Inhibitor inclusion compound nitrogen fertilizer composition

Abstract

Fertilizer compositions comprising a cured nitrogen fertilizer melt comprising one or more than one cyclodextrin-inhibitor inclusion complex comprising at least one cyclodextrin and / or a derivative thereof complexed with an inhibitor, and methods for producing and using the same are disclosed. The inhibitor comprises at least one nitrification inhibitor and / or at least one urease inhibitor. One or more cyclodextrin-inhibitor inclusion complexes are uniformly dispersed throughout the solidified nitrogen fertilizer melt.

Description

Inhibitor inclusion complex nitrogen fertilizer composition

[0001] Cross-references to related applications

[0002] This application claims priority and benefit to European Patent Application No. EP23190387, filed on 8 August 2023. The contents of the referenced application are incorporated herein by reference. Background Technology

[0003]

[0004] A. Technical Field

[0005] This invention relates to the field of controlled-release fertilizer compositions. More generally, this invention relates to nitrogen fertilizer compositions comprising an inhibitor-inclusion complex dispersed in a solidified nitrogen fertilizer melt.

[0006] B. Background Technology

[0007] Fertilizers are chemical compositions added to plants and crops to provide nutrients that promote growth. Nitrogen, phosphorus, and potassium, or NPK, are found in many fertilizers, and these three major nutrients play a crucial role in plant nutrition and growth. Nitrogen is considered the most important nutrient; plants absorb more nitrogen than any other element. Nitrogen is essential for protein formation, which makes up a large part of most living tissues. The second major nutrient, phosphorus, is related to a plant's ability to utilize and store energy, including the process of photosynthesis. Potassium is the third major nutrient in commercial fertilizers. It helps enhance resistance to disease and plays an important role in increasing crop yield and overall quality. Potassium also protects plants, strengthens root systems, and prevents wilting in cold or dry weather.

[0008] Fertilizers offer different release profiles, with the release rates of nitrogen, phosphorus, and potassium nutrients varying. Most commercial fertilizers are quick-release (QRF) fertilizers, which release nutrients rapidly when applied to the soil. These QRF fertilizers can be impractical and / or unpredictable, especially during high-leaching events such as overwatering or flooding. Controlled-release (CRF) fertilizers contain plant nutrients in forms that plants cannot immediately absorb. Controlled-release fertilizers are typically coated or encapsulated with materials that control the rate, pattern, and duration of nutrient release from the plant. Many fertilizer production technologies have been developed, including attempts to slow down the release of fertilizer nutrients using polymeric components. Typically, encapsulating materials are non-biodegradable and accumulate in the soil and plants over time.

[0009] People have also tried coating or mixing fertilizers (e.g., urea fertilizers) with inhibitors, such as nitrification inhibitors and / or urease inhibitors. One of the problems with the coating and mixing process is that the nitrification inhibitors and / or urease inhibitors may be subjected to temperatures that can lead to degradation and reduce the effectiveness of these inhibitors. Summary of the Invention

[0010] Solutions to at least one or more of the aforementioned problems have been found. In one aspect, the solution may include forming a fertilizer composition having a nitrogen fertilizer and a cyclodextrin-inhibitor inclusion complex. When compounded with cyclodextrin, the inhibitor (e.g., a nitrification inhibitor and / or a urease inhibitor) may be thermally stable at temperatures exceeding the melting temperature of the nitrogen fertilizer (e.g., 140°C or higher). This may be advantageous because the complexes can contact and disperse throughout the molten nitrogen fertilizer, with reduced, minimized, or no degradation of the inhibitor. Once the molten nitrogen fertilizer is solidified (e.g., by cooling), the resulting fertilizer composition may comprise a solidified nitrogen fertilizer melt and one or more cyclodextrin-inhibitor inclusion complexes dispersed throughout the solidified melt. In one aspect, the fertilizer composition may comprise a continuous phase comprising the nitrogen fertilizer melt and a discontinuous phase comprising one or more (e.g., more than one) cyclodextrin-inhibitor complexes dispersed throughout the continuous phase. To avoid being bound by theory, it is believed that the complexation of the inhibitor with cyclodextrin provides thermal protection for the inhibitor, allowing it to contact molten nitrogen fertilizer with minimal or no degradation. Furthermore, the molten nitrogen fertilizer can act as a solvent-like agent on these complexes, enabling individual molecules of the cyclodextrin-inhibitor inclusion complex to be effectively dispersed throughout the molten nitrogen fertilizer. This allows the complex to be dispersed substantially uniformly or homogeneously throughout the molten nitrogen fertilizer; in some respects, this is similar to the dissolution of NaCl in water, where Na... + and Cl - The individual molecules of the cyclodextrin-inhibitor complex are uniformly or homogeneously dispersed throughout the continuous aqueous phase, but with one distinction—the cyclodextrin-inhibitor complex remains a complex, but dissolved in the molten nitrogen fertilizer as individual molecules of the complex. Once the molten nitrogen fertilizer solidifies, the individual molecules of the complex remain uniformly or homogeneously dispersed throughout the continuous network of the solidified nitrogen fertilizer melt. The solidified nitrogen fertilizer melt can include any of the fertilizers disclosed throughout this specification. An advantage of the fertilizer compositions of the present invention is that within the continuous network of the solidified nitrogen fertilizer melt, there is minimal or no separation or aggregation of the cyclodextrin-inhibitor inclusion complexes, which can effectively protect nitrogen during storage and / or use of the fertilizer composition. Furthermore, this effective dispersion of the complex molecules throughout the continuous solidified network allows for a reduction in the amount of inhibitor used to prepare the fertilizer composition.

[0011] This document discloses a fertilizer composition employing a renewable and biodegradable composite component and an inhibitor component encapsulated within the composite component to form an inhibitor encapsulation complex. The inhibitor encapsulation complex can be embedded in a nitrogen fertilizer. Upon exposure to moisture, at least a portion of the nitrogen fertilizer component can dissolve rapidly, providing an immediate release of fertilizer nutrients. In contrast, the inhibitor encapsulation complex has lower solubility and resists immediate dissolution, allowing the inhibitor component to slowly release its fertilizer nutrients over time. The resulting biphasic nutrient release profile provides both immediate and sustained nutrient release, making it ideal for crop fertilization. The composite component can spatially encapsulate one or more inhibitors within the encapsulation complex. The composite component can be a compound capable of forming an equilibrium with one or more inhibitors. The equilibrium can be a dynamic equilibrium, where the amount of inhibitor entering the encapsulation space of the composite component is similar to the amount of inhibitor leaving the encapsulation space of the composite component. The composite component can be a polymer, forming a polymer-inhibitor encapsulation complex. The polymer can be a polysaccharide and / or oligomer, such as cellulose, starch, cyclodextrin, and / or derivatives thereof. The complex component can be cyclodextrin and / or its derivatives, forming a cyclodextrin-inhibitor inclusion complex.

[0012] Cyclodextrins (CyD) can form inclusion complexes with various hydrophobic molecules or molecules with hydrophobic tails. The advantage of CyD complexing with these molecules is that the guest molecule is not fixed within the CyD but exists in dynamic equilibrium; therefore, the guest molecule can be slowly released in an aqueous environment via a trigger mechanism. Furthermore, the formed CyD / host complex can offer several advantages, such as protecting the guest molecule from more than one external environmental factor, such as light, heat, and biochemical degradation, as well as improving thermal stability, enhancing solubility, and reducing odor. However, the practical application of CyD as a host in agriculture is rarely reported. Here, we present formulations using CyD for urease inhibitors (NBTPT, NPPT, and NBPT) and nitrification inhibitors (DCD and DMPP), which are cheaper and more direct. The nitrification inhibitors prevent bacteria in the soil from converting ammonium nitrogen in manure into nitrates and reduce the risk of nitrate leaching and denitrification by using CyD. The optimized CyD-encapsulated inhibitors are easily mixable with urea melt and exhibit thermal stability.

[0013] In one aspect, the fertilizer composition comprises a nitrogen fertilizer and a cyclodextrin-inhibitor inclusion complex comprising at least one cyclodextrin and / or its derivatives in combination with an inhibitor, wherein the inhibitor comprises at least one nitrification inhibitor and / or at least one urease inhibitor, and wherein the at least one cyclodextrin-inhibitor inclusion complex is embedded in the nitrogen fertilizer. In another aspect, the fertilizer composition comprises a cyclodextrin-inhibitor inclusion complex embedded in a solidified nitrogen fertilizer melt. In some aspects, the cyclodextrin and / or its derivatives may comprise α-cyclodextrin, β-cyclodextrin, and / or γ-cyclodextrin. In some aspects, the cyclodextrin and / or its derivatives comprise γ-cyclodextrin.

[0014] In some respects, the inhibitor inclusion complex may contain a nitration inhibitor. The nitration inhibitor may be one or more of the following substances: 3,4-dimethylpyrazole phosphate (DMPP), thiourea (TU), dicyandiamide (DCD), 2-chloro-6-(trichloromethyl)pyridine (nitrapyrin), 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole (TERRAZOLE). TM ), 2-amino-4-chloro-6-methylpyrimidine (AM), 2-mercaptobenzothiazole (MBT), ammonium thiosulfate (ATS), 2-p-aminobenzenesulfonamide thiazole (ST), or combinations thereof.

[0015] In some aspects, the inhibitor inclusion complex may contain a urease inhibitor. The urease inhibitor may be one or more of the following substances: N-(n-butyl)-thiophosphate triamine (NBTPT), N-(n-butyl)-phosphate triamine, N-(n-propyl)-thiophosphate triamine, benzoylthiourea (BTU), hydroquinone, acetyloxyoxime acid (AHA), hydroxyurea (HU), and / or phenylphosphine diamide (PPDA). In some aspects, the urease inhibitor is N-(n-butyl)-thiophosphate triamine (NBTPT).

[0016] In some embodiments, the cyclodextrin-inhibitor inclusion complex comprises γ-cyclodextrin or a derivative thereof and NBTPT. In some embodiments, the cured nitrogen fertilizer melt comprises urea and the cyclodextrin-inhibitor inclusion complex, wherein the cyclodextrin-inhibitor inclusion complex comprises γ-cyclodextrin or a derivative thereof and NBTPT. In some embodiments, the molar ratio of γ-cyclodextrin or a derivative thereof to NBTPT in the cyclodextrin-inhibitor inclusion complex is 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, or 1:10, or any range or value between these values. In some embodiments, the molar ratio of γ-cyclodextrin or a derivative thereof to NBTPT in the cyclodextrin-inhibitor inclusion complex is 2:1, 1.5:1, 1:1, 1:1.5, or 1:2, or any range or value between these values. In some embodiments, the molar ratio of γ-cyclodextrin or its derivative to NBTPT in the cyclodextrin-inhibitor inclusion complex is 10:1 to 1:10; 5:1 to 1:5; 4:1 to 1:4; 2:1 to 1:2. In some embodiments, the molar ratio of γ-cyclodextrin or its derivative to NBTPT in the cyclodextrin-inhibitor inclusion complex is 2:1 to 1:2.

[0017] In some respects, inhibitor inclusion complexes can simultaneously contain nitration inhibitors and urease inhibitors, such as N-(n-butyl)-triamine phosphate and dicyandiamide. Some commercial sources of inhibitors and combination inhibitors include, but are not limited to, N-SERVE (BASF), NITROGARD (YARA), NITRIFICIN (NOVOZYMES), NITROGRAD PLUS (YARA), NITROGENFIXER PLUS (AGRI LIFE RESEARCH), UREA STABILIZER (PLANT FOOD TECHNOLOGY), UREAPLUS (BIOMIN), and NITROGNEX (AM CASTLE).

