Hydrogel compositions and methods of making and using thereof
Hydrogels and hydrogel foams composed of polymers, surfactants, and fatty acids provide protective barriers and nutrient delivery, addressing environmental and pest pressures in agriculture, improving crop productivity and reducing nutrient loss.
Patent Information
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- BREKLAND INC
- Filing Date
- 2025-11-28
- Publication Date
- 2026-06-04
AI Technical Summary
Agricultural crops face challenges from environmental pressures such as drought, extreme temperatures, soil degradation, pest infestations, and nutrient loss due to leaching and runoff, leading to reduced crop productivity and food security, with existing solutions being costly and inefficient.
Hydrogels and hydrogel foams composed of polymers, surfactants, and optionally fatty acids or alcohols, which can be formulated into non-foamed or foamed forms to provide protective barriers and deliver nutrients, using pH adjustments and air mixing to enhance stability and application.
The hydrogels and hydrogel foams offer cost-effective, adaptable solutions for improving soil moisture retention, protecting crops from abiotic and biotic stresses, and delivering nutrients, enhancing agricultural productivity and reducing pest-related damage.
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Figure US2025057415_04062026_PF_FP_ABST
Abstract
Description
Attorney Docket No.: BREK-002 / 01WO 349002-2005PCT INTERNATIONAL APPLICATIONHYDROGEL COMPOSITIONS AND METHODS OF MAKING AND USING THEREOFCROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims the benefit of priority to U. S. Provisional Application No.63 / 726,471 filed November 29, 2024, the contents of which are hereby incorporated by reference in their entirety for all purposes.FIELD
[0002] The present disclosure relates to compositions and formulations of hydrogel and its foam and methods of making and using thereof.BACKGROUND
[0003] Agricultural crops face a wide range of environmental and pest pressures that can impact yield and crop quality, resulting in potentially significant economic losses if left unprotected. These may include various abiotic factors such as drought, smoke, sun exposure, and frost, as well as numerous biotic factors such as fungi and insects. Globally, environmental pressures such as drought, extreme temperatures, and soil degradation, along with pest infestations, threaten crop yields and food security. Also, in agriculture, traditional fertilizer application methods often result in significant nutrient loss due to leaching, volatilization, and runoff, which not only reduce crop productivity but also contribute to environmental pollution.
[0004] Thus, there is a great need to address pressing challenges by improving soil moisture retention, delivering nutrients, and providing protective barriers against pests and environmental stresses. Hydrogels can offer a solution to address these critical issues for their biocompatibility, flexibility, high water content, and tunable properties. The urgent development of new hydrogel systems can meet the need for cost-effective and adaptable solutions to improve agricultural productivity and nutrient delivery systems, as well as mitigate pest-related damage and / or environmental pressures.1328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005SUMMARY OF THE DISCLOSURE
[0005] The present disclosure solves the problem facing the agricultural community, by providing hydrogels and hydrogel foams, which have application, inter alia, in crop protection and productivity.
[0006] The hydrogels and hydrogel foams of the present disclosure provide a new modality of protection that is greatly needed in the agricultural sector.
[0007] The present disclosure provides a composition comprising a polymer. In some embodiments, the composition further comprises a surfactant. In some embodiments, the composition further comprises a fatty acid or a fatty alcohol,
[0008] The present disclosure provides a composition comprising a polymer having at least one residue that is charged; and a surfactant selected from the group consisting of an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant. In some embodiments, a mixture of the charged polymer and the surfactant are capable of forming a charged polymer-surfactant complex under conditions of varying pH or in the presence of electrolytes. In some embodiments, the varying pH condition is between pH 2 and pH 11. In some embodiments, the composition further comprises a fatty alcohol or a fatty acid.
[0009] In some embodiments, the composition comprises a plurality of polymers and a plurality of surfactants. In some embodiments, the composition is a dry form, a liquid form, or an emulsion form. In some embodiments, the composition comprises a dry form of the composition that is dissolved in water to make a solution comprising the polymer, the surfactant, and optionally the fatty acid or the fatty alcohol. In some embodiments, the composition comprises a liquid form of the composition that is a solution comprising the polymer, the surfactant, and optionally the fatty acid or the fatty alcohol. In some embodiments, the composition comprises (i) a diy form of the composition is dissolved in water to make a solution comprising the polymer and the surfactant, and (ii) a paste form of the fatty acid or the fatty alcohol.
[0010] In some embodiments, the polymer, which is naturally or synthetically derived, is selected from the group consisting of gelatin, cellulose, hyaluronic acid, soy protein, whey protein, xanthan gum, pectin, carrageenan, chitosan, agarose, dextran, fibrin, poly (vinyl alcohol) (PVA), poly (ethylene glycol) (PEG), poly (ethylene oxide) (PEO), poly (2-hydroxyethyl methacrylate) (PHEMA), poly (acrylic acid) (PAA), and poly (acrylamide) (PAAm) and a combination thereof.2328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005
[0011] In some embodiments, a surfactant selected from the group consisting of an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant. In some embodiments, the fatty alcohol is selected from the group consisting of: myristyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol, palmitoleyl alcohol, oleyl alcohol, linoleyl alcohol, hnolenyl alcohol, arachidonyl alcohol, butanol, and a combination thereof. In some embodiments, the fatty acid is selected from the group consisting of: myristic acid, lauric acid, palmitic acid, stearic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, butyric acid, and a combination thereof.
[0012] In some embodiments, the composition is a dry form. In some embodiments, a dry form of the composition is dissolved in water to make a solution comprising the polymer, the surfactant, and optionally the fatty acid or the fatty alcohol. In some embodiments, the solution comprises about 0.05% to about 20% w / w of the polymer or about 0.5% to about 10% w / w of the polymer. In some embodiments, the solution comprises about 0.01% to about 10% w / w of the surfactant or about 0.01% to about 5% w / w of the surfactant. In some embodiments, the ratio between the polymer and the surfactant in the solution is about 0.5: 1 to about 20: 1 in w / w or about 1: 1 to about 10:1 in w / w. In some embodiments, the solution comprises about 0.01% to about 1% w / w of the fatty acid or the fatty alcohol or about 0.05% to about 1% w / w of the fatty acid or the fatty alcohol.
[0013] In some embodiments, the polymer is destabilized. In some embodiments, the solution is heated above the gel point of the polymer. In some embodiments, the heated solution is cooled down to below its phase change point if it is heated above its phase change point. In some embodiments, pH of the solution is adjusted with a buffer to near isoelectric point of the polymer. In some embodiments, the buffer is selected from the group consisting of: citric acid, sodium citrate, acetic acid, sodium acetate, ammonia, ammonium chloride, sodium carbonate, sodium bicarbonate, phosphate, histidine, and a combination thereof.
[0014] In some embodiments, the pH-adjusted solution is formed into a hydrogel. In some embodiments, the hydrogel is biodegradable. In some embodiments, the hydrogel is aerosolized in fine mist. In some embodiments, the hydrogel is applied as a continuous sprayed stream or sprayed clumps. In some embodiments, the hydrogel is applied as a gel or a gel paste. In some embodiments, the hydrogel is sprayed as fine foam droplets. In some embodiments, the hydrogel is applied to a target. In some embodiments, the pH-adjusted solution is mixed with air in a ratio of about 1:2 to about 1:50 to be formed into foam. In some embodiments, the air content of the3328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005foam is about 0.1% to about 99%. In some embodiments, the foam is biodegradable. In some embodiments, the foam is applied to a target.
[0015] The present disclosure provides a hydrogel, comprising a) about 0.05% to about 20% w / w of a polymer; b) optionally, about 0.01% to about 10% w / w of a surfactant; c) optionally, about 0.01% to about 1% w / w of a fatty acid or a fatty alcohol; and d) water. In some embodiments, the ratio between the polymer and the surfactant in the hydrogel is about 0.5:1 to about 20:1 in w / w. In some embodiments, the hydrogel comprises about 0.5% to about 10% w / w of the polymer. In some embodiments, the hydrogel comprises about 0,01% to about 5% w / w of the surfactant. In some embodiments, the hydrogel comprises about 0.05% to about 1% w / w of the fatty acid or the fatty alcohol. In some embodiments, the ratio between the polymer and the surfactant in the hydrogel is about 1:1 to about 10:1 in w / w. In some embodiments, the hydrogel is aerosolized in fine mist. In some embodiments, the hydrogel is applied as a continuous sprayed stream or sprayed clumps. In some embodiments, the hydrogel is applied as a gel or a gel paste. In some embodiments, the hydrogel is sprayed as fine foam droplets. In some embodiments, the hydrogel is applied to a target.
[0016] The present disclosure provides a hydrogel foam, comprising a) about 0.05% to about 20% w / w of a polymer; b) optionally, about 0.01% to about 10% w / w of a surfactant; c) optionally, about 0.01% to about 1% w / w of a fatty acid or a fatty alcohol; d) water; and e) compressed air. In some embodiments, the ratio between the polymer and the surfactant in the hydrogel foam is about 0.5:1 to about 20: 1 in w / w. In some embodiments, the hydrogel foam comprises about 0.5% to about 10% w / w of the polymer. In some embodiments, the hydrogel foam comprises about 0.01% to about 5% w / w of the surfactant. In some embodiments, the hydrogel foam comprises about 0.05% to about 1% w / w of the fatty acid or the fatty alcohol. In some embodiments, the ratio between the polymer and the surfactant in the hydrogel foam is about 1: 1 to about 10: 1 in w / w. In some embodiments, the air content of the hydrogel foam is about 0.1% to about 99%. In some embodiments, the hydrogel foam is applied to a target.
[0017] The present disclosure provides a formulation, comprising: (a) a dry form of a polymer, when dissolved in water, having about 0.05% to about 20% w / w; (b) optionally, a dry form of a surfactant, when dissolved in water, having about 0.01% to about 10% w / w; (c) optionally, a dry form of a fatty acid or a fatty alcohol, when dissolved in water, about 0.01% to about 1% w / w. In some embodiments, the formulation is dissolved in water. In some embodiments the formulation4328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005in water is heated 2°C above its phase change point. In some embodiments, the formulation in water is cooled down to 2CC below its phase change point, if it is heated 2°C above its gel point.
[0018] The present disclosure provides a kit, comprising: a dry form of formulation ‘A’ comprising: (1) a dry form of a polymer; a dry form of a surfactant; and a dry form of a buffer selected from the group consisting of: citric acid, sodium citrate, hydrochloric acid, acetic acid, sodium acetate, ammonia, ammonium chloride, sodium carbonate, sodium bicarbonate, and a combination thereof and (2) an emulsion / paste form of formulation ‘B’ comprising: a fatty acid or a fatty alcohol. In some embodiments, the polymer is dissolved in water and has about 0.05% to about 20% w / w in a solution. In some embodiments, the surfactant is a dry form, a liquid form, or an emulsion form. In some embodiments, the surfactant is dissolved in water and has about 0.01% to about 10% w / w in a solution. In some embodiments, the fatty acid or the fatty alcohol is a dry form, a liquid form, or an emulsion form. In some embodiments, the fatty acid or the fatty alcohol is dissolved in water and has about 0.01% to about 1% w / w in a solution. In some embodiments, the buffer is selected from the group consisting of: citric acid, sodium citrate, hydrochloric acid, acetic acid, sodium acetate, ammonia, ammonium chloride, sodium carbonate, sodium bicarbonate, and a combination thereof.
[0019] The present disclosure provides a dry composition, comprising: (a) a first component comprising a dry form of a polymer, a surfactant, and a buffer; and (b) a second component comprising a paste form of (i) a fatty acid or a fatty alcohol and (ii) a surfactant. In some embodiments, the polymer is gelatin. In some embodiments, the surfactant is an anionic surfactant. In some embodiments, the surfactant is sodium lauryl sulfoacetate (SLSA). In some embodiments, the buffer is citric acid or sodium citrate. In some embodiments, the fatty acid is myristic acid. In some embodiments, the first and second components are combined and then dissolved in water to form a hydrogel or a hydrogel foam. In some embodiments, the water-dissolved composition comprises about 0.05% to about 20% w / w of the polymer. In some embodiments, the water-dissolved composition comprises about 0.01% to about 10% w / w of the surfactant. In some embodiments, the water-dissolved composition comprises about 0.01% to about 1% w / w of the fatty acid.
[0020] The present disclosure provides a dry composition, comprising a dry form of a polymer, a surfactant, a buffer, and a fatty acid or a fatty alcohol. In some embodiments, the polymer is gelatin. In some embodiments, the surfactant is an anionic surfactant. In some embodiments, the surfactant5328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005is sodium lauryl sulfoacetate (SLSA). In some embodiments, the buffer is citric acid or sodium citrate. In some embodiments, the fatty acid is myristic acid.
[0021] The present disclosure provides a liquid composition, comprising: a solution comprising a dry form of a polymer, a surfactant, a buffer, and a fatty acid or a fatty alcohol is dissolved in water.
[0022] The present disclosure provides a composition, comprising: a dry form of gelatin, a dry form of sodium lauryl sulfoacetate, and a dry form or a paste form of myristic acid, wherein the composition is dissolved in water. In some embodiments, the water-dissolved composition comprises about 0.05% to about 20% w / w of gelatin, about 0.01% to about 10% w / w of sodium lauryl sulfoacetate, and about 0.01% to about 1% w / w of myristic acid. In some embodiments, composition, comprising: about 2.5% w / w of gelatin, about 0.9% of sodium lauryl sulfoacetate, and about 0.1% of myristic acid, dissolved in water.
[0023] The present disclosure provides a method of manufacturing a hydrogel, comprising the steps of: mixing water with a dry composition taught herein and producing the hydrogel.
[0024] The present disclosure provides a method of manufacturing a hydrogel foam, comprising the steps of: mixing water with a dry composition taught herein, mixing a solution of step a) with air in a ratio of the solution about 1:2 to about 1:50; and producing the hydrogel foam.
[0025] The present disclosure provides a method of making a non-foamed or foamed hydrogel, comprising: a) mixing water with a formulation comprising: (i) a polymer; (ii) a surfactant; and ( iii) optionally, a fatty acid; b) optionally, adding a buffer to the formulation dissolved in water; and c) applying the solution to a device, thereby forming a non-foamed or foamed hydrogel. In some embodiments, the polymer is a dry form, a liquid form, or an emulsion form. In some embodiments of the method, the polymer is dissolved in water and has about 0.5% to about 10% w / w in a solution. In some embodiments, the surfactant is a dry form, a liquid form, or an emulsion form. In some embodiments of the method, the surfactant is dissolved in water and has about 0.01% to about 5% w / w m a solution. In some embodiments, the fatty acid or the fatty alcohol is a dry form, a liquid form, or an emulsion form. In some embodiments of the method, the fatty acid is dissolved in water and has about 0.05% to about 1% w / w in a solution. In some embodiments of the method, the polymer is selected from the group consisting of gelatin, cellulose, hyaluronic acid, soy protein, whey protein, xanthan gum, pectin, carrageenan, chitosan, agarose, dextran, fibrin, poly (vinyl alcohol) (PVA), poly (ethylene glycol) (PEG), poly (ethylene oxide) (PEO),6328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005poly (2-hydroxyethyl methacrylate) (PHEMA), poly (acrylic acid) (PAA), and poly (acrylamide) (PAAm) and a combination thereof. In some embodiments of the method, the gelatin is a denatured form of collagen. In some embodiments of the method, the cellulose comprises ester and, or ether derivates. In some embodiments of the method, the fatty acid is selected from the group consisting of: myristic acid, lauric acid, palmitic acid, stearic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, butyric acid, and a combination thereof. In some embodiments of the method, the fatty alcohol is selected from the group consisting of: myristyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol, palmitoleyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, arachidonyl alcohol, butanol, and a combination thereof. In some embodiments of the method, a buffer selected from the group consisting of: citric acid, sodium citrate, acetic acid, sodium acetate, ammonia, ammonium chloride, sodium carbonate, sodium bicarbonate, phosphate, histidine, and a combination thereof.
[0026] The present disclosure provides a method of producing a hydrogel, comprising the steps of: a) mixing water with a dry form of a composition comprising (i) a polymer, (ii) a surfactant, and optionally a fatty acid or a fatty alcohol to make a solution; b) adjusting pH of the solution with a buffer to near isoelectronic point of the polymer; and c) producing the hydrogel. In some embodiments of the method, optionally, the solution of step a) is heated 2°C above the phase change point of the polymer. In some embodiments of the method, optionally, the heated solution is cooled down to about 2°C below its phase change point if it is heated 2°C above its phase change point.
[0027] The present disclosure provides a method of producing a hydrogel foam, comprising the steps of: a) mixing water with a dry form of a composition comprising (i) a polymer, (ii) a surfactant, and optionally a fatty acid or a fatty alcohol to make a solution; b) adjusting pH of the solution with a buffer to near isoelectronic point of the polymer; c) mixing the solution of step b) with air in a ratio of the solution about 1: 10 to about 1:20; and d) producing the hydrogel foam. In some embodiments, optionally, the solution of step a) is heated 2°C above the phase change point of the polymer. In some embodiments, optionally, the solution is cooled to about 2°C below its phase change point if it is heated 2°C above its phase change point.
[0028] The present disclosure provides a method of protecting a target from a stressor, comprising applying the hydrogel or the hydrogel foam comprising the composition taught herein to a target. In some embodiments, the target is a plant or an area m which the plant or crop is growing. In7328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005some embodiments, the stressor is an abiotic stressor. In some embodiments, the abiotic stressor is smoke, sun exposure, or frost. In some embodiments, the stressor is a biotic stressor. In some embodiments, the biotic stressor is a fungus, a bacterium, a pathogen, an insect, or a pest.
[0029] The present disclosure provides a method of delivering an agricultural compound to a target, comprising a) mixing the agricultural compound with the hydrogel or the hydrogel foam comprising the composition taught herein; and b) applying the hydrogel or the hydrogel foam to a target. In some embodiments, the agricultural compound is a fertilizer, a pesticide, a growth regulator, a soil amendment, a biostimulant, an attractant (e.g., pheromone and kairomone), or a fumigant. In some embodiments, a plant or an area in which the plant or crop is growing.BRIEF DESCRIPTION OF THE DRAWINGS
[0030] FIG. 1 is a workflow for making a hydrogel and a hydrogel foam, respectively, using a charged polymer (e.g., gelatin) with a charged surfactant (e.g., SLES) and a fatty acid (e.g., myristic acid). As presented in Fig. 1, Example Formulation comprises a solution comprising 2% gelatin w / w, 0.3% SEES w / w, 0.1% myristic acid (MA) in water, with pH adjusted near isoelectric point of gelatin.
[0031] Fig. 2 is a schematic depiction of polymers (e.g., polyvinyl alcohol, protein, lignin, hydrolyzed collagen, pectin, chitosan, alginate, starch, cellulose, or carrageenan) and functional residues (e.g., hydroxyl, amine, or carboxyl) that promote electrostatic interactions.
[0032] Fig. 3 presents an image showing structural stability of Type B Gelatin foams prepared with SLES surfactant before and after pH adjustment. Foams prepared at pH 7 hold some structure but coarsen and collapse more than foams prepared at pH 4.7.
[0033] Fig. 4 presents an image showing structural stability of Type A Gelatin foams before and after pH adjustment. Foams at high pH (e g., pH 10 or pH 10.5) remain more stable.
[0034] Fig. 5 presents an image showing structural stability of Type B Gelatin foams prepared with SLSA surfactant.
[0035] Fig. 6 presents an image showing structural stability of soy protein isolate (SPI) foam prepared with SLS surfactant (2% SPI with SLS and MA) at pH 4.5.DETAILED DESCRIPTIONDefinitions8328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005
[0036] While the following terms are believed to be well understood by one of ordinary skill in the art, the following definitions are set forth to facilitate explanation of the presently disclosed subject matter.
[0037] The term “a” or “an” may refer to one or more of that entity, i.e. can refer to plural referents. As such, the terms “a” or “an”, “one or more” and “at least one” are used interchangeably herein. In addition, reference to “an element” by the indefinite article “a” or “an” does not exclude the possibility that more than one of the elements is present, unless the context clearly requires that there is one and only one of the elements.
[0038] Reference throughout this specification to “one embodiment”, “an embodiment”, “one aspect”, or “an aspect” means that a particular feature, structure or characteristic described in connection with the embodiment is included in at least one embodiment of the present di sclosure. Thus, the appearances of the phrases “in one embodiment” or “in an embodiment” in various places throughout this specification are not necessarily all referring to the same embodiment. Furthermore, the particular features, structures, or characteristics can be combined in any suitable manner in one or more embodiments.
[0039] As used herein, the terms “about” or “approximately” when used in conjunction with numerical values and / or ranges generally refer to those numerical values and / or ranges near to a recited numerical value and / or range. In some instances, the terms “about” and “approximately” may mean the value plus or minus a range of 10%. The terms “about” and “approximately” may be used interchangeably.
[0040] As used herein, the term “hydrogel” refers to a solid like material composed of a three-dimensional network of polymers that hold a minimum of 10% water by weight. The hydrogel is a dense, water-filled gel. The hydrogel contains minimal air or no air mixed in. In one embodiment, the hydrogel comprises a polymer. In another embodiment, the hydrogel comprises a polymer and a surfactant. In further embodiments, the hydrogel comprises a polymer, a surfactant, and a fatty acid or a fatty alcohol.
[0041] As used herein, the term “hydrogel foam” refers to a foam, that is a porous material, formed by having air or gas within a hydrogel or a hydrogel matrix. As used herein, the term “foamed hydrogel” refers to a hydrogel with a dispersed gas phase forming either closed and, or open celled gas vesicles within the hydrogel. The terms “foamed hydrogel” and “hydrogel foam” can be used interchangeably.9328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005
[0042] As used herein, the term “natural polymer” refers to polymers which have natural sources, and may or may not, have been modified, including the addition or removal of the polymer’s functional groups.
[0043] As used herein, the term “biodegradable” refers to a substance that may be broken down into smaller components by bacteria, fungi and other living organisms.
[0044] As used herein, the term “compressed air” refers to air that is pressurized to a higher pressure than the surrounding atmospheric pressure.
