic anhydride 2.0 gm, 20.4 mmole
- methylene-bis-acrylamide 25 mg
- acrylic acid 26.25 mmole
- 1.8 gm (26.5 mmole) of sodium formate and 125 mg of ammonium persulfate were dissolved in 2.0 ml of distilled water.
- the solutions were combined to achieve a final volume of 9.0 ml.
- the combined solution was poured into a plastic box.
- Example 5 Synthesis of a gel containing formic acid in crosslinked polyacrylie acid for laboratory comparison
- Sodium formate (8.2 gm, 120.6 mmole) and 50 mg of methylenebisacrylamide were dissolved in 15 ml of distilled water. To that solution was added 26 gm (125.4 mmole) of 2- acrylamido-2-methyl-l-propanesulfonic acid (AMPS) and 200 mg of ammonium persulfate. Final volume prior to polymerization was 17.7 ml. Nitrogen was bubbled through the solution, which was then polymerized in an oven at about 55 0 C overnight.
- AMPS 2- acrylamido-2-methyl-l-propanesulfonic acid
- the gels prepared according to Examples 3-6 above were each placed in a plastic box (42 x 29 x 15 cm) having covers that were propped open at one end using a piece of glass tubing (0.6 cm in diameter).
- the formic acid vapor concentrations were measured at periodic intervals by inserting tubing into the box from which vapor was drawn through a solution containing a pH indicator dye in a vial using a hand pump.
- Formic acid vapors were measured by preparing a solution of 0.1 mg/ml Congo Red (turns from red to blue between pH 5 and 3) and 0.01 mM NaOH in distilled water.
- Vapors from a box containing the gel to be tested were bubbled through the solution using a Draeger accuro pump (Fisher Scientific).
- the pump pulls 100 cc of vapor per stroke according to the manufacturer's specifications.
- the number of strokes required to turn the solution from red to blue provided a relative measure of the formic acid vapor concentration in the box. If the solution did not start to turn color by 20 strokes, the measurement was recorded as 20+ strokes. If, by 20 strokes, the solution had started to turn color, pumping was continued and the actual number of stokes to turn the color from red to blue was recorded.
- release of formic acid vapors from the polymer gel compositions was controlled by varying the composition of the polymer gels.
- the polymer gel prepared according to the procedure of Example 5 included formic acid in polyacrylic acid. This formulation demonstrated the highest relative concentration of formic acid vapors in the first day, followed by a significant decrease in the concentration by two days (the lowest relative vapor concentration at day 2), and this lower concentration (relative to the other gel formulations) was maintained for the duration of the experiment.
- the polymer gel prepared according to Example 3 included formic acid and sodium formate in polyacrylic acid. This formulation demonstrated a relatively slower release rate than Example 5, as the vapor concentration was lower at Day 1, but relatively higher than the formulation of Example 5 at Days 2 through 4.
- the polymer gel prepared according to Example 4 included formic acid and sodium formate in poly(acrylic/maleic) acid.
- the results for this polymer gel show that the addition of maleic anhydride to the polymer matrix slowed release of formic acid vapors relative to the gel formulation prepared according to Example 3.
- the vapor concentrations for this gel were lower than those of the gel of Example 3 for Days 1-4; however, at Days 5 and 6, the relative concentration was higher than that of Example 3.
- the polymer gel prepared according to Example 6 included sodium formate and polyAMPS. This polymer gel showed a relatively slower release rate than the gels prepared in Examples 3 and 4. The vapor concentrations for this gel were relatively higher than those of Examples 3 and 4 until approximately Day 4.
- results illustrate that inclusion of a salt of formic acid (in the present examples, sodium formate) slowed the release of formic acid vapors from the polymeric matrices.
- polymer gel prepared using polyAMPS slowed release of formic acid vapors from the material.
