COMBINATIONS OF DICARBOXYLATE AND SULFONATE REPEAT UNIT CONTAINING POLYMERS AND TANNIC ACIDS AND THEIR USES FOR

INHIBITING UREASE

FIELD OF THE INVENTION

[001] The subject matter described herein relates generally to compositions and methods of use of combinations of dicarboxylate and sulfonate repeat unit containing polymers and tannic acids for inhibiting urease.

BACKGROUND

[002] It has long been known to the art of agriculture that application of nitrogen- containing nutrients to growing plants is highly advantageous in enhancing agricultural productivity. Urea by itself and urea-containing compositions of various origin are both of high utility in supplying the nitrogen with the overall goal of enhancing nitrogen nutrient availability to plants. A wide range of such compositions are well known to the art and are used in agricultural context to provide nitrogen as a nutrient to plants. However, due to action of urease enzyme that can be found in various soils and elsewhere, urea-containing nitrogen nutrient products can experience, under certain conditions, very high rates of loss of nitrogen available to the plant.

[003] That is, the vast majority of the nitrogen which is used for fertilization purposes is in the form of urea or urea-comprising fertilizers. Urea itself, however, is a form of nitrogen which is minimally taken up, or not at all, since it is relatively rapidly hydrolyzed in the soil by the ubiquitous enzyme, urease to give ammonia and carbon dioxide (Mobley, H. L. T., Island, M. D., Hausinger, R. P. (1995) Molecular biology of microbial ureases, Microbiol. Rev. 59, 452-480). During this process, gaseous ammonia may be released into the atmosphere and is then no longer available in the soil for the plants, thus reducing the efficacy of the fertilization.

[004] The processes whereby urease enzyme catalyzes relatively rapid decomposition of urea to (among other products) ammonia, which is subsequently lost to the atmosphere is known to the art as volatilization. Volatilization results in a decreased efficiency of nitrogen fertilizer use, decreased yields, plant symptoms of nitrogen deficiency, undesirable odors, harmful ammonia gas concentrations in certain settings, causes need for much greater and more costly amounts of nitrogen fertilizers, creates atmospheric pollution, can cause plant injury (sometimes termed fertilizer burn), can cause undesirable pH changes in soil, and can cause other problems.

[005] Effective urease inhibition has long been sought. The main focus of such efforts from a practical perspective has been the identification and study of urease enzymes, and there has been a continuous effort spanning many decades aimed at finding various ways of inhibiting this enzyme, thus achieving volatilization control. While these efforts have yielded small molecule urease inhibitors, many of the compounds lack stability. Additionally, the compounds and methods must also induce minimal or no damage to plants, be environmentally sensitive, and satisfy a number of other criteria to be considered a practical solution.

[006] It is important to find compounds and methods that are effective, safe, practical and convenient in practice as well as economically favorable. What is therefore needed and addressed by the subject matter described herein are such compositions and methods for inhibiting urease exterior to the plant without impacting urease activity within the plant, thereby improving fertilizer efficiency, which would lead to better plant growth and yields.

SUMMARY OF THE INVENTION

[007] In one aspect, the subject matter described herein is directed to a composition comprising, i) a polyanionic polymer(s) having a plurality of pendant carboxylate and sulfonate groups, and ii) tannic acid.

[008] In one aspect, the subject matter described herein is directed to a composition comprising, i) a polyanionic copolymer(s) having a plurality of pendant carboxylate and sulfonate groups, and ii) tannic acid.

[009] In one aspect, the subject matter described herein is directed to a composition comprising, i) a polyanionic terpolymer(s) having a plurality of pendant carboxylate and sulfonate groups, and ii) tannic acid.

[0010] In one aspect, the subject matter described herein is directed to a composition comprising, i) a polyanionic tetrapolymer(s) having a plurality of pendant carboxylate and sulfonate groups, and ii) tannic acid.

[0011] In another aspect, the subject matter described herein is directed to formulations suitable for use in agriculture, where the formulations comprise, i) a polyanionic polymer(s) having a plurality of pendant carboxylate and sulfonate groups, ii) tannic acid, and iii) a carrier. [0012] In another aspect, the subject matter described herein is directed to formulations suitable for use in agriculture, where the formulations comprise, i) a polyanionic copolymer(s) having a plurality of pendant carboxylate and sulfonate groups, ii) tannic acid, and iii) a carrier.

[0013] In another aspect, the subject matter described herein is directed to formulations suitable for use in agriculture, where the formulations comprise, i) a polyanionic terpolymer(s) having a plurality of pendant carboxylate and sulfonate groups, ii) tannic acid, and iii) a carrier.

[0014] In another aspect, the subject matter described herein is directed to formulations suitable for use in agriculture, where the formulations comprise, i) a polyanionic tetrapolymer(s) having a plurality of pendant carboxylate and sulfonate groups, ii) tannic acid, and iii) a carrier.

[0015] In another aspect, the subject matter described herein is directed to a granular fertilizer comprising, a coated granule comprising a nitrogen fertilizer, wherein the granule is coated with a composition comprising, i) a polyanionic polymer(s) having a plurality of pendant carboxylate and sulfonate groups, and ii) tannic acid.

[0016] In another aspect, the subject matter described herein is directed to a granular fertilizer comprising, a coated granule comprising a nitrogen fertilizer, wherein the granule is coated with a composition comprising, i) a polyanionic copolymer(s) having a plurality of pendant carboxylate and sulfonate groups, and ii) tannic acid.

[0017] In another aspect, the subject matter described herein is directed to a granular fertilizer comprising, a coated granule comprising a nitrogen fertilizer, wherein the granule is coated with a composition comprising, i) a polyanionic terpolymer(s) having a plurality of pendant carboxylate and sulfonate groups, and ii) tannic acid.

[0018] In another aspect, the subject matter described herein is directed to a granular fertilizer comprising, a coated granule comprising a nitrogen fertilizer, wherein the granule is coated with a composition comprising, i) a polyanionic tetrapolymer(s) having a plurality of pendant carboxylate and sulfonate groups, and ii) tannic acid.

[0019] In another aspect, the subject matter described herein is directed to methods of fertilizing a plant the soil in the area of the plant with a composition comprising, i) a polyanionic polymer(s) having a plurality of pendant carboxylate and sulfonate groups, and ii) tannic acid.

[0020] In another aspect, the subject matter described herein is directed to methods of fertilizing a plant the soil in the area of the plant with a composition comprising, i) a polyanionic copolymer(s) having a plurality of pendant carboxylate and sulfonate groups, and ii) tannic acid.

[0021] In another aspect, the subject matter described herein is directed to methods of fertilizing a plant the soil in the area of the plant with a composition comprising, i) a polyanionic terpolymer(s) having a plurality of pendant carboxylate and sulfonate groups, and ii) tannic acid.

[0022] In another aspect, the subject matter described herein is directed to methods of fertilizing a plant the soil in the area of the plant with a composition comprising, i) a polyanionic tetrapolymer(s) having a plurality of pendant carboxylate and sulfonate groups, and ii) tannic acid.

[0023] In another aspect, the subject matter described herein is directed to methods of inhibiting urease by contacting urease with a composition comprising, i) a polyanionic polymer(s) having a plurality of pendant carboxylate and sulfonate groups, and ii) tannic acid.

[0024] In another aspect, the subject matter described herein is directed to methods of inhibiting urease by contacting urease with a composition comprising, i) a polyanionic copolymer(s) having a plurality of pendant carboxylate and sulfonate groups, and ii) tannic acid.

[0025] In another aspect, the subject matter described herein is directed to methods of inhibiting urease by contacting urease with a composition comprising, i) a polyanionic terpolymer(s) having a plurality of pendant carboxylate and sulfonate groups, and ii) tannic acid.

[0026] In another aspect, the subject matter described herein is directed to methods of inhibiting urease by contacting urease with a composition comprising, i) a polyanionic tetrapolymer(s) having a plurality of pendant carboxylate and sulfonate groups, and ii) tannic acid.

[0027] In another aspect, the subject matter described herein is directed to methods of preparing the compositions and formulations.

[0028] These and other aspects are fully described below. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] FIG. 1 is a graph illustrating testing on winter wheat with UAN applied at emergence from spring dormancy. Yield as a % of the fertilized check; 6 reps x 2 locations; LSD at P=0.90. [0030] FIG. 2 is a graph illustrating testing on maize with UAN applied at V4-6 stage as a sidedress. Grain yield as a % of the fertilized check; 5-6 reps across each of 9 locations; LSD calculated at P=0.80.

[0031] FIG. 3 is a graph illustrating testing on maize with urea applied prior to planting. Grain yield as a % of the fertilized check; 6 reps across each of 5 locations; LSD calculated at P=0.80.