[0045] As used herein, the term “compressed gas” refers to a gas, or a mixture of gasses, which are at a pressure above ambient,
[0046] As used herein, the term “isoelectric point (pl)” refers to the pH value at which the molecule carries no electrical charge. The pl is important for zwitterionic molecules such as amino acids, peptides, and proteins. The pl value is used to indicate the global basic or acidic character of a zwitterionic molecule, and compounds with pl > 7 can be considered basic, and those with pl < 7 can be considered acidic. For complex molecules such as proteins, the isoelectric point is useful in the description of acidic or basic character. Below the pl, that is at lower pH, the molecule is positively charged because acidic groups remain protonated. At the pl, the molecule has no net charge as the positive and negative charges are equal. Above the pl, that is at higher pH, the molecule is negatively charged due to deprotonation of acidic groups.
[0047] As used herein, the term “acidic isoelectric point” refers to that the pH at which a molecule, such as a polymer, an ammo acid, or a protein, has no net electric charge, and this pl value is in the acidic pH range, that is below 7.
[0048] As used herein, the term “alkaline isoelectric point” refers to pH at which a molecule, such as a polymer, an amino acid, or a protein, has no net electric charge, and this pl value is in the alkaline pH range, that is above 7.
[0049] As used herein, the term “near isoelectric point” refers to the condition where the pH of the environment is close to the isoelectric point (pl) of a molecule, such a polymer, an amino acid, or a protein. At this pH, the molecule has minimal net electrical charge, and the number of positive charges nearly balances the number of negative charges. In some embodiments, about + / - 0.2 of the isoelectric point of a material (e.g., a polymer, an amino acid, or a protein) is near isoelectric point.10328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005
[0050] As used herein, the term “surfactant” or “surface-active agent” is a compound that lowers the surface tension between two substances, such as a liquid and a gas or a liquid and a solid. Surfactants contain both hydrophilic (water-loving) and hydrophobic (water-repelling) regions, allowing them to interact with and stabilize hydrophobic and hydrophilic components in a mixture. In embodiments, surfactants can modify the gel's mechanical and surface properties and also enhance compatibility with hydrophobic components (e.g., fatty acids or fatty alcohols). The surfactant can facilitate the formation of stable, homogenous hydrogel using electrostatic interactions. Cationic surfactants are surfactants in which the hydrophilic head group carries a positive charge in aqueous solution, while anionic surfactants are surfactants in which the hydrophilic head group carries a negative charge in aqueous solution. Nonionic surfactants do not carry any electrical charge on their hydrophilic head group, and amphoteric surfactants contain both positive and negative charges within the same molecule, allowing them to behave as either cationic or anionic depending on the pH of the solution
[0051] As used herein, the term “gel point,” “sol-gel point,” and “phase change point,” each of which are interchangeably used, refer to temperature at which a polymer has a reversible change in viscosity such that the material changes from a liquid state to a solid state. As an example, most thermosensitive hydrogel polymers will convert from solid to liquid as the temperature increases past the gel point. Similarly, if temperatures decrease to below the gel point, the material will convert from a liquid to a solid-like state.Smoke
[0052] For growers of fruit that are to be fermented into alcoholic beverages (e.g., wine), smoke damage can pose a significant economic risk. Wildfires can generate large amounts of smoke and aerosols that can drift into agricultural cropland. During wildfires, the combustion of lignin during the burning of wood releases volatile phenols into the atmosphere, such as cresols and syringols. During wildfire events, smoke can drift from the fire affected area towards agricultural production areas. When fruit is exposed to smoke and these volatile phenol compounds, the volatile phenols can penetrate the skin of the fruit and bind with sugars in the fruit to form glycoside-“bound” phenols that stay in the fruit until harvest. Following the harvest of the fruit and during the fermentation of the fruit, the glycoside-“bound” phenols that are within the fruit will remain with the fruit juices throughout the fermentation process and can impart unwanted flavors to the11328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005alcoholic beverage, generating what is often referred to as “smoke taint”. This problem is costly, as it may require that the fruit be used for another lower value use (e.g., fruit juice), or that the fruit be discarded entirely.
[0053] Most solutions aiming to solve the challenge of smoke taint focus on removing or reducing the impact of the smoke taint after exposure to smoke. Two approaches are typically employed, (a) Careful harvesting and fruit processing techniques to reduce the amount of glycoside-“bound” phenols that are released into the crushed fruit juice, and (b) Use of additives during the fruit juicing and fermentation process to remove some or all of the glycoside-“bound” phenols that are in the fruit juice. For example, hand harvesting of grapes has been found to reduce the risk of smoke taint by minimizing the amount of non-grape material, which might have high glycoside-“bound” phenols, that is introduced into the fruit crushing phase. In another example, activated carbon has been blended into grape juice tanks after grape crushing, but prior to fermentation. The activated carbon can bind a portion of the glycoside-“bound” phenols in the grape juice, the activated carbon was then separated from the juice reducing the phenols in the grape juice. Overall, these solutions can aid in reducing the risk of smoke taint, but are typically expensive, require operational changes to implement and only show moderate results.
[0054] Some attempts have been made to try and prevent volatile phenols from being adsorbed into fruit flesh during exposure to smoke through the application of protective layer to fruit. Trials using plastic bags to cover and isolate fruit from smoke have shown to be successful to eliminate the risk of smoke taint contamination in fruit, however these have primarily been to show the viability of coating fruit as a protection mechanism as plastic bags are impractical as a scalable solution. Trials of commercially viable products have focused on sprayable coatings. For example, kaolin, a clay-based barrier coating that is typically used to protect grapes from sun damage, has been applied to grapes to protect them from smoke taint. Results have thus far been mixed, three challenges appear to limit the feasibility of existing sprayable products, (a) existing sprayable solutions may not form a continuous barrier, (b) the coating may also bind volatile phenols and if not properly removed be blended into the juice during juicing, and (c) the high cost of material to form a thick enough coat. The result has been that to date, commercially available solutions to solve smoke taint have been limited to post-exposure removal techniques rather than protective methods.12328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005
[0055] The present disclosure provides that non-foamed and / or foamed hydrogel can offer several unique advantages to mitigate this challenge, (a) foamed hydrogel has a high air porosity thus generating a sufficiently thick coating to protect the fruit can be done relatively cost effectively, (b) applying a thicker coating of foamed hydrogel lowers the risk of cracks or non-continuous coverage, (c) as the hydrogel or foamed hydrogel is generated from a liquid formulation, it’s easy to include a phenol chelator or an agent that ensure phenols are not to be bound, whichever is shown to be more effective, and (d) hydrogel and foamed hydrogel is flexible thus reducing the likelihood of forming cracks where smoke can penetrate, Non-foamed and / or foamed hydrogel shows promise as a smoke taint solution for fruit growers.Sun Exposure
[0056] For growers of fruit for consumption as a fresh product, and for certain transformed fruit products (e.g., wine), sunburn is a significant risk with the potential for severe economic impacts. Sunburn is a physiological disorder that affects the visual and organoleptic properties of fresh fruit. Excessive exposure to high temperatures, UV radiation and photosynthetically active radiation, can cause damage to the surface of the fruit and cause the plant to respond in a variety of ways to protect itself from further damage. The combination of these factors can lead to visual imperfection on the surface of the fruit, reducing the potential value of the fruit for sale as high-valued fresh product, and it can also lead to a reduction in the quality of the fruit for processing purposes. For instance, in grapes meant for use in white wines, sunburn can lead to an accentuation of undesirable tasting notes, including an increase in smoky flavors and a reduction in fruity notes, leading to a reduction in the value of the resulting wine.
[0057] Different techniques have been utilized to protect fruit, but each technique typically only focuses on a single risk factor (e.g., high temperatures, UV radiation). To combat high temperatures, growers have irrigated fields with water to cool fruit and surrounding air. This has proven effective, however consumes significant volumes of fresh water and does little to protect crops from UV radiation and photosynthetically active radiation. To combat UV radiation, growers have sprayed crops with kaolin solutions, a natural opaque clay that can adhere to fruit and reflect radiation to reduce damage. Similar to the use of irrigation for heat, kaolin and other coating sprays protect against radiation but offer little protection from high temperatures.13328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005
[0058] The present disclosure provides that non-foamed and / or foamed hydrogel can offer several unique advantages to mitigate this challenge, specifically that it may be capable of solving several issues at once. Spraying fruit with non-foamed and / or foamed hydrogel offers two degrees of protection, (a) as an insulator the foamed hydrogel can reduce the temperature of the fruit relative to the surrounding air, and (b) the hydrogel can shield the fruit from radiation, both UV and photosynthetically active radiation. Additionally, other opacity enhancers that block different radiation bands can be used to further increase protection against UV radiation, photosynthetically active radiation, or both. Non-foamed and / or foamed hydrogel shows promise as a sun protection solution for fruit growers.Frost
[0059] In yet another example, for growers of crops such as grains (e.g., wheat, rice, corn, barley, oats, sorghum, millet, etc.) legumes (e.g., soybeans, peas, lentils, chickpeas, beans, etc,), fruits (e.g., grapes, peaches, bananas, citrus fruit (e.g., oranges, lemons), pears, and apples, blueberries, black berries, raspberries, etc.) as well as vegetables (e.g., lettuces, tomatoes, herbs, etc.), frost presents a significant risk of economic damage. In early spring when crops begin to sprout, bud or blossom, short overnight frost events where temperatures reach below 32°F for several hours, can lead to devastating crop damage.
[0060] Growers employ a combination of active and passive protection systems to protect crops against damage from frost. Passive methods include site selection (e.g., sloped hill), crop row orientation, installation of wind barriers including planting trees or installing windbreaks, and selection of more frost-resistant crop varieties. In many instances, passive frost protection methods may not be enough, thus growers are increasingly utilizing active frost protection systems, which require activity and recurring costs on the part of the grower to protect the crop.
[0061] There are two approaches to actively protecting crops from frost; one approach is to actively increase the temperature of the air surrounding the crop, the second is to create a boundary to separate the frost sensitive parts of crops from cold or cooling air. Active heating is the most common technique with three systems in common use; (a) mixing air using a wind machine to break up cold sinks, (b) warming air by using active heaters, and (c) warming the crop and surrounding air by spraying water onto crops either through irrigation or with portable sprayers. All three systems can be effective but have limitations. Mixing air requires costly wind turbines,14328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005which only work for radiation frosts with steep inversion layers and only provide 3-5°F (1.7-2.8°C) of warming. Warming air requires significant amounts of fuel to burn - typically fossil fuels - and thus is often too expensive for most growers and is highly polluting. Irrigation based protection consumes significant quantities of water, however, this is often no longer viable for many agricultural regions as water shortages become more common.
[0062] The alternative to actively heating crops and surrounding air is to create a boundary to separate the frost sensitive parts of crops from cold and cooling air. One approach utilized in several commercially available systems uses plastic or other rigid materials to cover crops and form a warm air pocket beneath the material boundary. However, these systems are typically expensive and too labor intensive to be used extensively with most commercial crops. Another approach uses foamed hydrogel to create an insulating barrier on crops. Foamed hydrogels that have a sufficient air fraction can provide excellent thermal insulation characteristics, and, if sufficiently (i.e., thickness and continuousness) applied to plants, can effectively seal and protect crops from freezing conditions. The method of application of non-foamed and / or foamed hydrogels for frost protection typically consists of a combination of the following steps: a formulation comprising a polymer and optionally a surfactant and / or a fat (e.g., fatty acid or fatty alcohol) is mixed with water to form a hydrogel solution; the hydrogel solution is placed into a mobile applicator or apparatus to generate a hydrogel; the hydrogel solution is aerated to form a foam; either the hydrogel per se or the foamed hydrogel (i.e., a foamed type of hydrogel) is applied to a portion of a plant to form a boundary with surrounding air.
[0063] The present disclosure presents that non-foamed and / or foamed hydrogels applied using this, or similar methods, show promise in field testing to protect crops, however existing systems have major deficiencies and have thus been largely limited to niche markets such as protecting horticultural crops or some low-lying crops such as strawberries and lettuce.
[0064] Two characteristics define non-foamed and / or foamed hydrogel’s effectiveness in protecting crops, (a) insulation endurance — specifically a hydrogel’s ability to remain stable for long periods of time and maintain its insulation and barrier forming capacity. This includes its ability to withstand various external and environmental forces (e.g., wind, dry conditions), (b) Rheological properties - specifically, as it relates to a hydrogel’s mechanical strength, which will determine if the hydrogel is strong enough to hold onto the plant when at a thickness that provides sufficient insulation. Prior innovations have focused on improving foam persistence (i.e., longevity15328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005and stability), primarily by adding chemical additives to the foam concentrate that improve foam bubble stability. These additives include water-soluble surface-active polymers, metal salts that form metal-ligand bonds with water soluble polymers, and different surfactant combinations. There have also been attempts to improve persistence by adding chemical additives that adsorb water and improve the foams’ resistance to dry environments and high winds.
[0065] Despite extensive research, prior foams have poor rheological properties, consisting of an aqueous foam that flow similarly to a liquid, and thus have insufficient mechanical strength to hold onto standing crops or trellised crops (e.g., apples, grapes). Due to this, the use of foams has been largely limited low-lying crops (e.g., strawberries, lettuce).
[0066] The present disclosure provides that non-foamed and / or foamed hydrogels hydrogel can offer several unique advantages to mitigate these challenges, (a) the hydrogel enables a higher mechanical strength such that the hydrogel can hold onto standing or trellised crops in sufficient thickness to protect the crop from frost, (b) the improved hydrogel endurance allows the hydrogel to protect crops for several hours to days, and (c) the hydrogel enables the foamed hydrogel to endure a broader range of external pressures such as wind, light rain and high daytime heat.Fungal pressure
[0067] Another example of external pressures for growers of commercial crops such as grapes, soybeans, wheat or potatoes is fungal infections. For grapes specifically, downy mildew is a significant economic challenge. This fungus spreads through the release of spores from infected dead leaves. The fungus attacks a new host by landing on and penetrating the fruit or leaves, where it then begins to reproduce inside the plant. Left unchecked, fungal attacks weaken plants, which significantly reduces fruit quality and yield and even sometimes leads to death.
[0068] Growers combat fungal pressures using a combination of passive and active methods. Passive methods are typically a combination of cultivation practices that help to limit the propensity of conditions that encourage fungal growth and reduce the likelihood for fungal spores to spread and propagate. These include canopy and foliage management to reduce humid conditions, double pruning to reduce the risk of fungal infiltration in fresh cuts, and removal of potential fungal spreaders (e.g., infected wild plants) in and around fields.
[0069] Active methods rely exclusively on the use of fungicides, sprays which kill fungi and their spores. As fungicides typically don’t have long residence times, effective prevention of fungal16328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005outbreaks requires continuous re-application of fungicides throughout the growing season, which is both expensive and introduces potential environmental side-effects due to the toxic nature of fungicides. Alternatively, farmers have explored covering crops with a barrier coating that inhibits the penetration of fungi into the plant. However, this approach remains relatively limited and is difficult to apply, as its continuous coverage is critical for effectiveness.
[0070] The present disclosure provides that non-foamed and / or foamed hydrogel can offer several unique advantages to mitigate this challenge, (a) non-foamed and / or foamed hydrogel can form a protective barrier over plants which remains thin enough to allow sunlight to penetrate, (b) as hydrogel is an aqueous medium, pesticides can be incorporated into the solution and remain active for longer periods of time, and (c) as foamed hydrogel has a high porosity it can be applied liberally decreasing the risk of cracks for spores to pass through and keeping costs reasonable due to the low material requirements.Insects
[0071] Similar to fungal infections, insects can attack crops through a variety of means, decreasing the yield and quality of fruit, impacting many growers of crops, such as grains (e.g., wheat, rice, corn, barley, oats, sorghum, millet, etc.) legumes (e.g., soybeans, peas, lentils, chickpeas, beans, etc.), fruits (e.g., grapes, peaches, bananas, citrus fruit (e.g., oranges, lemons), pears, and apples, blueberries, black berries, raspberries, etc.) as well as vegetables (e.g., lettuces, tomatoes, herbs, etc.). Some examples of leaf and fruit damaging insects include the grape-berry moth, carpophilus beetle, diamondback moth, Colorado potato beetle, grape-flea beetle and redbanded leafroller, adult and larval stages of insects, which can consume the leaf, flower and fruit flesh. To combat this, insects are commonly actively managed, typically through the application of insecticides. Applied either as a preventative measure or during an outbreak, growers will spray an insecticide effective against the target insect, ensuring broad application throughout the plants canopy to kill any live insects. However, since outbreaks may only affect small portions of a field, they are challenging to identify and locate, and thus, preventative applications are often necessary to manage insect pressures. As insecticides are typically contact killers and do not offer residual protection following application, multiple preventative applications are often necessary to ensure low insect pressure throughout the season.17328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005
[0072] Alternative methods have been attempted in the past to mitigate insect pressures. For example, thin netting covering either the whole plant, or just the fruit, has been effective preventative measures to reduce the threat of flying insects. However, this approach is labor intensive and impractical for most crops, especially larger tree species such as apples, peaches or pears. Barrier forming applications that coat leaves or fruit, including coating containing insecticides, could be an effective remedy, however no current commercial product of this type has seen widespread use to date.
[0073] The present disclosure provides that non-foamed and / or foamed hydrogel can offer several unique advantages to mitigate this challenge. First, the hydrogel can form a protective barrier over plants which remains thin enough to allow sunlight to penetrate. Second, as hydrogel is an aqueous medium, pesticides can be incorporated into the solution and remain active for longer periods of time. Lastly, as foam has a high porosity, the material requirements for this are relatively low, which keeps costs reasonable.Polymer
[0074] A polymer used for making hydrogels is a molecule consisting of repeating units (monomers) that form a three-dimensional network capable of absorbing and retaining significant amounts of water. Polymers can be natural or synthetic and exhibit a wide range of physical, chemical, and mechanical properties depending on their composition and structure.
[0075] Hydrogels are networks of hydrophilic polymer chains that swell and retain large amounts of water while maintaining their mechanical structure. By definition, hydrogels are a network of polymers that absorb and retain significant amounts of water, making them a semi-solid gel-like substance. The hydrophilicity of hydrogel is due to the high density of hydrophilic functional groups such as -NH2, -COOH, -OH, -CONH2 and SO3H on the polymer peptides. The concentration of polymer in solutions to achieve a stable hydrogel can vary greatly depending on each polymer’s hydrophilicity (i.e., swelling degree) and the properties of the solution (e.g., pH, ionic strength, temperature), from less than about 1 % up to about 90% by weight,
[0076] Hydrogel polymers can be divided into two groups, synthetic and natural. Synthetic polymers are derived from petroleum products, including for example, polyvinyl alcohol (PVA), polyethylene glycol (PEG), polyethylene oxide (PEO), Polyacrylamide (PAM), poly (2- hydroxyethyl methacrylate) (PHEMA), Poly(N-isopropylacrylamide) (PNIPAM), polyacrylic acid (PAA), and polyacrylamide (PAAm). There is an extensive and broad range of synthetic 18328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005polymers with variations in polymer morphology, constituent monomers and functional groups, monomer and functional group arrangement, and polymer length, which allow for a very broad range of properties. In most cases, however, synthetic polymers have poor or no biodegradability, limiting their use as an agricultural applicant to only low concentrations due to potential accumulation issues in soil. The notable exception is polyvinyl alcohol which has been shown to have moderate biodegradability in field conditions, including Suzuki et al (1973).
[0077] Natural polymers in contrast are derived from organic sources such as wood, algae or shellfish. Examples include gelatin, collagen, agarose, alginate, hyaluronic acid, soy protein, whey protein, xanthan gum, pectin, carrageenan, dextran, chitosan, fibrin, cellulose and its derivatives (such as carboxymethyl cellulose (CMC), and hydroxypropyl cellulose (HPC). Natural polymers are readily biodegradable, and functionalization of these polymers to improve their properties, such as functionalization of cellulose with esters in the case of methyl cellulose, can improve polymer properties without significantly reducing biodegradability.
[0078] In some embodiments, gelatin and its polymeric counterparts provide a wide range of options for hydrogel formulation, with properties tailored for specific applications.
[0079] As a major component of the solution, and in certain cases the most important component after water, the polymers specifications are crucial to achieving the foams overall characteristics. In an embodiment of this disclosure, the polymer should meet several specifications. The polymer must be water-soluble, this includes polymers that have poor water-solubility as a single component in water, but can achieve about 50% about 55%, about 60%, about 65%, about 70%, about 75% or more water solubility when dissolved with a chemical additive that aids its dissolution, for example salt or an acid. The polymer must have a sufficiently low viscosity to allow the solution to be foamed, this is ideally a viscosity below 300 centipoises (cP) at concentration of about 5% by weight in solution, a viscosity below 1000 centipoises (cP) at concentration of about 10% by weight in solution, a viscosity below 3000 centipoises (cP) at concentration of about 0.1% by weight in solution, a viscosity below 1200 centipoises (cP) at concentration of about 8% by weight in solution, a viscosity below 900 centipoises (cP) at concentration of about 9% by weight in solution, or a viscosity below 150 centipoises (cP) at concentration of about 1% by weight in solution. In some embodiments, the polymer is biodegradable, enabling its widespread use on agricultural land. In further embodiments, a foamed hydrogel of the present disclosure, comprising a polymer and a crosslinker, is also biodegradable.19328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005
[0080] The crosslinking of the polymer depends on the available polymer functional groups. In an embodiment of this disclosure, the polymer will have at high density of one, or a combination of the following functional groups; -NH₂, -COOH, -OH, -CONH₂, or SO₃H. In further embodiments, a functional group of the polymer is -NH2, -COOH, or -OH.
[0081] Several potential polymers are detailed in Fig. 2, these include: polyvinyl alcohol, proteins (e.g., soy protein and whey protein), lignin (e.g., oxidized versions of lignin such as oxidized kraft lignin and oxidized lignosulphonate), gelatin, pectin, denatured collagen, chitosan, alginate, carrageenan, starch and cellulose including the esters and ethers of both starch and cellulose.