Abstract
Description
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
MX2007000418A MX2007000418A (en) | 2004-07-12 | 2005-07-12 | Methods and reagents for treating honeybees for parasitic mites. |
BRPI0513206-1A BRPI0513206A (en) | 2004-07-12 | 2005-07-12 | controlled release composition for the treatment of domestic bees, method for the control of parasitic mites on domestic bees, kit for the treatment of parasitic mites on domestic bees, and method for producing a non-flowable polymeric gel for controlled release of acid vapors formic |
EP05770767A EP1781099A1 (en) | 2004-07-12 | 2005-07-12 | Methods and reagents for treating honeybees for parasitic mites |
CA002572867A CA2572867A1 (en) | 2004-07-12 | 2005-07-12 | Methods and reagents for treating honeybees for parasitic mites |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/889,399 US7137864B2 (en) | 2004-07-12 | 2004-07-12 | Methods and reagents for treating honeybees for parasitic mites |
US10/889,399 | 2004-07-12 |
Publications (1)
Publication Number | Publication Date |
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WO2006017310A1 true WO2006017310A1 (en) | 2006-02-16 |
Family
ID=35004239
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2005/024738 WO2006017310A1 (en) | 2004-07-12 | 2005-07-12 | Methods and reagents for treating honeybees for parasitic mites |
Country Status (6)
Country | Link |
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US (1) | US7137864B2 (en) |
EP (1) | EP1781099A1 (en) |
BR (1) | BRPI0513206A (en) |
CA (1) | CA2572867A1 (en) |
MX (1) | MX2007000418A (en) |
WO (1) | WO2006017310A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011029754A3 (en) * | 2009-09-14 | 2011-12-22 | Basf Se | Dispenser comprising a polyester membrane for control of mites in bee hives |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8293258B2 (en) * | 2000-05-18 | 2012-10-23 | John I. Hass, Inc. | Pesticide treatments made from hop extracts |
US8153146B2 (en) * | 2000-05-18 | 2012-04-10 | John I. Haas | Pesticide and fungicide treatments made from hop extracts |
US7767234B2 (en) * | 2006-03-31 | 2010-08-03 | John I. Haas, Inc. | Compositions and methods for controlling a honey bee parasitic mite |
AU2007300565B2 (en) * | 2006-09-25 | 2013-06-27 | Haas, John I. | Methods for treating or preventing infestation |
EP2086312A2 (en) * | 2006-11-15 | 2009-08-12 | HAAS, John I. | Compositions and methods for inhibiting a honey bee pathogen infection on controlling a hive infestation |
US8414934B2 (en) * | 2008-02-08 | 2013-04-09 | John I. Haas, Inc. | Compositions and methods for arachnid control |
US20110171324A1 (en) * | 2010-01-14 | 2011-07-14 | Richard William Clemente | Method of treating or preventing disease in bees |
US20140127968A1 (en) | 2011-06-06 | 2014-05-08 | Gene Probasco | Methods and compositions for controlling a honey bee parasitic mite infestation |
BR112015016129A2 (en) | 2013-01-07 | 2017-07-11 | Haas Inc John I | corrugated strip for use in reducing a parasitic mite infestation of the honey bee; corrugated strip prepared by dipping an absorbent strip into a liquid composition; aluminum packaging prepared by dipping a corrugated absorbent strip into a liquid composition; man-made beehive; honey bee product; method of reduction of a parasitic mite infestation of the honey bee in a bee hive; and kit for treating or preventing a parasitic mite infestation |
US20150123801A1 (en) * | 2013-11-01 | 2015-05-07 | Eltopia Communications, LLC | Monitoring the state of a beehive |
US11771065B2 (en) * | 2015-08-20 | 2023-10-03 | Api Holdings, Llc | Formulations and methods for promoting honeybee health |
CA3043388A1 (en) | 2018-05-14 | 2019-11-14 | John I. Hass, Inc. | Compositions and methods for controlling a honey bee parasitic mite infestation |
KR20240025265A (en) * | 2022-08-18 | 2024-02-27 | 농업회사법인 비센 바이오 주식회사 | A formic composition for removing honeybee mites gelled with polymer absorbent and container packaging sets including the same |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997047193A1 (en) * | 1996-06-13 | 1997-12-18 | Vita (Europe) Limited | Method for the control of infestations of honeybee colonies |