[0018] In some respects, the inhibitor inclusion complex is thermally stable at or above 130°C, such as 140°C, or in any range of the following temperatures: 130°C, 131°C, 132°C, 133°C, 134°C, 135°C, 136°C, 137°C, 138°C, 139°C, 140°C, 141°C, 142°C, 143°C, 144°C, 145°C, 146°C, 147°C, 148°C, 149°C, 150°C, 151°C, 152°C, 153°C, 154°C, 155°C. 156℃, 157℃, 158℃, 159℃, 160℃, 161℃, 162℃, 163℃, 164℃, 165℃, 166℃, 167℃, 168℃, 169℃, 170℃, 171℃, 172℃, 173℃, 174℃, 175℃, 176℃, 177℃, 178℃, 179℃, 180℃, 181℃, 182℃, 183℃, 184℃, 185℃, 186℃, 187℃, 188℃, 189℃, 190℃, 191℃, 192℃, 193℃, 194℃, 195℃, 196℃, 197℃, 198℃, 199℃ and 200℃. In some respects, the inhibitor inclusion complex is stable in the pH range of 4 to 11, such as 5 to 10, or at any of the following pH values, less than, greater than, between any two of the following pH values, or in any range of the following pH values: 4, 5, 6, 7, 8, 9, 10, and 11.

[0019] One aspect of the present invention relates to a fertilizer composition. The fertilizer composition may comprise 80% to 99.9999% by weight of nitrogen fertilizer and / or 0.0001% to 15% by weight of an inhibitor inclusion complex. In some aspects, the composition may comprise at least any, at most any, equal to any one, or between any two of the following nitrogen fertilizers by weight: 80% by weight, 81% by weight, 82% by weight, 83% by weight, 84% by weight, 85% by weight, 86% by weight, 87% by weight, 88% by weight, 89% by weight, 90% by weight, 91% by weight, 92% by weight, 93% by weight, 94% by weight, 95% by weight, 96% by weight, 97% by weight, 98% by weight, 99% by weight, or 100% by weight. In some aspects, the composition may comprise at least one, at most one, equal to one, or between any two of the following by weight percentages of an inhibitor inclusion complex: 0.0001 wt%, 0.0005 wt%, 0.001 wt%, 0.002 wt%, 0.003 wt%, 0.004 wt%, 0.005 wt%, 0.006 wt%, 0.007 wt%, 0.008 wt%, 0.009 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, or 15 wt%. In some aspects, the fertilizer composition further comprises a wetting agent, a carrier, a filler, and / or a binder. In one respect, nitrogen fertilizer includes urea. In some respects, urea includes solidified urea melt. In some respects, the fertilizer composition is homogeneous.

[0020] In some aspects, the fertilizer composition comprises an inhibitor and a degradation product of said inhibitor in a ratio of 80:20 to 100:0. In some aspects, the ratio is, at least, at most, or between 80:20, 85:15, 90:10, 95:5, 99:1, or 100:0. In some aspects, the fertilizer composition comprises an inhibitor contained in an inhibitor inclusion complex and an inhibitor not contained in the inhibitor inclusion complex in a ratio of 80:20 to 100:0. In some aspects, the ratio is, at least, at most, or between 80:20, 85:15, 90:10, 95:5, 99:1, or 100:0.

[0021] Some aspects of this disclosure relate to a method for controlled release of an inhibitor into soil, plants, water, or combinations thereof, the method comprising applying a fertilizer composition to said soil, plants, water, or combinations thereof. In some aspects of the method, the inhibitor is released from the inhibitor inclusion complex for at least 21 days after the fertilizer composition is applied to the soil, plants, water, or combinations thereof. The inhibitor may be released from the inhibitor inclusion complex for at least, at most, or between 21, 22, 23, 24, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100 days.

[0022] Some aspects of this disclosure relate to a method for producing a fertilizer composition, the method comprising: (a) contacting an inhibitor with at least one composite component to generate an inhibitor inclusion complex; and (b) contacting the inhibitor inclusion complex with a nitrogen fertilizer to form an inhibitor inclusion complex embedded in the nitrogen fertilizer. In some cases, the nitrogen fertilizer is a molten nitrogen fertilizer, and the molten nitrogen fertilizer is solidified to form an inhibitor inclusion complex embedded in the nitrogen fertilizer. In some aspects of the method, steps a and b are performed as a one-pot synthesis and / or a multi-step synthesis. In some other aspects, the method further includes mechanical mixing and / or cooling.

[0023] In some respects, inhibitor inclusion complexes are prepared by contacting a solution, such as a methanolic solution of NBTPT, with another solution, such as an aqueous solution of γ-cyclodextrin or a derivative thereof. In other respects, inhibitor inclusion complexes are prepared by mechanically mixing NBTPT in solid form with γ-cyclodextrin or a derivative thereof in solid form.

[0024] One aspect of this disclosure relates to a fertilization method comprising contacting soil, plants, water, or a combination thereof with a fertilizer composition disclosed herein. In another aspect of the fertilization method, the fertilizer composition is added directly in solid form, and / or added to water prior to contact with soil, plants, or both.

[0025] The following aspects 1 to 44 of the invention are also disclosed. Aspect 1 relates to a fertilizer composition comprising: a nitrogen fertilizer; and a cyclodextrin-inhibitor inclusion complex comprising at least one cyclodextrin and / or its derivatives compounded with an inhibitor, wherein the inhibitor comprises at least one nitrification inhibitor and / or at least one urease inhibitor, and wherein at least one cyclodextrin-inhibitor inclusion complex is embedded in the nitrogen fertilizer.

[0026] Aspect 2 relates to a fertilizer composition according to aspect 1, wherein the cyclodextrin-inhibitor inclusion complex is embedded in a solidified nitrogen fertilizer melt.

[0027] Aspect 3 relates to a fertilizer composition according to any one of Aspects 1 and 2, wherein the cyclodextrin-inhibitor inclusion complex is thermally stable at a temperature of 140°C or above and / or stable in a pH range of 5 to 10.

[0028] Aspect 4 relates to a fertilizer composition according to any one of Aspects 1 to 3, wherein the cyclodextrin and / or its derivatives include α-cyclodextrin, β-cyclodextrin and / or γ-cyclodextrin.

[0029] Aspect 5 relates to a fertilizer composition according to any one of Aspects 1 to 4, wherein the nitrification inhibitor comprises 3,4-dimethylpyrazole phosphate (DMPP), thiourea (TU), dicyandiamide (DCD), 2-chloro-6-(trichloromethyl)pyridine (chlorpyrifos), and 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole (TERRAZOLE). TM ), 2-amino-4-chloro-6-methylpyrimidine (AM), 2-mercaptobenzothiazole (MBT), ammonium thiosulfate (ATS), 2-p-aminobenzenesulfonamide thiazole (ST), or combinations thereof.

[0030] Aspect 6 relates to a fertilizer composition according to any one of Aspects 1 to 5, wherein the urease inhibitor comprises N-(n-butyl)-thiophosphate triamine, N-(n-butyl)-phosphate triamine, N-(n-propyl)-thiophosphate triamine, benzoylthiourea (BTU), hydroquinone, acetyloxyoxime acid (AHA), hydroxyurea (HU), and / or phenylphosphamide (PPDA).

[0031] Aspect 7 relates to a fertilizer composition according to any one of Aspects 1 to 6, comprising 90% to 99% by weight of the nitrogen fertilizer; and / or about 0.001% to 10% by weight of the cyclodextrin-inhibitor inclusion complex.

[0032] Aspect 8 relates to a fertilizer composition according to any one of Aspects 1 to 7, which further comprises a wetting agent, a carrier, a filler and / or a binder.

[0033] Aspect 9 relates to a fertilizer composition according to any one of Aspects 1 to 8, wherein the fertilizer composition comprises an inhibitor and a degradation product of the inhibitor in a ratio of 80:20 to 100:0.

[0034] Aspect 10 relates to a fertilizer composition according to any one of Aspects 1 to 9, wherein the fertilizer composition comprises an inhibitor contained in the cyclodextrin-inhibitor inclusion complex and an inhibitor not contained in the cyclodextrin-inhibitor inclusion complex in a ratio of 80:20 to 100:0.

[0035] Aspect 11 relates to a fertilizer composition according to any one of aspects 1 to 10, wherein the nitrogen fertilizer comprises urea.

[0036] Aspect 12 relates to a fertilizer composition according to aspect 11, wherein the urea comprises a solidified urea melt.

[0037] Aspect 13 relates to a fertilizer composition according to any one of aspects 1 to 12, wherein the fertilizer composition is homogeneous.

[0038] Aspect 14 relates to a method of controlled release of an inhibitor into soil, plants, water or a combination thereof, the method comprising applying a fertilizer composition according to any one of aspects 1 to 13 into said soil, plants, water or a combination thereof.

[0039] Aspect 15 relates to the method according to aspect 14, wherein the inhibitor is released from the cyclodextrin-inhibitor inclusion complex for at least 21 days after the fertilizer composition is applied to soil, plants, water or a combination thereof.

[0040] Aspect 16 relates to a method for producing a fertilizer composition according to any one of Aspects 1 to 13, the method comprising: (a) contacting the inhibitor with at least one cyclodextrin and / or a derivative thereof to generate a cyclodextrin-inhibitor inclusion complex; and (b) contacting the cyclodextrin-inhibitor inclusion complex with molten nitrogen fertilizer and solidifying the molten nitrogen fertilizer to form a cyclodextrin-inhibitor inclusion complex embedded in the nitrogen fertilizer.

[0041] Aspect 17 relates to the method according to aspect 16, wherein steps a and b are performed as a one-pot synthesis and / or a multi-step synthesis.

[0042] Aspect 18 relates to a method according to any one of aspects 16 and 17, wherein step b further comprises mechanical mixing and / or cooling.

[0043] Aspect 19 relates to a method of fertilization, which includes contacting soil, plants, water or a combination thereof with a fertilizer composition according to any one of aspects 1 to 13.

[0044] Aspect 20 relates to a fertilization method according to aspect 19, wherein the fertilizer composition is added directly in solid form and / or added to water before contact with soil, plants, or soil and plants.

[0045] Aspect 21 relates to a fertilizer composition according to any one of aspects 1 to 13 or a method according to any one of aspects 14 to 20, wherein the cyclodextrin and / or its derivatives are replaced with polymers of non-cyclodextrin and / or their derivatives.

[0046] Aspect 22 relates to a fertilizer composition according to aspect 21, wherein the polymer is a polysaccharide and / or oligosaccharide.

[0047] Aspect 23 relates to the fertilizer composition according to aspect 22, wherein the polymer is cellulose, starch and / or a derivative thereof.

[0048] Aspect 24 relates to a fertilizer composition comprising: a solidified nitrogen fertilizer melt; the melt comprising: one or more cyclodextrin-inhibitor inclusion complexes comprising at least one cyclodextrin and / or its derivatives in combination with an inhibitor, wherein the inhibitor comprises at least one nitrification inhibitor and / or at least one urease inhibitor, and wherein the one or more cyclodextrin-inhibitor inclusion complexes are uniformly dispersed throughout the solidified nitrogen fertilizer melt.

[0049] Aspect 25 relates to a fertilizer composition according to aspect 24, comprising: a continuous phase including the nitrogen fertilizer melt; and a discontinuous phase including one or more cyclodextrin-inhibitor complexes dispersed throughout the continuous phase.

[0050] Aspect 26 relates to a fertilizer composition according to aspect 25, wherein one or more cyclodextrin-inhibitor complexes are uniformly dispersed throughout the continuous phase.