[0082] The present disclosure teaches that a gelatin with an acidic isoelectric point (pH 4.5-5.5) can be used to make a non-foamed and / or foamed hydrogel. When gelatin (with the acidic isoelectric point) alone is used, it forms a foamed gel that collapses rapidly. Adding an anionic surfactant improves foam stability, allowing the formation of a semi-stable foam with macrostructure. However, this foam is not strong enough to adhere to plants and lacks the ability to maintain microstructure. When gelatin is formulated with an anionic surfactant at a pH just below its isoelectric point (i.e., near the isoelectric point of the gelatin), it produces a strong, stable foam.
[0083] The present disclosure further teaches that gelatin with an alkaline isoelectric point (around pH 9) can be used to make a non-foamed and / or foamed hydrogel. When the gelatin with the alkaline isoelectric point is formulated with a cationic surfactant at a pH just above its isoelectric point (i.e., near the isoelectric point of the gelatin), it forms a strong, stable foam.
[0084] In some embodiments, chitosan can be used to make a non-foamed and / or foamed hydrogel. With an isoelectric point in the pH 5 range, chitosan forms a stable foam when combined with an anionic surfactant and adjusted to a pH below its isoelectric point (i.e., near the isoelectric point of the gelatin).
[0085] This system using polymer and surfactant to make hydrogels is expected to work with any molecule that exhibits a charge-based structure, particularly complex, amino acid- based molecules, as presented in the Examples. These molecules are most likely to possess charged groups that can be manipulated using the mechanisms described above. To ensure broad applicability, inventors have focused on identifying molecules with similar properties as described in Fig. 2, as these are likely to exhibit comparable behavior in this system.20328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005
[0086] The optimal concentration will vary depending on the specific components used, including the polymer and surfactant. For instance, the gelatin system of the present disclosure can produce a stable foam at concentrations as low as 1% w / w, but this threshold may change depending on the grade of gelatin or the type of polymer used. Each formulation can be optimized on a case-by-case basis.
[0087] Certain embodiments of this disclosure have a blend of polymers, whose combined properties may offer advantages.Surfactant
[0088] Foaming requires a surface-active agent to stabilize the air-water interface between the bubble and the surrounding solution. This may either be achieved by the surface-active properties of the polymer in solution, for instance polyvinyl alcohol, or by the addition of a surfactant to solution. In some embodiments, the surfactant is biodegradable and non-toxic. Potential surfactants include sodium lauryl sulphate (SLS), sodium laureth sulphate (SLES), Sodium Lauryl Sulfoacetate (SLSA), disodium Laureth Sulfosuccinate (DLSS), cocoamidopropyl betaine (CAPS), coco betaine, triton-X, tween-20, and tween-80.
[0089] The present disclosure teaches that a surfactant can be used to form a hydrogel from a polymer by modifying the physical and chemical interactions to facilitate gelation, stabilize the polymer and its matrix, and enhance the hydrogel's properties. Surfactants, such as SLES (Sodium Lauryl Ether Sulfate), can mediate interactions between hydrophobic and hydrophilic components and influence the self-assembly or crosslinking of polymers.
[0090] In some embodiments, anionic surfactants contain anionic functional groups at their head, such as sulfate, sulfonate, phosphate, and carboxylates. Exemplary lists of anionic surfactants include, but are not limited to, (i) sulfate - ammonium lauryl sulfate (ALS), sodium lauryl sulfate (SLS), sodium dodecyl sulfate, (SDS), sodium lauryl ether sulfate (SLES), sodium myreth sulfate, sodium lauryl sulfoacetate (SLSA); (ii) sulfonate - Sodium Dodecylbenzene Sulfonate (SDBS), Alpha-Olefin Sulfonates (AOS), Sodium Xylenesulfonate; (iii) Phosphates - Sodium Lauryl Phosphate and Sodium Alkyl Phosphate; and (iv) carbonylates - Sodium Stearate and Sodium Oleate.21328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005
[0091] In some embodiments, cationic surfactants, which are surfactants with a positively charged head group in aqueous solution. The cationic head groups are pH-dependent primary', secondary, or tertiary' amines, and primary and secondary amines become positively charged at pH < 10.
[0092] Exemplary lists of cationic surfactants include, but are not limited to, permanently charged quaternary ammonium salts, such as cetrimonium bromide (CTAB), cetylpyridinium chloride (CPC), benzalkonium chloride (BAC), benzethonium chloride (BZT), dimetliyldioctadecylammonium chloride (DODMAC), and dioctadecyldimethylammonium bromide (DODAB), Cetrimonium Chloride and Stearyltrimethylammonium Chloride.
[0093] In some embodiments, the surfactant in the hydrogel is a nonionic surfactant including, but not limited to sorbitan esters (e.g. SPAN 20, SPAN 80), polysorbates (e.g. TWTEN 20, TWEEN 80), polyethylene oxide hydrocarbons (e.g. TritonX-15, Triton X-100), and Cocoamide etheylenes (e.g. Coco Monoethanolamide (CMEA), cocamide Diethanolamine (CDEA)).
[0094] In some embodiments, the surfactant in the hydrogel is an amphoteric surfactant including, but not limited to, cocamidopropyl betame (CAPB), Lauryl Betaine, Coco-Betaine, Lauryl dimethylamine oxide, cocamidopropyl hydroxy sultaine (CAI IS), and Sodium Cocoamphoacetate.
[0095] The present disclosure teaches that surfactants are added to hydrogels to modify their properties, improve stability, and enable compatibility between hydrophilic polymers (e.g., gelatin) and hydrophobic additives or components.
[0096] In some embodiments, anionic surfactants have a negatively charged hydrophilic head group, which influences their behavior in hydrogel formation. In some embodiments, anionic surfactants can lower the surface tension between the aqueous polymer solution (e.g., gelatin) and any hydrophobic components (e.g., fatty acids), which can promote uniform dispersion of hydrophobic additives within the hydrogel. Ionic interactions are formed between the negatively charged surfactant and positively charged regions on the polymer (e.g., gelatin’s amine groups). By this charged interaction, the hydrogel is strengthened, providing improved mechanical properties.
[0097] In some embodiments, cationic surfactants have a positively charged hydrophilic head group and interact with negatively charged groups on polymers (e.g., gelatin’s carboxyl groups). These ionic interactions can act as crosslinking points, stabilizing the network structure of the hydrogel.22328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005
[0098] The present disclosure provides a composition used for forming a non-foamed hydrogel and / or a foamed hydrogel, which comprises a polymer. In some embodiments, the composition comprises a polymer and a surfactant. In some embodiments, the surfactant is anionic if the polymer has acidic isoelectric point. In other embodiments, the surfactant is cationic if the polymer has alkaline isoelectric point.
[0099] The present disclosure provides a composition, comprising: a polymer having at least one residue that is charged; and a surfactant selected from the group consisting of an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant. In some embodiments, a mixture of the charged polymer and the surfactant are capable of forming a charged polymer-surfactant complex under conditions of varying pH or in the presence of electrolytes. In some embodiments, the composition comprises a plurality of polymers and a plurality of surfactants. In some embodiments, the charged polymer-surfactant complex is processed into a hydrogel or a hydrogel foam. In some embodiments, the varying pH condition is between pH 2 and pH 11. In some embodiments, the varying pH condition is between pH 3 and pH 5. In some embodiments, the varying pH condition is between pH 9 and pH I I. In some embodiments, the composition further comprises a faty alcohol or a faty acid. In some embodiments, the pH- djusted solution is formed into a hydrogel.
[0100] In some embodiments, the composition is a dry form, a liquid form, or an emulsion form. In some embodiments, a dry form of the composition is dissolved in water to make a solution comprising the polymer, the surfactant, and optionally the fatty acid or the fatty alcohol. In some embodiments, a liquid form of the composition is a solution comprising the polymer, the surfactant, and optionally the fatty acid or the fatty alcohol. In some embodiments, (i) a dry form of the composition is dissolved in water to make a solution comprising the polymer and the surfactant, and (ii) a paste form of the fatty acid or the fatty alcohol. In some embodiments, the fatty acid paste is made by emulsifying the fatty acid with an emulsifier (commonly a surfactant or mixture thereof). In further embodiments, the fatty acid paste can be made from any fatty acid taught herein (e.g., myristic acid) and any surfactant taught herein (e.g., SLSA), and be used in the hydrogel formulation for foaming. In some embodiments, the fatty acid made for the fatty acid paste can be the fatty acid taught herein, including myristic acid. In some embodiments, the fatty acid can become a paste form with an appropriate emulsifying agent.23328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005
[0101] In some embodiments, the essential requirement for the surfactant in this system is that the surfactant’s charge must be compatible with the polymer system. For polymers formulated at a pH below their isoelectric point, an anionic surfactant, or surfactant mixture with a net negative charge produces the most stable interactions. For polymers formulated at a pH above their isoelectric point, a cationic surfactant, or surfactant mixture with a net positive charge, produces the most stable interactions. In further embodiments, the formulation is adjusted to a pH just below the isoelectric point for acidic polymers or just above for alkaline polymers to promote the desired interaction. The surfactant, or blend of surfactants, must function as an effective foaming agent.
[0102] The required concentration of the surfactant will vary depending on the application (e.g., insulation versus delivery) and the specific polymer / surfactant combination. Defining precise concentration bounds can be determined, as these depend on the chara cteristics of the components and the intended use case.
[0103] In some embodiments, the polymer, which is naturally derived or synthetically derived, is selected from the group consisting of gelatin, cellul ose, hyaluronic acid, soy protein, whey protein, xanthan gum, pectin, carrageenan, chitosan,, agarose, dextran, fibrin, poly (vinyl alcohol) (PVA), poly (ethylene glycol) (PEG), poly (ethylene oxide) (PEG), poly (2-hy dr oxy ethyl methacrylate) (PHEM / X), poly (acrylic acid) (PAA), and poly (acrylamide) (PAAm) and a combination thereof. In some embodiments, the gelatin is a denatured form of collagen and the cellulose comprises ester or ether derivates.
[0104] The present disclosure provides the composition further comprising (i) a fatty alcohol comprising myristyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol, palmitoleyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, arachidonyl alcohol, butanol, and a combination thereof, or (ii) a fatty acid comprising myristic acid, lauric acid, palmitic acid, stearic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, butyric acid, or a combination thereof.
[0105] In some embodiments, the composition is a dry form, a liquid form, an emulsion form, or a paste form. In some embodiments, a dry form of the composition is dissolved in water to make a solution comprising the polymer, and optionally, the surfactant and the fatty acid or the fatty alcohol. In some embodiments, the solution or a liquid / emulsion form of the composition comprises about 0.01% to about 20% w / w of the polymer, about 0.05% to about 15% w / w of the polymer, about 0.1% to about 10% w / w of the polymer, about 0.5% to about 10% w / w of the24328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005polymer, about 0.01% to about 5% w / w of the polymer, or about 0.5% to about 4% w / w of the polymer.
[0106] In some embodiments, the solution or a liquid / emulsion form of the composition comprises about 0.01% to about 10% w / w of the surfactant, about 0.01% % to about 9% w / w of the surfactant, about 0.01% to about 8% w / w of the surfactant, about 0.01% to about 7% w / w of the surfactant, about 0.01% to about 6% w / w of the surfactant, about 0.01% to about 5% w / w of the surfactant, or about 0.01% to about 5% w / w of the surfactant.
[0107] In some embodiments, the ratio between the polymer and the surfactant in the solution or the liquid / emulsion form of the composition is about 0.5:1 to about 20:1 in w / w, about 0.5:1 to about 15:1 in w / w, about0.5:l to about 10:1 in w / w, orabout l:! to about 10:1 in w / w.
[0108] In further embodiments, the solution or the liquid / emulsion form of the composition comprises about 0.01% to about 1% w / w of the fatty acid or the fatty alcohol, about 0.05% to about 1 % w / w of the fatty acid or the fatty alcohol, or, about 0.05% to about 0,5% w / w of the fatty acid or the fatty alcohol,
[0109] When the polymer is used to make the hydrogel of the present disclosure is destabilized or dissolved.
[0110] In some embodiments, the polymer is destabilized due to thermal destabilization or chemical destabilization. In some embodiments, the polymer is dissolved as molecular mobility of the polymer increases. In some embodiments, the thermal destabilization of the polymer is caused by heating, such as exposure to high temperatures, which can disrupt the bonds within polymer chains. In other embodiments, the chemical destabilization of the polymer is caused by changing pH level, which can break bonds or alter interaction of functional groups with acids, bases, or oxidizing agents.
[0111] When a polymer is destabilized, it means that the polymer's structural integrity, functionality, or stability is compromised, often resulting in changes to its physical or chemical properties.
[0112] The present disclosure teaches that the solid polymer is destabilized and / or dissolved into a liquid state. The present disclosure teaches that the molecular mobility is increased in the polymer and the solid state of the polymer is changed. Each polymer has a different gel or phase-change point. The solid polymer is turned into a liquid state at about 10°C or higher, about 15°C or higher, about 20cC or higher, about 25°C or higher, about 30°C or higher, about 31 °C or higher about25328017736Attorney Docket No.: BREK-002 / 01WO 349002-200532CC or higher, about 33°C or higher about 34°C or higher, about 35°C or higher, about 36°C or higher, about 37°C or higher, about 38°C or higher, about 38°C or higher, about 40°C or higher, about 41 °C or higher, about 42°C or higher, about 43°C or higher, about 44°C or higher, about 45°C or higher, about 46CC or higher, about 47°C or higher, about 48°C or higher, about 49°C or higher, about 50cC or higher, about 51CC or higher, about 52CC or higher, about 53CC or higher, about 54CC or higher, about 55°C or higher, about 56°C or higher, about 57°C or higher, about 58CC or higher, about 59°C or higher, about 60°C or higher, about 61°C or higher, about 62°C or higher, about 63°C or higher, about 64°C or higher, about 65°C or higher.
[0113] The present disclosure teaches that the solution is heated to about 10°C or higher, about 15°C or higher, about 20°C or higher, about 25°C or higher, about 30°C or higher, about 31 °C or higher about 32°C or higher, about 33°C or higher about 34°C or higher, about 35°C or higher, about 36°C or higher, about 37°C or higher, about 38°C or higher, about 38°C or higher, about 40°C or higher, about 41 °C or higher, about 42°C or higher, about 43°C or higher, about 44°C or higher, about 45°C or higher, about 46°C or higher, about 47°C or higher, about 48°C or higher, about 49°C or higher, about 50°C or higher, about 51 °C or higher, about 52°C or higher, about 53°C or higher, about 54°C or higher, about 55°C or higher, about 56°C or higher, about 57°C or higher, about 58°C or higher, about 59°C or higher, about 60°C or higher, about 61 °C or higher, about 62°C or higher, about 63°C or higher, about 64°C or higher, or about 65°C or higher. In some embodiments, the solution is heated above about 10°C and up to about 65°C. In some embodiments, the solution is heated at least about 1°C, at least about 2°C, or at least about 3 °C above the gel point of the polymer. In other embodiments, the solution is heated above the gel point of the polymer.
[0114] In some embodiments, the heated solution is cooled down to about 40°C or lower, about 39°C or lower, about 38°C or lower, about 37°C or lower, about 36°C or lower, about 35°C or lower, about 34°C or lower, about 33°C or lower, about 32°C or lower, about 31°C or lower, about 30°C or lower, about 25°C or lower, about 20°C or lower, about 15°C or lower, or about 10°C or lower. In other embodiments the heated solution is cooled to about 10°C-40°C if it is heated above about 45°C. In some embodiments, the heated solution is cooled down to at least about I °C, at least about 2°C, or at least about 3 °C below its gel point if it is heated at least about I °C, at least about 2°C, or at least about 3°C above its gel point. In other embodiments, the heated solution is cooled down to below its gel point if it is heated above its gel point.26328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005
[0115] In some embodiments, pH of the solution is adjusted with a buffer to near isoelectric point of the polymer. In some instances, pH is adjusted using HC1 or NaOH without any buffer added.
[0116] In some embodiments, pH of the solution is adjusted with a buffer to about 0.5 to about 0.01 lower than the isoelectric point (pl) of the polymer. In some embodiments, the condition below pl makes the polymer slightly positively charged (+), in which anionic surfactant would work best. In other embodiments, the condition above the pl makes the polymer negative, which means that a cationic surfactant would work best. In some embodiments, an acidic buffer is selected from the group consisting of: citric acid, sodium citrate, acetic acid, sodium acetate, and a combination thereof. In other embodiments, pH of the solution is adjusted with a buffer to about 0,5 to about 0.01 higher than the isoelectric point, if the solution comprises the polymer having alkaline isoelectric point. In other embodiments, a base buffer is selected from the group consisting of: ammonia, ammonium chloride, sodium carbonate, sodium bicarbonate, phosphate, histidine, and a combination thereof. In further embodiments, about + / - 0.2 of the isoelectric point of the polymer is near isoelectric point. In further embodiments, the buffer is selected from the group consisting of: citric acid, sodium citrate, acetic acid, sodium acetate, ammonia, ammonium chloride, sodium carbonate, sodium bicarbonate, phosphate, histidine, and a combination thereof.
[0117] The present disclosure teaches that the pH-adjusted solution is formed into a hydrogel, which is aerosolized in fine mist and applied to a target. The present disclosure teaches the pH-adjusted solution is formed into a hydrogel, which is applied as a continuous sprayed stream or sprayed clumps. In some embodiments, the hydrogel is applied as a gel or a gel paste. In some embodiments, hydrogel is applied to a target. The present disclosure teaches the pH-adjusted solution is formed into a hydrogel, which is applied to a target. In other embodiments, the pH-adjusted solution is mixed with air in a ratio of about 1:2 to about 1:50 or about 1:5 to about 1:30 to be formed into a hydrogel foam. In other embodiments, the pH-adjusted solution is mixed with air in a ratio of about 1:15 to be formed into a hydrogel foam. In other embodiments, the air content of the hydrogel foam is about 0.1% to about 99%. In other embodiments, the hydrogel foam is biodegradable and is applied to a target. In some embodiments, the target includes, not is limited to, crops, such as grains (e.g., wheat, rice, corn, barley, oats, sorghum, millet, etc.) legumes (e.g., soybeans, peas, lentils, chickpeas, beans, etc.), fruits (e.g., grapes, peaches, bananas, citrus fruit (e.g., oranges, lemons), pears, and apples, blueberries, black berries, raspberries, etc.) as well as vegetables (e.g., lettuces, tomatoes, herbs, etc.). In some embodiments, the target is a plant or27328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005an area in which the plant or crop is growing. In some embodiments, the stressor is an abiotic stressor. In some embodiments, the abiotic stressor is smoke, sun exposure, or frost. In some embodiments, the stressor is a biotic stressor. In some embodiments, the biotic stressor is a fungus, a bacterium, a pathogen, an insect, or a pest.
[0118] In some embodiments, gelatin is about 0.5% to about 4% w / w. In some embodiments, the ratio between gelatin and surfactant is 6.7-10 parts gelatin to 1 part surfactant. In some embodiments, a solution comprising a gelatin and a surfactant optionally with a fatty acid or a fatty alcohol can foam across a large range of pH. For example, ideal chemical / physical properties to make hydrogel from type B gelatin can come out in the 4.7-7 range.
[0119] The effectiveness of the system varies depending on the materials used. Some polymers require a very specific pH to perform optimally, while others have a broader operational range. For example, the type B gelatin system of the present disclosure produces a reasonably stable foam across a pH range of 4.7 to 7 (or potentially higher). However, foam quality and performance significantly improve as the pH approaches 4,7, where it performs best for type B gelatin.
[0120] In some embodiments, polymers with acidic isoelectric points are paired with anionic surfactants and formulated at a pH within ±0.2 units of their isoelectric point.Dry and liquid compositions
[0121] The present disclosure provides a dry composition, comprising: (a) a first component comprising a dry form of a polymer, a surfactant, and a buffer; and (b) a second component comprising a paste form of (i) a fatty acid or a fatty alcohol and (li) a surfactant. In some embodiments of the dry compositions, the polymer is gelatin. In some embodiments of the dry compositions, surfactant is an anionic surfactant. In some embodiments of the dry compositions, the surfactant is sodium lauryl sulfoacetate (SLSA). In some embodiments of the dry compositions, the buffer is citric acid or sodium citrate. In some embodiments of the dry compositions, the fatty acid is myristic acid. In some embodiments of the dry compositions, the first and second components are combined and then dissolved in water to form a hydrogel or a hydrogel foam. In some embodiments of the dry compositions, the water-dissolved composition comprises about 0.05% to about 20% w / w of the polymer. In some embodiments of the dry compositions, the water- dissolved composition comprises about 0.01% to about 10% w / w of the surfactant. In some28328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005embodiments of the dry compositions, the water-dissolved composition comprises about 0.01% to about 1% w / w of the fatty acid.
[0122] The present disclosure further provides a dry composition, comprising: a dry form of a polymer, a surfactant, a buffer, and a fatty acid or a fatty alcohol. In some embodiments of the dry compositions, the polymer is gelatin. In some embodiments of the dry compositions, the surfactant is an anionic surfactant. In some embodiments of the dry compositions, the surfactant is sodium lauryl sulfoacetate (SLSA). In some embodiments of the dry compositions, the buffer is citric acid or sodium citrate. In some embodiments of the dry compositions, the fatty acid is myristic acid. In some embodiments of the dry compositions, the dry composition is dissolved in water to form a hydrogel or a hydrogel foam. In some embodiments of the dry compositions, the water-dissolved composition comprises about 0.05% to about 20% w / w of the polymer. In some embodiments of the dry compositions, the water-dissolved composition comprises about 0.01% to about 10% w / w of the surfactant. In some embodiments of the dry compositions, the water-dissolved composition comprises about 0.01% to about 1 % w / w of the fatty acid.