DETAILED DESCRIP ION

[0032] The presently disclosed subject matter will now be described more fully hereinafter. However, many modifications and other embodiments of the presently disclosed subject matter set forth herein will come to mind to one skilled in the art to which the presently disclosed subject matter pertains having the benefit of the teachings presented in the foregoing descriptions. Therefore, it is to be understood that the presently disclosed subject matter is not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the appended claims. In other words, the subject matter described herein covers all alternatives, modifications, and equivalents. In the event that one or more of the incorporated literature, patents, and similar materials differs from or contradicts this application, including but not limited to defined terms, term usage, described techniques, or the like, this application controls. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in this field. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety.

[0033] It has been unexpectedly found that combination compositions comprising dicarboxylate and sulfonate repeat unit containing polymers and tannic acids exhibit significantly improved urease inhibition performance in a synergistic fashion. In some embodiments, the polymer can be a copolymer, terpolymer, or tetrapolymer having a plurality of pendant carboxylate and sulfonate groups. The polymer can be, but is not limited to, a random copolymer, alternating copolymer, periodic copolymer, statistical copolymer, block copolymer, gradient copolymer, graft copolymer, or star copolymer. In some embodiments, the polymers contain, for example, a polyanionic terpolymer or tetrapolymer comprising maleic repeat units, itaconic repeat units, and sulfonate- containing repeat units. It is contemplated that other polyanionic polymers can work, provided they contain at least about 1% by mole aliphatic sulfonate pendant groups. However, copolymers of maleic and itaconic acids that do not contain the sulfonate groups do not show such synergistic properties. Furthermore, it has been found that certain aqueous solutions of tannic acid and polymers, in particular copolymers, having a plurality of pendant carboxylate and sulfonate groups, in particular, at low pH where hydrolytic decomposition would be expected, exhibit unexpected levels of stability. Included among useful properties of the combination compositions are: relatively favorable toxicology and health profiles, good water solubility, low volatility, stability over suitable time periods, potential for regulatory compliance, and the use of renewable resources.

[0034] The combination compositions provide synergistic inhibition of urease activity and can inhibit the nitrification processes within soil. In the present compositions, inhibition of urease is focused on the soil and not within the plant. Urease inhibition within the plant is undesirable as it leads to urea accumulation and toxicity. Thus, increased crop yields can be realized owing to the fact that naturally occurring and fertilizer-supplied nitrogen (and phosphate) sources can be more efficiently utilized by plants and that internal urease within the plant is not inhibited. In some embodiments, the combination compositions, formulations and methods provide sustainable agriculture, comprising nutrient use efficiency, especially nitrogen (N)-use efficiency.

[0035] The combination compositions can be applied directly to soil in an aqueous dispersion or solid form and in amounts effective for controlling nitrification, urease activity, and phosphate fixation. The combination compositions can be used in conjunction with solid ammoniacal fertilizer (e.g., urea), or with fluid fertilizers (e.g., gaseous fertilizers or liquid UAN (urea-ammonium nitrate)) containing ammoniacal nitrogen.

[0036] In general, the study of urease enzyme and its inhibition dates back to at least early 1930' s (Biochem J. 1933; 27(4): 1116-1122). The use of catechol, benzoquinone, and related compounds for the inhibition of urease enzyme is known. These compounds were highly effective urease inhibitors under certain conditions at concentrations of about one part per million by weight in solution. However, due to substantial reasons having to do with cost, safety, convenience, stability, and ease of use, many potential compounds do not find use for urease inhibition on a commercial basis in an agricultural context. Significant research has been performed regarding urease inhibition by these classes of small molecule compounds, and they have mostly been found to have urease control effects that are not very long-lived, on the order of 3-14 days. [0037] A number of compounds belonging to the phosphoramide class have also been used as urease inhibitors, either on their own, or as phosphoramide precursors (e.g. thiophosphoramides as relatively inactive precursor that react to become phosphoramides on exposure to air). Some of these materials are used for urease inhibition in an agricultural context. However, they suffer from a number of disadvantages. The compound N-(n-butyl) thiophosphoric triamide (NBPT), a member of phosphoramide class, is widely known to be used for this purpose in a number of products. These compounds are not highly stable, and thus their proper storage is often impractical, costly, or even impossible for some users (e.g. farmers, agricultural product distributors). Typically, manufacturer storage directions for products containing NBPT require storage of such products at temperatures that do not exceed about 36-38 °C. Further, another symptom of the undesirable stability is that when urea is treated with NBPT-based materials, the treated urea's NBPT content rapidly decreases.

[0038] It is highly undesirable to those in agriculture production for fertilizer to rapidly lose its desired properties since it cannot be stored conveniently for a suitable amount of time and have it maintain its intended properties. Product labels also indicate that UAN solutions with NBPT must be used within at most 10 weeks of NBPT addition. This is often highly inconvenient for product sellers, who are thus unable to store treated product for suitable amount of time.

[0039] Another very important NBPT-related problem is that the product is effective for inhibiting urease enzyme inside the plant. While inhibiting undesirable urease activity in soil is desirable, NBPT also inhibits urease in plants. Zanin, et al. (Frontiers in Plant Science, vol. 6, article 1007 (November 19, 2015)); Zanin, et al. (Frontiers in Plant Science, vol. 7, article 845 (June 22, 2016)). It is well known that plants being supplied with urea as a source of nitrogen absorb urea and then use internal urease enzyme in order to utilize it further as a source of nitrogen. When plant urease is inhibited, plant tissues accumulate urea, which is not broken down in the presence of a urease inhibitor. This accumulation of urea is harmful to plants, and can result in severe tissue necrosis, which is a major factor that reduces potential yields of productive agriculture. That is, even when NBPT is successfully used for urease inhibition, this may simultaneously cause plants being treated using prior art to be sufficiently impaired to significantly decrease their yield potential. (Id.) Additionally, this issue is not restricted to NBPT, but to the more general prior art class of phosphoramides. Studies have shown that a different phosphoramide limited accumulation of nitrogen in plant tissues, and caused a decrease in amino acid content of rapeseed roots and shoots. Arkoun, et al. (Plant Soil, 362, 79-97 (2013)).

[0040] Yet another aspect of NBPT and related compound performance that is undesirable is the fact that the effects of the material on urease activity tend to be relatively short-lived, with typical control times being, according to manufacturer directions, about 7-14 days. While the potential urease control is transient, the necrosis is final.

[0041] The ultimate goal of the practice of urease inhibition is improvement in plant crop yield. That is, that either more yield can be achieved using the same amount of nitrogen fertilizer, or yield can be maintained while decreasing fertilizer expenditure, or better yet increasing yield with lower fertilizer expenditure. Therefore, if urease is inhibited but yields are not sufficiently improved in a cost-effective way, a product is of low utility for productive agriculture.

[0042] In general, this is related to improving of nitrogen use efficiency, which is a very important aspect of overall agricultural efficiency improvement. Hendrickson teaches (J. Prod. Agric, 5:131-137 (1992)) that on average, when used with UAN, NBPT gives about 1.6 bushels/acre average improvement in yield (Hendrickson Figure 3), with about 40% of trials resulting in significant yield losses (this being result of 87 trials and 487 comparisons). Considering the additional "all in" cost of using NBPT (which includes purchasing, treating fertilizer, and applying treated fertilizer to the field, or otherwise making nitrogen available to plants in context of productive agriculture), this data indicates a significant need for improved performance in general, and cost/performance in particular in terms of improved yields.

[0043] Additionally, the label on NBPT refers to possible toxic effects on humans. It has long been desired to create urease inhibitors that have better toxicological and health profiles than NBPT and related small molecules, and have better usability, stability on stored treated fertilizer, and are easier to store, transport, and apply. It is further desirable that treatment levels that have been applied to fertilizer not be susceptible to rapid change with time in storage.

[0044] Certain triarylmethane compounds have been previously reported to have some urease inhibiting activity in early 1930's. (Biochem J. 1932; 26(5): 1685- 1696). The use of quinone class of compounds to inhibit urease activity in agricultural context is disclosed in U.S. Patent No. 3,515,532. The patent discloses the use of at least one quinone and at least one polyhydric phenol in compositions comprising said quinone, phenol, and urea in an agricultural context. Catechol and benzoquinone may not have the desired efficacy. J. S. Tomar et al. (Can. J. Soil Sci. 64:51-60 (Feb. 1984).

[0045] There has been a significant interest in use of natural products and derivatives thereof as part of urease inhibiting formulations. A review article by Modolo et al. (Journal of Advanced Research (2015) 6, 35-44) discusses many such candidates. However, it is important to provide greater inhibition of urease at lower concentrations because nitrogen fertilizer treatments that require very high doses to be effective are expensive, difficult to apply, and thus of lower utility in improving nitrogen nutrient utilization efficiency in agriculture.

[0046] Tannic acid is a urease inhibitor. Tannic acid is a class of molecules composed of a number of different naturally occurring compounds derived from plants, and tannins more generally. Use of a range of compositions containing tannic acid as part of plant extracts and a number of other ingredients has been previously taught in EP 0582147 A2, where such compositions are taught as useful urease inhibitors when applied as a cosmetic composition to diaper area. Use of a composition containing tannic acid in a similar application was also disclosed in U.S. Patent No. 6,911,196. However, what is not addressed in such cosmetic applications to skin are teachings pertaining to fertilizer application to soil in the context of agriculture.