[0051] Aspect 27 relates to a fertilizer composition according to any one of aspects 24 to 26, wherein the melting temperature of the discontinuous phase comprising the nitrogen fertilizer melt is 140°C or below, preferably 130°C to 135°C.

[0052] Aspect 28 relates to a fertilizer composition according to any one of Aspects 24 to 26, wherein: the nitrogen fertilizer melt comprises at least 90% by weight, preferably at least 95% by weight, more preferably at least 98% by weight, and even more preferably at least 99% by weight of the fertilizer composition; and the one or more cyclodextrin-inhibitor inclusion complex comprises at most 10% by weight, preferably at most 5% by weight, more preferably at most 2% by weight, or even more preferably at most 1% by weight of the fertilizer composition.

[0053] Aspect 29 relates to a fertilizer composition according to any one of Aspects 24 to 26, wherein the cyclodextrin-inhibitor inclusion complex is thermally stable at a temperature of 140°C or above and / or stable in a pH range of 5 to 10.

[0054] Aspect 30 relates to a fertilizer composition according to any one of aspects 24 to 26, wherein the cyclodextrin and / or its derivatives include α-cyclodextrin, β-cyclodextrin and / or γ-cyclodextrin, preferably γ-cyclodextrin.

[0055] Aspect 31 relates to a fertilizer composition according to any one of Aspects 24 to 26, wherein the nitrification inhibitor comprises 3,4-dimethylpyrazole phosphate (DMPP), thiourea (TU), dicyandiamide (DCD), 2-chloro-6-(trichloromethyl)pyridine (chlorpyrifos), and 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole (TERRAZOLE). TM ), 2-amino-4-chloro-6-methylpyrimidine (AM), 2-mercaptobenzothiazole (MBT), ammonium thiosulfate (ATS), 2-p-aminobenzenesulfonamide thiazole (ST), or combinations thereof.

[0056] Aspect 32 relates to a fertilizer composition according to any one of aspects 24 to 26, wherein the urease inhibitor comprises N-(n-butyl)-thiophosphate triamine, N-(n-butyl)-phosphate triamine, N-(n-propyl)-thiophosphate triamine, benzoylthiourea (BTU), hydroquinone, acetyloxyoxime acid (AHA), hydroxyurea (HU) and / or phenylphosphine diamide (PPDA), preferably N-(n-butyl)-thiophosphate triamine.

[0057] Aspect 33 relates to a fertilizer composition according to any one of aspects 24 to 26, wherein: the solidified nitrogen fertilizer melt is a urea fertilizer melt; and the inhibitor is a urease inhibitor, preferably N-(n-butyl)-thiophosphate triamine.

[0058] Aspect 34 relates to a fertilizer composition according to any one of aspects 24 to 26, further comprising a wetting agent, a carrier, a filler and / or a binder.

[0059] Aspect 35 relates to a fertilizer composition according to any one of aspects 24 to 26, wherein the fertilizer composition comprises an inhibitor and a degradation product of the inhibitor in a ratio of 80:20 to 100:0.

[0060] Aspect 36 relates to a fertilizer composition according to any one of Aspects 24 to 26, wherein the fertilizer composition comprises an inhibitor contained in one or more cyclodextrin-inhibitor inclusion complexes and an inhibitor not complexed with cyclodextrin in a ratio of 80:20 to 100:0.

[0061] Aspect 37 relates to a fertilizer composition according to any one of aspects 24 to 26, wherein the nitrogen fertilizer melt comprises urea.

[0062] Aspect 38 relates to a fertilizer composition according to any one of aspects 24 to 26, wherein the fertilizer composition is homogeneous.

[0063] Aspect 39 relates to a method for controlled release of an inhibitor into soil, plants, water or a combination thereof, the method comprising applying a fertilizer composition according to any one of aspects 24 to 38 to the soil, plants, water or a combination thereof.

[0064] Aspect 40 relates to the method according to aspect 39, wherein the inhibitor is released from one or more cyclodextrin-inhibitor inclusion complexes for at least 21 days after the fertilizer composition is applied to soil, plants, water or a combination thereof.

[0065] Aspect 41 relates to a method for producing a fertilizer composition according to any one of aspects 24 to 38, the method comprising: (a) contacting the inhibitor with one or more cyclodextrins and / or their derivatives to generate one or more cyclodextrin-inhibitor inclusion complexes; and (b) contacting the one or more cyclodextrin-inhibitor inclusion complexes with molten nitrogen fertilizer; and (c) solidifying the molten nitrogen fertilizer to form the fertilizer composition.

[0066] Aspect 42 relates to the method according to aspect 41, wherein the molten nitrogen fertilizer dissolves one or more cyclodextrin-inhibitor inclusion complexes such that individual molecules of the complex are dispersed throughout the molten nitrogen fertilizer.

[0067] Aspect 43 relates to a method according to any one of aspects 41 to 42, wherein: steps (a) and (b) are carried out as a one-pot synthesis and / or a multi-step synthesis, and / or step (b) further comprises mixing the one or more cyclodextrin-inhibitor inclusion complex with the molten nitrogen fertilizer.

[0068] Aspect 44 relates to a fertilization method comprising contacting soil, plants, water or a combination thereof with a fertilizer composition according to any one of aspects 24 to 38, preferably wherein the fertilizer composition is added directly in solid form, and / or the fertilizer composition is added to water before contact with soil, plants or soil and plants.

[0069] The following includes definitions of various terms and phrases used throughout this specification.

[0070] The term "fertilizer" is defined as a material applied to soil or plant tissue to provide one or more plant nutrients necessary or beneficial to plant growth and / or to act as a stimulant or enhancer to increase or strengthen plant growth. Non-limiting examples of fertilizers include materials having one or more of the following substances: urea, ammonium nitrate, calcium ammonium nitrate, urea-calcium sulfate adduct, one or more superphosphates, binary NP fertilizers, binary NK fertilizers, binary PK fertilizers, NPK fertilizers, molybdenum, zinc, copper, boron, cobalt, and / or iron. In some aspects, fertilizers include agents that enhance plant growth and / or enhance the ability of plants to benefit from fertilizers, such as, but not limited to, biostimulants, urease inhibitors, and nitrification inhibitors.

[0071] The term "nutrient" is defined as a chemical element or substance that is useful for the normal growth and development of plants. Non-limiting examples of nutrients include N, P, K, Ca, Mg, S, B, Cu, Fe, Mn, Mo, Zn, Se, and Si, or compounds thereof.

[0072] The term "granule" can include solid materials. Granules can have a variety of shapes, including, but not limited to, spherical, puck, elliptical, rod-shaped, elongated, or irregular shapes. The term "prill" refers to a small solid sphere formed by the condensation of a liquid. The term "pellet" refers to a round, compacted block of fertilizer. The term "powder" refers to dried granules produced by grinding, crushing, or decomposing a fertilizer composition.

[0073] The terms “about” or “approximately” are defined as close to the range understood by one of ordinary skill in the art. In one non-limiting embodiment, these terms are defined as deviations within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.

[0074] The terms “weight%”, “volume%”, or “molar%” refer to the percentage by weight, volume, or mole of a component, respectively, based on the total weight of the component, the total volume of the material, or the total number of moles. In a non-limiting example, 10 grams of a component in 100 grams of material constitutes 10% by weight of that component.

[0075] The term “basically” and its variations are defined as including the range of 10%, 5%, 1%, or 0.5%.

[0076] The terms “suppress” or “reduce” or “prevent” or “avoid” or any variations thereof, when used in the claims and / or specification, include any measurable reduction or complete suppression made to achieve the desired result.

[0077] The term “effective” as used in the specification and / or claims means sufficient to achieve the desired, anticipated, or desired result.

[0078] When an element is used without a quantifier in conjunction with the terms "comprising," "including," "containing," or "having" in the claims or description, it may refer to "one," but it is also consistent with the meaning of "one or more," "at least one," and "one or more than one."

[0079] The words “contain,” “have,” “include,” or “contain” are inclusive or open-ended and do not exclude additional, unlisted elements or methods.

[0080] The inhibitor inclusion complex nitrogen fertilizer composition and its production method of the present invention may "comprising," "essentially constitute," or "consist of" the specific ingredients, components, compositions, steps, etc., disclosed in the full text of the specification. Regarding the transitional phrase "essentially constitute," in a non-limiting aspect, the essential and novel feature of the inhibitor inclusion complex nitrogen fertilizer composition of the present invention lies in the presence of urease and / or nitrification inhibitors complexed with the complex component (e.g., cyclodextrin). Attached Figure Description

[0081] The advantages of the present invention will become apparent to those skilled in the art from the following detailed description and with reference to the accompanying drawings.

[0082] Figures 1(A) through 1(E) SEM images and EDX mappings: (A) Urea surface coated with 0.1 wt% NBTPT; (B) Urea surface coated with 0.1 wt% NBTPT at higher magnification; (C) EDX analysis of spherical particles; (D) Urea surface melt-mixed with 0.1 wt% NBTPT / NBTPT / CyD; and (E) 0.1 wt% NBTPT / NBTPT / CyD surface at higher magnification.

[0083] Figures 2A and 2B show the thermogravimetric (TG) curves of the γ-CD:NBTPT complexes listed in Table 1. Figure 2A shows the TG data over the temperature range of 0°C to 500°C. Figure 2B shows the TG data over the temperature range of 100°C to 250°C. In Figures 2A and 2B, for each TG curve, the γ-CD:NBTPT molar ratio of the complex for which the TG data was obtained is shown.

[0084] Figures 3A and 3B show the TG curves of the γ-CD:NBTPT complexes listed in Table 1. In Figures 3A and 3B, the initial bumps caused by residual moisture in the γ-CD (see Figure 2A) have been removed. Figure 3A shows the TG data over the temperature range of 0°C to 500°C, and Figure 3B shows the TG data over the temperature range of 80°C to 250°C. In Figures 3A and 3B, for each TG curve, the γ-CD:NBTPT molar ratio of the complex for which the TG data was obtained is shown.

[0085] Figure 4A shows the TG curves of the γ-CD:NBTPT:urea complexes listed in Table 2. In Figure 4A, for each TG curve, the molar ratio of γ-CD:NBTPT:urea for which TG data was obtained is shown. Figure 4B shows the TG-DTA curves of γ-CD:NBTPT (molar ratio 1:1) and γ-CD:NBTPT:urea (molar ratio 1:1:1).

[0086] Figures 5A to 5D show the thermogravimetric-differential thermal analysis (TG-DTA) curves of samples B4 (Table 1), B13 (Table 3), and B14 (Table 3). Figure 5A shows the TG (left y-axis) and DTA (right y-axis) of the samples in the temperature range of 0℃ to 500℃; Figure 5B shows the TG of the samples in the temperature range of 20℃ to 295℃; Figure 5C shows the DTA of the samples in the temperature range of 20℃ to 70℃; and Figure 5D shows the DTA of the samples in the temperature range of 200℃ to 300℃.

[0087] Figures 6A to 6F show the γ-CD / NBTPT complex. 31 P NMR spectrum. Figure 6A shows NBTPT (unrecombined) NMR spectrum. 31 P NMR spectrum; Figure 6B shows the complex with a γ-CD / NBTPT molar ratio of 1:4. 31 P NMR spectrum; Figure 6C shows the complex with a γ-CD / NBTPT molar ratio of 1:3. 31 P NMR spectrum; Figure 6D shows the complex with a γ-CD / NBTPT molar ratio of 1:2. 31 P NMR spectrum; Figure 6E shows the complex with a γ-CD / NBTPT molar ratio of 1:1. 31 P NMR spectrum; and Figure 6F shows the complex with a γ-CD / NBTPT molar ratio of 2:1. 31 P NMR spectra. The insets of the figures in Figures 6A to 6F show the degradation of NBTPT over time, determined based on the P=S peak (approximately 61 ppm).