[0123] The present disclosure also teaches a liquid composition, comprising: a solution comprising a dry form of a polymer, a surfactant, a buffer, and a faty acid or a fatty alcohol is dissolved in water. In some embodiments of the liquid compositions, the polymer is gelatin. In some embodiments of the liquid compositions, the surfactant is an anionic surfactant. In some embodiments of the liquid compositions, the surfactant is sodium lauryl sulfoacetate (SLSA). In some embodiments of the liquid compositions, the buffer is citric acid or sodium citrate. In some embodiments of the liquid compositions, the faty acid is myristic acid. In some embodiments of the liquid compositions, the liquid composition comprises about 0.05% to about 20% w / w of the polymer. In some embodiments of the liquid compositions, the liquid composition comprises about 0.01% to about 10% w / w of the surfactant. In some embodiments of the liquid compositions, the liquid composition comprises about 0.01% to about 1% w / w of the fatty acid.Non-foamed hydrogels
[0124] The present disclosure provides compositions and formulation of non-foamed hydrogels, which are solid-like, three-dimensional polymer networks that absorb and retain water without mixing or incorporating air or gas to create foam. Non-foamed hydrogel has a high density due to the lack of air pockets and is general ly non-porous or minimally porous. The hydrogel is made by polymerization or crosslinking of hydrophilic polymers in water.29328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005
[0125] In some embodiments, these hydrogels can be made from polymers, such as gelatin or degraded collagen, proteins, by optionally introducing surfactants (e.g., SEES) and fatty acids or fatty alcohols. In some embodiments, the addition of surfactants and / or fatty acids electrostatically modifies the hydrogel’s properties to achieve desired characteristics, such as enhanced mechanical strength, improved elasticity, flexibility, or biocompatibility.
[0126] In some embodiments, gelatin as a natural polymer derived from collagen is capable of forming gels through reversible physical crosslinking. Gelatin is a degraded collagen, which is hydrolyzed or partially broken-down collagen that retains the ability to form hydrogels. When the surfactant (e.g., SM'. S) is mixed with gelatin, it can increase its interaction with hydrophobic substances and help to disperse fatty acids or other hydrophobic components evenly throughout the hydrogel matrix. The hydrogel made from gelatin with anionic surfactant and fatty acid / fatty alcohol has the enhanced mechanical properties, stability, elasticity, flexibility, biocompatibility, durability, and / or wettability.
[0127] In some embodiments, the polymer (e.g., gelatin or degraded collagen) is dissolved in water, typically by heating. The surfactant (e.g., SEES) and fatty acid are added to the solution, with mixing to ensure uniform dispersion. Then, the pH is adjusted to make the solution to be slightly acidic or neutral conditions in order to optimize gel formation and surfactant compatibility.
[0128] The mixture is cooled to form a stable hydrogel through physical crosslinking, such as hydrogen bonding or hydrophobic interactions. The non-foamed hydrogels, with no air mixed in, lack air pockets, resulting in a dense and smooth texture.
[0129] Tailorable properties for specific applications through the selection of polymers, surfactants, and additives (such as fatty acid or fatty alcohol). Non-foamed hydrogels can provide diverse functionality, by imposing natural polymer with the benefits of surfactant-modified properties for a wide range of practical applications in agriculture (such as seed / fruit / plant part protection, seed coating, soil amendments, etc. ), food (such as food processing and food science), cosmetics, therapeutics, and medicines (such as drug delivery).
[0130] The present disclosure provides a hydrogel comprising: a) about 0.05% to about 20% w / w of a polymer; b) about 0.01% to about 10% w / w of a surfactant; c) optionally, about 0.01% to about 1% w / w of a fatty acid or a fatty alcohol; and d) water. In some embodiments, the ratio between the polymer and the surfactant in the hydrogel is about 0.5:1 to about 20:1 in w / w. In some embodiments, the hydrogel comprises about 0.5% to about 10% w / w of the polymer. In some30328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005embodiments, the hydrogel comprises about 0.01% to about 5% w / w of the surfactant. In some embodiments, the hydrogel comprises about 0.05% to about 1% w / w of the fatty acid or the fatty alcohol. In some embodiments, the ratio between the polymer and the surfactant in the hydrogel is about 1:1 to about 10:1 in w / w. In some embodiments, the polymer is a plurality of polymers. In some embodiments, the surfactant is a plurality of surfactants.
[0131] In some embodiments, the polymer in the hydrogel includes, but is not limited to, gelatin, cellulose, hyaluronic acid, soy protein, whey protein, xanthan gum, pectin, carrageenan, chitosan,, agarose, dextran, fibrin, poly (vinyl alcohol) (PV A), poly (ethylene glycol) (PEG), poly (ethylene oxide) (PEO), poly (2-hydroxy ethyl methacrylate) (PHEMA), poly (acrylic acid) (PAA), and poly (acrylamide) (PAAm) and a combination thereof.
[0132] In some embodiments, the surfactant in the hydrogel is an anionic surfactant including, but not limited to, ammonium lauryl sulfate (ALS), sodium lauryl sulfate (SLS), sodium dodecyl sulfate, (SDS), sodium lauryl ether sulfate (SLES), sodium lauryl sulfoacetate (SLSA), sodium myreth sulfate, Sodium Dodecyl benzene Sulfonate (SDBS), Alpha-Olefin Sulfonates (AOS), Sodium Xylenesulfonate, Sodium Lauryl Phosphate, Sodium Alkyl Phosphate, Sodium Stearate, or Sodium Oleate.
[0133] In some embodiments, the surfactant is a cationic surfactant including, but not limited to, cetrimonium bromide (CTAB), cetylpyridinium chloride (CPC), benzalkonium chloride (BAC), benzethonium chloride (BZT), dimethyldioctadecylammonium chloride (DODMAC), dioctadecyldimethylammonium bromide (DODAB), Cetrimonium Chloride, or Stearyltrimethylammonium Chloride.
[0134] In some embodiments, the surfactant in the hydrogel is a nonionic surfactant including, but not limited to sorbitan esters (e.g. SPAN 20, SPAN 80), polysorbates (e.g. TWEEN 20, TWEEN 80), polyethylene oxide hydrocarbons (e.g. Triton X-l 5, Triton X-l 00), and Cocoamide etheylenes (e.g. CMEA, CDEA).
[0135] In some embodiments, the surfactant in the hydrogel is an amphoteric surfactant including, but not limited to, cocamidopropyl betaine (CAPB), Lauryl Betaine, Coco-Betaine, Lauryl dimethylamine oxide, cocamidopropyl hydroxysultaine (CARS), and Sodium Cocoamphoacetate.
[0136] In some embodiments, the fatty alcohol in the hydrogel includes, but is not limited to, myristyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol, palmitoleyl alcohol, oleyl alcohol, linoleyl alcohol, Imolenyl alcohol, arachidonyl alcohol, butanol, and a combination thereof. In31328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005further embodiments, the fatty acid in the hydrogel includes, but is not limited to, myristic acid, lauric acid, palmitic acid, stearic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, butyric acid, and a combination thereof.
[0137] In some embodiments, the hydrogel is in an emulsion form or a paste form. In further embodiments, the hydrogel, which is biodegradable, is aerosolized in fine mist. In some embodiments, the hydrogel is applied as a continuous sprayed stream or sprayed clumps. In some embodiments, the hydrogel is applied as a gel or a gel paste. In some embodiments, the hydrogel is applied to a target.Foamed Hydrogels
[0138] The hydrogel foam is a porous material formed by incorporating air or gas within a hydrogel matrix, creating a structure with interconnected air-filled cavities. The hydrogel foam has a low density because of the incorporation of air or gas. The hydrogel foam contains less water due to air pockets replacing part of the volume and is created by introducing air or gas into the hydrogel during its formation or by mechanical foaming. This results in a lightweight, spongy, and elastic material that retains some water while offering enhanced flexibility and mechanical properties, making it suitable for applications like cushioning, absorbent materials, insulation and spray ble coatings.
[0139] The present disclosure provides a method of generating, and the composition of, a foamed hydrogel that coats a part of a plant to protect components of the plant from various external pressures specified above. The method of this disclosure centers around, (a) the innovative concept of using a thermoset hydrogel as a foam matrix, (b) generating said thermoset hydrogel shortly before its application onto plants, and (c) the use of non-toxic and degradable polymers m the formulation.
[0140] In order to protect crops from or mitigate the impact of the range of abiotic and biotic environmental factors listed above, there are several material property and operational factors that must be achieved. Though individual properties or methods have been described in the prior art, the disclosed combination of formulation and method of use has not. Foam is used in a variety of applications in agriculture, including as a field marker, in washing or cleaning crops during harvest, and some previous attempts have been made to use foam as a frost protective coating. However, in these previous applications, foams had poor mechanical properties, and / or poor longevity, making them of little use for the applications listed above. Similarly, hydrogels are used 32328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005extensively m food processing and food science and have been used in agriculture as soil amendments and seed coatings, however these cases focus on the hydration properties of the hydrogel rather than the insulation and mechanical properties. Finally, a critical requirement for the use of hydrogel in agriculture is that it remains non-toxic and biodegradable with limited impact to the surrounding environment. Spray-on foamed systems, which are used in a range of industries, often utilize polyurethane foams, which rely on toxic solvents and are not biodegradable, making them not suitable in agricultural applications. The combination of water soluble, non-toxic and biodegradable is not found in previous art.
[0141] The present disclosure provides a hydrogel foam comprising a) about 0.05% to about 20% w / w of a polymer; b) about 0,01% to about 10% w / w of a surfactant; c) optionally, about 0.01% to about 1 % w / w of a fatty acid and / or a fatty alcohol; d) water and e) compressed air. In some embodiments, the ratio between the polymer and the surfactant in the hydrogel foam is about 0.5: 1 to about 20:1 in w / w. In some embodiments, the hydrogel foam comprises about 0.5% to about 10% w / w of the polymer. In some embodiments, the hydrogel foam comprises about 0.01% to about 5% w / w of the surfactant. In some embodiments, the hydrogel foam comprises about 0.05% to about 1% w / w of the fatty acid or the fatty alcohol. In some embodiments, the ratio between the polymer and the surfactant in the hydrogel foam is about 1:1 to about 10:1 m w / w.
[0142] In some embodiments, the polymer in the hydrogel foam includes, but is not limited to, gelatin, cellulose, hyaluronic acid, soy protein, whey protein, xanthan gum, pectin, carrageenan, chitosan, agarose, dextran, fibrin, poly (vinyl alcohol) (PVA), poly (ethylene glycol) (PEG), poly (ethylene oxide) (PEO), poly (2-hydroxy ethyl methacrylate) (PHEMA), poly (acrylic acid) (PAA), and poly (acrylamide) (PAAm) and a combination thereof.
[0143] In some embodiments, the surfactant in the hydrogel foam is an anionic surfactant including, but not limited to, ammonium lauryl sulfate (ALS), sodium lauryl sulfate (SLS), sodium dodecyl sulfate, (SDS), sodium lauryl ether sulfate (SLES), sodium lauryl sulfoacetate (SLSA), sodium myreth sulfate, Sodium Dodecylbenzene Sulfonate (SDBS), Alpha-Olefin Sulfonates (AOS), Sodium Xylenesulfonate, Sodium Lauryl Phosphate, Sodium Alkyl Phosphate, Sodium Stearate or Sodium Oleate.
[0144] In some embodiments, the surfactant in the hydrogel foam is a cationic surfactant including, but not limited to, cetrimonium bromide (CTAB), cetylpyridinium chloride (CPC), benzalkonium chloride (BAC), benzethonium chloride (BZT), dimethyldioctadecylammonium33328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005chloride (DODMAC), dioctadecyldimethylammonium bromide (DODAB), Cetrimonium Chloride and Stearyltrimethylammonium Chloride.
[0145] In some embodiments, the surfactant in the hydrogel foam is a nonionic surfactant including, but not limited to, sorbitan esters (e.g. SPAN 20, SPAN 80), polysorbates (e.g. TWEEN 20, TWEEN 80), polyethylene oxide hydrocarbons (e.g. Triton X-15, Triton X-100), and Cocoamide etheylenes (e.g. CMEA, CDEA).
[0146] In some embodiments, the surfactant in the hydrogel foam is an amphoteric surfactant including, but not limited to, cocamidopropyl betaine (CAPB, Lauryl Betaine, Coco-Betaine, Lauryl dimethylamine oxide, cocamidopropyl hydroxysultaine (CAHS), and Sodium Cocoamphoacetate.
[0147] In some embodiments, the fatty alcohol in the hydrogel foam is selected from the group consisting of: myristyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol, palmitoleyl alcohol, oleyl alcohol, Imoleyl alcohol, Imolenyl alcohol, arachidonyl alcohol, butanol, and a combination thereof. In further embodiments, the fatty acid in the hydrogel foam is selected from the group consisting of: myristic acid, lauric acid, palmitic acid, stearic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, butyric acid, and a combination thereof. In further embodiments, the hydrogel, which is biodegradable, is aerosolized in fine mist. In further embodiments, the hydrogel is applied as a continuous sprayed stream or sprayed clumps. In further embodiments, the hydrogel is applied as a gel or a gel paste. In further embodiments, the hydrogel is applied to a target.
[0148] In order to achieve the desired performance targets, an embodiment of the foam must meet certain specifications. In an embodiment, the foam may have stiffening, hardening, solidification, a hydrogel matrix, the mechanical strength to maintain shape and adhere to applied surface, and be biodegradable.
[0149] Foamed hydrogels are composed of three or more critical chemical parts that function together. These are a polymer, a surfactant, and a compressed gas capable of foaming a hydrogel into a foamed hydrogel. In some embodiments, foamed hydrogels are composed of (i) three critical chemical parts that function together and (ii) a surfactant. In further embodiments, additional additives may be used to provide additional functional properties, including fats (such as a fatty acid or a fatty alcohol) or secondary / tertiary surfactants to improve foam stability and functional properties and polymers to improve water retention and modify viscosity.34328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005
[0150] In some embodiments, the foamed hydrogel of the present disclosure has an improved foaming ability with an increased mechanical strength, thereby holding onto a target, which is a plant, a crop, or an area where the plant or crop is growing.
[0151] In some embodiments, the hydrogel comprising a polymer solution, prior to being foamed, has a water content of about 50% to about 99.5%, about 60% to about 99.5%, about 70% to about 99.5%, or about 80% to about 99.5% by weight, when gas porosity is less than 1%. In some embodiments, the foamed hydrogel, after being foamed by compressed air or gas, has a gas porosity of about 0% to about 99%, about 10% to about 99%, about 20% to about 99%, about 30% to about 99%, about 40% to about 99%, or about 50% to about 99% by volume. In some embodiments, the foamed hydrogel has gas bubbles. In other embodiments, the air content of the hydrogel foam is about 0.1% to about 99%. In other embodiments, the hydrogel foam is biodegradable and is applied to a target.
[0152] In some embodiments, the surfactant readily interacts with the polymer to form a hydrophobic interactions and / or electrostatic interactions from about -10°C to about 65°C, 0°C to about 65°C, 5°C to about 65°C, I0°C to about 65°C, 15°C to about 65°C, 20°C to about 65°C,, 25°C to about 65°C, or 30°C to about 65°C, and relative humidity between about 0.1% to 100%.
[0153] In some embodiments, the hydrogel has a polymer concentration of about 0.05% to about 20% by weight, about 0.1% to about 15% by weight, about 0.5% to about 10% by weight, about 0.01% to about 5% by weight by weight.
[0154] In some embodiments, the hydrogel has a surfactant concentration of about 0.01% to about 10% by weight or about 0.01% to about 5% by weight by weight, when gas porosity is less than 1%.Agricultural foam
[0155] Aqueous foams have found use in agriculture in several forms. The most common commercial use today is as a temporary7marker, or tracer, where, for example, the foam is deposited on the ground to demarcate where pesticides have been previously applied and where they have not. Another use is as a pest management tool. In one example, foam heated to a high temperature is applied to undesi rable plants, burning the leaves or other parts of the plant, the foam allows for high area coverage to coat large portions of the plant, but it’s high air fraction enables it to have a low thermal mass meaning the heat dissipates rapidly after application. In another example, a pesticide solution is foamed, which improves the pesticide contact with target pests,35328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005such as plants or insects, and reduces the risk of off-target application, improving safety and reducing waste. In another case, there have been attempts to use foam as a frost protective coating, however this has had limited commercial success to date. As noted above, foams for frost protection in previous studies have insufficient mechanical strength, which limits their use to crops on the ground or as a very thin layer offering limited protection.
[0156] In the foam-use cases listed above, previous studies have exclusively used a single solution application, where formulation components, or a formulation concentrate, are mixed with water to form a single solution, compressed gas or a blowing agent is then added to this solution to generate a foam, and the foam is applied to the crop or field. In using a single solution, the advantage is that these foams may use existing commercially available foam application equipment. However, it means that the mechanical strength of the foam is limited by the viscosity of the foaming solution prior to air injection. For instance, patent AU2004319107B2, which is incorporated by reference in its entirety, disclosing a formulation for a frost protection foam specifically noted that “the water dispersion can have a relatively low viscosity so that it can be readily sprayed in conventional commercial spray systems”. Also, high-strength agricultural hydrogel foam is described in W02024250025A2, which is incorporated by reference in its entirety.
[0157] In an embodiment of this disclosure, the present disclosure teaches that the foam is made from a solution (comprising a polymer, a surfactant and / or a fatty acid or a fatty alcohol) and compressed air / gas, which allow for the electrostatic interaction of components in the solution that may stabilize the physical structure.
[0158] The present disclosure provides that a hydrogel foam is used for insulating a target from external, environmental stresses, such as drought, smoke, sun exposure, and frost, as well as numerous biotic factors such as fungi and insects. Foam insulation requires the presence of air for proper formation. While stable foam can be achieved across a range of pH, temperatures, and concentrations, identifying the optimal conditions is essential for maximizing foam performance. Further refinement is likely needed to determine the best formulation for insulation applications.
[0159] The present disclosure provides that a non-foamed or foamed hydrogel can be used as a delivery platform. This application involves incorporating materials into the gel solution and spraying it out of a nozzle, either without air or with a small amount of air (<50%). This approach may work as a simple gelatin solution without requiring a surfactant or pH adjustment. However,36328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005it is possible that the destabilizing method for leveraging pH adjustments and surfactant interactions may still be necessary to ensure foam stability.Formulations and kits
[0160] The present disclosure provides a dry formulation, comprising: (a) a dry form of a polymer, when dissolved in water, having about 0.05% to about 20% w / w; (b) a dry form of a surfactant, when dissolved in water, having about 0.01% to about 10% w / w; (c) optionally, a dry form of a fatty acid, when dissolved in water, about 0.01% to about 1% w / w. In some embodiments, the formulation is dissolved in water. In some embodiments, the formulation in water is 2°C above the gel point of the polymer. In some embodiments, the formulation in water is cooled to 2°C below the gel point of the polymer, if it is heated 2°C above its gel point. In some embodiments, the formulation in water is heated up above the melting point of the components then cooled to just above the sol-gel transition point.
[0161] In some embodiments of the formulation, the polymer is selected from the group consisting of gelatin, cellulose, hyaluronic acid, soy protein, whey protein, xanthan gum, pectin, carrageenan, chitosan,, agarose, dextran, fibrin, poly (vinyl alcohol) (PVA), poly (ethylene glycol) (PEG), poly (ethylene oxide) (PEO), poly (2-hydroxy ethyl methacrylate) (PHEMA), poly (acrylic acid) (PAA), and poly (acrylamide) (PA / Xm) and a combination thereof. In some embodiments of the formulation, the gelatin is a denatured form of collagen. In some embodiments of the formulation, the cellulose comprises ester and, or ether derivates. In some embodiments of the formulation, the fatty alcohol is selected from the group consisting of: myristyl alcohol, lauiyl alcohol, cetyl alcohol, steaiyl alcohol, palmitoleyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, arachidonyl alcohol, butanol, and a combination thereof. In some embodiments of the formulation, the fatty acid is selected from the group consisting of: myristic acid, lauric acid, palmitic acid, stearic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, butyric acid, and a combination thereof.
[0162] The present disclosure provides a kit, comprising: (1) a dry form of formulation ‘A’ comprising: a diy form of a polymer; a dry form of a surfactant; and a diy form of a buffer selected from the group consisting of: citric acid, sodium citrate, hydrochloric acid, acetic acid, sodium acetate, ammonia, ammonium chloride, sodium carbonate, sodium bicarbonate, and a combination thereof and (2)an emulsion / paste form of formulation ‘B’ comprising: a fatty acid or a fatty37328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005alcohol. In some embodiments of the kits, the dry form of the polymer is dissolved in water and has about 0.05% to about 20% w / w in a solution. In some embodiments of the kits, the dry form of the surfactant is dissolved in water and has about 0.01% to about 10% w / w in a solution. In some embodiments of the kits, the dry form of the fatty acid or the fatty alcohol is dissolved in water and has about 0.01% to about 1% w / w in a solution. In some embodiments of the kits, the formulation mixed with buffer is present in a liquid form, an emulsion form, or a paste form. In some embodiments of the kits, the formulation is heated about 2CC above the phase change point of the fatty acid or fatty alcohol.
[0163] In some embodiments, the fatty acid paste is made by emulsifying the fatty acid with an emulsifier (commonly a surfactant or mixture thereof). In further embodiments, the fatty acid paste can be made from any fatty acid taught herein (e.g., myristic acid) and any surfactant taught herein (e.g., SLSA), and be used in the hydrogel formulation for foaming. In some embodiments, the fatty acid made for the fatty acid paste can be the fatty acid taught herein, including myristic acid. In some embodiments, the fatty acid can become a paste form with an appropriate emulsifying agent.