[0047] An application of tannic acid with nitrogen fertilizers has been suggested by Gres in U.S. Patent No. 8,211,200, herein incorporated by reference in its entirety, wherein various tannic acids and related compounds are among the materials comprising a controlled release fertilizer composition that is granular in nature and used for slow, controlled release. Another slow release nitrogen fertilizer composition with tannic acid has been suggested by U.S. Patent Appl. Pub. No. 2010/0058822 Al, herein incorporated by reference in its entirety.

[0048] What would be desirable in large scale agricultural use is granular fertilizer that lacks slow or controlled release functionality. The use of slow and or sustained release nitrogen fertilizers can result in suboptimal results since the fertilizer is releasing the same amount at times of peak plant demand for nitrogen and at times when plant demand for nitrogen is low. Yet another aspect of the desired properties would be the ability to apply liquid fertilizers. Disclosed herein are combination compositions useful on in granular and in liquid nitrogen fertilizers that are, preferably, not slow or sustained release. The art does not provide useful means for addressing urease-induced nitrogen loss from these desirable fertilizers. Therefore, there exists a need for a composition that is useful for controlling the deleterious effects of urease enzyme in agriculture and that provides the desirable formulations for large-scale use. Such compositions are described herein and possess a number of unique features, including, but not limited to, for use with traditional nitrogen fertilizers that contain urea and are granular (e.g. various granular urea fertilizers) while lacking slow or sustained release functionality. The combination compositions are effective at enhancing nitrogen efficiency utilization of fertilizer by way of reducing volatilization losses of nitrogen. It is a further object that the combination compositions have a favorable toxicological profile, and contain significant amounts of ingredients derived from renewable resources. I. Definitions

[0049] As used herein, "tannic acid" or "tannin" and the like refers to both condensed and hydrolyzable tannins known to the art. The term includes both single molecules and various mixtures thereof without limitation. The molecules can be extracted from tannin-containing vegetable, plant and forestry products. As is known in the art, the definition by White, Bate-Smith, Swain and Haslam (known as WBSSH definition) describes tannins as molecules that satisfy all of the following requirements: 1) are water-soluble phenolic compounds; 2) have molecular masses between 500 and 4000 Daltons; and 3) possess 12 to 16 phenolic hydroxyl groups and 5 to 7 aromatic rings per 1000 Daltons; and 4) give the usual phenolic reactions, namely the formation of intense blue-black complexes upon treatment with iron(III) salts, and the ability to precipitate gelatin, alkaloids and proteins from solution. It is well known that tannic acid and related compounds contain significant numbers of ester functional groups that serve to bond the different parts of tannic acid and related compounds' molecules together. It is further well known to the art of organic chemistry reactions that such ester groups are susceptible to hydrolysis in the presence of water, and if such hydrolysis were to take place to an appreciable amount, tannic acid would be decomposed to a variety of other molecules.

[0050] In some embodiments, the term "tannic acid" or "tannin" and the like refers to a polyhydric phenol compound forming gallic acid by hydrolysis and is shown by the following chemical formulae I-III:

[0051] Tannic acid molecules may vary depending on parent plants, conditions of plant growth, methods of extraction, etc. As an example, pharmacopoeial tannic acid (Chinesegal lotannin) contains eight gallic acid groups bonded to a glucose residue and on the same plane thereof as shown in a formula II and a further two gallic acid groups are bonded in a vertical direction. J. Shore: J. Soc. Dyers Colorists, 87, 3 (1971). However, the core of the molecule is not necessarily limited to glucose as, in some embodiments, it may be a cellulose based compound. Further, dimer of gallic acid represented by a formula III obtained by hydrolysis of tannic acid can be used as well. Thus, tannic acid is a compound contained widely in plants in nature, and tannic acid includes compounds having partially different chemical structures. Additionally, synthetic tannins can be used in the compositions and methods disclosed herein provided there is a synergistic effect.

[0052] In some embodiments, the tannic acid or tannin comprises pentagalloylglucose, having the following structure, Formula IV:

[0053] Commercial tannic acid preparations comprising pentagalloylglucose are known. In some embodiments, pentagalloylglucose comprises about 90%, about 91%, about 92%, about 93%, about 94%, about 95%, about 96%, about 97%, about 98%, about 99% or about 100% of the tannic acid composition to be used in the combinations described herein. In some embodiments, the pentagalloylglucose is present in a range including and/or spanning the aforementioned values.

[0054] In some embodiments, the polyanionic species comprises a polyanionic polymer having a plurality of pendant carboxylate and sulfonate groups. The polyanionic polymer can be, but is not limited to, a copolymer having a plurality of pendant carboxylate and sulfonate groups, a terpolymer having a plurality of pendant carboxylate and sulfonate groups, or a tetrapolymer having a plurality of pendant carboxylate and sulfonate groups. As used herein, a copolymer contains two or more different repeat units. As used herein, a terpolymer contains three or more different repeat units. As used herein, a tetrapolymer contains four or more different repeat units. The polymer can be, but is not limited to, a random copolymer, alternating copolymer, periodic copolymer, statistical copolymer, block copolymer, gradient copolymer, graft copolymer, or star copolymer.

[0055] In some embodiments, the polyanionic polymer comprises a dipolymer having two repeating units wherein one of repeating units contains a carboxylate group and the other repeating unit contains a sulfonate group. In some embodiments, the polyanionic polymer comprises a terpolymer having three or more repeating units wherein at least one of the repeating units contains a carboxylate group and at least one of the repeating units contains a sulfonate group. In some embodiments, the polyanionic polymer comprises a tetrapolymer wherein at least one of the repeating units contains a carboxylate group and at least one of the repeating units contains a sulfonate group. In some embodiments, the polyanionic polymer comprised a tetrapolymer wherein with at least one repeating unit is a maleic repeat unit, at least one or the repeating units is an itaconic repeat unit, and at least one of the repeating units contains a sulfonate group.

[0056] In some embodiments, a polyanionic polymer comprises a copolymer comprising the structure represented by: poly(Aa-co-Bb-co-Cc-co-Dd)

wherein A is a first repeat unit containing a carboxylate group, B is a second repeat unit containing a sulfonate group, C is optional and if present is a third repeat unit, and D is optional and if present is fourth repeat unit. Repeat units C and D may be charged or uncharged and, if charged, can contain carboxylate or sulfonate groups, a and b are independently integers greater than or equal to 1. c and d are independently integers greater than or equal to zero. In some embodiments, a polyanionic polymer can contain additional repeat units. In some embodiments, A is a maleic repeat unit. In some embodiments, C is an itaconic repeat unit. In some embodiments, B is a methallylsulfonate-containing repeat unit. In some embodiments, D is an allylsulfonate- containing repeat unit.

[0057] As used herein, a tetrapolymer refers to a polyanionic tetrapolymer(s) that contain monomers having a sulfonate moiety and at least three and optionally more repeat units per molecule (preferably from about 10-500). These polymers include those described as Class I polymers in U.S. Patent Pub. Nos. 2016/0174549 Al and 2017/0183492 Al, each of which is herein incorporated by reference in its entirety. Tetrapolymers include partial or complete salts of the polymers. Terpolymers include dicarboxylate and sulfonate repeat unit containing polymers include the polymers described as Class IA polyanionic polymers in U.S. Patent Pub. No. 2017/0183492 Al, herein incorporated by reference in its entirety.

[0058] As used herein, "T5" refers to a tetrapolymer or a partial sodium salt thereof having a pH of about 1, with a repeat unit molar composition of maleic at about 45 mole percent, itaconic at about 50 mole percent, methallylsulfonate at about 4 mole percent, and allylsulfonate at about 1 mole percent. In some embodiments, variants of the T5 polymer include mixed sodium and zinc partial salts having about 5% w/w Zn on a metals basis and with a pH of about 3. In some embodiments, the T5 polymer is made by reacting the T5 tetrapolymer with basic zinc carbonate in water. In some embodiments, the polymer may be made by reaction with zinc metal.

[0059] As used herein, "inhibit urease," "urease inhibition" and similar terms refer to a decrease in the activity of urease, as compared to the activity of urease in the absence of an inhibitory composition or as compared to the activity of urease in the presence of individual components of the combination compositions described herein. In some embodiments, the term "inhibit" means a decrease in urease activity of at least about 5%, at least about 6%, at least about 7%, at least about 8%, at least about 9%, at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, or at least about 95%. In other embodiments, inhibit means a decrease in urease activity of about 5% to about 25%, about 25% to about 50%, about 50% to about 75%, or about 75% to 100%. In some embodiments, inhibit means a decrease in urease activity of about 95% to 100%, e.g., a decrease in activity of 95%, 96%, 97%, 98%, 99%, or 100%. In some embodiments, the inhibition occurs in a range including and or spanning the aforementioned values. Such decreases can be measured using a variety of techniques that would be recognizable by one of skill in the art, including in vitro enzyme assays.