[0088] Figure 7 shows the γ-CD / NBTPT complex (1:1 molar ratio) after 17 days. 31 P NMR spectrum.

[0089] Figures 8A and 8B show the heat-treated γ-CD:NBTPT:urea and γ-CD:NBTPT complexes. 31 P NMR spectra. Figure 8A shows the γ-CD:NBTPT:urea (molar ratio 1:1:1) at room temperature (rt) and after heat treatment at 140 °C, 160 °C and 180 °C. 31 Figure 8B shows the γ-CD:NBTPT (molar ratio 1:1) NMR spectra at room temperature and after heat treatment at 140 °C, 160 °C, and 180 °C. 31 P NMR spectrum.

[0090] Figure 9 shows the Overhausen-enhanced spectrum of the γ-CD:NBTPT 1:1 (molar ratio) complex in a rotating coordinate system. The x-axis at the bottom of the figure is expanded.

[0091] Figures 10A and 10B illustrate solution-based NBTPT urease inhibition. Figure 10A shows the half-maximum inhibitory concentration (IC50) of NBTPT. 50 The calculations were performed. Figure 10B shows the urease inhibition results at different NBTPT / γ-CDs molar ratios (2:1 to 1:4) with a NBTPT concentration of 0.6 µmol.

[0092] Figures 11A to 11F show the urease inhibition rates of heat-treated encapsulated γ-CD / NBTPT (with or without urea). Figure 11A shows the urease inhibition rate of heat-treated encapsulated γ-CD / NBTPT (with urea) after heat treatment at 140 °C. Figure 11B shows the urease inhibition rate of heat-treated encapsulated γ-CD / NBTPT (with urea) after heat treatment at 160 °C. Figure 11C shows the urease inhibition rate of heat-treated encapsulated γ-CD / NBTPT (with urea) after heat treatment at 180 °C. Figure 11D shows the urease inhibition rate of heat-treated encapsulated γ-CD / NBTPT (without urea) after heat treatment at 140 °C. Figure 11E shows the urease inhibition rate of heat-treated encapsulated γ-CD / NBTPT (without urea) after heat treatment at 160 °C. Figure 11F shows the urease inhibition rate of heat-encapsulated γ-CD / NBTPT (without urea) after heat treatment at 180 °C.

[0093] Figures 12A to 12C show the urease activity measurements of soil samples. Figure 12A shows the urease content for various soil types. Figure 12B shows the ammonia volatilization test results for the samples listed in Table 8 before encapsulation. Figure 12C shows the ammonia volatilization test results for the samples listed in Table 8 after encapsulation and heat treatment.

[0094] Figure 13 shows the ammonia production of the samples listed in Table 8 on day 15.

[0095] Figure 14 shows the Job diagram of the γ-CD:NBTPT complex.

[0096] While the invention is readily adaptable to various modifications and alternatives, specific embodiments thereof are illustrated by way of example with reference to the accompanying drawings. The drawings may not be drawn to scale. Detailed Implementation

[0097] A fertilizer composition comprising a nitrogen fertilizer and an inhibitor inclusion complex, the inhibitor inclusion complex comprising at least one composite component compounded with an inhibitor. The inhibitor may include at least one nitrification inhibitor and / or at least one urease inhibitor. The inhibitor inclusion complex may be embedded within the nitrogen fertilizer. A controlled-release fertilizer composition may include an inhibitor inclusion complex comprising at least one nitrification inhibitor and / or at least one urease inhibitor component, wherein the inhibitor inclusion complex is encapsulated / embedded and / or dispersed throughout the nitrogen fertilizer melt. The inhibitor inclusion complex may be encapsulated / embedded within the nitrogen fertilizer or provided on the surface of the nitrogen fertilizer. The nitrogen fertilizer component may include urea. The inclusion complex may be destroyed over time, imparting controlled-release functionality to the inhibitor and mitigating nitrogen loss from nitrification or hydrolysis in the fertilizer. Other advantages of the fertilizer composition include the ability to provide the desired composite component size, such as cyclodextrin types like α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, and / or their derivatives, depending on the size of the inhibitor molecules to be compounded with the composite component. The inhibitor inclusion complex can improve the thermal stability of the inhibitor in the complex compared to inhibitors not included in the inclusion complex.

[0098] In some cases, the complex component is a polymer. In some cases, the polymer is an oligomer. In some cases, the polymer is a polysaccharide, oligosaccharide, and / or its derivatives. The polymer can be cellulose, starch, and / or its derivatives. In some cases, the polymer is a cyclodextrin. Cyclodextrins are a class of cyclic oligosaccharides containing a macrocyclic ring structure with glucose subunits linked by α-1,4 glycosidic bonds. Cyclodextrins can be produced from starch through enzymatic conversion. Typical cyclodextrins can contain six to eight glucose monomer units in a conical shape. For example, α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin contain 6, 7, and 8 glucose subunits, respectively. These cyclodextrins have a ring shape, with the larger and smaller openings of the ring exposing the secondary and primary hydroxyl groups on the outer side of the ring, respectively. Due to this arrangement, the interior of the ring is not hydrophobic, but much less hydrophilic than the outer side, capable of accommodating hydrophobic molecules. In contrast, the exterior is sufficiently hydrophilic, giving the cyclodextrin (or its complexes) water solubility. These polysaccharides and / or their derivatives are primarily obtained from natural sources, such as wood pulp and other plant sources, and can form the renewable framework of the fertilizer compositions disclosed herein.

[0099] A. Fertilizer composition

[0100] The fertilizer composition may comprise from about 80% to 99.9999% by weight of nitrogen fertilizer and / or from about 0.0001% to 15% by weight of an inhibitor inclusion complex. The fertilizer composition may comprise at least one, at most one, equal to one, or between any two of the following nitrogen fertilizers by weight: 80% by weight, 81% by weight, 82% by weight, 83% by weight, 84% by weight, 85% by weight, 86% by weight, 87% by weight, 88% by weight, 89% by weight, 90% by weight, 91% by weight, 92% by weight, 93% by weight, 94% by weight, 95% by weight, 96% by weight, 97% by weight, 98% by weight, 99% by weight, or 100% by weight. In some cases, the nitrogen fertilizer may be a solidified nitrogen fertilizer melt. In some cases, the nitrogen fertilizer includes urea, urea melt, and / or NPK. In some aspects, based on the total weight of the fertilizer composition, the fertilizer composition may contain 0.0001 wt% to 10 wt%, or at least any one, equal to any one, or between any two of the following wt% inhibitor inclusion complexes: 0.0001 wt%, 0.0002 wt%, 0.0003 wt%, 0.0004 wt%, 0.0005 wt%, 0.0006 wt%, 0.0007 wt%, 0.0008 wt%, 0.0009 wt%, 0.001 wt%, 0.002 wt%, 0.003 wt%, 0.004 wt%, 0.005 wt%, 0.006 wt%, 0.007 wt%, 0.008 wt%, 0.009 wt%, 0.01 wt%, 0.02 wt%, 0.03 wt%, 0.04 wt%, 0.05 wt%, 0.06 wt%, 0.07 wt%. The percentages are as follows: 0.08 wt%, 0.09 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.2 wt%, 1.4 wt%, 1.6 wt%, 1.8 wt%, 2 wt%, 2.2 wt%, 2.4 wt%, 2.6 wt%, 2.8 wt%, 3 wt%, 3.2 wt%, 3.4 wt%, 3.6 wt%, 3.8 wt%, 4 wt%, 4.2 wt%, 4.4 wt%, 4.6 wt%, 4.8 wt%, 5 wt%, 5.2 wt%, 5.4 wt%, 5.6 wt%, 5.8 wt%, 6 wt%, 6.2 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, 8.5 wt%, 9 wt%, 9.5 wt%, 10 wt%. In some cases, the fertilizer composition also includes a wetting agent, a carrier, a filler, and / or a binder.

[0101] In some cases, the complex component contains cyclodextrin. In some cases, the inhibitor inclusion complex contains α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, and / or their derivatives. In some cases, the inhibitor inclusion complex contains at least one nitration inhibitor and / or at least one urease inhibitor. In some cases, the nitration inhibitor includes 3,4-dimethylpyrazole phosphate (DMPP), thiourea (TU), dicyandiamide (DCD), 2-chloro-6-(trichloromethyl)pyridine (chlorpyrifos), and 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole (TERRAZOLE). TM ), 2-amino-4-chloro-6-methylpyrimidine (AM), 2-mercaptobenzothiazole (MBT), ammonium thiosulfate (ATS), 2-p-aminobenzenesulfonamide thiazole (ST), or combinations thereof. In some cases, urease inhibitors include N-(n-butyl)-triamine thiophosphate, N-(n-butyl)-triamine phosphate, N-(n-propyl)-triamine thiophosphate, benzoylthiourea (BTU), hydroquinone, acetyloxyoxime acid (AHA), hydroxyurea (HU), and / or phenylphosphamide (PPDA). In some cases, the inhibitor inclusion complex may simultaneously contain a nitration inhibitor and a urease inhibitor, such as N-(n-butyl)-triamine phosphate and dicyandiamide, such as NITRIFICIN. TM .

[0102] In some cases, the fertilizer composition comprises an inhibitor and its degradation product in a ratio of 80:20 to 100:0 or less, equal to any one of the following ratios, or between any two of the following ratios: 81:19, 82:18, 83:17, 84:16, 85:15, 86:14, 87:13, 88:12, 89:11, 90:10, 91:9, 92:8, 93:7, 94:6, 95:5, 96:4, 97:3, 98:2, 99:1, and 100:0.

[0103] In some cases, the fertilizer composition contains an inhibitor included in the inhibitor inclusion complex and an inhibitor not included in the inhibitor inclusion complex in a ratio of 80:20 to 100:0 or less, equal to any one of the following ratios or between any two of the following: 81:19, 82:18, 83:17, 84:16, 85:15, 86:14, 87:13, 88:12, 89:11, 90:10, 91:9, 92:8, 93:7, 94:6, 95:5, 96:4, 97:3, 98:2, 99:1, and 100:0.

[0104] B. Method for preparing fertilizer compositions

[0105] A method for producing a fertilizer composition comprising an inhibitor inclusion complex encapsulated within a nitrogen fertilizer is disclosed. In some aspects, the method includes the steps of: (a) contacting an inhibitor with at least one composite component to generate an inhibitor inclusion complex; and (b) contacting the inhibitor inclusion complex with a nitrogen fertilizer to form an inhibitor inclusion complex embedded in the nitrogen fertilizer.