[0164] The present disclosure provides a kit, comprising: (1) a formulation comprising: a dry form of a polymer; a dry or paste form of a surfactant; and optionally, a dry form of a fatty acid; wherein the polymer is dissolved in water and has about 0.5% to about 10% w / w in a solution; wherein the surfactant is dissolved in water and has about 0.01% to about 5% w / w in a solution; and wherein the fatty acid is dissolved in water and has about 0.05% to about 1% w / w in a solution; and (2) optionally, a buffer selected from the group consisting of: citric acid, sodium citrate, hydrochloric acid, acetic acid, sodium acetate, ammonia, ammonium chloride, sodium carbonate, sodium bicarbonate, and a combination thereof. In some embodiments of the kit, the polymer is selected from the group consisting of gelatin, cellulose, hyaluronic acid, soy protein, whey protein, xanthan gum, pectin, carrageenan, chitosan,, agarose, dextran, fibrin, poly (vinyl alcohol) (PVA), poly (ethylene glycol) (PEG), poly (ethylene oxide) (PEO), poly (2-hydroxyethyl methacrylate) (PHEMA), poly (acrylic acid) (PAA), and poly (acrylamide) (PAAm) and a combination thereof. In some embodiments of the kit, gelatin can be used as a polymer. In some embodiments, gelatin can vary based on (1) source of the collagen (e.g. cow, pig, fish) and (2) processing technique (acid or base hydrolyzed). In further embodiments, the gelatin is a denatured form of collagen. In some embodiments of the kit, the cellulose comprises ester and, or ether derivates. In some embodiments of the kit, the fatty acid is selected from the group consisting of: myristic acid, lauric acid, palmitic38328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005acid, stearic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, butyric acid, and a combination thereof. In some embodiments of the kit, the fatty alcohol is selected from the group consisting of: myristyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol, palmitoleyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, arachidonyl alcohol, butanol, and a combination thereof.Application to target
[0165] To be applied to agricultural targets such as crops or on the ground near crops, an embodiment of the foam must meet certain specifications that ensure that the foam will not have negative impacts for the plant, or the surrounding environment. The specific concern is biodegradation of the foam in natural environments. In agricultural environments, which may include fields with planted crops, harvested forests, water bodies downstream of agricultural fields and harvested forests, and settings downwind of agriculture field and harvested forests, degradability of the foam is necessary to ensure that the foam does not persist in the environment, causing harm or having undesirable impacts. Harm or undesirable impacts may include blocking sunlight and reducing plant’s ability to grow, trapping nutrients and reducing plant’s ability to find sufficient nutrients, being consumed by wild or domestic animals and insects causing harm or death to these animals or insects, or reducing a local areas beauty impacting tourism or property value. In some embodiments, the target includes, not is limited to, crops, such as grains (e.g., wheat, rice, corn, barley, oats, sorghum, millet, etc.) legumes (e.g., soybeans, peas, lentils, chickpeas, beans, etc.), fruits (e.g., grapes, peaches, bananas, citrus fruit (e.g., oranges, lemons), pears, and apples, blueberries, black berries, raspberries, etc.) as well as vegetables (e.g., lettuces, tomatoes, herbs, etc.)
[0166] Foam degradation is primarily controlled by the polymer, as the polymer typically makes up the backbone and bulk of the structure. For most foams, once the polymer begins to break down, the structure will collapse, allowing for the degradation of the foam into smaller peptides and molecules of its components, eventually reaching microscopic sizes. An embodiment of the foam may be composed of a polymer that is biodegradable in natural environments within sufficient time to not impact the environment, which is typically within weeks to a year. In some embodiments, the foamed hydrogel is biodegraded within hours, days, weeks, months, or years. In further embodiments, the foamed hydrogel is biodegraded within 1 hour, within 2 hours, within 3 hours, within 4 hours, within 5 hours, within 6 hours, within 12 hours, within 1 day, within 2 days,39328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005within 3 days, within 4 days, within 5 days, within 6 days, within 1 week, within 2 weeks, within 2 weeks, within 3 weeks, within 4 weeks, within 1 month, within 2 months, within 3 months, within 4 months, within 5 months, within 6 months, within 7 months, within 8 months, within 9 months, within 10 months, within 11 months, within 12 months, within 1 year, or within 2 years.
[0167] In one embodiment of the foam, the biodegradable polymers are naturally derived, and include, but are not limited to, a selection of proteins such as soy and whey protein, lignin, denatured collagen, chitosan, starch, alginate, pectin, carrageenan, or cellulose. In another embodiment of the foam, the biodegradable polymer includes, but is not limited to, a water-soluble synthetic polymer, such as polyvinyl alcohol.
[0168] In one embodiment of the foam, biodegradable and nonbiodegradable, synthetic polymers include, but are not limited to, polyethelyne glycol (PEG) and polyacrylamides. In another embodiment of the foam, synthetic polymers, such as, polyethelyne glycol (PEG) and polyacrylamides may not be included, as their degradation relies on abiotic processes such as oxidation or UV radiation, which is very slow with the potential to then build-up in natural environments over time.Hydrogels mechanical properties
[0169] Hydrogels are three-dimensional networks of water-insoluble polymers that hold a large quantity of water and can be tuned to switch between liquid-like state to solid-like state with a broad range of mechanical properties. These unique and diverse properties are of utility in a variety of industries and applications including medical uses such as soft contact lenses and tissue and joint implants, and pharmaceuticals such as slow or triggered-release formulations. A problem to be solved by the present disclosure was to improve the mechanical properties of the foam, whereby the transition from a liquid-like state to a solid-like state, commonly known as gel formation, gel point, or sol-gel transition, will increase the mechanical strength of the foam, improving the foams ability to hold onto crops and withstand environmental pressures such as wind.
[0170] Foamed hydrogels are hydrogels with a gas phase trapped within the hydrogel forming closed or open celled gas vesicles. Due to their rheological behavior, foamed hydrogels require that the gas be emplaced during the liquid phase prior to gel formation. However, the mechanical strength provided by the hydrogel is necessary to ensure that the foam holds and remains on the plant. A problem to be solved by the present disclosure is the emplacement of the foamed hydrogel40328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005onto the crop, such that the solution can both be adequately aerated to generate a foam or stable gel, and that the gel or foam have sufficient mechanical strength to be emplaced and hold onto the crop. To achieve this, an embodiment of the foam is generated by combining a (a) compressed gas, (b) a polymer, (c) a surfactant, which is then applied as an aqueous foamed solution to the crop. In an embodiment of this disclosure, the polymer and surfactant will interact in solution to form a stable low viscosity solution, compressed gas will then be added to form small bubbles in the solution, the addition of the gas will destabilize the polymer-surfactant interaction and lead to the precipitation of the polymer which will begin to interact with itself to increase the solution viscosity and form a stable hydrogel foam. In another embodiment, the initial surfactant-polymer solution is held at a temperature above its sol-gel point before, and during the addition of the compressed air, the foamed solution is then allowed to cool slowly in ambient conditions to a temperature below its sol-gel point such that the polymer further interacts with itself to provide additional mechanical strength allowing it to hold onto the crop.
[0171] The key to this disclosure is using a polymer - surfactant combination that electrostatically interact, which causes a rapid increase in viscosity and mechanical strength to allow the hydrogel to form and entrap the gas and hold onto the plant. In addition, the timing of the warming and the cooling of the foamed solution above and below its gel point can control its mechanical strength. In some embodiments, the cooling can be a strength-enhancer but is not necessarily required for stability because a number of combinations of polymers in the taught formulation can be achieved with the electrostatic interaction, not a temperature impact.
[0172] The mechanical strength of the resulting hydrogel will be broadly determined by the strength of the physical interaction of the polymers, and the density of polymer molecules in solutions. In the present disclosure two separate mechanisms drive an increase in the mechanical strength of the foam, (a) the properties of the polymer, such as its molecular weight, and its interaction with the surfactant, and (b) the temperature of the solution and whether it’s above or below its gel point temperature.
[0173] Polymers can interact with the hydrophobic tails of surfactants, leading to aggregation within the polymer network. Surfactants typically have amphiphilic structures with hydrophobic tails and hydrophilic heads. Hydrophobic interactions can result in reinforcement of the gel network, depending on the concentration and compatibility of the components. Also, polymers and surfactants with polar functional groups can form hydrogen bonds, enhancing the physical cross-41328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005linking in the hydrogel, contributing to the stability and elasticity of the hydrogel structure. The present disclosure teaches that physical and electrostatic interactions between the polymers and surfactants can act synergistically to enhance the mechanical strength and water-holding capacity of hydrogels. For example, electrostatic attractions can initiate the assembly of polymer-surfactant complexes, while hydrophobic interactions further stabilize the network.
[0174] The present disclosure teaches creating a foam stabilized by “physical crosslinks” formed through electrostatic interactions. The primary mechanism is the charge-induced instability of the polymer, influenced by solution conditions and interactions with surfactants. It is theorized that destabilized polymers are more prone to “interact” and “entangle,” facilitating the formation of a stable structure. The secondary thermos-responsive mechanism also contributes to stability by physical crosslinking. Cooling induces interactions between polymer chains, leading to selfassembly and stabilization of the hydrogel’s physical structure. This differs from chemical crosslinking as it relies on reversible, non-covalent physical interactions.
[0175] Certain molecules, such as biopolymers or proteins, exhibit a property called the isoelectric point (distinct from piezoelectricity). The isoelectric point refers to the pH at which a molecule has no net charge. This property plays a critical role m molecular stability.
[0176] Molecules are typically least stable at their isoelectric point. Stability in solution is defined by the molecule’s ability to remain soluble and maintain its native structure.
[0177] A key driver of molecule stability in solution are the charges across the surface of the molecule. These charges cause individual molecules to readily repel one another, preventing aggregation. However, when the net charge is removed and neutralized (as at the isoelectric point), this repulsion diminishes, promoting instability and molecular interactions. Accordingly, the molecules will collide and aggregate with self-assembly and potential precipitation from solutions.
[0178] The present disclosure teaches that the polymer is destabilized by formulating it at a pH near its isoelectric point — generally but not exclusively slightly below the pl if the isoelectric point is acidic, or slightly above it if alkaline. To enhance this effect, inventors pair the molecule with a suitable surfactant: typically, an anionic surfactant for polymers with acidic isoelectric points or a cationic surfactant for those with alkaline isoelectric points, however, mixtures of cationic, anionic, nonionic, and amphoteric surfactants can also be selected to achieve similar interactions.
[0179] The interaction of the surfactant and polymer at prescribed pH induces molecular instability. Essentially, the molecule’s stability is on a knives-edge. When air is introduced into42328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005the formulation, this balance is disrupted, triggering molecular assembly into higher-order, precipitated structures that achieve a new, stable state. This final transition may be driven by one or both of the following mechanisms: 1) air- water interactions that are known to be destabilizing for proteins: and 2) rapid concentrating of the polymer by introducing air bubbles that rapidly decrease the volume it occupies - high concentrations are known to also destabilize polymers.
[0180] In some embodiments, for a molecule with an acidic isoelectric point, inventors formulate the solution just below that value. At this pH, the polymer is mostly neutral but carries a slight positive charge. Below the isoelectric point, a molecule has a net positive charge; above it, a net negative charge. When an anionic surfactant is introduced, its negatively charged head binds electrostatically to the positively charged regions of the polymer, leaving the surfactant’s hydrophobic tail extending into the solution. This interaction destabilizes the polymer, making it highly prone to precipitation and hardening, which in turn stabilizes the foam,
[0181] In other embodiments, the molecule is formulated exactly at its isoelectric point, where it has no net charge. In this scenario, the surfactant’s hydrophobic tail interacts with the neutral polymer, driving molecular instability and / or promoting precipitation.Methods of producing a non-foamed and / or foamed hydrogel
[0182] The present disclosure provides a method of producing a hydrogel, comprising the steps of: (a) mixing water with a dry form of a composition comprising (i) a polymer, (ii) a surfactant, and optionally a fatty acid and or a fatty alcohol; (b) adjusting pH of the solution with a buffer, acid or base, to near isoelectronic point of the polymer; and (c) producing the hydrogel. In some embodiments, optionally, the composition in water is heated above the gel point of the polymer by at least 1°C, at least 2°C, or at least 3°C. In some embodiments, optionally, the solution of step b) is cooled down to about 5°C, about 4°C, about 3 °C, or about 2°C below the gel point, if it is heated 1°C, at least 2°C, or at least 3 °C above the gel point in step b).
[0183] The present disclosure provides a method of producing a hydrogel foam, comprising the steps of: (a) mixing water with a dry form of a composition comprising (i) a polymer, (ii) a surfactant, and optionally a fatty acid; (b) adjusting pH of the solution with a buffer, acid or base, to near isoelectronic point of the polymer; (c) mixing the solution of step d) with air in a ratio of the solution about 1:2 to about 1:50; and (d) producing the hydrogel foam. In some embodiments, optionally, the composition in water is heated above the gel point of the polymer. In some43328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005embodiments, optionally, the solution of step b) is cooled down to below the gel point, if it is heated above the gel point in step b).
[0184] The present disclosure provides a method of making a non-foamed or foamed hydrogel, comprising: (a) mixing water with a formulation comprising: (i) a dry form of a polymer; (li) a dry or paste form of a surfactant; and (iii) optionally, a dry form of a fatty acid; (b) adding a buffer to the formulation dissolved in water; and (c) applying the solution to a device, thereby forming a non-foamed or foamed hydrogel. In some embodiments, the polymer is dissolved in water and has about 0,05% to about 20% w / w in a solution. In some embodiments, the surfactant is dissolved in water and has about 0,01% to about 10% w / w in a solution. In some embodiments, the fatty acid is dissolved in water and has about 0.01% to about 1% w / w in a solution. In some embodiments, the polymer is selected from the group consisting of gelatin, cellulose, hyaluronic acid, soy protein, whey protein, xanthan gum, pectin, carrageenan, chitosan, agarose, dextran, fibrin, poly (vinyl alcohol) (PVA), poly (ethylene glycol) (PEG), poly (ethylene oxide) (PEO), poly (2-hydroxy ethyl methacrylate) (PHEMA), poly (acrylic acid) (PAA), and poly (acrylamide) (PAAm) and a combination thereof. In some embodiments, the gelatin is a denatured form of collagen. In some embodiments, the cellulose comprises ester and, or ether derivates. In some embodiments, the fatty acid is selected from the group consisting of: myristic acid, lauric acid, palmitic acid, stearic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, butyric acid, and a combination thereof. In some embodiments, the fatty alcohol is selected from the group consisting of: myristyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol, palmitoleyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, arachidonyl alcohol, butanol, and a combination thereof. In some embodiments, a buffer selected from the group consisting of: citric acid, sodium citrate, acetic acid, sodium acetate, ammonia, ammonium chloride, sodium carbonate, sodium bicarbonate, phosphate, histidine, and a combination thereof.
[0185] In some embodiments of the methods, the air content of the hydrogel foam is about 0.1% to about 99%.Methods of protecting a target using a hydrogel and / or a hydrogel foam
[0186] The present disclosure provides a method of protecting a target from a stressor, comprising applying the hydrogel or the hydrogel foam comprising the composition of the disclosure to a target. In some embodiments, the target is a plant or an area in which the plant or crop is growing.44328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005In some embodiments, the stressor is an abiotic stressor. In some embodiments, the abiotic stressor is smoke, sun exposure, or frost. In some embodiments, the stressor is a biotic stressor. In some embodiments, the biotic stressor is a fungus, a bacterium, a pathogen, an insect, or a pest.Methods of delivering an agricultural compound to a target
[0187] The present disclosure provides a method of delivering an agricultural compound to a target, comprising: a. mixing the agricultural compound with the hydrogel or the hydrogel foam comprising the composition of the disclosure; and b. applying the hydrogel or the hydrogel foam to a target. In some embodiments, the agricultural compound is a fertilizer, a pesticide, a growth regulator, a soil amendment, a biostimulant, an atractant (e.g,, pheromone and kairomone), or a fumigant. In some embodiments, a plant or an area in which the plant or crop is growing.Methods of manufacturing a hydrogel and a hydrogel foam
[0188] The present disclosure provides a method of manufacturing a hydrogel, comprising the steps of: (a) mixing water with a dry composition taught herein and (b) producing the hydrogel.
[0189] The present disclosure provides a method of manufacturing a hydrogel foam, comprising the steps of: (1) mixing water with a dry composition taught herein, (b) mixing a solution of step a) with air in a ratio of the solution about 1:2 to about 1:50; and (c) producing the hydrogel foam.EXAMPLES
[0190] The following examples are given for the purpose of illustrating various embodiments of the disclosure and are not meant to limit the present disclosure in any fashion. Changes therein and other uses which are encompassed within the spirit of the disclosure, as defined by the scope of the claims, will occur to those skilled in the art.Example 1: Method of generating a continuously foamed Type B Gelatin and sodium laureth sulphate (STS) hydrogel
[0191] Step 1
[0192] At ambient conditions between 15°C and 25°C, a polymer solution was prepared with the following composition in 500ml containers that had been cleaned 3 times with water. Using a balance to measure out each component, the polymer solution was composed of 2% of Type B Gelatin, 0.3% sodium laureth sulphate and 0.1% of myristic acid, in distilled water for a total mass 45328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005of 400g. In order to minimize clumping of the gelatin and ensure proper homogenization, gelatin was added to the solution at room temperature and allowed to mix for 5 minutes before adding additional components. After mixing, the remaining components were added and the solution was heated to 60°C and mixed for 5 minutes to dissolve the gelatin and myristic acid. Next, the solution was cooled to 40°C and pH adjusted to pH 4.6-4.8 to promote the interaction of the surfactant and the polymer.
[0193] Step 2
[0194] Using a compressed-air-foaming (CAF) device, the polymer solution and air were mixed through a diffuser at 50 mL / mm liquid, IL / min air. The solution is homogenized through turbulent mixing and passed through a custom diffuser at a pressure of 18 psi, both of which have residence times of below 10 seconds.
[0195] Step 3
[0196] As the foam exits the CAF device, it was deposited onto a 14 inch thick grape vine branch at ambient temperature and allowed to cool and crosslink fully forming a 3cm thick coat of foam and left to rest overnight.
[0197] Results
[0198] Continuously forming gelatin hydrogel foams were successfully prepared using the CAF. The foam readily held on a branch and successfully offers insulation to plants from cold temperatures. When formulated without pH adjustment or using neutral or cationic surfactants, foams would collapse and lose structural features critical to insulative properties.
[0199] Fig. 1 shows how to prepare a non-foamed hydrogel (gel) and a foamed hydrogel (foam) using a charged polymer (e.g., gelatin) with a charged surfactant (e.g., SLSA) and a fatty acid (e.g., myristic acid). Example Formulation refers to a solution comprising 2% gelatin w / w, 0.9% SLSA w / w, 0.1% myristic acid in water, with pH adjusted.Example 2: Method of generating a continuously foamed Type B Gelatin and sodium lauryl ether sulfate (SLES) hydrogel
[0200] Step 1
[0201] At ambient conditions between 15°C and 25°C, a polymer solution was prepared with the following composition in 500ml containers that had been cleaned 3 times with water. Using a balance to measure out each component, the polymer solution was composed of 2% of Type B46328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005Gelatin, 0.3% sodium laureth ether sulfate (SEES) and 0.1% of myristic acid, in distilled water for a total mass of 400g. In order to minimize clumping of the gelatin and ensure proper homogenization, gelatin was added to the solution at room temperature and allowed to mix for 5 minutes before adding additional components. After mixing, the remaining components were added and the solution was heated to 60°C and mixed for 5 minutes to dissolve the gelatin and myristic acid. Next, the solution was cooled to 40°C and pH adjusted to pH 4.6-4.8 to promote the interaction of the surfactant and the polymer.
[0202] Step 2
[0203] Using a compressed-air-foaming (CAF) device, the polymer solution and air were mixed through a diffuser at 50 mL / min liquid, IL / min air. The solution is homogenized through turbulent mixing and passed through a custom diffuser at a pressure of 18 psi, both of which have residence times of below 10 seconds.
[0204] Step 3
[0205] As the foam exits the CAF device, it was deposited onto a ’4 meh thick grape vine branch at ambient temperature and allowed to cool and crosslink fully forming a 3cm thick coat of foam and left to rest overnight.
[0206] Results
[0207] Continuously forming gelatin hydrogel foams were successfully prepared using the CAF, as presented in Fig. 3. The foam readily held on a branch and successfully offers insulation to plants from cold temperatures. When formulated without pH adjustment or using neutral or cationic surfactants, foams would collapse and lose structural features critical to insulative properties.Example 3: Method of generating a continuously foamed Type B Gelatin and sodium lauryl sulfoacetate (SLSA) hydrogel
[0208] Step 1
[0209] At ambient conditions between 15°C and 25°C, a polymer solution was prepared with the following composition in 500ml containers that had been cleaned 3 times with water. Using a balance to measure out each component, the polymer solution was composed of 2.5% of Type B Gelatin, 0.9% sodium lauryl sulfoacetate (SLSA) and 0.1% of myristic acid, in distilled water for a total mass of 400g. In order to minimize clumping of the gelatin and ensure proper47328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005homogenization, gelatin was added to the solution at room temperature and allowed to mix for 5 minutes before adding additional components. After mixing, the remaining components were added and the solution was heated to 60°C and mixed for 5 minutes to dissolve the gelatin and myristic acid. Next, the solution was cooled to 40°C and pH adjusted to pH 4.6-4.7 to promote the interaction of the surfactant and the polymer.
[0210] Step 2
[0211] Using a compressed-air-foaming (CAF) device, the polymer solution and air were mixed through a diffuser at 50 mL / min liquid, IL / min air. The solution is homogenized through turbulent mixing and passed through a custom diffuser at a pressure of 18 psi, both of which have residence times of below 10 seconds.
[0212] Step 3
[0213] As the foam exits the CAF device, it was deposited onto a ’4 meh thick grape vine branch at ambient temperature and allowed to cool and crosslink fully forming, a 3cm thick coat of foam and left to rest overnight.
[0214] Results
[0215] Continuously forming gelatin hydrogel foams were successfully prepared using the CAF. The foam readily held on a branch and successfully offers insulation to plants from cold temperatures. Similar to sodium laureth sulphate (SLS), sodium lauryl sulfoacecate (SLSA) also formed a stable foam, as presented in Fig. 5. When formulated without pH adjustment or using neutral or cationic surfactants, similar to example 1, foams would collapse and lose structural features critical to insulative properties.Example 4: Method of generating a continuously foamed Type A Gelatin hydrogel
[0216] Step 1
[0217] At ambient conditions between 15°C and 25°C, a polymer solution was prepared with the following composition in 500ml containers that had been cleaned 3 times with water. Using a balance to measure out each component, the polymer solution was composed of 2% of Type A Gelatin, 0.3% Cetyltrimethylammonium bromide (CTAB) and 0.1% of myristic acid, in distilled water for a total mass of 400g. In order to minimize clumping of the gelatin and ensure proper homogenization, gelatin was added to the solution at room temperature and allowed to mix for 5 minutes before adding additional components. After mixing, the remaining components were48328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005added and the solution was heated to 60°C and mixed for 5 minutes to dissolve the gelatin and myristic acid. Next, the solution was cooled to 40°C and pH adjusted using 2N HC1 and 2N NaOH to pH 10.4-10.6 to promote the interaction of the surfactant and the polymer.