[0060] The term "nitrogen-use efficiency" refers technically to the mass of agriculture produce per unit nitrogen consumed and economically to the value of product(s) produced per unit nitrogen consumed, reflecting uptake and utilization efficiency. [0061] As used herein, "ammoniacal nitrogen" is a broad term embracing fertilizer compositions containing ammoniacal nitrogen (NH4) as well as fertilizer compositions and other compounds which are precursors of ammoniacal nitrogen or that cause ammoniacal nitrogen to be generated when the fertilizers or compounds undergo various reactions such as hydrolysis. As a non-limiting example, the polyanionic polymers, e.g., tetrapolymers, described herein may be applied to or mixed with urea or other nitrogen-containing fertilizers which have no ammoniacal nitrogen as such. However, such fertilizers will undergo reactions in the soil to generate ammoniacal nitrogen in situ. Nitrogen fertilizers include ammoniacal nitrogen fertilizers and urea or other precursor nitrogen-containing fertilizers.

[0062] The term "synergistic effect" means that urease inhibitory activity is increased to an extent greater than that resulting from an additive effect. An additive effect is the expected effect due to each active compound acting individually. A synergistic effect occurs to a significantly greater degree than an additive effect. The expected activity for a given combination of two active compounds can be calculated as follows (cf. Colby, S. R., "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations", Weeds 15, pages 20-22, 1967). The synergistic effect of the active ingredient combination used in accordance with the embodiments allows the total application rate of the substances to achieve the same effect to be reduced.

[0063] As used herein, "plant" and "crop plant" includes cereals (such as wheat, barley, rye, triticale, sorghum/millet and oats), maize, soya, rice, potatoes, cotton, oilseed rape and fruit species (with the fruits apples, pears, citrus fruit and grapes) sunflower, bean, coffee, beet (for example sugar beet and fodder beet), peanut, oilseed rape, poppy, olive, coconut, cocoa, sugar cane, tobacco, vegetables (such as tomato, cucumbers, onions and lettuce), turf and ornamentals. Plants of interest include plant species grown for the purposes of providing animal nutrition, including but not limited to various grasses and leguminous plants known to the art of animal nutrition. Such plants may either be harvested in various ways known to the art and subsequently used for animal nutrition, or the plants may be consumed (in whole or in part) by animals while the plants are still growing, or while they are still attached to soil. Plants of interest also include any plant used in productive agriculture and needing a nitrogen nutrient supply as these plants would benefit from the compositions described herein. Transgenic plants are also included. [0064] By the term "contact" or "contacting" it is intended to allow the compositions and formulations to come in physical communication with the soil adjacent or in the vicinity of the plant. Contacting can be by any conventional means.

[0065] The term "stable" or "stability" refers to a composition or component of a composition that does not substantially produce degradation products under control conditions for certain periods of time.

[0066] As used herein, a "formulation that does not contain sustained release functionality" and similar terms means that the formulation does not contain excipient or additive levels that function to appreciably extend or sustain the release of fertilizer from the formulation. Those of skill in this field are well aware of the components and properties of sustained release fertilizers.

[0067] As used herein, the term "adjacent" means near, in the vicinity, proximal and the like. A combination composition applied in an area adjacent to a plant would deliver effective urease inhibition in the area to affect the plant.

[0068] Additional definitions are set forth herein below.

II. Combination Products

[0069] In some embodiments, the subject matter described herein is directed to compositions, also referred to herein as combination compositions, comprising i) a polyanionic polymer(s) having a plurality of pendant carboxylate and sulfonate groups , and ii) tannic acid. The polyanionic polymer can be a copolymer, terpolymer, or tetrapolymer. Exemplary polymers include, but are not limited to, the polymers described as Class I and IA polymers in U.S. Patent Pub. Nos. 2016/0174549 Al and 2017/0183492 Al, each of which is herein incorporated by reference in its entirety.

[0070] In some embodiments, the subject matter described herein is directed to compositions comprising, i) a polyanionic polymer comprising a maleic-itaconic copolymer and sulfonate repeat units; and ii) tannic acid.

[0071] In some embodiments, the polyanionic polymer and the tannic acid are present in synergistic amounts. In some embodiments, compositions include those where the polyanionic polymer and tannic acid are present in a ratio of from about 5:1 to about 1:5; or from about 4:1 to about 1:4; or about 1.5:4; or about 2:3; or about 3:2; or about 4:1.5; or about 4:1. Useful ratios in compositions also include ratios of 4.5:1; 4:1; 3.5:1; 3:1; 2.5:1; 2:1; 1.5:1; 1:1; 1:1.5; 1:2; 1:2.5; 1:3; 1:3.5; 1:4 and 1:4.5. In some embodiments, the weight ratios may range from 99:1 to 1:99 (or 99:1, 98:2, 97:3, 96:4, 95:5, 94:6, 93:7, 92:8, 91:9, 90:10, 89:11, 88:12, 87:13, 86:14, 85:15, 84:16, 83:17, 82:18, 81:19, 80:20, 79:21, 78:22, 77:23, 76:24, 75:25, 74:26, 73:27, 72:28, 71:29, 70:30, 69:31, 68:32, 67:33, 66:34, 65:35, 64:36, 63:37, 62:38, 61:39, 60:40, 59:41, 58:42, 57:43, 56:44, 55:45, 54:46, 53:47, 52:48, 51:49, 50:50, 49:51, 48:52, 47:53, 46:54, 45:55, 44:56, 43:57, 42:58, 41:59, 40:60, 39:61, 38:62, 37:63, 36:64, 35:65, 34:66, 33:67, 32:68, 31:69, 30:70, 29:71, 28:72, 27:73, 26:74, 25:75, 24:76, 23:77, 22:78, 21:79, 20:80, 19:81, 18:82, 17:83, 16:84, 15:85, 14:86, 13:87, 12:88, 11:89, 10:90, 9:91, 8:92, 7:93, 6:94, 5:93, 4:96, 3:97, 2:98 or 1:99). In some embodiments, the ratios occur in a range including and/or spanning the aforementioned values.

[0072] In some embodiments, polyanionic polymers include the following repeat units: maleic at about 30-55 mole percent, or about 40-50 mole percent, or about 45 mole percent; itaconic at about 35-65 mole percent, or about 40-60 mole percent, or about 50 mole percent; methallylsulfonic at about 1-7 mole percent, or about 3-6 mole percent, or about 4 mole percent; and allylsulfonic at about 0.1-3 mole percent, or about 0.5-2 mole percent, or about 1 mole percent. This type of polymer is typically produced as a partial alkali metal salt (preferably sodium) at a pH of from about 0.2-3, or from about 0.3-2, or about 1. In some embodiments, the polymer of this type is a partial sodium salt having a pH of about 1, with a repeat unit molar composition of maleic 45 mole percent, itaconic 50 mole percent, methallylsulfonic 4 mole percent, and allylsulfonic 1 mole percent. This specific polymer is referred to herein as the "T5" polymer. Other useful polyanionic polymers include those where the polyanionic polymer comprises from about 48% to about 52% itaconic repeat units. Useful polyanionic polymers also include those where the polyanionic polymer comprises from about 43% to about 47% maleic repeat units. Useful polyanionic polymers include those where the polyanionic polymer comprises from about 3% to about 7% sulfonate repeat. Useful polyanionic polymers include those where the polyanionic polymer comprises from about 50% itaconic repeat units, about 45% maleic repeat units, and about 5% sulfonate repeat units. In some embodiments, the polyanionic polymer is a terpolymer or tetrapolymer.

[0073] The sulfonate repeat unit can be, but is not limited to, a methallylsulfonate or an allylsulfonate. In some embodiments, the polyanionic polymer comprises a methallylsulfonate, an allylsulfonate or both. In some embodiments, the polyanionic polymer comprises about 50% itaconic repeat units, about 45% maleic repeat units, about 4% methallylsulfonate repeat units, and about 1% allylsulfonate repeat units. When both methallylsulfonate and allylsulfonate are present, the methallylsulfonate and allylsulfonate components can be present in a ratio of about 5:1, 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, or 1:5, methallylsulfonate to allylsulfonate. In some embodiments, the ratios occur in a range including and/or spanning the aforementioned values.

[0074] The combination composition includes tannic acid as described above. In some embodiments, the tannic acid is a commercially available ACS grade tannic acid. In some embodiments, the tannic acid is a powder. In some embodiments, the tannic acid comprises pentagalloylglucose.

[0075] In some embodiments, the pH of the aqueous solutions of combination compositions should be acidic, for example, below a pH of about 5, below a pH of about 4.5, below a pH of about 4.0, below a pH of about 3.5, below a pH of about 3.0, below a pH of about 2.5, below a pH of about 2.0, below a pH of about 1.5, such as pH of about 1.0. To control pH, the combination compositions may optionally comprise ingredients that control pH of the combination compositions used for treating fertilizer, or even the pH of liquid aqueous nitrogen containing fertilizers. In some embodiments, the pH of the solution is present in a range including and/or spanning the aforementioned values.