[0106] In step a) above, suitable composite component materials are first determined. In some aspects, the composite component may be α-cyclodextrin and / or its derivatives. In some aspects, the cyclodextrin material may be β-cyclodextrin and / or its derivatives. In some aspects, the cyclodextrin material may be γ-cyclodextrin and / or its derivatives. In some aspects, any of the above-mentioned cyclodextrin derivatives may be replaced by other composite components, such as polymers, such as other polysaccharides, oligosaccharides and / or their derivatives, such as cellulose, starch and / or their derivatives. In some aspects, the inhibitor may be a urease inhibitor or a nitration inhibitor, or a combination thereof. In one aspect, it includes both a urease inhibitor and a nitration inhibitor. In one aspect, the inhibitor may be a urease inhibitor. Suitable urease inhibitors include, but are not limited to, N-(n-butyl)-thiophosphate triamine (NBTPT), N-(n-butyl)-phosphate triamine (NBPT), N-(n-propyl)-thiophosphate triamine (NPPT), benzoylthiourea (BTU), hydroquinone, acetyloxyoxime acid (AHA), hydroxyurea (HU), and / or phenylphosphamide (PPDA). In one aspect, the inhibitor may comprise NBTPT, NBPT, NPPT, and / or PPDA, or combinations thereof. In another aspect, the inhibitor may be a nitrification inhibitor. Suitable nitrification inhibitors include, but are not limited to, 3,4-dimethylpyrazole phosphate (DMPP), dicyandiamide (DCD), thiourea (TU), 2-chloro-6-(trichloromethyl)-pyridine (chlorpyrifos), 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole (marketed under the trade name TERRAZOLE® by OHP Inc., USA), 2-amino-4-chloro-6-methylpyrimidine (AM), 2-mercaptobenzothiazole (MBT), or 2-p-aminobenzenesulfonamidethiazole (ST), and any combination thereof. In one aspect, the nitrification inhibitor may comprise DMPP, DCD, TU, chlorpyrifos, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole, AM, MBT, or ST, or combinations thereof. In one aspect, the fertilizer composition may comprise NBTPT, DMPP, TU, DCD, PPDA, nitrapyrin, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole, AM, MBT, or ST, or combinations thereof. Urease inhibitors and / or nitrification inhibitors are mixed with the above-described suitable composite components in a mixing vessel and mixed under appropriate temperature and pressure to generate an inhibitor inclusion complex. In some cases, the inhibitor inclusion complex is formed within 1 to 2 hours. In some aspects, the mixture may be heated in a temperature range of about 40°C to about 200°C.In some respects, the formed inhibitor inclusion complex is thermally stable at temperatures of 130°C or above, such as 140°C or above, or at least any one, equal to any one, or between any two of the following temperatures: 130°C, 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, and 300°C. In some respects, the resulting inhibitor inclusion complex is stable in a pH range of 4 to 11, for example, a pH range of 5 to 10, or at least any one of the following, equal to any one of, or between any two of the following pH values: 4, 5, 6, 7, 8, 9, 10, and 11.

[0107] In step b) above, the inhibitor inclusion complex from step a can be contacted with solid nitrogen fertilizer material, molten nitrogen fertilizer material, or nitrogen fertilizer solution, and mixed under suitable pressure and temperature (e.g., 65°C, 40 MPa) to form an inhibitor inclusion complex embedded in the nitrogen fertilizer. The inhibitor inclusion complex can be embedded in a homogeneous and stable nitrogen fertilizer. In some aspects, the inhibitor inclusion complex and nitrogen fertilizer (e.g., urea) can be contacted at temperatures up to or below 250°C, at least one of the following temperatures, equal to one of the following temperatures, or between any two of the following temperatures: 20°C, 30°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C. The temperatures are 115℃, 120℃, 125℃, 130℃, 135℃, 140℃, 145℃, 150℃, 155℃, 160℃, 165℃, 170℃, 175℃, 180℃, 185℃, 190℃, 195℃, 200℃, 205℃, 210℃, 215℃, 220℃, 225℃, 230℃, 235℃, 240℃, 245℃, and 250℃. In some aspects, steps a and b of the method are carried out as a one-pot synthesis and / or a multi-step synthesis. By subsequently mechanically mixing and / or cooling and solidifying the molten nitrogen fertilizer, a fertilizer composition comprising an inhibitor inclusion complex embedded in the nitrogen fertilizer is obtained. In some aspects, the source of the nitrogen fertilizer is urea. In some aspects, the source of the nitrogen fertilizer is NPK.

[0108] The fertilizer provided by the above steps contains inhibitors (e.g., nitrification inhibitors and / or urease inhibitors) that can be non-covalently bonded to or spatially encapsulated within the composite component host material. These inhibitor inclusion complexes can be physically embedded in the nitrogen fertilizer and can be found on the surface of the nitrogen fertilizer material. In some cases, water can then be removed from the mixture. In some cases, the above steps provide inhibitor inclusion complexes embedded / encapsulated in the nitrogen fertilizer, such as a solidified nitrogen fertilizer melt. Different techniques can be employed before, during, or after drying to provide solid fertilizer compositions in powder, crystal, granule, or pellet form.

[0109] In some cases, the produced fertilizer composition may contain a small amount of water. The free water content of the fertilizer composition may be less than 0.6 wt%, less than 0.5 wt% water, or 0.25 wt% to less than 0.6 wt% water. In some cases, the free water content is, less than, greater than, or between the following wt%, or any range thereof: 0.5 wt%, 0.4 wt%, 0.3 wt%, 0.2 wt%, 0.1 wt%, or 0 wt%.

[0110] Fertilizer compositions can be formulated as powders, crystals, granules, or pellets. In some non-limiting aspects, the powder may comprise particles having an average particle size that is, is less than, is greater than, or falls between, or any range thereof: 1 micrometer, 2 micrometer, 3 micrometer, 4 micrometer, 5 micrometer, 6 micrometer, 7 micrometer, 8 micrometer, 9 micrometer, 10 micrometer, 11 micrometer, 12 micrometer, 13 micrometer, 14 micrometer, 15 micrometer, 20 micrometer, 30 micrometer, 40 micrometer, 50 micrometer, 60 micrometer, 70 micrometer, 80 micrometer, 90 micrometer, 100 micrometer, 200 micrometer, 300 micrometer, 400 micrometer, 500 micrometer, 600 micrometer, 700 micrometer, 800 micrometer, or 900 micrometer. In some embodiments, the particles may be elongated particles, or substantially spherical particles or other shapes, or combinations of these shapes. Non-limiting examples of shapes include spherical, disc-shaped, elliptical, rod-shaped, elongated, or irregular shapes.

[0111] In some cases, fertilizer compositions may include a coating on their surface. In some cases, the coating may contain plant nutrients, additional inhibitors such as urea hydrolysis inhibitors and / or nitrification inhibitors, agents that slow or increase the degradation rate of granules and / or fertilizers, agents that repel water and / or provide a hydrophobic layer, agents that reduce or increase the reactivity of granules and / or fertilizers, agents that provide additional benefits to plants, agents that increase the stability and / or compressive strength of granules and / or fertilizers, pH buffers, desiccants, biostimulants, microorganisms, etc., or any combination thereof. The coating may be a commercially available coating, oil, fertilizer, micronutrient, talc, seaweed and / or seaweed extract, bacteria, wax, etc. In some cases, the coating may contain surfactants. In some cases, the coating contains waxes, surfactants, and / or amine compounds.

[0112] In some aspects, the fertilizer composition contains a coating, such as a core comprising an inhibitor inclusion complex encapsulated within a nitrogen fertilizer, and a shell coating providing a surrounding coating. In other aspects, the fertilizer composition contains an inhibitor inclusion complex within a nitrogen fertilizer matrix, such as extruded fertilizer granules.

[0113] In some aspects, the fertilizer composition comprises a nitrogen fertilizer as a matrix, said matrix containing an inhibitor inclusion complex, a complex component and / or an inhibitor, and optional other ingredients, such as additional nutrients, inhibitors, alkaline materials, acidic materials, one or more biostimulants, one or more microorganisms, etc. In some aspects, the fertilizer composition comprises a coated core, an inhibitor inclusion complex encapsulated within the coating, and nitrogen fertilizer. The core may include plant nutrients, urea hydrolysis inhibitors and / or nitrification inhibitors, agents that slow down or increase the degradation rate of the granules, agents that repel water and / or provide a hydrophobic layer, agents that reduce or increase the reactivity of the granules, agents that provide additional benefits to the plant, agents that increase the stability and / or compressive strength of the granules, pH buffers, desiccants, microorganisms, etc., or any combination thereof.

[0114] The fertilizer compositions disclosed herein can also be included in blended or compounded fertilizer compositions containing other fertilizers, such as other fertilizer granules. Additional fertilizers can be selected based on the specific needs of particular soil types, climates, or other growing conditions to maximize the efficacy of the fertilizer composition in promoting plant growth and crop yield. Other fertilizer granules may be granules of urea, superphosphate (SSP), triple superphosphate (TSP), ammonium sulfate, monoammonium phosphate (MAP), diammonium phosphate (DAP), potassium chloride (MOP), and / or potassium sulfate (SOP), etc.

[0115] C. Methods of using fertilizer compositions

[0116] The fertilizer compositions disclosed herein can be used to increase the amount of nitrogen in soil, and optionally phosphorus and / or potassium, and to promote plant growth. Such methods may include applying an effective amount of a composition comprising the fertilizer composition disclosed herein to the soil. Methods may include increasing the growth and yield of crops, trees, ornamental plants, etc., such as palm trees, coconut trees, rice, wheat, corn, barley, oats, and soybeans. Methods may include applying the fertilizer compositions disclosed herein to at least one of soil, organisms, liquid carriers, liquid solvents, etc.

[0117] Non-limiting examples of plants that can benefit from the fertilizers disclosed herein include vines, trees, shrubs, stalked plants, ferns, etc. These plants can include orchard crops, vines, ornamental plants, food crops, timber, and harvested plants. These plants can include gymnosperms, angiosperms, and / or ferns. Gymnosperms can include plants from the families Araucariaceae, Cupressaceae, Pinaceae, Podocarpus, Sciadopitaceae, Taxaceae, Cycadaceae, and Ginkgoaceae. Angiosperms can include those from the following families: Aceraceae, Agavaceae, Anacardiaceae, Annonaceae, Apocynaceae, Aquifoliaceae, Araliaceae, Arecaceae, Asphodelaceae, Asteraceae, Berberidaceae, Betulaceae, Bignoniaceae, Bombacaceae, Boraginaceae, Burseraceae, Buxusaceae, Lauraceae, Cannabaceae, Brusselschildaceae, Caprifoliaceae, Caricaceae, Casuarinaceae, Celastraceae, Cercidiaceae, Prunaceae, Clusiaceae, Combretaceae, Cornaceae, Tanneraceae, Davidsoniacea, Ebenaceae, Elaeagnaceae, Ericaceae, Euphorbiaceae, Fabaceae, Fagaceae, Curcumaceae, Hamamelidaceae, Aesculaceae, Illicaceae, Juglandaceae, Lauraceae, Lepidaceae, Lythraceae, Magnolia. Plants belonging to the following families: Malvaceae, Melastomataceae, Meliaceae, Moraceae, Moringaceae, Mandinaceae, Myricaceae, Myrsinaceae, Ardisiaceae, Myrtaceae, Quercus acutissima, Nyctaginaceae, Nelumbo nucifera, Aristolochiaceae, Oleaceae, Oxalisceae, Pandanaceae, Papaveraceae, Phyllanthaceae, Pittosporum, Platanaceae, Poaceae, Polygonaceae, Proteaceae, Punicaceae, Rhamnaceae, Mangroveaceae, Rosaceae, Rubiaceae, Rutaceae, Salicaceae, Sapindaceae, Sapotaceae, Simaroubaceae, Solanaceae, Sterculiaceae, Strelitziaceae, Styraxaceae, Styraxaceae, Styraxaceae, Styraxaceae, Styraxaceae, Styraxaceae, Styraxaceae, Styraxaceae, Theaceae, Erythrinaceae, Thymelaeaceae, Tiliaceae, Ulmaceae, Verbenaceae, and / or Vitaceae.

[0118] The effectiveness of a composition containing the fertilizer composition disclosed herein can be determined by measuring the amounts of nitrogen, phosphorus, and potassium, or nitrogen, phosphorus, and potassium, in the soil at different times after the fertilizer composition has been applied to the soil. It should be understood that different soils have different characteristics, which may affect the stability of nitrogen in the soil. The effectiveness of the fertilizer composition can also be directly compared with other fertilizer compositions by performing side-by-side comparisons under the same conditions in the same soil.