[0218] Step 2
[0219] Using a compressed-air-foaming (CAF) device, the polymer solution and air were mixed through a diffuser at 50 mL / min liquid, IL / min air. The solution is homogenized through turbulent mixing and passed through a custom diffuser at a pressure of 23 psi, both of which have residence times of below 10 seconds.
[0220] Step 3
[0221] As the foam exits the CAF device, it was deposited onto a 14 meh grape vine branch at ambient temperatures and allowed to cool and crosslink fully forming a 3cm thick coat of foam and left to rest overnight.
[0222] Results
[0223] Continuously forming type A gelatin hydrogel foams were successfully prepared at alkaline pH using the CAF, as presented in Fig. 4. When prepared at neutral or acidic pH, the surfactant did not sufficiently interact with the Type A gelatin, resulting in poor mechanical properties and ultimate collapse of the foam (in less than 5 minutes). When formulated without pH adjustment or using neutral or anionic surfactants, foams would collapse and lose structural features critical to insulative properties.Example 5: Method of generating a continuously foamed chitosan hydrogel
[0224] Step 1
[0225] At ambient conditions between 15°C and 25°C, a polymer solution and a crosslinker solution were prepared with the following compositions in 500ml containers that had been cleaned 3 times with water. Using a balance to measure out each component, the polymer solution was composed of 2% of chitosan, 0.5% glacial acetic acid, and 0.3% Cetyltrimethylammonium bromide (CTAB), in distilled water for a total mass of 200g. The solution was then allowed to blend for 30 minutes at 50°C to ensure it was homogenized. The pH was then adjusted to pH 4.7 to promote dissolution of the chitosan and the interaction of the surfactant and the chitosan.
[0226] Step 249328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005
[0227] Using a compressed-air-foaming (CAF) device, the polymer solution and air were mixed through a diffuser at 50 mL / min liquid, IL / min air. The solution is homogenized through turbulent mixing and passed through a custom diffuser at a pressure of 20 psi, both of which have residence times of below 10 seconds.
[0228] Step 3
[0229] As the foam exits the CAT device, it was deposited onto a flat tray and allowed to crosslink fully forming a 3 cm thick coat of foam and left to rest overnight.
[0230] Results
[0231] Continuously forming chitosan hydrogel foams were successfully prepared using the CAF. When formed at alkaline pH, foams would collapse and lose structural features critical to insulative properties.Example 6: Method of generating continuously foamed alginate hydrogel
[0232] Step 1
[0233] At ambient conditions between 15°C and 25°C, a polymer solution will be prepared using Alginate (Sodium Alginate). The solution will be formulated with 0.3% SLES or 0.3% w / w CT AB and adjust to pH 5 and pH 6, respectively. These pH targets are just below and above the isoelectric point of sodium alginate and thus, will encourage electrostatic interactions with the respective surfactant.
[0234] Step 2
[0235] Using a compressed-air-foaming (CAF) device, the polymer solution and air will be mixed through a diffuser at 50 mL / min liquid, IL / min air. The solution will be homogenized through turbulent mixing and passed through a custom diffuser at a pressure whatever pressure is necessary to maintain the target air flow (likely 20-3 Opsi).
[0236] Anticipated Results
[0237] Similar to the other examples provided, it is expected that the alginate solution will form into a mechanical stable hydrogel foam. This will result from the electrostatic interactions that occur when a polymer near its isoelectric point, interacts with a surfactant insulation. The interaction will be enhanced through the introduction of air, which serves to concentrate the polymer solution (thus encouraging polymer chain collisions) and the creation of a destabilizing air water interface, that further promotes polymer aggregation.50328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005Example 7: Method of generating a continuously foamed whey protein isolate (WPI) and sodium laureth sulphase (SLS) hydrogel
[0238] Step 1
[0239] At ambient conditions between 15°C and 25°C, a polymer solution was prepared with the following composition in 500ml containers that had been cleaned 3 times with water. Using a balance to measure each component, the polymer solution was composed of 2% of whey protein isolate (WPI), 0.3% sodium laureth sulphate (SLS) and 0.1% of myristic acid, in distilled water for a total mass of 400g. In order to minimize clumping of the soy protein and ensure proper homogenization, soy protein was added to the solution at room temperature and allowed to mix for 5 minutes before adding additional components. After mixing, the remaining components were added, and the solution was heated to 60°C and mixed for 5 minutes to dissolve the myristic acid. Next, the solution was cool ed to 25°C and pH adjusted to pH 5.3 to promote the interaction of the surfactant and the polymer.
[0240] Step 2
[0241] Using a compressed-air-foaming (CAF) device, the polymer solution and air were mixed through a diffuser at 50 mL / min liquid, I L / min air. The solution is homogenized through turbulent mixing and passed through a custom diffuser at a pressure of 18 psi, both of which have residence times of below 10 seconds.
[0242] Step 3
[0243] As the foam exits the CAF' device, it was deposited onto a flat tray and allowed to stabilize forming a 3 cm thick coat of foam and left to rest overnight.
[0244] Results
[0245] Continuously forming whey protein isolate hydrogel foams were successfully prepared using the CAF. When formed at alkaline pH or without adding myristic acid, foams would collapse and lose structural features critical to insulative properties.Example 8: Method of generating a continuously foamed soy-protein isolate (SPI) and sodium laureth sulphase (SLS) hydrogel
[0246] Step 1
[0247] At ambient conditions between 15°C and 25°C, a polymer solution was prepared with the following composition in 500ml containers that had been cleaned 3 times with water. Using a51328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005balance to measure each component, the polymer solution was composed of 2% of soy protein isolate (SPI), 0.3% sodium laureth sulphate (SLS) and 0.1% of myristic acid, in distilled water for a total mass of 400g. In order to minimize clumping of the soy protein and ensure proper homogenization, soy protein was added to the solution at room temperature and allowed to mix for 5 minutes before adding additional components. After mixing, the remaining components were added, and the solution was heated to 60°C and mixed for 5 minutes to dissolve the myristic acid. Next, the solution was cooled to 25°C and pH adjusted to pH 4.5 to promote the interaction of the surfactant and the polymer.
[0248] Step 2
[0249] Using a compressed-air-foaming (CAF) device, the polymer solution and air were mixed through a diffuser at 50 mL / mm liquid, IL / min air. The solution is homogenized through turbulent mixing and passed through a custom diffuser at a pressure of 18 psi, both of which have residence times of below 10 seconds.
[0250] Step 3
[0251] As the foam exits the C / XF device, it was deposited onto a flat tray and allowed to stabilize forming a 3cm thick coat of foam and left to rest overnight.
[0252] Results
[0253] Continuously forming soy protein isolate hydrogel foams were successfully prepared using the CAF, as presented in Fig. 6. When formed at alkaline pH or without adding myristic acid, foams would collapse and lose structural features critical to insulative properties.Example 9: Method of generating a continuously foamed soy-protein isolate and xanthan gum hydrogel
[0254] Step 1
[0255] At ambient conditions between 15°C and 25°C, a polymer solution was prepared with the following composition in 500ml containers that had been cleaned 3 times with water. Using a balance to measure out each component, the polymer solution was composed of 2% of soy protein isolate, 0.3% sodium laureth sulphate, 0.1% of myristic acid and 0.1% xanthan gum, in distilled water for a total mass of 400g. In order to minimize clumping of the soy protein and xanthan gum, and ensure proper homogenization, both were added to the solution at room temperature and allowed to mix for 30 minutes before adding additional components. After mixing, the remaining52328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005components were added, and the solution was heated to 60°C and mixed for 5 minutes to dissolve the myristic acid. Next, the solution was cooled to 25°C and pH adjusted to pH 4.5 to promote the interaction of the surfactant and the polymers.
[0256] Step 2
[0257] Using a compressed-air-foaming (CAF) device, the polymer solution and air were mixed through a diffuser at 50 mL / min liquid, IL / min air. The solution is homogenized through turbulent mixing and passed through a custom diffuser at a pressure of 18 psi, both of which have residence times of below 10 seconds.
[0258] Step 3
[0259] As the foam exits the CAF device, it was deposited onto a flat tray and allowed to stabilize forming a clump of foam with a 3cm radius and left to rest overnight.
[0260] Results
[0261] Continuously forming soy protein isolate and xanthan gum hydrogel foams were successfully prepared using the CAF. The addition of the xanthan gum foamed a higher density and more stable foam, which could offer better insulation properties in certain situations demonstrating the ability to blend several polymers to yield different beneficial properties.Example 10: Method of protecting a plant
[0262] Step 1
[0263] Once the risk of a potential frost has been established, using available resources, such as weather forecasts, knowledge of the plant’s location and local geography, and historical knowledge of how other frost events have occurred in this area, estimate the maximum potential temperature that could occur.
[0264] Step 2
[0265] Using a compressed-air foaming device, apply the foam manufactured according to Examples 1-4, to the part of the plant that requires protection. Coat the plant with sufficient foam to protect against the maximum freezing temperature which has been estimated in step 1. For example, for a -7°C frost, it may require 5cm thick coating of foam, for a -2CC it may only require a 3 cm thick coating of foam.Example 11: Method of generating a foamed hydrogel insecticide lure53328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005
[0266] Step 1
[0267] At ambient conditions between 15°C and 25°C, a polymer solution was prepared with the following composition in 500ml containers that had been cleaned 3 times with water. Using a balance to measure out each component, the polymer solution was composed of 3% of Type B Gelatin, 0.3% sodium laureth sulphate and 0.1% of myristic acid, in distilled water for a total mass of 400g. In order to minimize clumping of the gelatin and ensure proper homogenization, gelatin was added to the solution at room temperature and allowed to mix for 5 minutes before adding additional components. After mixing, the remaining components were added, and the solution was heated to 60°C and mixed for 5 minutes to dissolve the gelatin and myristic acid. Next, the solution was cooled to 40°C.
[0268] Step 2
[0269] Using a balance, a formulated spinosad insecticide, either Entrust by Corteva, or an identical or substantially similar product such as Estero by Atticus, was added into the formulation to achieve a spinosad concentration of 1000 ppm by weight. Ethanol and isoamyl alcohol, which when volatized attract carpophilus beetles, we’re each added to the mixture to achieve a concentration of 0.5% by weight for each. Using HC1, the pH was then adjusted to a pH 4.8 to promote the interaction of the surfactant and the polymer to form a stable foam.
[0270] Step 3
[0271] Using a compressed-air-foaming (CAF) device, the solution and air were mixed through a diffuser at 50 mL / min liquid, IL / min air. The solution was homogenized through turbulent mixing and passed through a custom diffuser at a pressure of 18 psi, both of which have residence times of below 10 seconds.
[0272] Step 4
[0273] As the foam exits the CAF' device, it was deposited onto a flat tray and allowed to stabilize forming a round clump of foam with a radius of 3-4 cm.
[0274] Results
[0275] At ambient temperatures between 20-25cC, the foam clumps were then placed in a chamber with carpophilus beetles, an insect that is causing significant damage in tree nut crops globally. The attractant encouraged beetles to burrow into the foam, where they were exposed to insecticide. The foam achieved 100% mortality of all exposed beetles within 24 hours. The addition of an insecticide and an attractant did require the pH to be slightly adjusted to 4.8 compared to 4.5 in54328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005example 1 to achieve a similar foam stability. However, despite the additional of these new components to the mixture, the interaction of the polymer and surfactant at the right pH still allowed the foam to maintain its structural stability over the 24 hour trial, which was critical for its use case as a carrier.Example 12: Method of manufacturing formulation component dry-packs: Two Part - “A” and “B” - Dry-Packs
[0276] Step 1
[0277] For dry preparation of the formulation, formulation components will be dry-packed to support preparation of a target volume of foam formulation on farm just prior to application. As an example, the following procedure will support preparation of 100 kg of foam formulation on farm. To make 100kg final solution, components will be combined in dry-packs “A” and “B” as follows: Gelatin: 2,5kg; SLSA: 0,9kg; Sodium Citrate: 0,73kg; Citric Acid: 0.48kg,
[0278] Packaging will include the appropriately sized airtight bag or plastic container labeled component “A”.
[0279] Step 2
[0280] Myristic / Xcid will be prepared as a paste in a separate dry-pack container. For this example, the concentrate paste will be prepared as a 100kg batch.
[0281] Combine 2.0kg of SLSA and 30.0kg of Myristic Acid in 100kg of water. Heat to 65C. Package the resulting paste in an airtight container - dispensed in 0.44kg aliquots - labeled component “B”
[0282] Step 3
[0283] Package component “A” and “B” together for transport to the customer.Example 13: Preparing Foam formulation for Use on Farm
[0284] Step 1
[0285] To prepare the polymer solution to the correct concentration, a machine operator first determines the level of water necessary, as prescribed on the packaging. For this example, inventors assume materials are packaged such that they are to be dissolved in 100kg of water. The operator first fills the solution tank of his compressed-air-foam (CAF) spraying machine with 100 kg of water using a measuring system on the machine, ideally a measuring stick or probe.55328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005
[0286] Step 2
[0287] Once 100 kg of water has been added to the CAF machine, the operator will pour the dry formulation contents of 1 package of component “A” and 1 package of component “B” into the tank. The operator will then mix the solution to ensure homogeneity, either by hand mixing with a stirring instrument, or using a stirring device that is installed in the solution tank of the CAF for this purpose.Example 14: Method of manufacturing formulation component as a single dry-pack
[0288] Step 1
[0289] For dry preparation of the formulation, formulation components will be dry-packed to support preparation of a target volume of foam formulation on farm just prior to application. As an example, the following procedure will support preparation of 100 kg of foam formulation on farm. To make 100kg final solution, components will be combined m dry-pack as follows: Gelatin: 2,5kg; SLSA: 0,9kg; Sodium Citrate: 0,73kg; Citric Acid: 0.48kg; Myristic Acid: 0.1kg,
[0290] Step 2
[0291] Combine the components as outlined above into the appropriate sized air-tight container. Labeled “Formulation Dry Pack”
[0292] Step 3
[0293] Package component “Formulation Diy Pack” and transport to customer.Example 15: Preparing Foam formulation from a single dry-pack
[0294] Step 1
[0295] To prepare the polymer solution to the correct concentration, a machine operator first determines the level of water necessary', as prescribed on the packaging. For this example, inventors assume materials are packaged such that they are to be dissolved in 100kg of water. The operator first fills the solution tank of his compressed-air-foam (CAF) spraying machine with 100 kg of water using a measuring system on the machine, ideally a measuring stick or probe.
[0296] Step 2
[0297] Once 100 kg of water has been added to the CAF machine, the operator will pour the dry formulation contents of 1 package of “Formulation Dry' Pack” as prepared in example 7. The operator will then mix the solution to ensure homogeneity, either by hand mixing with a stirring56328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005instrument, or using a stirring device that is installed in the solution tank of the CAF for this purpose.Example 16: Method of manufacturing polymer concentrates
[0298] Step 1
[0299] To manufacture 100 kg final solution, the following components will be dissolved in water; To make 100kg final solution: components as follows: Gelatin: 2.5kg; SLSA: 0.9kg; Myristic Acid: 0,10kg; Sodium Citrate: 0.73kg; Citric Acid: 0.48kg.
[0300] A 110-liter reinforced plastic container will be selected.
[0301] Step 2
[0302] In a separate container large enough to hold 110 liters of liquid, add 97.19 kg di tilled water and mix in the components described in step 1 and mix by hand with a cleaned stirring instrument. It is not necessary to blend the solution in a separate container and blending can be completed in the transport container, however it is often easier to blend in a separate container and then pour the final product into the container for transport.
[0303] Step 3
[0304] Pour the blended concentrate solution into the plastic container for transport and seal the container.Example 17: Method of diluting concentrate for use on farm
[0305] Step 1
[0306] To prepare the polymer solution to the correct concentration, a machine operator first determines the level of water necessary, as prescribed on the packaging. For this example, inventors assume materials are packaged such that they are to be dissolved in 100kg of water. The operator first fills the solution tank of his compressed-air-foam (CAF) spraying machine with 100 kg of water using a measuring system on the machine, ideally a measuring stick or probe.