[0076] The polymers taught herein can be used in any suitable form, either as acids, or as various salts.

[0077] As a result of the improvement in nitrogen efficiency or phosphate fixation after application of the combination compositions, the combination compositions can provide increased yield. Increased yield can refer to total biomass per hectare, yield per hectare, kernel/fruit weight, seed size and/or hectoliter weight as well as to increased product quality, comprising: improved processability relating to size distribution (kernel, fruit, etc.), homogenous riping, grain moisture, better milling, better vinification, increased juice yield, harvestability, digestibility, sedimentation value, falling number, pod stability, storage stability, improved fiber length/strength/uniformity, increase of milk and/or meat quality of silage fed animals; further comprising improved marketability relating to improved fruit/grain quality, size distribution (kernel, fruit, etc.), increased storage/shelf- life, firmness/softness, taste (aroma, texture, etc.), grade (size, shape, number of berries, etc.), number of berries/fruits per bunch, crispness, freshness, coverage with wax, frequency of physiological disorders, color, etc.; further comprising increased desired ingredients such as e.g. protein content, fatty acids, oil content, oil quality, amino acid composition, sugar content, acid content (pH), sugar/acid ratio (Brix), polyphenols, starch content, nutritional quality, gluten content/index, energy content, taste, etc.; and further comprising decreased undesired ingredients such as e.g. less mycotoxines, less aflatoxines, geosmin level, phenolic aromas, lacchase, polyphenol oxidases and peroxidases, nitrate content, etc.

[0078] The combination compositions can contain further additives as described elsewhere herein, and can be formulated in any useful formulation.

III. Formulations

[0079] Formulated products containing the various embodiments disclosed herein can, in addition to urease inhibiting component(s), contain additional useful ingredients known to the art, such as solvent(s), colorant(s), coating performance enhancement additive(s) of various types, dust control additives, and other additives that are useful in the context of agriculture, including but not limited to pesticides, plant nutrients, and the like. The formulated products can be in form of solids, solutions, and any other materials known to the art. Any method of providing mixtures, coatings, and other compositions containing urease inhibitors taught herein that are agriculturally useful is within the scope of the present disclosure. Exemplary formulations and additives are described in U.S. Patent Appl. Pub. No. 2016/0272553, herein incorporated by reference in its entirety.

[0080] Examples of such uses would include application of various solutions containing combination compositions taught herein with optional other ingredients, e.g. solvent(s), colorants, film formers, dust control additives, other urease inhibitors, etc. to granular solids that are useful sources of nitrogen in agricultural context. An example of such a solid can be granular urea. The products of such application would be coated, or impregnated, or other agriculturally useful products that contain combination compositions taught herein. Other examples would include providing mixtures of combination compositions taught herein with optional other ingredients, e.g. solvent(s), colorants, other urease inhibitors, etc. with fluid nitrogen sources in agricultural context. An example of such a fluid can be product known to the art as UAN, or urea-ammonium nitrate aqueous solution.

[0081] Formulations comprising a polyanionic polymer(s), having a plurality of pendant carboxylate and sulfonate groups, and tannic acid can be in any useful form. Depending on their desired physical and/or chemical properties, formulations can be in the form of liquids, solids, capsule suspensions, concentrates, encapsulated granules, fine granules, flowable concentrates, ready-to-use solutions, dustable powders, emulsifiable concentrates, oil-in-water emulsions, water-in-oil emulsions, macrogranules, microgranules, oil-dispersible powders, oil-miscible flowable concentrates, oil-miscible liquids, foams, pastes, soluble concentrates, microemulsion, oil-based suspension concentrate, suspension concentrate, and dispersible concentrate. In some embodiments, the formulation is an emulsifiable concentrate or a soluble concentratesuspension concentrates, soluble concentrates, suspensions, wettable powders, soluble powders, dusts and granules, water-soluble and water-dispersible granules or tablets, water-soluble and water-dispersible powders, wettable powders, microencapsulations in polymeric substances and in coating materials. For purposes of the present disclosure, "ready-to- use" refers to compositions that are not in a concentrate form but rather which may be applied without modification of the relative amounts of components within the product. In some embodiments, compositions and formulations are provided in concentrates for end- use tank-mixing. Customary applications are, for example, dilution in water and subsequent spraying of the resulting spray liquid, application after dilution in oil, or direct application without dilution.

[0082] In some embodiments, the subject matter described herein is directed to compositions comprising; i) a polyanionic polymer(s) having a plurality of pendant carboxylate and sulfonate groups; ii) tannic acid, and iii) at least one agriculturally acceptable carrier, which can be a solvent as described elsewhere herein, e.g., water. In some embodiments, the composition comprises: i) a polyanionic polymer, such as a terpolymer or tetrapolymer, comprising about 48 to about 52% maleic repeat units, about 43 to about 47% itaconic repeat units, and about 3 to about 7% sulfonate repeat units; ii) tannic acid; and iii) at least one agriculturally acceptable carrier. In some embodiments, the composition comprises: i) a polyanionic polymer, such as a terpolymer or tetrapolymer, comprising about 50% maleic repeat units, 45% itaconic repeat units, and about 5% sulfonate repeat units; ii) tannic acid comprising pentagalloylglucose; and iii) at least one agriculturally acceptable carrier. In some embodiments, the polymer, such as a terpolymer or tetrapolymer, and the tannic acid are present in a ratio of about 4:1 to about 1 :4. In some embodiments, the polymer, such as a terpolymer or tetrapolymer, and the tannic acid are present in a ratio of about 2:3.

[0083] In some embodiments, the compositions can be combined with urea fertilizers selected from solid, liquid, granular, UAN, e.g., 28-0-0, and 32-0-0 fertilizers. Accordingly, in some embodiments, the subject matter described herein is directed to compositions comprising; i) a polyanionic polymer(s) having a plurality of pendant carboxylate and sulfonate groups; ii) tannic acid, iii) a fertilizer, and optionally iv. at least one agriculturally acceptable carrier, which can be a solvent as described elsewhere herein, e.g., water.

[0084] In some embodiments, the composition is in the form of a granular fertilizer composition comprising, a coated granule comprising a nitrogen fertilizer, wherein the granule is coated with a composition comprising; i) a polyanionic polymer(s) having a plurality of pendant carboxylate and sulfonate groups; ii) tannic acid. In some embodiments, the coating can comprise a combination composition as discussed elsewhere herein; and the fertilizer is selected from fertilizers described elsewhere herein.

[0085] The amount of coating can be from about 0.02 mL solution to about 20 mL solution per about 80 g to about 120 g granules of fertilizer. The amount of coating preferably is sufficient to provide a continuous or semi-continuous coat over the granule and/or provide an effective amount of urease inhibition at a desired dose.

[0086] In some embodiments, the fertilizer composition does contain sustained release functionality. In some embodiments, the fertilizer composition is stable for at least 1 month at room temperature. In some embodiments, the fertilizer composition is stable for at least 2 months, or at least 3 months, or at least 4 months, or at least 5 months, or at least 6 months at room temperature.

[0087] The pH of the formulation is preferably acidic. In some embodiments, the pH is selected from the group consisting of below about 7, below about 6, below about 5, below about 4, below about 3, below about 2, below about 1, and about 1.

[0088] In some embodiments, a carrier is or includes one or more solvents. Suitable organic solvents include all polar and non-polar organic solvents usually employed for formulation purposes. Solvents can be, but are not limited to, ketones, e.g. methyl-isobutyl-ketone and cyclohexanone, amides, e.g. dimethyl formamide and alkanecarboxylic acid amides, e.g. N,N-dimethyl decaneamide and N,N-dimethyl octanamide, furthermore cyclic solvents, e.g. N-methyl-pyrrolidone, N-octyl-pyrrolidone, N-dodecylpyrrolidone, N-octyl-caprolactame, N-dodecyl-caprolactame and butyrolactone, furthermore strong polar solvents, e.g. dimethylsulfoxide, and aromatic hydrocarbons, e.g. xylol, SOLVESSO™, mineral oils, e.g. white spirit, petroleum, alkyl benzenes and spindle oil, also esters, e.g. propyleneglycol-monomethylether acetate, adipic acid dibutylester, acetic acid hexylester, acetic acid heptylester, citric acid tri-n-butylester and phthalic acid di-n-butylester, and also alcohols, e.g. benzyl alcohol and l-methoxy-2-propanol. Useful liquid solvents are essentially: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or dichloromethane, aliphatic hydrocarbons such as cyclohexane or paraffins, for example mineral oil fractions, mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulphoxide, and also water. The solvent can be present in an amount of from about 1% to about 99% w/w, for example, about 5% to about 75%, or about 15% to about 70%, or about 25% to about 65%, or about 35% to about 60%, or about 40% to about 55%, or about 45% to about 50%. In some embodiments, the solvent is water.