[0119] In one respect, the fertilizer compositions disclosed herein may have a density greater than that of water. This may allow the granules and / or fertilizer to sink in the water rather than float. This may be particularly advantageous when applied to crops that are at least partially or completely submerged in water. A non-limiting example of such a crop is rice, as the ground of rice paddies is typically submerged in water. Therefore, when applying the fertilizer composition to such crops, the granules and / or fertilizer can be evenly distributed on the underwater ground. In contrast, granules and / or fertilizers with a density less than that of water tend to remain in or on the water surface, which may result in the granules and / or fertilizer being washed away and / or agglomerated, neither of which allows for a uniform distribution of the granules and / or fertilizer on the underwater ground.

[0120] Example

[0121] The invention will be described in more detail through specific embodiments. The following embodiments are for illustrative purposes only and are not intended to limit the invention in any way. Those skilled in the art will readily recognize that various non-critical parameters can be changed or modified to produce substantially the same results.

[0122] Example 1

[0123] Methods for preparing fertilizer granules and analyzing their properties

[0124] A. Materials

[0125] Industrial-grade urea was purchased from SABIC, Riyadh, Saudi Arabia. N-(n-butyl)-triamine thiophosphate (NBTPT) powder was purchased from Hangzhou SAMICH (HK) Ltd., or Tokyo Kasei Kogyo Co. DCD powder was purchased from SIGMA ALDRICH / ALZCHEM, Germany. Cyclodextrin was available from Fujifilm Wako Pure Chemical Industries, Ltd.

[0126] Figures 1A and 1B show that NBTPT coated on urea pellets appears as small spheres, primarily on the surface, with particle sizes ranging from 50 µm to 150 µm. In contrast, the melt-mixed samples show that NBTPT is uniformly dispersed in urea, with no visible NBTPT particles on the surface (Figures 1D and 1E). EDX analysis indicates that the spherical particles have high phosphorus (P) and sulfur (S) content. In contrast, no P and S were detected on the urea surface, indicating that the spherical particles are NBTPT, which does not mix well with urea. A suitable amount of NBTPT methanol solution was sprayed onto urea pellets and air-dried. Molten urea containing NBTPT / CyD was prepared by adding a suitable amount of NBTPT / CyD to molten urea at 140 °C.

[0127] B. Methods for preparing cyclodextrin-inhibitor inclusion complexes and their characterization

[0128] As described below, a cyclodextrin-inhibitor inclusion complex is prepared by mechanically and / or heating and / or using a solvent to mix NBTPT and / or DCD with cyclodextrin, thereby forming a cyclodextrin-inhibitor inclusion complex. The total amount of cyclodextrin and NBTPT and / or DCD can be from 0.0001% by weight to 15% by weight relative to the total weight of the fertilizer composition (containing nitrogen fertilizer). In some cases, no other components are used. In some cases, different amounts of additional components are used. In some cases, other complex components are used as supplements or substitutes for cyclodextrin to be complexed with the inhibitor. In some cases, other nitrification inhibitors and / or urease inhibitors are used as supplements or substitutes for NBTPT and / or DCD.

[0129] B1. Thermogravimetric / Differential Thermal Analysis (TG / DTA) of the NBTPT γ-cyclodextrin (γ-CD) Complex

[0130] A solvent-based method for preparing samples containing γ-CD and NBTPT: An aqueous solution of γ-CD is mixed with a methanol solution of NBTPT to prepare the samples listed in Table 1. The steps for preparing samples (B1 to B7) include:

[0131] Preparation of stock solutions: NBTPT was dissolved in methanol ([Sol. F]), and γ-CD was dissolved in distilled water ([Sol. C1x]). Diluted solutions of [Sol. C1x] were prepared ([Sol. C2x] to [Sol. C8x]).

[0132] Mixed solutions: Mix solutions of different volumes to achieve the desired γ-CD:NBTPT molar ratio.

[0133] Sample preparation: Dispense each mixed solution into sample vials (1 mL per vial, containing 10 mg NBTPT).

[0134] Freeze-drying: The sample is pre-frozen and freeze-dried, and then stored under dry conditions.

[0135] Table 1. γ-CD:NBTPT Samples

[0136]

[0137] *DW = Distilled Water

[0138] Solvent-based method for preparing samples containing γ-CD, NBTPT, and urea: Samples containing γ-CD, NBTPT, and urea were prepared and are listed in Table 2. The steps for preparing samples (B8 to B11) include:

[0139] Sample preparation (liquid method): Samples with different molar ratios of γ-CD, NBTPT and urea are prepared by mixing solutions of γ-CD, NBTPT and urea.

[0140] Freeze-drying: Freeze-dry the prepared sample.

[0141] Table 2. Samples containing γ-CD:NBTPT:urea

[0142]

[0143] Mechanical mixing-based methods were used for sample preparation. The preparation of γ-CD:NBTPT samples based on mechanical mixing involved mechanically mixing γ-CD and NBTPT using a mortar and pestle. The preparation of γ-CD:NBTPT:urea samples based on mechanical mixing involved mechanically mixing γ-CD, NBTPT, and urea using a mortar and pestle. Table 3 lists the samples prepared based on mechanical mixing.

[0144] Table 3. Samples prepared by mechanical mixing

[0145]

[0146] Results: The TGA study investigated the effects of γ-CD and urea on the thermal stability of NBTPT. The weight loss curves (TG curves) of urea-containing and urea-free samples were analyzed. TG data showed that the presence of γ-CD increased the temperature at which NBTPT experienced a second major weight loss event, indicating improved thermal stability (Figures 2A and 2B). The presence of urea made precise quantification of the stabilization effect more challenging. Furthermore, the method of preparing the γ-CD:NBTPT composite significantly affected its thermal properties. Samples prepared by solvent-based methods differed in their melting point and decomposition behavior compared to samples prepared by mechanical mixing.

[0147] Figures 2A and 2B show the TG curves for samples B1 to B7. Temperature is plotted on the x-axis, and TG is plotted on the y-axis. Figure 2A shows data within the temperature range of 0°C to 500°C, and Figure 2B shows data within the temperature range of 100°C to 250°C. The initial weight loss of the complex containing γ-CD is due to water encapsulated in γ-CD. Figures 3A and 3B show the TG curves for samples B1 to B7, omitting the initial residual moisture. Figure 3A shows data within the temperature range of 0°C to 500°C, and Figure 3B shows data within the temperature range of 80°C to 250°C. The raw data indicate that γ-CD contains 10.1% water. Based on Figures 3A and 3B, the second weight loss of the γ-CD:NBTPT complex only occurs at temperatures above NBTPT. Therefore, thermal stability of NBTPT is achieved using γ-CD. The ratios shown in Figures 2A to 2B and Figures 3A to 3B are the γ-CD:NBTPT molar ratios.

[0148] Figure 4A shows the TG curves for samples B8 to B12. The samples were not heated before the experiment. The ratio shown in Figure 4A is the molar ratio of γ-CD:NBTPT:urea. Figure 4B shows the TG-DTA curves for samples B4 (γ-CD:NBTPT molar ratio 1:1) and B10 (γ-CD:NBTPT:urea molar ratio 1:1:1). The two curves differ slightly in the first weight loss portion. This difference is believed to be due to the amount of water contained in the γ-CD.

[0149] Figures 5A to 5D show the TG and DTA curves of samples B4, B13, and B14. As shown in Table 1, B4 was prepared using a solvent-based method with a γ-CD:NBTPT molar ratio of 1:1. As shown in Table 3, B13 was prepared using a mechanical mixing-based method with a γ-CD:NBTPT molar ratio of 1:1; B14 was prepared using a mechanical mixing-based method with a γ-CD:NBTPT:urea molar ratio of 1:1:1. Figure 5A shows the TG (left y-axis) and DTA (right y-axis) of the samples in the temperature range of 0°C to 500°C; Figure 5B shows the TG of the samples in the temperature range of 20°C to 295°C; Figure 5C shows the DTA of the samples in the temperature range of 20°C to 70°C; and Figure 5D shows the DTA of the samples in the temperature range of 200°C to 300°C. Figures 5A to 5D show that the melting point (DTA) of NBTPT is approximately 60°C, and the decomposition temperature varies when using the mechanical mixing-based preparation method. This suggests that mechanically mixed reagents may differ from lyophilized reagents.

[0150] B2. Stability study of NBTPT γ-cyclodextrin (γ-CD) complex in acidic media

[0151] By using 31The degradation of NBTPT in an acidic environment was determined by P NMR spectroscopy, and the stability of the NBTPT γ-cyclodextrin (γ-CD) complex in acidic media was studied.

[0152] Sample preparation: The lyophilized sample containing γ-CD and NBTPT (approximately 10 mg) (prepared using the method described in Part B1) was dissolved in water (250 mL) by sonication.

[0153] Acidic environment: Add an acidic buffer solution (CH3COOH / CH3COONa, 500mM, pH 5.0) to the sample solution (250mL). pH=5 is an extreme condition for any plant.

[0154] NMR analysis: The H3PO4 solution in D2O (placed in a capillary tube) was used as... 31 Reference for p NMR experiments.

[0155] Through observation 31 The signal at 61 ppm on the P NMR spectrum was used to specifically monitor the degradation of NBTPT.

[0156] γ-CD / NBTPT complex 31 The pNMR spectra are shown in Figures 6A to 6F. Figure 6A shows the NBTPT (unrecombined) NMR spectrum. 31 P NMR spectrum; Figure 6B shows the complex with a γ-CD / NBTPT molar ratio of 1:4. 31 P NMR spectrum; Figure 6C shows the complex with a γ-CD / NBTPT molar ratio of 1:3. 31 P NMR spectrum; Figure 6D shows the complex with a γ-CD / NBTPT molar ratio of 1:2. 31 P NMR spectrum; Figure 6E shows the complex with a γ-CD / NBTPT molar ratio of 1:1. 31 P NMR spectrum; and Figure 6F shows the complex with a γ-CD / NBTPT molar ratio of 2:1. 31 P NMR spectra. The insets in each figure show the degradation of NBTPT over time, determined based on the P=S peak (approximately 61 ppm).

[0157] Figures 6A to 6F show that the γ-CD / NBTPT complex is unstable under liquid acidic conditions, and the P=S peak of NBTPT weakens within 5 hours.

[0158] 17 days later, the γ-CD / NBTPT 1:1 complex 31 P NMR data: Measurements were taken of the γ-CD:NBTPT = 1:1 (molar ratio) complex in acetate buffer after 17 days. 31P NMR. As can be seen from Figure 7, the P=S peak (approximately 60 ppm) completely disappeared, and the P=O peak (approximately 52 ppm) was not detected, leaving only a 42 ppm peak. This result was also observed in other complexes.

[0159] B3. Thermal stability study of NBTPT γ-cyclodextrin (γ-CD) complex

[0160] Samples were prepared by heat treatment. Samples containing γ-CD and NBTPT, as well as samples containing γ-CD, NBTPT, and urea, were prepared for the heating experiments. Lyophilized samples (prepared using the method described in Section B1) were heated at 140°C, 160°C, and 180°C for 30 minutes, respectively. 31 P-NMR and 1 The samples were studied using H-NMR.

[0161] Figure 8A shows the results of heat treatment at room temperature (rt) and at 140°C, 160°C, and 180°C with γ-CD:NBTPT:urea (molar ratio 1:1:1). 31 Figure 8B shows the γ-CD:NBTPT (molar ratio 1:1) NMR spectra at room temperature and after heat treatment at 140 °C, 160 °C and 180 °C. 31 P NMR spectrum. As shown in Figures 8A and 8B, the P=S peak still exists after heating. 1 Another peak appeared in the H-NMR (Figure 9). The amount of residual NBTPT in the gCD:NBTPT=1:1 and 1:2 samples was calculated, and it was observed that NBTPT decreased with increasing heating temperature regardless of the presence of urea. Table 4 shows the integral of P=S in Figure 8A, and Table 5 shows the integral of P=S in Figure 8B.