[0307] Step 2
[0308] Once 100 kg of water has been added to the CAF machine, the operator will pour the dry formulation contents of 1 package into the tank. The operator will then mix the solution to ensure homogeneity, either by hand mixing with a stirring instrument, or using a stirring device that is installed in the solution tank of the CAF for this purpose.57328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005
[0309] While various inventive embodiments have been described and illustrated herein, those of ordinary' skill in the art will readily envision a variety of other means and / or structures for performing the function and / or obtaining the results and / or one or more of the advantages described herein, and each of such variations and / or modifications is deemed to be within the scope of the inventive embodiments described herein. More generally, those skilled in the art will readily appreciate that all parameters, dimensions, materials, and configurations described herein are meant to be exemplary and that the actual parameters, dimensions, materials, and / or configurations will depend upon the specific application or applications for which the inventive teachings is / are used. Those skilled in the art will recognize or be able to ascertain using no more than routine experimentation, many equivalents to the specific inventive embodiments described herein. It is, therefore, to be understood that the foregoing embodiments are presented by way of example only and that, within the scope of the appended claims and equivalents thereto; in venti ve embodiments may be practiced otherwise than as specifically described and claimed. Inventive embodiments of the present disclosure are directed to each individual feature, system, article, material, kit, and / or method described herein. In addition, any combination of two or more such features, systems, articles, materials, kits, and / or methods, if such features, systems, articles, materials, kits, and / or methods are not mutually inconsistent, is included within the inventive scope of the present disclosure.INCORPORATION BY REFERENCE
[0310] All references, articles, publications, patents, patent publications, and patent applications cited herein are incorporated by reference in their entireties for all purposes. However, mention of any reference, article, publication, patent, patent publication, and patent application cited herein is not, and should not be taken as an acknowledgment or any form of suggestion that they constitute valid prior art or form part of the common general knowledge m any country in the world.AU2004319107B2Tomoo Suzuki, Yoshihiro Ichihara, Masaru Yamada, Kenzo Tonomura, Some Characteristics of Pseudomonas 0-3 which Utilizes Polyvinyl Alcohol, Agricultural and Biological Chemistry, Volume 37, Issue 4, 1 April 1973, Pages 747-756.58328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005NUMBERED EMBODIMENTS OF THE DISCLOSURE
[0311] Subject matter contemplated by the present disclosure is set out in the following numbered embodiments:Composition1. A composition, comprising:a. a polymer having at least one residue that is charged; andb. a surfactant selected from the group consisting of an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant,wherein a mixture of the charged polymer and the surfactant are capable of forming a charged polymer-surfactant complex under conditions of varying pH or in the presence of electrolytes.2. The composition of embodiment 1, wherein the composition comprises a plurality of polymers and a plurality of surfactants.3. The composition of embodiment 1 or 2, wherein the charged polymer-surfactant complex is processed into a hydrogel or a hydrogel foam,4. The composition of embodiment I or 2, wherein the polymer is selected from the group consisting of: gelatin, cellulose, hyaluronic acid, soy protein, whey protein, xanthan gum, pectin, carrageenan, chitosan, agarose, dextran, fibrin, poly (vinyl alcohol) (PVA), poly (ethylene glycol) (PEG), poly (ethylene oxide) (PEO), poly (2-hydroxyethyl methacrylate) (PHEMA), poly (acrylic acid) (PAA), and poly (acrylamide) (PAAm) and a combination thereof.5. The composition of embodiment 4, wherein the gelatin is a denatured form of collagen.6. The composition of embodiment 4, wherein the cellulose comprises ester or ether derivates.7. The composition of embodiment 1 or 2, wherein the anionic surfactant is selected from the group consisting of: ammonium lauryl sulfate (ALS), sodium lauiyl sulfate (SLS), sodium dodecyl sulfate, (SDS), sodium lauiyl ether sulfate (SLES), sodium myreth sulfate, sodium lauryl sulfoacetate (SLSA), Sodium Dodecylbenzene Sulfonate (SDBS), Alpha-Olefin Sulfonates (AOS), Sodium Xylenesulfonate, Sodium Lauryl Phosphate, Sodium Alkyl Phosphate, Sodium Stearate, Sodium Oleate, and a combination thereof.8. The composition of embodiment 1 or 2, wherein the cationic surfactant is selected from the group consisting of: cetrimonium bromide (CTAB), cetylpyridinium chloride (CPC), benzalkonium chloride (BAC), benzethonium chloride (BZT),59328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005dimethyldioctadecylammonium chloride (DODMAC), and dioctadecyldimethylammonium bromide (DODAB), Cetrimonium Chloride, and a combination thereof.9. The composition of embodiment 1 or 2, wherein the nonionic surfactant is selected from the group consisting of: sorbitan monolaurate (SPAN 20), sorbitan monooleate (SPAN 80), polysorbate 20 (TWEEN 20), polysorbate 80 (TWEEN 80), Octylphenol Ethoxylate (Triton X-l 5), Octyl phenol ethoxylate (Triton X-l 00), Coco Monoethanolamide (CMEA), cocamide Diethanolamine (CDEA) and a combination thereof.10. The composition of embodiment 1 or 2, wherein the amphoteric surfactant is selected from the group consisting of: cocamidopropyl betaine (CAPB), Lauryl Betaine, Coco-Betaine, Lauryl dimethylamine oxide, cocamidopropyl hydroxysultame (CALLS), Sodium Cocoamphoacetate, and a combination thereof.11. The composition of any one of embodiments 1-10, wherein the varying pH condition is between pH 2 and pH 11,12. The composition of embodiment 1, further comprising:c. a fatty alcohol or a fatty acid.13. The composition of embodiment 12, wherein the fatty alcohol is selected from the group consisting of: myristyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol, palmitoleyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, arachidonyl alcohol, butanol, and a combination thereof.14. The composition of embodiment 12, wherein the fatty acid is selected from the group consisting of: myristic acid, lauric acid, palmitic acid, stearic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, butyric acid, and a combination thereof.15. The composition of any one of embodiments 1-14, wherein the composition is a dry form, a liquid form, or an emulsion form.16. The composition of any one of embodiments 1-15, wherein the composition comprises a dry form of the composition that is dissolved in water to make a solution comprising the polymer, the surfactant, and optionally the fatty acid or the fatty alcohol.17. The composition of any one of embodiments 1-15, wherein the composition comprises a liquid form of the composition that is a solution comprising the polymer, the surfactant, and optionally the fatty acid or the fatty alcohol.60328017736Attorney Docket No.: BREK-002 / 01WO 349002-200518. The composition of any one of embodiments 1-15, wherein the composition comprises (i) a dry form of the composition is dissolved in water to make a solution comprising the polymer and the surfactant, and (ii) a paste form of the fatty acid or the fatty alcohol. 19. The composition of any one of embodiments 16-18, wherein the solution comprises about 0.05% to about 20% w / w of the polymer.20. The composition of any one of embodiments 16-18, wherein the solution comprises about 0.01% to about 10% w / w of the surfactant.21. The composition of any one of embodiments 16-18, wherein the solution comprises about 0.01% to about 5% w / w of the surfactant.22. The composition of any one of embodiments 16-21, wherein the ratio between the polymer and the surfactant in the solution is about 0.5:1 to about 20: 1 in w / w.23. The compositi on of any one of embodiments 16-22, wherein the ratio between the polymer and the surfactant in the solution is about 1: 1 to about 10: 1 in w / w.24. The composition of embodiment 16 or 17, wherein the solution comprises about 0.01% to about 1% w / w of the fatty acid or the fatty alcohol.25. The composition of embodiment 24, wherein the solution comprises about 0.05% to about 1% w / w of the fatty acid or the fatty alcohol.26. The composition of any one of embodiments 16-25, wherein the solution is heated above the gel point of the polymer.27. The composition of embodiment 26, wherein the heated solution is cooled to below its gel point if it is heated above its gel point.28. The composition of any one of embodiments 16-27, wherein pH of the solution is adjusted with a buffer to near isoelectric point of the polymer.29. The composition of embodiment 28, wherein the buffer is selected from the group consisting of: citric acid, sodium citrate, acetic acid, sodium acetate, ammonia, ammonium chloride, sodium carbonate, sodium bicarbonate, phosphate, histidine, and a combination thereof.30. The composition of embodiment 28 or 29, wherein the pH-adjusted solution is formed into a hydrogel.31. The composition of embodiment 30, wherein the hydrogel is biodegradable.61328017736Attorney Docket No.: BREK-002 / 01WO 349002-200532. The composition of embodiment 30 or 31, wherein the hydrogel is aerosolized in fine mist or sprayed as a fine foam droplet.33. The composition of embodiment 30 or 31, wherein the hydrogel is applied as a continuous sprayed stream or a sprayed clump.34. The composition of embodiment 30 or 31, wherein the hydrogel is applied to a target. 35. The composition of embodiment 28 or 29, wherein the pH-adjusted solution is mixed with air in a ratio of about 1:2 to about 1: 50 to be formed into foam.36. The composition of embodiment 35, wherein the air content of the foam is about 0,1% to about 99%.37. The composition of embodiment 35 or 36, wherein the foam is biodegradable.38. The composition of embodiment 35 or 36, wherein the foam is applied to a target.Hydrogel Composition1. A hydrogel, comprising:a. about 0.05% to about 20% w / w of a polymer;b. about 0.01% to about 10% w / w of a surfactant;c. optionally, about 0.01% to about 1% w / w of a fatty acid or a fatty alcohol; and d. water.wherein the ratio between the polymer and the surfactant in the hydrogel is about 0.5:1 to about 20: 1 in w / w.2. The hydrogel of embodiment 1, wherein the hydrogel comprises about 0.5% to about 10% w / w of the polymer.3. The hydrogel of embodiment 1, wherein the hydrogel comprises about 0.01% to about 5% w / w of the surfactant.4. The hydrogel of embodiment 1, wherein the hydrogel comprises about 0.05% to about 1% w / w of the fatty acid or the fatty alcohol.5. The hydrogel of embodiment 1, wherein the ratio between the polymer and the surfactant in the hydrogel is about 1: 1 to about 10:1 in w / w.6. The hydrogel of any one of embodiments 1-5, wherein the polymer is selected from the group consisting of gelatin, cellulose, hyaluronic acid, soy protein, whey protein, xanthan gum, pectin, carrageenan, chitosan, agarose, dextran, fibrin, poly (vinyl alcohol) (PVA),62328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005poly (ethylene glycol) (PEG), poly (ethylene oxide) (PEO), poly (2-hydroxyethyl methacrylate) (PHEMA), poly (acrylic acid) (PAA), and poly (acrylamide) (PAAm) and a combination thereof.7. The hydrogel of embodiment 1, wherein the polymer is a plurality of polymers.8. The hydrogel of embodiment 1, wherein the surfactant is a plurality' of surfactants.9. The hydrogel of embodiment 6, wherein the gelatin is a denatured form of collagen. 10. The hydrogel of embodiment 6, wherein the cellulose comprises ester and, or ether derivates.11. The hydrogel of embodiment 1, wherein the surfactant is selected from the group consisting of an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.12. The hydrogel of embodiment 11, wherein the anionic surfactant is selected from the group consisting of: ammonium lauryl sulfate (ALS), sodium lauryl sulfate (SLS), sodium dodecyl sulfate, (SDS), sodium lauryl ether sulfate (SLES), sodium myreth sulfate, sodium lauryl sulfoacetate (SLSA), Sodium Dodecylbenzene Sulfonate (SDBS), Alpha-Olefin Sulfonates (AOS), Sodium Xylenesulfonate, Sodium Lauryl Phosphate, Sodium Alkyl Phosphate, Sodium Stearate, Sodium Oleate, and a combination thereof.13. The hydrogel of embodiment 11, wherein the cationic surfactant is selected from the group consisting of: cetrimonium bromide (CTAB), cetylpyridinium chloride (CPC), benzalkonium chloride (BAC), benzethomum chloride (BZT), dimethyldioctadecylammonium chloride (DODMAC), and dioctadecyldimethylammonium bromide (DODAB), Cetrimonium Chloride, and a combination thereof.14. The hydrogel of embodiment 11, wherein the nonionic surfactant is selected from the group consisting of: sorbitan monolaurate (SPAN 20), sorbitan monooleate (SPAN 80), polysorbate 20 (TWEEN 20), polysorbate 80 (TWEEN 80), Octylphenol Ethoxylate (Triton X-l 5), Octyl phenol ethoxylate (Triton X-l 00), Coco Monoethanolamide (CMEA), cocamide Diethanolamine (CDEA) and a combination thereof.15. The hydrogel of embodiment 11, wherein the amphoteric surfactant is selected from the group consisting of: cocamidopropyl betaine (CAPB), Lauryl Betaine, Coco-Betaine,63328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005Lauryl dimethylamine oxide, cocamidopropyl hydroxysultaine (CARS), Sodium Cocoaniphoacetate, and a combination thereof.16. The hydrogel of embodiment 1, wherein the fatty acid is selected from the group consisting of: myristic acid, lauric acid, palmitic acid, stearic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, butyric acid, and a combination thereof.17. The hydrogel of embodiment 1, wherein the fatty alcohol is selected from the group consisting of: myristyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol, palmitoleyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, arachidonyl alcohol, butanol, and a combination thereof.18. The hydrogel of any one of embodiments 1-17, wherein the hydrogel is biodegradable. 19. The hydrogel of any one of embodiments 1-18, wherein the hydrogel is aerosolized in fine mist or sprayed as fine foam droplets.20. The hydrogel of any one of embodiments 1-18, wherein the hydrogel is applied as a continuous sprayed stream or a sprayed clump,21. The hydrogel of any one of embodiments 1-20, wherein the hydrogel is applied to a target.Hydrogel foam Composition1. A hydrogel foam, comprising:a. about 0.05% to about 20% w / w of a polymer;b. about 0.01% to about 10% w / w of a surfactant;c. optionally, about 0.01% to about 1% w / w of a fatty acid or a fatty alcohol; d. water; ande. compressed air,wherein the ratio between the polymer and the surfactant in the hydrogel foam is about 0.5:1 to about 20: 1 in w / w.2. The hydrogel foam of embodiment 1, wherein the hydrogel foam comprises about 0.5% to about 10% w / w of the polymer.3. The hydrogel foam of embodiment 1, wherein the hydrogel foam comprises about 0.01% to about 5% w / w of the surfactant.4. The hydrogel foam of embodiment 1, wherein the hydrogel foam comprises about 0.05% to about 1% w / w of the fatty acid or the fatty alcohol.64328017736Attorney Docket No.: BREK-002 / 01WO 349002-20055. The hydrogel foam of embodiment 1, wherein the ratio between the polymer and the surfactant in the hydrogel foam is about 1: 1 to about 10: 1 in w / w.6. The hydrogel foam of embodiment 1, wherein the polymer is selected from the group consisting of gelatin, cellulose, hyaluronic acid, soy protein, whey protein, xanthan gum, pectin, carrageenan, chitosan, agarose, dextran, fibrin, poly (vinyl alcohol) (PVA), poly (ethylene glycol) (PEG), poly (ethylene oxide) (PEO), poly (2-hydroxyethyl methacrylate) (PHEMA), poly (acrylic acid) (PAA), and poly (acrylamide) (PAAm) and a combination thereof.7. The hydrogel foam of embodiment 1, wherein the polymer is a plurality of polymers. 8. The hydrogel foam of embodiment 1, wherein the surfactant is a plurality of surfactants.9. The hydrogel foam of embodiment 6, wherein the gelatin is a denatured form of collagen.10. The hydrogel foam of embodiment 6, wherein the cellulose comprises ester and, or ether denvates.11. The hydrogel foam of embodiment 1, wherein the surfactant is selected from the group consisting of an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.12. The hydrogel foam of embodiment 11, wherein the anionic surfactant is selected from the group consisting of: ammonium lauryl sulfate (ALS), sodium lauryl sulfate (SLS), sodium dodecyl sulfate, (SDS), sodium lauryl ether sulfate (SLES), sodium myreth sulfate, sodium lauryl sulfoacetate (SLSA), Sodium Dodecylbenzene Sulfonate (SDBS), Alpha-Olefin Sulfonates (AOS), Sodium Xylenesulfonate, Sodium Lauryl Phosphate, Sodium Alkyl Phosphate, Sodium Stearate, Sodium Oleate, and a combination thereof.13. The hydrogel foam of embodiment 11, wherein the cationic surfactant is selected from the group consisting of: cetrimonium bromide (CTAB), cetylpyridinium chloride (CPC), benzalkonium chloride (BAC), benzethonium chloride (BZT), dimethyldioctadecylammonium chloride (DODMAC), and dioctadecyldimethylammonium bromide (DODAB), Cetrimonium Chloride, and a combination thereof14. The hydrogel foam of embodiment 11, wherein the nonionic surfactant is selected from the group consisting of: sorbitan monolaurate (SPAN 20), sorbitan monooleate (SPAN 80), polysorbate 20 (TWEEN 20), polysorbate 80 (TWEEN 80), Octylphenol Ethoxylate65328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005(Triton X-l 5), Octyl phenol ethoxylate (Triton X-l 00), Coco Monoethanolamide (CMEA), cocamide Diethanolamine (CDEA) and a combination thereof.15. The hydrogel foam of embodiment 11, wherein the amphoteric surfactant is selected from the group consisting of cocamidopropyl betaine (CAPB), Lauryl Betaine, Coco-Betaine, Lauryl dimethylamine oxide, cocamidopropyl hydroxysultaine (CARS), Sodium Cocoamphoacetate, and a combination thereof.16. The hydrogel foam of embodiment 1, wherein the fatty acid is selected from the group consisting of: myristic acid, lauric acid, palmitic acid, stearic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, butyric acid, and a combination thereof, 17. The hydrogel foam of embodiment 1, wherein the fatty alcohol is selected from the group consisting of: myristyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol, palmitoleyl alcohol, oleyl alcohol, Imoleyl alcohol, linolenyl alcohol, arachidonyl alcohol, butanol, and a combination thereof.18. The hydrogel foam of any one of embodiments 1-17, wherein the air content of the hydrogel foam is about 0.1% to about 99%.19. The hydrogel foam of any one of embodiments 1-18, wherein the hydrogel foam is biodegradable.20. The hydrogel foam of any one of embodiments 1-19, wherein the hydrogel foam is applied to a target.Formulation1. A formulation, comprising:a. a diy form of a polymer, when dissolved in water, having about 0.05% to about 20% w / w;b. a dry form of a surfactant, when dissolved in water, having about 0.01% to about 10% w / w; andc. a dry form of a fatty acid or a fatty alcohol, when dissolved in water, having about 0.01% to about 1% w / w.2. The formulation of embodiment 1, wherein the fatty acid or fatty alcohol is dissolved in water with a portion of the surfactant.66328017736Attorney Docket No.: BREK-002 / 01WO 349002-20053. The formulation of embodiment 2, wherein a mixture of the surfactant and the fatty acid or fatty alcohol is heated about 2CC above the phase change point of the fatty acid or fatty alcohol.4. The formulation of embodiment 3, wherein a liquid form of the formulation is cooled to about 2°C below its phase change point, if it is heated about 2CC above its phase change point.5. The formulation of embodiment 1, wherein the polymer is selected from the group consisting of gelatin, cellulose, hyaluronic acid, soy protein, whey protein, xanthan gum, pectin, carrageenan, chitosan, agarose, dextran, fibrin, poly (vinyl alcohol) (PVA), poly (ethylene glycol) (PEG), poly (ethylene oxide) (PEO), poly (2-hydroxy ethyl methacrylate) (PHEMA), poly (acrylic acid) (PAA), and poly (acrylamide) (PAAm) and a combination thereof.6. The formulation of embodiment 5, wherein the gelatin is a denatured form of collagen. 7. The formulation of embodiment 5, wherein the cellulose comprises ester and, or ether derivates.8. The formulation of embodiment 1, wherein the surfactant is selected from the group consisting of an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.9. The formulation of embodiment 8, wherein the anionic surfactant is selected from the group consisting of: ammonium lauryl sulfate (ALS), sodium lauiyl sulfate (SLS), sodium dodecyl sulfate, (SDS), sodium lauiyl ether sulfate (SLES), sodium myreth sulfate, sodium lauryl sulfoacetate (SLSA), Sodium Dodecylbenzene Sulfonate (SDBS), Alpha-Olefin Sulfonates (AOS), Sodium Xylenesulfonate, Sodium Lauryl Phosphate, Sodium Alkyl Phosphate, Sodium Stearate, Sodium Oleate, and a combination thereof.10. The formulation of embodiment 8, wherein the cationic surfactant is selected from the group consisting of: cetrimonium bromide (CTAB), cetylpyridinium chloride (CPC), benzalkonium chloride (BAC), benzethonium chloride (BZT), dimethyldioctadecylammonium chloride (DODMAC), and dioctadecyldimethylammonium bromide (DODAB), Cetrimonium Chloride, and a combination thereof.67328017736Attorney Docket No.: BREK-002 / 01WO 349002-200511. The formulation of embodiment 8, wherein the nonionic surfactant is selected from the group consisting of: sorbitan monolaurate (SPAN 20), sorbitan monooleate (SPAN 80), polysorbate 20 (TWEEN 20), polysorbate 80 (TWEEN 80), Octylphenol Ethoxylate (Triton X-l 5), Octyl phenol ethoxylate (Triton X-l 00), Coco Monoethanolamide (CMEA), cocamide Diethanolamine (CDEA) and a combination thereof.12. The formulation of embodiment 8, wherein the amphoteric surfactant is selected from the group consisting of: cocamidopropyl betaine (CAPB), Lauryl Betaine, Coco-Betaine, Lauryl dimethylamine oxide, cocamidopropyl hydroxysultaine (CAHS), Sodium Cocoamphoacetate, and a combination thereof.13. The formulation of embodiment 1, wherein the fatty acid is selected from the group consisting of: myristic acid, lauric acid, palmitic acid, stearic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, butyric acid, and a combination thereof.14. The formulation of embodiment 1, wherein the fatty alcohol is selected from the group consisting of: myristyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol, palmitoleyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, arachidonyl alcohol, butanol, and a combination thereof.Kit1. A kit, comprising:(1) a dry form of formulation A’ comprising:a. a dry form of a polymer;b. a dry form of a surfactant; andc. a dry form of a buffer selected from the group consisting of: citric acid, sodium citrate, hydrochloric acid, acetic acid, sodium acetate, ammonia, ammonium chloride, sodium carbonate, sodium bicarbonate, and a combination thereof and(2) an emulsion / paste form of formulation ‘B’ comprising: a fatty acid or a fatty alcohol.2. The kit of embodiment 1, wherein the dry form of the polymer is dissolved in water and has about 0.05% to about 20% w / w in a solution;68328017736Attorney Docket No.: BREK-002 / 01WO 349002-20053. The kit of embodiment 1, wherein the dry form of the surfactant is dissolved in water and has about 0.01% to about 10% w / w in a solution; and4. The kit of embodiment 1, wherein the dry form of the fatty acid or the fatty alcohol is dissolved in water and has about 0.01% to about 1% w / w in a solution.5. The kit of embodiment 1, wherein the formulation mixed with buffer is present in a liquid form, an emulsion form, or a paste form.6. The kit of embodiment 5, wherein the formulation is heated about 2°C above the phase change point of the fatty acid or faty alcohol,7. The kit of embodiment 1, wherein the polymer is selected from the group consisting of gelatin, cellulose, hyaluronic acid, soy protein, whey protein, xanthan gum, pectin, carrageenan, chitosan, agarose, dextran, fibrin, poly (vinyl alcohol) (PVA), poly (ethylene glycol) (PEG), poly (ethylene oxide) (PEO), poly (2-hydroxy ethyl methacrylate) (PHEMA), poly (acrylic acid) (PAA), and poly (acrylamide) (PAAm) and a combination thereof.8. The kit of embodiment 7, wherein the gelatin is a denatured form of collagen.9. The kit of embodiment 7, wherein the cellulose comprises ester and, or ether derivates.10. The kit of embodiment 1, wherein the surfactant is selected from the group consisting of an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.11. The kit of embodiment 10, wherein the anionic surfactant is selected from the group consisting of: ammonium lauryl sulfate (ALS), sodium lauryl sulfate (SLS), sodium dodecyl sulfate, (SDS), and sodium lauryl ether sulfate (SLES), and sodium myreth sulfate, sodium lauryl sulfoacetate (SLSA), Sodium Dodecylbenzene Sulfonate (SDBS), Alpha- Olefin Sulfonates (AOS), Sodium Xylenesulfonate, Sodium Lauryl Phosphate and Sodium Alkyl Phosphate, Sodium Stearate, Sodium Oleate, and a combination thereof.12. The kit of embodiment 10, wherein the cationic surfactant is selected from the group consisting of: cetrimonium bromide (CTAB), cetylpyridinium chloride (CPC), benzalkonium chloride (BAC), benzethonium chloride (BZT), dimethyldioctadecylammonium chloride (DODMAC), and dioctadecyldimethylammonium bromide (DODAB), Cetrimonium Chloride, and a combination thereof.69328017736Attorney Docket No.: BREK-002 / 01WO 349002-200513. The