[0089] Formulations can include carriers and fillers. A carrier is a natural or synthetic, organic or inorganic substance for admixing or combining with the compositions for better applicability, including, but not limited to, for application to plants or plant parts. The carrier, which may be solid or liquid, is generally inert and should be suitable for use in agriculture. Useful solid or liquid carriers include: for example ammonium salts and natural rock dusts, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic rock dusts, such as finely divided silica, alumina and natural or synthetic silicates, resins, waxes, solid fertilizers, water, alcohols, especially butanol, organic solvents, mineral and vegetable oils, and derivatives thereof. Mixtures of such carriers can likewise be used.

[0090] Suitable solid filler and carrier include inorganic particles, e.g. carbonates, silicates, sulphates and oxides with an average particle size of between 0.005 and 20 μιη, preferably of between 0.02 to 10 μιη, for example ammonium sulphate, ammonium phosphate, urea, calcium carbonate, calcium sulphate, magnesium sulphate, magnesium oxide, aluminum oxide, silicium dioxide, so-called fine-particle silica, silica gels, natural or synthetic silicates, and alumosilicates and plant products like cereal flour, wood powder/sawdust and cellulose powder.

[0091] Useful solid carriers include, for example: crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite, and synthetic granules of inorganic and organic meals, and also granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks.

[0092] Formulations can include other additional components, for example protective colloids, binders, extenders, adhesives, tackifiers, thickeners, thixotropic substances, penetrants, stabilizers, sequestrants, surfactants, complexing agents, etc. In general, the compositions can be combined with any solid or liquid additive commonly used for formulation purposes.

[0093] In the formulations, it is possible to use tackifiers such as carboxymethylcellulose, and natural and synthetic polymers in the form of powders, granules or lattices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids. Further additives may be mineral and vegetable oils. If the extender used is water, it is also possible to employ, for example, organic solvents as auxiliary solvents.

[0094] The formulations may additionally comprise surfactants. Useful surfactants are emulsifiers and/or foam formers, dispersants or wetting agents having ionic or nonionic properties, or mixtures of these surfactants. Examples of these are salts of polyacrylic acid, salts of lignosulphonic acid, salts of phenolsulphonic acid or naphthalenesulphonic acid, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (preferably alkylphenols or arylphenols), salts of sulphosuccinic esters, taurine derivatives (preferably alkyl taurates), phosphoric esters of polyethoxylated alcohols or phenols, fatty esters of polyols, and derivatives of the compounds containing sulphates, sulphonates and phosphates, for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates, protein hydrolysates, lignosulphite waste liquors and methylcellulose. The presence of a surfactant is necessary if one of the active ingredients and/or one of the inert carriers is insoluble in water and when application is effected in water. The proportion of surfactants is between 5 and 40 percent by weight of the composition.

[0095] Suitable surfactants (adjuvants, emulsifiers, dispersants, protective colloids, wetting agent and adhesive) include all common ionic and non-ionic substances, for example ethoxylated nonylphenols, polyalkylene glycolether of linear or branched alcohols, reaction products of alkyl phenols with ethylene oxide and/or propylene oxide, reaction products of fatty acid amines with ethylene oxide and/or propylene oxide, furthermore fattic acid esters, alkyl sulfonates, alkyl sulphates, alkyl ethersulphates, alkyl etherphosphates, arylsulphate, ethoxylated arylalkylphenols, e.g. tristyryl-phenol- ethoxylates, furthermore ethoxylated and propoxylated arylalkylphenols like sulphated or phosphated arylalkylphenol-ethoxylates and -ethoxy- and -propoxylates. Further examples include, but are not limited to, natural and synthetic surfactants, water soluble polymers (e.g. lignosulphonates, gelatine, gum arabic, phospholipides, starch, hydrophobic modified starch, cellulose derivatives, cellulose ester and cellulose ether), polyvinyl alcohol, polyvinyl acetate, polyvinyl pyrrolidone, polyacrylic acid, polymethacrylic acid, co- polymerisates of (meth)acrylic acid and (meth)acrylic acid esters, co-polymerisates of methacrylic acid and methacrylic acid esters which are neutralized with alkalimetal hydroxide, and condensation products of optionally substituted naphthalene sulfonic acid salts with formaldehyde.

[0096] As used herein, the term "alkyl" refers to a fully saturated aliphatic hydrocarbon group. The alkyl moiety may be branched or straight chain. Examples of branched alkyl groups include, but are not limited to, iso-propyl, sec-butyl, t-butyl and the like. Examples of straight chain alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl and the like.

[0097] As used herein, "aryl" refers to a carbocyclic (all carbon) monocyclic or multicyclic (such as bicyclic) aromatic ring system (including fused ring systems where two carbocyclic rings share a chemical bond) that has a fully delocalized pi-electron system throughout all the rings. The number of carbon atoms in an aryl group can vary. For example, the aryl group can be a C ₆ -C ₁₄ aryl group, a C ₆ -Cio aryl group or a C ₆ aryl group. Examples of aryl groups include, but are not limited to, benzene, naphthalene and azulene. An aryl group may be substituted or unsubstituted.

[0098] The formulations may comprise colorants and dyes. Dyes include inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyes such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

[0099] Antifoams which may be present in the formulations include e.g. silicone emulsions, long-chain alcohols, fatty acids and their salts as well as fluoroorganic substances and mixtures thereof.

[0100] Thickeners include polysaccharides, e.g. xanthan gum or veegum, silicates, e.g. attapulgite, bentonite as well as fine-particle silica.

[0101 ] The amounts of active ingredients in the compositions and formulations are generally between 0.05 and 99% by weight, 0.01 and 98% by weight, preferably between 0.1 and 95% by weight, more preferably between 0.5 and 90% of active ingredients, most preferably between 10 and 70% by weight. Depending on the formulation and desired route of application, one of ordinary skill in the art can determine appropriate amounts of active ingredients and additives, and the amount of active ingredient(s) and additive(s) in the formulations may vary in a broad range. The concentration of the active ingredients in the application forms is generally between 0.000001 to 95% by weight. [0102] As described elsewhere herein, the formulations mentioned can be prepared in a manner known, for example by mixing the active ingredients with at least one customary extender, solvent or diluent, adjuvant, emulsifier, dispersant, and/or binder or fixative, wetting agent, water repellent, if appropriate desiccants and UV stabilizers and, if appropriate, dyes and pigments, antifoams, preservatives, inorganic and organic thickeners, adhesives, gibberellins and also further processing auxiliaries and also water. Depending on the formulation type to be prepared further processing steps are necessary, e.g. wet grinding, dry grinding and granulation.

[0103] The formulations can include other known active ingredients, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, growth regulators, herbicides, fertilizers, and the like.

IV. Methods

[0104] The methods described herein involve treatment of urease enzyme and areas that contain urease.

[0105] In some embodiments, the subject matter described herein is directed to a method of inhibiting urease, comprising contacting urease with an effective amount of a composition comprising, i) a polyanionic polymer(s) having a plurality of pendant carboxylate and sulfonate groups; and ii) tannic acid.

[0106] In some embodiments, the subject matter described herein is directed to a method of inhibiting urease, comprising contacting an area containing urease, such as soil, with an effective amount of a composition comprising, i) a polyanionic polymer(s) having a plurality of pendant carboxylate and sulfonate groups; and ii) tannic acid. In some embodiments, the soil is adjacent to or near a plant, such as, a crop plant.

[0107] In some embodiments, the subject matter described herein is directed to a method of fertilizing a plant, comprising contacting an area adjacent to the plant containing urease with an effective amount of a composition comprising, i) a polyanionic polymer(s) having a plurality of pendant carboxylate and sulfonate groups; ii) tannic acid, and iii) a fertilizer. In some embodiments, the area adjacent to the plant is soil near the plant, which can be a crop plant.

[0108] When the combination compositions are used in the form of aqueous dispersions in intimate contact with or dispersed in nitrogen fertilizers, the product is typically applied to soil adjacent growing plants or pre-applied to soils subject to nitrification. Aqueous polymer mixtures are typically used with liquid and dry fertilizers at relatively low levels up to about 2% by volume (e.g., 0.01-2% by volume) based upon the total volume of the liquid fertilizer material taken as 100% by volume. In such uses, it is also preferred that the pH levels should be acidic, for example, below about 3, more preferably below about 2, and most preferably below or at about 1. Moreover, such aqueous dispersions advantageously contain from about 10-85% by weight solids, more preferably from about 30-65% by weight solids, and most preferably about 40% by weight solids.

[0109] An effective amount of the combination composition is an inhibitory amount as measured by the percentage of urease inhibition. The inhibition can be a percentage as described elsewhere herein. In some embodiments, the dose of tannic acid in the combination compositions as measured by ppm is from about 0.5 to about 50 ppm. These doses include from about 1.0 to about 40 ppm; from about 2.0 to about 20 ppm; from about 3.0 to about 10 ppm; from about 4 to about 6 ppm; and about 5 ppm. Many such doses are considered suboptimal doses of tannic acid, but when applied in a combination composition have been shown to provide excellent inhibition.