[0162] Table 4: γ-CD:NBTPT:Urea (molar ratio 1:1:1) 31 P NMR

[0163]

[0164] Table 5: γ-CD:NBTPT (molar ratio 1:1) 31 P NMR

[0165]

[0166] B4. Determination of the binding constant between γ-CD and NBTPT

[0167] The binding constant (Ka), describing the strength of the interaction between NBTPT and γ-CD, was determined using the Benesi-Hildebrand method. A methanol-based NBTPT solution (5 mM) and an aqueous γ-CD solution (125 mM) were prepared. Different volumes of these solutions were mixed with water to achieve a final volume of 500 µL, maintaining a constant NBTPT concentration (1 mM) and a series of γ-CD concentrations (50 mM to 100 mM). These mixtures were then freeze-dried, and the resulting solid was dissolved in D₂O. 1 ¹H NMR analysis. The change in chemical shift (Δδi [CD]) of each proton (i) in NBTPT at each γ-CD concentration was calculated using the following formula:

[0168]

[0169] A linear relationship was obtained by plotting 1 / Δδi[γ-CD] against 1 / [γ-CD]. The binding constant (Ka) and the chemical shift change (Δδi Cpx) of NBTPT in the pure complex were determined from the equations of the intercepts and slopes of these lines.

[0170] Based on NMR measurements of the NBTPT / γ-CD=1:1 (molar ratio) complex, the shift value (Dd) of the butyl chain of NBTPT was calculated. The results are listed in Table 6, and the calculated Ka is 5.17±6.28.

[0171] Table 6: Binding constants between γ-CD and NBTPT.

[0172]

[0173] B5. Rotational coordinate system Overhouse effect enhanced spectroscopy (ROESY) measurement of γ-CD:NBTPT 1:1 (molar ratio) complex.

[0174] NMR samples of a 1:1 (molar ratio) γ-CD:NBTPT complex (10 mg) were prepared, and the ROSEY spectrum of the 1:1 complex was measured in D2O. The ROSEY spectrum (Figure 9) shows that the butyl chain on NBTPT may interact with the H3 and H5 groups of γ-CD to form the complex.

[0175] B6. Evaluation of urease inhibitory activity

[0176] Preparation of NBTPT solutions: Stock solution: Dissolve NBTPT in methanol (20 mg / mL or 120 mM concentration). Working solution: Dilute the stock solution with Tris-HCl buffer (pH=8.0) to prepare solutions with different NBTPT concentrations (0 µM to 600 µM).

[0177] Preparation of lyophilized samples. Dissolution: Dissolve the lyophilized sample in methanol (20 mg / mL or 120 mM NBTPT). Centrifugation: Centrifuge the solution to remove any insoluble substances. Dilution: Dilute the supernatant to a concentration of 6 mM NBTPT with Tris-HCl buffer (pH=8.0).

[0178] Urease inhibition assay (Jackbean urease): The urease solution (derived from Jackbean, Fujifilm Wako Pure Chemicals) was prepared to a concentration of 2 µg / mL in buffer (50 mM Tris-HCl, pH 8.0). 100 µl of the prepared urease solution was mixed with 100 µl of the prepared sample solution and incubated at 37 °C for 30 minutes.

[0179] Ammonia detection: Ammonia production was quantified using a glutamate dehydrogenase system. The chemicals and concentrations used in this study are shown in Table 7. Changes in absorbance at 340 nm (a decrease in NADPH) measured over 20 minutes provided an indication of urease activity. NADPH deprotonates to NADP via a reaction with ammonia. + At that time, the peak intensity decreases.

[0180] Urease assay: Urea + H₂O = CO₂ + NH₃ (urease). K₂O + NH₃ + NADPH = L-glutamate + NADP₃ + +H2O (glutamate dehydrogenase). The decrease in absorbance at 340 nm due to NADPH oxidation is directly proportional to the ammonia concentration. L-glutamate dehydrogenase reacts specifically with ammonia.

[0181] Table 7: Components of the Urea Inhibition Assay

[0182]

[0183] Calculation: Enzyme activity is defined as 1 U = 1 mmol of urea degraded per minute. For accuracy, the measurement was repeated three times.

[0184] Results: Encapsulation with γ-CD was expected to reduce the urease inhibitory activity of NBTPT. This study aimed to evaluate the urease inhibitory activity of the prepared encapsulated γ-CD / NBTPT using enzymatic methods and to select samples that maintained urease inhibitory activity. The urease inhibitory activity of heat-treated encapsulated γ-CD / NBTPT was also evaluated. As shown in Figure 10A, the half-maximal inhibitory concentration (IC50) of NBTPT... 50 The concentration was approximately 0.65 µM. In solution-based inhibition studies, 0.60 µM was used. Regardless of the NBTPT / γ-CD ratio, the final NBTPT concentration was always maintained at 0.60 µM to ensure fair comparisons.

[0185] The urease inhibition efficiency of pure NBTPT decreased from 61.5% to 40% after lyophilization, indicating relatively low stability in water at room temperature (Fig. 10A). In contrast, the urease inhibition efficiency of samples encapsulated with γ-CD (2:1, 1:1, 1:2, 1:3, 1:4 (NBTPT / γ-CD molar ratio)) did not show any decrease, and NBTPT was observed to be stabilized through encapsulation (Fig. 10B). Interestingly, pure γ-CD showed an inhibition efficiency of approximately 30%, indicating non-competitive inhibitory properties (Fig. 10B).

[0186] The urease inhibition efficiencies of heat-treated and encapsulated γ-CD / NBTPT (with or without urea) at different temperatures are shown in Figures 11A to 11F. Figures 11A to 11C show the urease inhibition rates of heat-treated and encapsulated γ-CD / NBTPT (with urea). When the γ-CD / NBTPT ratio was 2:1, 1:1, or 1:2, no decrease in NBTPT activity was observed at treatments at 140°C, 160°C, or 180°C; at a 1:4 ratio, no activity was observed at any temperature. Figures 11D to 11F show the urease inhibition rates of urea-free, heat-treated and encapsulated γ-CD / NBTPT. Encapsulation with γ-CD improved the activity of NBPT at each temperature treatment of 140°C, 160°C, and 180°C. The y-axis of each graph in Figures 11A to 11F shows the urease inhibition rate (%). Heat treatment was performed under a nitrogen atmosphere, and the NBTPT concentration was 6 µM during the inhibition test. All encapsulated samples were heat-treated together with urea, resulting in enhanced inhibition efficiency. This enhancement was particularly significant at a heat treatment temperature of 140 °C.

[0187] Soil urease activity assessment: Objective: To select soils with appropriate urease activity for further testing. Procedure: Mix urea solution (80 mM) with soil samples. Incubate at 37°C for 1 hour. Measure the ammonia produced (enzymatic method). Calculate enzyme activity using the same method as above.

[0188] Urea hydrolysis inhibition test in soil: Objective: To evaluate the inhibitory effect of the following substances on urease: NBTPT alone; encapsulated NBTPT + γ-CD; and mechanically mixed NBTPT + γ-CD. Effect of heating on these samples.

[0189] Table 8 lists the samples used for soil urease activity, outlines the specific conditions of the soil tests, and details the sample preparation methods for different inhibitor formulations.

[0190] Overall objective: These experiments aimed to evaluate the effectiveness of NBTPT, whether used alone or in combination with γ-CD, in inhibiting urease activity in real soil environments. This contributes to understanding the potential of NBTPT-based formulations in improving fertilizer efficiency.

[0191] Soil preparation:

[0192] Add urea: Collect soil from the vegetable garden. Mix 2g of urea granules with 500g of soil. This gives the soil a final urea concentration of 0.4%, simulating fertilization.

[0193] Adding the sample: Table 9 outlines the different methods of adding the sample (NBTPT formulation) to the soil. Dissolve the sample in distilled water (200 µL). Add this solution to 10 g of soil. The control sample (without NBTPT) is also added to 200 µL of distilled water to maintain consistent moisture content.

[0194] Soil ammonia volatilization test

[0195] Setup: Place 10g of the prepared soil into a glass vial and seal tightly. Store the vial in a controlled environment at 30°C.

[0196] Ammonia measurement: The ammonia concentration in the top space of the vial is measured using a gas detection tube.

[0197] Measurements were taken on days 2, 4, 8, 11, and 15 to track the accumulation of ammonia over time.

[0198] Experimental Objective

[0199] Urease activity: Urea in the soil is broken down into ammonia by urease, and the ammonia may escape into the atmosphere (volatilization).

[0200] Inhibition effect: This experiment aims to observe whether different NBTPT formulations can inhibit urease activity, thereby reducing ammonia loss.

[0201] Time course: Measuring ammonia over several consecutive days can reveal the effectiveness and persistence of the inhibitory effect.

[0202] Results: The urease activity measurements for the four soil types are shown in Figure 12A. Significant differences in urease activity were observed among the soils. Although no other assessments besides urease activity were performed on the tested soils in this study, it is speculated that soil 1 may contain a higher concentration of urease-producing microorganisms. Soil 1 exhibited the highest urease activity among the four soil types, and its activity significantly decreased after sterilization at 121°C for 20 minutes, as shown in Figure 12A. Soil 1 was selected for the soil tests shown in Figures 12B and 12C. Figure 12B shows the ammonia volatilization test of the samples listed in Table 8 before encapsulation, and Figure 12C shows the ammonia volatilization test of the samples listed in Table 8 after encapsulation and heat treatment.

[0203] Figure 12B shows the results of the soil test on day 15. The tested samples are listed in Table 8. Samples 2 and 3 represent urea-containing soil that has undergone heat treatment, producing ammonia from day 2 of the test. The results indicate that heat treatment of urea has no effect on urease activity. In samples 4 and 5, NBTPT and heat-treated NBTPT were added to the urea-containing soil, respectively. Under these conditions, ammonia production in samples 4 and 5 was suppressed until day 4. Until day 8, the behavior of heat-treated NBTPT was similar to that of NBTPT, but on day 15, ammonia production was significantly reduced compared to NBTPT. The reason for the increased stability of heat-treated NBTPT is unclear, as a decrease in activity was observed after freeze-drying. Furthermore, NBTPT is generally considered unstable under heat treatment. However, a mild heat treatment at 150°C for 5 minutes may be the reason for the better performance, by which NBTPTO was produced, with a potency 100 times that of NBTPT.

[0204] Ammonia production on day 15 of the soil test is shown in Figure 13. The NBTPT / γ-CD mixture after heat treatment and mechanical mixing showed a significant reduction in ammonia production. The ammonia production inhibition effect of all samples was similar to that of NBTPT. However, their behavior was the same as NBTPT. On the other hand, samples treated by mixing NBTPT and γ-CD in a mortar and then heat-treated at 150°C for 5 minutes under a nitrogen flow showed three times the inhibition of ammonia formation compared to NBTPT.

[0205] Table 8: Samples used for soil urease activity

[0206]

[0207]

[0208] B7. Job Method

[0209] Prepare γ-CD aqueous solution (10 mM) and NBTPT methanol solution (10 mM).

[0210] The two solutions were mixed in test tubes at different ratios, with a total volume of 1 mL, and then freeze-dried.

[0211] The resulting solid was dissolved in 1 mL of D₂O, and then... 1 Analysis was performed using H NMR.