kit of embodiment 10, wherein the nonionic surfactant is selected from the group consisting of: sorbitan monolaurate (SPAN 20), sorbitan monooleate (SPAN 80), polysorbate 20 (TWEEN 20), polysorbate 80 (TWEEN 80), Octylphenol Ethoxylate (Triton X-l 5), Octyl phenol ethoxylate (Triton X-l 00), Coco Monoethanolamide (CMEA), cocamide Diethanolamine (CDEA) and a combination thereof.14. The kit of embodiment 10, wherein the amphoteric surfactant is selected from the group consisting of: cocamidopropyl betaine (CAPB), Lauryl Betaine, Coco-Betaine, Lauryl dimethylamine oxide, cocamidopropyl hydroxysultaine (CAHS), and Sodium Cocoamphoacetate, and a combination thereof.15. The kit of embodiment 1, wherein the fatty acid is selected from the group consisting of:myristic acid, lauric acid, palmitic acid, stearic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, butyric acid, and a combination thereof.16. The kit of embodiment 1, wherein the fatty alcohol is selected from the group consisting of: myristyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol, palmitoleyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, arachidonyl alcohol, butanol, and a combination thereof.Methods of producing a hydrogel1. A method of producing a hydrogel, comprising the steps of:a. mixing water with a dry form of a composition comprising (i) a polymer, (li) a surfactant, and optionally a fatty acid or a fatty alcohol to make a solution; b. adjusting pH of the solution with a buffer to near isoelectronic point of the polymer;andc. producing the hydrogel.2. The method of embodiment 1, wherein, optionally, the solution of step a) is heated about 2°C above the gel point of the polymer.3. The method of embodiment 2, wherein, optionally, the heated solution is cooled to about 2°C below its gel point if it is heated about 2°C above its gel point.4. The method of embodiment 1, wherein the polymer is selected from the group consisting of gelatin, cellulose, hyaluronic acid, soy protein, whey protein, xanthan gum, pectin, carrageenan, chitosan, agarose, dextran, fibrin, poly (vinyl alcohol) (PV A), poly (ethylene70328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005glycol) (PEG), poly (ethylene oxide) (PEO), poly (2-hydroxyethyl methacrylate) (PHEMA), poly (acrylic acid) (PAA), and poly (acrylamide) (PAAm) and a combination thereof.5. The method of embodiment 1, wherein the polymer is a plurality of polymers.6. The method of embodiment 1, wherein the surfactant is a plurality of surfactants.7. The method of embodiment 4, wherein the gelatin is a denatured form of collagen.8. The method of embodiment 4, wherein the cellulose comprises ester and, or ether derivates.9. The method of embodiment 1, wherein the surfactant is selected from the group consisting of an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.10. The method of embodiment 9, wherein the anionic surfactant is selected from the group consisting of: ammonium lauryl sulfate (ALS), sodium lauryl sulfate (SLS), sodium dodecyl sulfate, (SDS), and sodium lauryl ether sulfate (SLES), and sodium myreth sulfate, sodium lauryl sulfoacetate (SLSA), Sodium Dodecylbenzene Sulfonate (SDBS), Alpha- Olefin Sulfonates (AOS), Sodium Xylenesulfonate, Sodium Lauryl Phosphate and Sodium Alkyl Phosphate, Sodium Stearate, Sodium Oleate, and a combination thereof.11. The method of embodiment 9, wherein the cationic surfactant is selected from the group consisting of: cetrimonium bromide (CTAB), cetylpyridinium chloride (CPC), benzalkonium chloride (BAC), benzethonium chloride (BZT), dimethyldioctadecylammonium chloride (DODMAC), and dioctadecyldimethylammonium bromide (DODAB), Cetrimonium Chloride, and a combination thereof.12. The method of embodiment 9, wherein the nonionic surfactant is selected from the group consisting of: sorbitan monolaurate (SPAN 20), sorbitan monooleate (SPAN 80), polysorbate 20 (TWEEN 20), polysorbate 80 (TWEEN 80), Octylphenol Ethoxylate (Triton X-l 5), Octyl phenol ethoxylate (Triton X-l 00), Coco Monoethanolamide (CMEA), cocamide Diethanolamine (CDEA) and a combination thereof.13. The method of embodiment 9, wherein wherein the amphoteric surfactant is selected from the group consisting of: cocamidopropyl betaine (CAPB), Lauryl Betaine, Coco-Betaine, Lauryl dimethylamine oxide, cocamidopropyl hydroxysultaine (CAHS), and Sodium Cocoamphoacetate, and a combination thereof.71328017736Attorney Docket No.: BREK-002 / 01WO 349002-200514. The method of embodiment 1, wherein the fatty acid is selected from the group consisting of: myristic acid, lauric acid, palmitic acid, stearic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, butyric acid, and a combination thereof.15. The method of embodiment 1, wherein the fatty alcohol is selected from the group consisting of: myristyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol, palmitoleyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, arachidonyl alcohol, butanol, and a combination thereof.16. The method of embodiment 1, wherein the solution comprises about 0.05% to about 20% w / w of the polymer.17. The method of embodiment 1, wherein the solution comprises about 0.5% to about 10% w / w of the polymer.18. The method of embodiment 1, wherein the solution comprises about 0,01% to about 10% w / w of the surfactant.19. The method of embodiment 1, wherein the solution comprises about 0.01% to about 5% w / w of the surfactant.20. The method of embodiment 1, wherein the ratio between the polymer and the surfactant in the solution is about 0.5:1 to about 20: 1 in w / w.21. The method of embodiment 1, wherein the ratio between the polymer and the surfactant in the solution is about 1:1 to about 10:1 in w / w.22. The method of embodiment 1, wherein the solution comprises about 0.01% to about 1% w / w of the fatty acid or the fatty alcohol.23. The method of embodiment 1, wherein the solution comprises about 0.05% to about 1% w / w of the fatty acid or the fatty alcohol.24. The method of embodiment 1, wherein, after step b), the adjusted pH of the solution is near isoelectric point of the polymer.25. The method of embodiment 1, wherein the buffer is selected from the group consisting of:citric acid, sodium citrate, acetic acid, sodium acetate, ammonia, ammonium chloride, sodium carbonate, sodium bicarbonate, phosphate, histidine, and a combination thereofMethods of producing a hydrogel foam1. A method of producing a hydrogel foam, comprising the steps of:72328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005a. mixing water with a dry form of a composition comprising (i) a polymer, (ii) a surfactant, and optionally a fatty acid or a fatty alcohol to make a solution; b. adjusting pH of the solution with a buffer to near isoelectronic point of the polymer;c. mixing the solution of step b) with air in a ratio of the solution about 1:2 to about 1:50; andd. producing the hydrogel foam.2. The method of embodiment 1, wherein, optionally, the solution of step a) is heated about 2°C above the gel point of the polymer.3. The method of embodiment 2, wherein, optionally, the heated solution is cooled to about 2°C below its gel point if it is heated about 2°C above its gel point.4. The method of embodiment 1, wherein the polymer is selected from the group consisting of gelatin, cellulose, hyaluronic acid, soy protein, whey protein, xanthan gum, pectin, carrageenan, chitosan, agarose, dextran, fibrin, poly (vinyl alcohol) (PVA), poly (ethylene glycol) (PEG), poly (ethylene oxide) (PEO), poly (2-hy dr oxy ethyl methacrylate) (PHEMA), poly (acrylic acid) (PAA), and poly (acrylamide) (PAAm) and a combination thereof.5. The method of embodiment 1, wherein the polymer is a plurality of polymers.6. The method of embodiment 1, wherein the surfactant is a plurality of surfactants.7. The method of embodiment 4, wherein the gelatin is a denatured form of collagen.8. The method of embodiment 4, wherein the cellulose comprises ester and, or ether derivates.9. The method of embodiment 1, wherein the surfactant is selected from the group consisting of an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.10. The method of embodiment 9, wherein the anionic surfactant is selected from the group consisting of: ammonium lauryl sulfate (ALS), sodium lauryl sulfate (SLS), sodium dodecyl sulfate, (SDS), and sodium lauryl ether sulfate (SLES), and sodium myreth sulfate, sodium lauryl sulfoacetate (SLSA), Sodium Dodecylbenzene Sulfonate (SDBS), Alpha- Olefin Sulfonates (AOS), Sodium Xylenesulfonate, Sodium Lauryl Phosphate and Sodium Alkyl Phosphate, Sodium Stearate, Sodium Oleate, and a combination thereof.73328017736Attorney Docket No.: BREK-002 / 01WO 349002-200511. The method of embodiment 9, wherein the cationic surfactant is selected from the group consisting of: cetrimonium bromide (CTAB), cetylpyridinium chloride (CPC), benzalkonium chloride (BAC), benzethonium chloride (BZT), dimethyldioctadecylammonium chloride (DODMAC), and dioctadecyldimethylammonium bromide (DODAB), Cetrimonium Chloride, and a combination thereof.12. The method of embodiment 9, wherein the nonionic surfactant is selected from the group consisting of: sorbitan monolaurate (SPAN 20), sorbitan monooleate (SPAN 80), polysorbate 20 (TWEEN 20), polysorbate 80 (TWEEN 80), Octylphenol Ethoxylate (Triton X-l 5), Octyl phenol ethoxylate (Triton X-l 00), Coco Monoethanolamide (CMEA), cocamide Diethanolamine (CDEA) and a combination thereof.13. The method of embodiment 9, wherein the amphoteric surfactant is selected from the group consisting of: cocamidopropyl betaine (CAPB), Lauryl Betaine, Coco-Betaine, Lauryl dimethylamine oxide, cocamidopropyl hydroxysultaine (CAHS), and Sodium Cocoamphoacetate, and a combination thereof.14. The method of embodiment 1, wherein the fatty acid is selected from the group consisting of: myristic acid, lauric acid, palmitic acid, stearic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, butyric acid, and a combination thereof.15. The method of embodiment 1, wherein the fatty alcohol is selected from the group consisting of: myristyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol, palmitoleyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, arachidonyl alcohol, butanol, and a combination thereof.16. The method of embodiment 1, wherein the solution comprises about 0.05% to about 20% w / w of the polymer.17. The method of embodiment 1, wherein the solution comprises about 0.5% to about 10% w / w of the polymer.18. The method of embodiment 1, wherein the solution comprises about 0.01% to about 10% w / w of the surfactant.19. The method of embodiment 1, wherein the solution comprises about 0.01% to about 5% w / w of the surfactant.74328017736Attorney Docket No.: BREK-002 / 01WO 349002-200520. The method of embodiment 1, wherein the ratio between the polymer and the surfactant in the solution is about 0.5:1 to about 20: 1 in w / w.21. The method of embodiment 1, wherein the ratio between the polymer and the surfactant in the solution is about 1:1 to about 10:1 in w / w.22. The method of embodiment 1, wherein the solution comprises about 0.01% to about 1% w / w of the fatty acid or the fatty alcohol.23. The method of embodiment 1, wherein the solution comprises about 0.05% to about 1% w / w of the fatty acid or the fatty alcohol,24. The method of embodiment 1, wherein, after step b), the adjusted pH of the solution is near isoelectric point of the polymer.25. The method of embodiment 1, wherein the buffer is selected from the group consisting of:citric acid, sodium citrate, acetic acid, sodium acetate, ammonia, ammonium chloride, sodium carbonate, sodium bicarbonate, phosphate, histidine, and a combination thereof.26. The method of embodiment 1, wherein the air content of the hydrogel foam is about 0.1% to about 99%.Methods of protecting a target using a hydrogel and / or a hydrogel foam of the invention 1. A method of protecting a target from a stressor, comprising: applying the hydrogel or the hydrogel foam comprising the composition of embodiment 1 to a target.2. The method of embodiment 1, wherein the target is a plant or an area in which the plant or crop is growing.3. The method of embodiment 1, wherein the stressor is an abiotic stressor.4. The method of embodiment 3, wherein the abiotic stressor is smoke, sun exposure, or frost.5. The method of embodiment 1, wherein the stressor is a biotic stressor.6. The method of embodiment 5, wherein the biotic stressor is a fungus, a bacterium, a pathogen, an insect, or a pest.Methods of delivering an agricultural compound to a target1. A method of delivering an agricultural compound to a target, comprising:a. mixing the agricultural compound with the hydrogel or the hydrogel foam comprising the composition of embodiment 1; and75328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005b. applying the hydrogel or the hydrogel foam to a target.2. The method of embodiment 1, wherein the agricultural compound is a fertilizer, a pesticide, a growth regulator, a soil amendment, a biostimulant, an attractant, or a fumigant.3. The method of embodiment 1, wherein a plant or an area in which the plant or crop is growing.Dry composition I1. A dry composition, comprising:a. a first component comprising a dry form of a polymer, a surfactant, and a buffer;andb. a second component comprising a paste form of (i) a fatty acid or a fatty alcohol and (u) a surfactant.2. The dry composition of embodiment 1, wherein the polymer is gelatin.3. The dry composition of embodiment 1, wherein the surfactant is an anionic surfactant. 4. The dry composition of embodiment 1 or 3, wherein the surfactant is sodium lauryl sulfoacetate (SLSA).5. The dry composition of embodiment I, wherein the buffer is citric acid or sodium citrate.6. The dry composition of embodiment 1, wherein the fatty acid is myristic acid.7. The dry composition of any one of embodiments 1-6, wherein the first and second components are combined and then dissolved in water to form a hydrogel or a hydrogel foam.8. The dry composition of embodiment 7, wherein the water-dissolved composition comprises about 0.05% to about 20% w / w of the polymer.9. The dry composition of embodiment 7, wherein the water-dissolved composition comprises about 0.01% to about 10% w / w of the surfactant.10. The dry composition of embodiment 7, wherein the water-dissolved composition comprises about 0.01% to about 1% w / w of the fatty acid.Dry composition II1. A dry composition, comprising:a dry form of a polymer, a surfactant, a buffer, and a fatty acid or a fatty alcohol.76328017736Attorney Docket No.: BREK-002 / 01WO 349002-20052. The dry composition of embodiment 1, wherein the polymer is gelatin.3. The dry composition of embodiment 1, wherein the surfactant is an anionic surfactant. 4. The dry composition of embodiment 1 or 3, wherein the surfactant is sodium lauryl sulfoacetate (SLSA).5. The dry composition of embodiment 1, wherein the buffer is citric acid or sodium citrate.6. The dry composition of embodiment 1, wherein the fatty acid is myristic acid.7. The dry composition of any one of embodiments 1-6, wherein the dry composition is dissolved in water to form a hydrogel or a hydrogel foam.8. The dry composition of embodiment 7, wherein the water-dissolved composition comprises about 0.05% to about 20% w / w of the polymer.9. The dry composition of embodiment 7, wherein the water-dissolved composition comprises about 0.01% to about 10% w / w of the surfactant,10. The dry composition of embodiment 7, wherein the water-dissolved composition comprises about 0.01% to about 1% w / w of the fatty acid.Liquid composition1. A liquid composition, comprising:a solution comprising a dry form of a polymer, a surfactant, a buffer, and a fatty acid or a fatty alcohol is dissolved in water.2. The liquid composition of embodiment 1, wherein the polymer is gelatin.3. The liquid composition of embodiment 1, wherein the surfactant is an anionic surfactant.4. The liquid composition of embodiment 1 or 3, wherein the surfactant is sodium lauryl sulfoacetate (SLSA).5. The liquid composition of embodiment 1, wherein the buffer is citric acid or sodium citrate.6. The liquid composition of embodiment 1, wherein the fatty acid is myristic acid.7. The liquid composition of embodiment 6, wherein the liquid composition comprises about 0.05% to about 20% w / w of the polymer.8. The liquid composition of embodiment 6, wherein the liquid composition comprises about 0.01% to about 10% w / w of the surfactant.9. The liquid composition of embodiment 6, wherein the liquid composition comprises about 0.01% to about 1% w / w of the fatty acid.77328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005Methods of manufacturing a hydrogel1. A method of manufacturing a hydrogel, comprising the steps of:a. mixing water with a dry composition of embodiment taught herein; and b. producing the hydrogel.Methods of manufacturing a hydrogel foam1. A method of manufacturing a hydrogel foam, comprising the steps of:a. mixing water with a dry composition of embodiment taught herein;b. mixing a solution of step a) with air in a ratio of the solution about 1:2 to about 1:50; andc. producing the hydrogel foam.Commercial products1. A composition, comprising: a dry form of gelatin, a dry form of sodium lauryl sulfoacetate, and a dry form or a paste form of myristic acid,wherein the composition is dissolved in water,wherein the water-dissolved composition comprises about 0.05% to about 20% w / w of gelatin;wherein the water-dissolved composition comprises about 0.01% to about 10% w / w of sodium lauryl sulfoacetate (SLSA); andwherein the water-dissolved composition comprises about 0.01% to about 1% w / w of myristic acid (MA).2. A composition, comprising: about 2.5% w / w of gelatin, about 0.9% of sodium lauryl sulfoacetate (SLSA), and about 0.1% of myristic acid (MA), dissolved in water.78328017736
Claims
Attorney Docket No.: BREK-002 / 01WO 349002-2005CLAIMSWhat is claimed is:
1. A composition, comprising:a. a polymer having at least one residue that is charged; andb. a surfactant selected from the group consisting of an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant,wherein a mixture of the charged polymer and the surfactant are capable of forming a charged polymer-surfactant complex under conditions of varying pH or in the presence of electrolytes.
2. The composition of claim 1, wherein the composition comprises a plurality of polymers and a plurality of surfactants.
3. The composition of claim 1 or 2, wherein the charged polymer-surfactant complex is processed into a hydrogel or a hydrogel foam.
4. The composition of claim 1 or 2, wherein the polymer is selected from the group consisting of: gelatin, cellulose, hyaluronic acid, soy protein, whey protein, xanthan gum, pectin, carrageenan, chitosan, agarose, dextran, fibrin, poly (vinyl alcohol) (PVA), poly (ethylene glycol) (PEG), poly (ethylene oxide) (PEO), poly (2-hy dr oxy ethyl methacrylate) (PHEMA), poly (acrylic acid) (PAA), and poly (acrylamide) (PAAm) and a combination thereof.
5. The composition of claim 4, wherein the gelatin is a denatured form of collagen.
6. The composition of claim 4, wherein the cellulose comprises ester or ether derivates.
7. The composition of claim 1 or 2, wherein the anionic surfactant is selected from the group consisting of: ammonium lauryl sulfate (ALS), sodium lauryl sulfate (SLS), sodium dodecyl sulfate, (SDS), sodium lauryl ether sulfate (SLES), sodium myreth sulfate, sodium lauryl sulfoacetate (SLSA), Sodium Dodecylbenzene Sulfonate (SDBS), Alpha-Olefin Sulfonates (AOS), Sodium Xylenesulfonate, Sodium Lauryl Phosphate, Sodium Alkyl Phosphate, Sodium Stearate, Sodium Oleate, and a combination thereof.
8. The composition of claim 1 or 2, wherein the cationic surfactant is selected from the group consisting of: cetrimonium bromide (CTAB), cetylpyridinium chloride (CPC), benzalkonium chloride (BAC), benzethonium chloride (BZT), dimethyldioctadecylammonium chloride (DODMAC), and79328017736Attorney Docket No.: BREK-002 / 01WO 349002-2005dioctadecyldimethylammonium bromide (DODAB), Cetrimonium Chloride, and a combination thereof.
9. The composition of claim 1 or 2, wherein the nonionic surfactant is selected from the group consisting of: sorbitan monolaurate (SPAN 20), sorbitan monooleate (SPAN 80), polysorbate 20 (TWEEN 20), polysorbate 80 (TWEEN 80), Octylphenol Ethoxylate (Triton X-l 5), Octyl phenol ethoxylate (Triton X-l 00), Coco Monoethanolamide (CMEA), cocamide Diethanolamine (CDEA) and a combination thereof.
10. The composition of claim 1 or 2, wherein the amphoteric surfactant is selected from the group consisting of: cocamidopropyl betaine (CAPB), Lauryl Betaine, Coco-Betaine, Lauryl dimethylamine oxide, cocamidopropyl hydroxysultaine (CAHS), Sodium Cocoamphoacetate, and a combination thereof.
11. The composition of any one of claims 1-10, wherein the varying pH condition is between pH 2 and pH 11.
12. The composition of claim 1, further comprising:d. a faty alcohol or a faty acid.
13. The composition of claim 12, wherein the fatty alcohol is selected from the group consisting of: myristyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol, palmitoleyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, arachidonyl alcohol, butanol, and a combination thereof.
14. The composition of claim 12, wherein the fatty acid is selected from the group consisting of: myristic acid, lauric acid, palmitic acid, stearic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, butyric acid, and a combination thereof.
15. The composition of claim 1, wherein the composition is a dry form, a liquid form, or an emulsion form.
16. The composition of claim 1, wherein the composition comprises a dry form of the composition, which is dissolved in water to make a solution comprising the polymer, the surfactant, and optionally the fatty acid or the fatty alcohol.
17. The composition of claim 1, w’herein the composition comprises a liquid form of the composition, which is a solution comprising the polymer, the surfactant, and optionally the fatty acid or the fatty alcohol.80328017736Attorney Docket No.: BREK-002 / 01WO 349002-200518. The composition of claim 16, wherein the composition comprises (i) a dry form of the composition is dissolved in water to make a solution comprising the polymer and the surfactant, and (ii) a paste form of the fatty acid or the fatty alcohol.
19. The composition of claim 16, wherein the solution comprises about 0.05% to about 20% w / w of the polymer.
20. The composition of claim 16, wherein the solution comprises about 0.01% to about 10% w / w of the surfactant.
21. The composition of claim 16, wherein the solution comprises about 0.01% to about 5% w / w of the surfactant.
22. The composition of claim 16, wherein the ratio between the polymer and the surfactant in the solution is about 0.5:1 to about 20: 1 in w / w.
23. The composition of claim 16, wherein the ratio between the polymer and the surfactant in the solution is about 1:1 to about 10:1 in w / w.
24. The composition of claim 16, wherein the solution comprises about 0.01% to about 1% w / w of the fatty acid or the fatty alcohol.
25. The composition of claim 24, wherein the solution comprises about 0.05% to about 1% w / w of the fatty acid or the fatty alcohol.
26. The composition of claim 16, wherein the solution is heated above the gel point of the polymer.
27. The composition of claim 26, wherein the heated solution is cooled to below its gel point if it is heated above its gel point.
28. The composition of claim 16, wherein pH of the solution is adjusted with a buffer to near isoelectric point of the polymer.
29. The composition of claim 28, wherein the buffer is selected from the group consisting of:citric acid, sodium citrate, acetic acid, sodium acetate, ammonia, ammonium chloride, sodium carbonate, sodium bicarbonate, phosphate, histidine, and a combination thereof.
30. The composition of claim 28, wherein the pH-adjusted solution is formed into a hydrogel.
31. The composition of claim 30, wherein the hydrogel is biodegradable.
32. The composition of claim 30, wherein the hydrogel is aerosolized in fine mist or sprayed as a fine foam droplet.81328017736Attorney Docket No.: BREK-002 / 01WO 349002-200533. The composition of claim 30, wherein the hydrogel is applied as a continuous sprayed stream or a sprayed clump.
34. The composition of claim 30, wherein the hydrogel is applied to a target.
35. The composition of claim 28, wherein the pH-adjusted solution is mixed with air in a ratio of about 1:2 to about 1: 50 to be formed into foam.
36. The composition of claim 35, wherein the air content of the foam is about 0.1% to about 99%.
37. The composition of claim 35, wherein the foam is biodegradable.
38. The composition of claim 35, wherein the foam is applied to a target.
39. A composition, comprising: a dry form of gelatin, a dry form of sodium lauryl sulfoacetate, and a dry form or a paste form of myristic acid,wherein the composition is dissolved in water,wherein the water-dissolved composition comprises about 0.05% to about 20% w / w of gelatin;wherein the water-dissolved composition comprises about 0.01% to about 10% w / w of sodium lauryl sulfoacetate (SLS / X); andwherein the water-dissolved composition comprises about 0.01% to about 1% w / w of myristic acid (MA).
40. A composition, comprising: about 2.5% w / w of gelatin, about 0.9% of sodium lauryl sulfoacetate (SLSA), and about 0.1% of myristic acid (MA), dissolved in water.
41. A method of manufacturing a hydrogel, comprising the steps of:a. mixing water with the composition of claim 1 or 39; andb. producing the hydrogel.
42. A method of manufacturing a hydrogel foam, comprising the steps of:a. mixing water with the composition of claim 1 or 39;b. mixing a solution of step a) with air in a ratio of the solution about 1:2 to about 1:50; andc. producing the hydrogel foam.82328017736