[0110] In some embodiments of these methods, compositions comprise: i) a polyanionic polymer comprising about 48 to about 52% maleic repeat units, about 43 to about 47% itaconic repeat units, and about 3 to about 7% sulfonate repeat units; ii) tannic acid; and iii) at least one agriculturally acceptable carrier. In some embodiments, compositions comprise: i) a polyanionic polymer comprising about 50% maleic repeat units, 45% itaconic repeat units, and about 5% sulfonate repeat units; ii) tannic acid comprising pentagalloylglucose; and iii) at least one agriculturally acceptable carrier. In some embodiments, the polymer and the tannic acid are present in a ratio of about 4: 1 to about 1 :4. In some embodiments, the polymer and the tannic acid are present in a ratio of about 2:3.

[011 1] The methods generally include contacting plant surroundings, by any customary treatment methods, for example by dipping, spraying, atomizing, irrigating, evaporating, dusting, fogging, broadcasting, foaming, painting, spreading-on, watering (drenching), drip irrigating and, in the case of propagation material, slurry treatment, incrustation, coating with one or more coats, etc. It is also possible to deploy the compositions or formulations by the ultra-low volume method or to inject the compositions or formulations into the soil. In some embodiments, the methods can be used on soil by placing, dropping, spreading, spraying, broadcasting, deep or sub-surface placement, localized placement, contact, band, hill, and row placement, knife-in, etc. and any other method. Also contemplated are treatment of above-ground parts of plants, of propagation stock, and of the soil. The soil may be in the area near or adjacent, i.e., vicinity, to a plant of interest, such as a crop plant.

[0112] When using the combination compositions and formulations, the application rates can be varied within a relatively wide range, depending on the kind of application and the crop. The application rate of the mixtures or compositions in the case of treatment of soil can be from 0.1 to 10,000 g/ha, preferably from 1 to 5000 g/ha, but also including from 10 to 1,000 g/ha, or 10 to 800 g/ha, or from 50 to 300 g/ha (in the case of application by watering or dripping, it is even possible to reduce the application rate, especially when inert substrates such as rockwool or perlite are used). In some embodiments, the combination composition products are applied at a level so that the amount of polymer applied is from about 10-150 g polymer per acre of soil, more preferably from about 30-125 g polymer per acre, and still more preferably from about 40- 120 g polymer per acre of soil. The application rates can be measured in fluid ounces as well. These application rates are merely by way of example and are not limiting as one of ordinary skill in this field can adjust the application rates as desired.

[0113] The methods of treatment provide contacting, i.e., use or application of the combination compositions and fertilizers together can be in a simultaneous, separate or sequential manner. That is, the combination compositions can be used to condition the soil prior to fertilizer application in a sequential manner, i.e. at different times, though they are to be applied one after the other within a reasonably short period, such as a few hours or days.

[0114] In some embodiments, the plant is a crop as described elsewhere herein. In some embodiments, the crop is selected from the group consisting of cereals (wheat, barley, oats, triticale, rye, and rice), maize, soya beans, potatoes, vegetables, peanuts, cotton, oilseed rape and fruit plants. In some embodiments, the crop is maize.

[0115] In some embodiments, the subject matter disclosed herein is directed to a method of increasing the yield of a crop comprising, applying to soil in the vicinity of the plant or in the area of future planting a composition comprising; i) a polyanionic polymer(s) having a plurality of pendant carboxylate and sulfonate groups; and ii) tannic acid. In some embodiments, the yield in bu/A is increased about 5% to about 25% as compared to an untreated crop, or about 5% to about 15% as compared to an untreated crop, or the yield in bu/A is increased about 10% as compared to an untreated crop. In some embodiments, the yield in bu/A is increased about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, about 15%, about 16%, about 17%, about 18%, about 19%, about 20%, 21%, about 22%, about 23%, about 24% or about 25%.

[0116] Improving nitrogen efficiency can provide additional effects, such as, a strengthening effect, abiotic stress tolerance, comprising temperature tolerance, drought tolerance and recovery after drought stress, water use efficiency (correlating to reduced water consumption), flood tolerance, ozone stress and UV tolerance, tolerance towards chemicals like heavy metals, salts, pesticides, etc., biotic stress tolerance, comprising increased fungal resistance and increased resistance against nematodes, viruses and bacteria. In context with the present disclosure, biotic stress tolerance preferably comprises increased fungal resistance, increased plant vigor, plant quality, reduced stand failure, improved appearance, increased recovery, improved greening effect and improved photosynthetic efficiency, earlier germination, better emergence, more developed root system and/or improved root growth, increased ability of tillering, more productive tillers, earlier flowering, increased plant height and/or biomass, shorting of stems, improvements in shoot growth, number of kernels/ear, number of ears/m ² , number of stolons and/or number of flowers, enhanced harvest index, bigger leaves, less dead basal leaves, improved phyllotaxy, earlier maturation/earlier fruit finish, homogenous riping, increased duration of grain filling, better fruit finish, bigger fruit/vegetable size, sprouting resistance and reduced lodging, delayed senescence, comprising improvement of plant physiology, a longer duration of green leaf coloration of the plant and thus comprising color (greening), water content, dryness etc., more developed root system, among other effects.

[0117] The inhibition of urease by the combination compositions can be used on the soil at any growth stage during development of the plant, including vegetative, emergence, pollination and reproductive stages, depending on the plant and the desired effect, or can be used on the soil in area of future planting.

[0118] In some embodiments, the subject matter described herein is also directed to method of preparing the combination composition comprising: i) contacting a solution comprising the polyanionic polymer with tannic acid under stirring to prepare a mixture. In some embodiments, the solution is an aqueous solution and the mixture is an aqueous. The method can further comprise after step i), step ii) adding water to the mixture. The method can further comprise heating the mixture during step i) and/or step ii)

[0119] In some embodiments, the subject matter described herein is also directed to method of preparing a fertilizer composition comprising, contacting the combination composition with a fertilizer to prepare a fertilizer composition. In some embodiments, the fertilizer is a urea-containing fertilizer. In some embodiments, the urea-containing fertilizer is a granular fertilizer, which is coated with a combination composition. The method for preparing the coated granules comprises, contacting a granular fertilizer with a combination composition in the form of a liquid solution, and optionally mixing the granular fertilizer and the liquid, and optionally allowing the liquid to dry to form a coated granular fertilizer. The liquid can be applied at a rate of about 0.02 mL solution to about 20 mL solution per about 80 g to about 120 g granules of fertilizer; from about 0.01 to about 5 mL per 100 g of fertilizer; or from about 0.1 mL to about 2 mL per 100 g of fertilizer. Coating solutions are at least about 30% solids, preferably 50% solids.

[0120] In some embodiments, when preparing the combination composition/liquid fertilizer formulations, the nitrogen-containing fertilizer material(s) can be suspended in water and the aqueous polymer mixture(s) then added thereto with or without mixing. No particular mixing regime or temperature conditions are required. In the case of solid fertilizers, the combination composition can be directly applied to the fertilizer, typically at a level of from about 0.01-10% by weight, more preferably from about 0.05-2% by weight, based upon the total weight of the final fertilizer product taken as 100% by weight. Normally, aqueous dispersions of the combination compositions are sprayed onto the solid fertilizers and allowed to dry, so that the polymeric dried residue remains on the surfaces of the fertilizers. V. Articles of Manufacture

[0121] In another aspect, described herein are articles of manufacture, for example, a "kit," containing the polyanionic polymer and the tannic acid. The kit comprises a container comprising the polymer. The tannic acid can be in the same container or the kit can further comprise a separate container comprising the tannic acid. The kit advantageously can contain pre-measured amounts, for example, in amounts set forth elsewhere herein, of each of the components such that, for example, a tank-mix can be easily prepared by the end-user by combining the contents of the kit in a solvent, such as water. The kit may further comprise a label or package insert, on or associated with the container. The term "package insert" is used to refer to instructions customarily included in agricultural packages, and can contain usage, application rates, and warnings concerning the use of the components. Suitable containers for inclusion in the kit include, for example, bottles, vials, syringes, blister pack, etc. The container may be formed from a variety of materials such as glass or plastic.

VI. Embodiments of the subject matter described herein include:

[0122] 1. A composition comprising:

i) a polyanionic copolymer comprising a plurality of first and second repeat units wherein the first repeat unit contains a carboxylate group and the second repeat unit contains a sulfonate group; and

ii) tannic acid.

[0123] 2. The composition of embodiment 1, wherein the polyanionic polymer comprises a terpolymer.

[0124] 3. The composition of embodiment 2, wherein the terpolymer comprise maleic repeat units and itaconic repeat units.

[0125] 4. The composition of embodiment 1, wherein the polyanionic polymer comprises a tetrapolymer.

[0126] 5. The composition of embodiment 4, wherein the tetrapolymer comprise maleic repeat units and itaconic repeat units.

[0127] 6. The composition of embodiment 5, wherein the tetrapolymer comprises one or more methallylsulfonate-containing repeat units and one or more allylsulfonate-containing repeat units.