CA2237484A1 (en) * | 1997-05-19 | 1998-11-19 | Danny A. Davis | Formulation for the controlled release of formic acid for use in the control of mites in honey bees (apis mellifera) |
US6037374A (en) * | 1997-11-19 | 2000-03-14 | The United States Of America As Represented By The Secretary Of Agriculture | Composition and method for the control of parasitic mites in honey bees |
RU2222189C2 (en) * | 2001-06-08 | 2004-01-27 | Баринов Артем Валерианович | Composition for protecting honey bees from parasite mites |
RU2225104C2 (en) * | 2002-05-28 | 2004-03-10 | Сохликов Алексей Борисович | Composition for fighting with parasitic ticks in honey bees |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4581042A (en) | 1984-06-22 | 1986-04-08 | Pro-Strength, Inc. | Composition for removing hard-water build-up |
US4927813A (en) | 1988-03-08 | 1990-05-22 | Bernstein Joel E | Method and composition for treating pediculosis capitis |
EP0712635B1 (en) * | 1994-05-13 | 2003-05-02 | Kuraray Co., Ltd. | Medical polymer gel |
DE4424786A1 (en) | 1994-07-14 | 1996-01-18 | Bayer Ag | Insecticide-containing gel formulations for evaporator systems |
US6475061B1 (en) | 2000-11-01 | 2002-11-05 | Board Of Trustees Of Michigan State University | Method and apparatus for control of mites in a beehive |
US6620025B2 (en) | 2001-04-12 | 2003-09-16 | Theodore W. Scheuneman | Evaporator for the treatment of honey bee diseases and undesirable hive conditions |
WO2002100433A1 (en) * | 2001-06-11 | 2002-12-19 | Takeda Chemical Industries, Ltd. | Medicinal compositions |
-
2004
- 2004-07-12 US US10/889,399 patent/US7137864B2/en not_active Expired - Fee Related
-
2005
- 2005-07-12 WO PCT/US2005/024738 patent/WO2006017310A1/en active Application Filing
- 2005-07-12 MX MX2007000418A patent/MX2007000418A/en unknown
- 2005-07-12 BR BRPI0513206-1A patent/BRPI0513206A/en not_active IP Right Cessation
- 2005-07-12 CA CA002572867A patent/CA2572867A1/en not_active Abandoned
- 2005-07-12 EP EP05770767A patent/EP1781099A1/en not_active Withdrawn
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997047193A1 (en) * | 1996-06-13 | 1997-12-18 | Vita (Europe) Limited | Method for the control of infestations of honeybee colonies |
CA2237484A1 (en) * | 1997-05-19 | 1998-11-19 | Danny A. Davis | Formulation for the controlled release of formic acid for use in the control of mites in honey bees (apis mellifera) |
US6037374A (en) * | 1997-11-19 | 2000-03-14 | The United States Of America As Represented By The Secretary Of Agriculture | Composition and method for the control of parasitic mites in honey bees |
RU2222189C2 (en) * | 2001-06-08 | 2004-01-27 | Баринов Артем Валерианович | Composition for protecting honey bees from parasite mites |
RU2225104C2 (en) * | 2002-05-28 | 2004-03-10 | Сохликов Алексей Борисович | Composition for fighting with parasitic ticks in honey bees |
Non-Patent Citations (3)
Title |
---|
DATABASE WPI Section Ch Week 200448, Derwent World Patents Index; Class A97, AN 2004-504595, XP002348336 * |
DATABASE WPI Section PQ Week 200416, Derwent World Patents Index; Class P14, AN 2004-166012, XP002348337 * |
JOURNAL OF VETERINARY MEDICINE SERIES B, vol. 48, no. 1, February 2001 (2001-02-01), pages 11 - 14, XP002348332, ISSN: 0931-1793 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011029754A3 (en) * | 2009-09-14 | 2011-12-22 | Basf Se | Dispenser comprising a polyester membrane for control of mites in bee hives |
CN102647911A (en) * | 2009-09-14 | 2012-08-22 | 巴斯夫欧洲公司 | Dispenser comprising a polyester membrane for control of mites in bee hives |
US9101132B2 (en) | 2009-09-14 | 2015-08-11 | Basf Se | Dispenser comprising a polyester membrane for control of mites in bee hives |
Also Published As
Publication number | Publication date |
---|---|
CA2572867A1 (en) | 2006-02-16 |
EP1781099A1 (en) | 2007-05-09 |
MX2007000418A (en) | 2007-06-25 |
US7137864B2 (en) | 2006-11-21 |
US20060009122A1 (en) | 2006-01-12 |
BRPI0513206A (en) | 2008-05-06 |
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