[0212] For each proportion (r) and each proton (i) of NBTPT, the chemical shift change (Dδ) i r The formula for calculating ) is:

[0213] r = [NBTPT] / ([NBTPT] + [CDα])

[0214]

[0215] For each proportion (1−r) and each proton (j) of γ-CD, the chemical shift change Dδ j 1-r The calculation formula is:

[0216]

[0217] Then r Dδ i r and (1−r)·Dδ j 1-r Plot r.

[0218] The resulting curve passes through a maximum value, where the r value corresponds to the proportion of the inclusion complex.

[0219] Based on the Job method, the curves shown in Figure 14 were obtained. Figure 14 shows the formation of the γ-CD and NBTPT complex in a 1:1 ratio.

[0220] B8. Conclusion

[0221] The results presented in sections B1 to B7 show that γ-CD and NBTPT can form a complex in a 1:1 ratio, and complete encapsulation can be achieved using liquid-phase preparation and freeze-drying methods. NBTPT encapsulated in γ-CD was found to be stable at high temperatures and remained stable even after heating for 30 minutes.

[0222] In model experiments, NBTPT, NBTPT / γ-CD capsules, and NBTPT / γ-CD capsule-mechanical mixtures all inhibited ammonia volatilization in the soil. In particular, the NBTPT / γ-CD capsule-mechanical mixture showed the highest inhibitory effect. However, the mechanism needs further investigation, such as whether heating enhances the inhibitory effect.

[0223] C. Granulation process

[0224] The cyclodextrin-inhibitor inclusion complex is provided as described above. The cyclodextrin-inhibitor inclusion complex can be moved within a granulator and sprayed with molten urea to produce fertilizer granules. The granulated fertilizer granules typically have a maximum size of approximately 4 mm. The granulation process both thickens the cyclodextrin-inhibitor inclusion complex with urea and dries the fertilizer granules.

[0225] The spraying rate of urea melt can be controlled to control the agglomeration of fertilizer particles.

[0226] Table 9 describes examples of granulation process parameters that can be used.

[0227] Table 9

[0228]

[0229] D. Sample Analysis

[0230] The purity of inhibitors, such as NBTPT and DCD, can be cross-validated using NMR, HPLC, and LCMS analyses.

[0231] A compressive strength analyzer can be used to measure the compressive strength of a portion of the sample to determine the strength of the fertilizer granules.

[0232] The stability of inhibitors in fertilizer granules can be measured using HPLC and LCMS.

[0233] A moisture analyzer can be used to measure the free moisture and total moisture content of fertilizer granules.

[0234] The final fertilizer granules are expected to have the following properties: compressive strength (kgf): 1.68 to 3.60; abrasion analysis (weight loss%): 0.11 to 1.50; impact resistance (broken particles%): 0.05 to 1.20; moisture analysis (weight%): 0.12 to 1; particle size distribution (particles): 2 mm to 4 mm (>90%); biuret content %: 1.05 to 3.8; and nitrogen content %: 36.8 to 46.3.

[0235] Nitrogen volatilization and nitrogen transformation (nitrification) can be measured in various soils and compared with urea alone, urea formulated with inhibitors not encapsulated in a cyclodextrin-inhibitor complex, and commercially available products such as AGROTAIN®, ESN®, and SUPERU®. Representative soils that represent a wider range of soil types can be used to measure nitrogen volatilization and nitrification. Greenville and Crowley soils are two such representative soils. Other soils may also be used in the experiments described herein.

[0236] Greenville soil, or Greenville clay loam, is a typical weathered tropical aging soil found in warm, humid environments. It is classified as fine-textured, kaolinite, thermal red kaolinite moist aging soil with a pH of 6.1 to 6. The soil contains 1.4% organic matter, approximately 0.06% total nitrogen, and has a CEC of 5.2 cmol / kg. Therefore, this soil has low organic matter content and low sulfur and nitrogen availability. Consequently, it is an ideal soil for nitrogen and sulfur testing with fertilizers.

[0237] Crowley soils consist of very deep, poorly drained, and very slow-permeable soils formed in Pleistocene clayey fluvial-marine sediments. These soils are found in nearly horizontal to very gently sloping areas, occurring on flat coastal plain terraces. Slopes are primarily less than 1%, but can reach up to 3%. The area where these soils are found receives an average annual rainfall of approximately 1549 mm (61 inches) and an average annual temperature of approximately 20 degrees Celsius (68 degrees Fahrenheit). The soils are fine-grained, montmorillonite, and thermally typical leached Albaqualfs.

[0238] Compared to AGROTAIN®, ESN®, SUPERU®, urea, and urea containing inhibitors not encapsulated in the cyclodextrin-inhibitor inclusion complex, nitrogen volatilization of various exemplary fertilizer granule samples can be determined as the percentage of nitrogen lost via ammonia volatilization relative to the applied nitrogen amount, or as the absolute mass of nitrogen lost via ammonia volatilization. It is anticipated that embodiments of the fertilizer granules disclosed herein will lose less than 20% by weight of the applied nitrogen amount after 20 days of soil exposure. It is also anticipated that embodiments of the fertilizer granules disclosed herein will lose less than 20% by weight of the applied nitrogen amount after 20 days of exposure to Greenville soil, and less than 20% by weight of the applied nitrogen amount after 20 days of exposure to Crowley soil. It is further anticipated that embodiments of the fertilizer granules disclosed herein, when tested under substantially the same conditions in specific soils, including Greenville soil, Crowley soil, or other soils, will exhibit lower levels of ammonia volatilization and / or nitrogen loss than AGROTAIN®, ESN®, and / or SUPERU®.

[0239] The stability of inhibitors, such as NBTPT, in cyclodextrin-inhibitor inclusion complexes can be monitored by measuring the inhibitor concentration in the cyclodextrin-inhibitor inclusion complex or nitrogen fertilizer granules containing such inclusion complexes after different storage times. This can be performed in a controlled environment to allow for comparison of different formulations. As demonstrated herein, fertilizer granules containing NBTPT in cyclodextrin-inhibitor inclusion complexes are expected to retain at least 90% of NBTPT after 30 days of storage in a sealed container at 22°C. It is expected that within 24 hours of granulation, the remaining NBTPT in the fertilizer granules will be at least 95% relative to the amount added during manufacturing. As demonstrated herein, it is expected that on day 30 after granulation, the remaining NBTPT in the fertilizer granules will be at least 90% relative to the amount added during manufacturing. It is expected that within 24 hours and / or on day 30 after granulation, the weight ratio of NBTPT to all NBTPT degradation products in the fertilizer granules will be at least 10:1. It is expected that the weight ratio of NBTPT to n-butylamine will be at least 20:1 within 24 hours after granulation and / or on day 30 after granulation.

Claims

1. A fertilizer composition comprising: a solidified nitrogen fertilizer melt, the melt comprising one or more cyclodextrin-inhibitor inclusion complexes, the cyclodextrin-inhibitor inclusion complexes comprising at least one cyclodextrin and / or its derivatives in combination with an inhibitor, wherein the inhibitor comprises at least one nitrification inhibitor and / or at least one urease inhibitor, and wherein the one or more cyclodextrin-inhibitor inclusion complexes are uniformly dispersed throughout the solidified nitrogen fertilizer melt.

2. The fertilizer composition according to claim 1, comprising: a continuous phase including the nitrogen fertilizer melt; and a discontinuous phase including one or more cyclodextrin-inhibitor complexes dispersed throughout the continuous phase.

3. The fertilizer composition according to claim 2, wherein one or more cyclodextrin-inhibitor complexes are uniformly dispersed throughout the continuous phase.

4. The fertilizer composition according to any one of claims 2 to 3, wherein the melting temperature of the discontinuous phase comprising the nitrogen fertilizer melt is 140°C or below, preferably 130°C to 135°C.

5. The fertilizer composition according to any one of claims 1 to 3, wherein: The nitrogen fertilizer melt comprises at least 90% by weight of the fertilizer composition, preferably at least 95% by weight, more preferably at least 98% by weight, or even more preferably at least 99% by weight; and the one or more cyclodextrin-inhibitor inclusion complex comprises at most 10% by weight of the fertilizer composition, preferably at most 5% by weight, more preferably at most 2% by weight, or even more preferably at most 1% by weight.

6. The fertilizer composition according to any one of claims 1 and 3, wherein the cyclodextrin-inhibitor inclusion complex is thermally stable at or above 140°C and / or stable in a pH range of 5 to 10.

7. The fertilizer composition according to any one of claims 1 to 3, wherein the cyclodextrin and / or its derivatives comprise α-cyclodextrin, β-cyclodextrin and / or γ-cyclodextrin, preferably γ-cyclodextrin.

8. The fertilizer composition according to any one of claims 1 to 3, wherein the nitrification inhibitor comprises 3,4-dimethylpyrazole phosphate (DMPP), thiourea (TU), dicyandiamide (DCD), 2-chloro-6-(trichloromethyl)pyridine (chlorpyrifos), and 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole (TERRAZOLE). TM ), 2-amino-4-chloro-6-methylpyrimidine (AM), 2-mercaptobenzothiazole (MBT), ammonium thiosulfate (ATS), 2-p-aminobenzenesulfonamide thiazole (ST), or combinations thereof.

9. The fertilizer composition according to any one of claims 1 to 3, wherein the urease inhibitor comprises N-(n-butyl)-thiophosphate triamine, N-(n-butyl)-phosphate triamine, N-(n-propyl)-thiophosphate triamine, benzoylthiourea (BTU), hydroquinone, acetyloxyoxime acid (AHA), hydroxyurea (HU) and / or phenylphosphine diamide (PPDA), preferably N-(n-butyl)-thiophosphate triamine.

10. The fertilizer composition according to any one of claims 1 to 3, wherein: The solidified nitrogen fertilizer melt is a urea fertilizer melt containing urea; and the inhibitor is a urease inhibitor, preferably N-(n-butyl)-thiophosphate triamine.

11. The fertilizer composition according to any one of claims 1 to 3, further comprising a wetting agent, a carrier, a filler, and / or a binder.

12. The fertilizer composition according to any one of claims 1 to 3, wherein the fertilizer composition comprises an inhibitor and a degradation product of the inhibitor in a ratio of 80:20 to 100:0, or wherein the fertilizer composition comprises an inhibitor contained in one or more cyclodextrin-inhibitor inclusion complexes and an inhibitor not complexed with cyclodextrin in a ratio of 80:20 to 100:

0.

13. The fertilizer composition according to any one of claims 1 to 3, wherein the nitrogen fertilizer melt comprises urea.

14. A method for producing a fertilizer composition according to any one of claims 1 to 13, the method comprising: (a) contacting the inhibitor with one or more cyclodextrins and / or their derivatives to generate one or more cyclodextrin-inhibitor inclusion complexes; and (b) contacting the one or more cyclodextrin-inhibitor inclusion complexes with molten nitrogen fertilizer; and (c) solidifying the molten nitrogen fertilizer to form the fertilizer composition, preferably wherein the molten nitrogen fertilizer dissolves the one or more cyclodextrin-inhibitor inclusion complexes such that individual molecules of the complexes are dispersed throughout the molten nitrogen fertilizer, and / or preferably, steps (a) and (b) are performed as a one-pot synthesis and / or a multi-step synthesis, and / or step (b) further includes mixing the one or more cyclodextrin-inhibitor inclusion complexes with the molten nitrogen fertilizer.

15. A method of fertilization, the method comprising contacting soil, plants, water or a combination thereof with a fertilizer composition according to any one of claims 1 to 13, preferably wherein the fertilizer composition is added directly in solid form, and / or the fertilizer composition is added to water before contact with soil, plants or soil and plants.

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