[0128] 7. The composition of any of embodiments 1-6, further comprising at least one agriculturally acceptable carrier.

[0129] 8. The composition of any of embodiments 1-7, wherein the polyanionic polymer and the tannic acid are present in synergistic amounts.

[0130] 9. The composition of any of embodiments 1-8, wherein the polyanionic polymer and tannic acid are present in a ratio of from about 4:1 to about 1:4.

[0131] 10. The composition of any of embodiments 1-9, wherein the polyanionic polymer comprises from about 48% to about 52% itaconic repeat units.

[0132] 11. The composition of any of embodiments 1-10, wherein the polyanionic polymer comprises from about 43% to about 47% maleic repeat units. [0133] 12. The composition of any of embodiments 1-11, wherein the polyanionic polymer comprises from about 3% to about 7% sulfonate repeat units.

[0134] 13. The composition of any of embodiments 2-12, wherein the polyanionic polymer comprises about 50% itaconic, about 45% maleic, and about 5% sulfonate repeat units.

[0135] 14. The composition of any of embodiments 1-13, wherein the sulfonate repeat units comprise methallylsulfonate.

[0136] 15. The composition of any of embodiments 1-13, wherein the sulfonate repeat units comprise allylsulfonate.

[0137] 16. The composition of any of embodiments 2-15, wherein the sulfonate repeat units comprise methallylsulfonate and allylsulfonate.

[0138] 17. The composition of any of embodiments 4-16, wherein the polyanionic polymer comprises about 50% itaconic repeat units, about 45% maleic repeat units, about 4% methallylsulfonate repeat units, and about 1% allylsulfonate repeat units.

[0139] 18. The composition of any of embodiments 16-17, wherein the methallylsulfonate and allylsulfonate components are present in a ratio of about 4:1.

[0140] 19. The composition of any of embodiments 1-18, wherein the polyanionic polymer and the tannic acid are present at a ratio from about 5:1 to about 1:5.

[0141] 20. The composition of embodiment 19, wherein the polyanionic polymer and the tannic acid are present at a ratio from about 4: 1 to about 1 :4.

[0142] 21. The composition of embodiment 20, wherein the polyanionic polymer and the tannic acid are present at a ratio of about 4: 1.

[0143] 22. The composition of embodiment 20, wherein the polyanionic polymer and the tannic acid are present at a ratio of about 2:3.

[0144] 23. The composition of embodiment 20, wherein the polyanionic polymer and the tannic acid are present at a ratio of about 1 :4.

[0145] 24. The composition of any of embodiments 1-23, wherein the tannic acid comprises pentagalloylglucose. [0146] 25. The composition of any of embodiments 2-24, comprising i) a polyanionic tetrapolymer comprising about 50% maleic repeat units, 45% itaconic repeat units, and about 5% sulfonate repeat units;

ii) tannic acid comprising pentagalloylglucose; and

iii) at least one agriculturally acceptable carrier,

wherein said tetrapolymer and said tannic acid are present in a ratio of about 2:3.

[0147] 26. The composition of embodiment 20, wherein the carrier is water.

[0148] 27. The composition of any of embodiments 1-26, further comprising a urea fertilizer.

[0149] 28. The composition of embodiment 27, wherein the urea fertilizer is a granular fertilizer or a liquid fertilizer.

[0150] 29. A granular fertilizer comprising, a coated granule comprising a nitrogen fertilizer, wherein the granule is coated with a composition of any of embodiments 1-24.

[0151] 30. The granular fertilizer of embodiment 29, wherein the nitrogen fertilizer comprises urea.

[0152] 31. The granular fertilizer of embodiment 29 or 30, wherein the granular fertilizer does not contain sustained release functionality.

[0153] 32. The granular fertilizer of any of embodiments 29-31, wherein the fertilizer is stable for at least 4 months at room temperature.

[0154] 33. A method of inhibiting urease, comprising contacting soil containing urease with an effective amount of the composition of any of embodiments 1- 24.

[0155] 34. A method of inhibiting urease, comprising contacting soil containing urease with an effective amount of the composition of any of embodiments 1- 26.

[0156] 35. A method of fertilizing a plant, comprising contacting soil around the plant with an effective amount of the composition of embodiment 27 or 28 or the granular fertilizer of any of embodiments 30-32. [0157] 36. A method of preparing the composition of any of embodiments 1-24, comprising: i) contacting an aqueous solution comprising the polyanionic polymer with tannic acid under stirring to prepare an aqueous mixture.

[0158] 37. The method of embodiment 36, further comprising after step i), ii) adding water to the aqueous mixture.

[0159] 38. The method of embodiment 37, further comprising heating the mixture during step i).

[0160] 39. A method of preparing a coated granular fertilizer comprising, contacting a granular fertilizer with a composition of any of embodiments 1-24.

[0161] 40. The method of embodiment 39, wherein the combination composition is in the form of a liquid solution, and the method further comprises mixing the granular fertilizer and the liquid and allowing the liquid to dry to form a coated granular fertilizer. [0162] The following examples are offered by way of illustration and not by way of limitation. Certain data are amenable for use in a Colby Analysis to show synergism. The Colby equation:

Expected value (E) = (X*Y)/100,

where X and Y are the effects of the active agents applied alone (expressed as % of control). The actual value determined for the effect is compared to the expected value. If greater = synergism; if less than = antagonism; if equal = additive.

EXAMPLES

Experimental conditions:

[0163] Temperature: controlled room temperature.

[0164] Tannic acid: ACS grade

[0165] T5: T5 tetrapolymer, which can be made according to the methods described in U.S. Patent Pub. Nos. 2016/0174549 Al and 2017/0183492 Al, each of which is herein incorporated by reference in its entirety, without any neutralization after polymerization

[0166] Urea analysis method: HPLC

[0167] All content is on actives basis, by weight [0168] Urease enzyme is commercial jackbean urease enzyme solution of about 800 units/ml

Example 1: Urease inhibition by tannic acid at pH 7

[0169] This experiment was conducted at a temperature of 20°C in closed glass containers. An aqueous solution containing 0.105 moles/L of monosodium phosphate was adjusted to a pH of 7.0 with sodium hydroxide. To 19.0 ml aliquots of this solution, with stirring, was added a suitable aqueous solution of a mixture of water and tannic acid. This gave tannic acid concentrations of 5.0 ppm and 50 ppm (10.0 microliters and 100 microliters, respectively, of a 1.00% aqueous solution) at end of test, followed by addition of commercial jackbean urease enzyme solution of known concentration, to add 40 units of enzyme (in about 50 microliters of suitable solvent). The mixture was allowed to stand for 18 hours, then 1.00 ml of freshly prepared urea solution (2.00 moles/L) to give an overall reaction concentration of 0.100 moles/L each for both urea and phosphate was added (total volume about 20 ml). Simultaneously, two more solutions were prepared in identical fashion, an enzyme- free control where both tannic acid and enzyme are omitted, and an enzyme control where enzyme is present without tannic acid. Solution urea concentration is measured accurately immediately in each of the four solutions, and again after a 120 minute interval. The concentration of urea in the enzyme-free solution is unchanged (less than 1.00% change from original reading) over 120 minutes. The concentration of urea in enzyme-containing solution without polymer drops by about 75% from its initial concentration. A linear scale is constructed to express urease enzyme inhibition, with 100% inhibition corresponding to urea decomposition rate in enzyme- free solution (essentially zero) and 0% inhibition corresponding to uninhibited urea loss rate. In this experiment, 5.0 ppm tannic acid gave 14% urease inhibition, and 50 ppm tannic acid gave 66% urease inhibition.

[0170] The experiment illustrates that using the reagents involved, urea does not decompose without being treated with urease. That is, the equipment and conditions do not decompose urea appreciably. It further illustrates that the enzyme being used is suitably active when urea is added to enzyme-containing solution that has not been treated with inhibitor, it is rapidly lost. The useful urease inhibition property of tannic acid is illustrated when treated urease fails to decompose urea at the same rate under same conditions where urease not treated with inhibitor succeeds in decomposing most of urea present. The dose-response relationship for tannic acid inhibition is illustrated. [0171] The example shows that tannic acid is a useful urease inhibitor, but it is not one that is highly effective at doses of 5.0 ppm. It is desirable that tannic acid performance per ppm used be significantly improved. Those skilled in the art can appreciate the usefulness of providing the same or better performance at lower doses of treatment.

Example 2: Urease inhibition by synergistic mixtures at pH 7

[0172] The experiment procedure of Example 1 was repeated with several treatments, with "% inhibition" for various treatments computed as described previously. The treatments were all 5.0 ppm total treatment, with various amounts of tannic acid and T5 to give a total of 5.0 ppm.

Results:

[0173] Treatment composed of "T5" tetrapolymer without any tannic present exhibited inhibition rate of 13% at 5.0 ppm dose.

[0174] Treatment composed of 4.0 ppm "T5" tetrapolymer and 1.0 ppm of tannic acid exhibited inhibition rate of 35 % .

[0175] Treatment composed of 2.0 ppm "T5" tetrapolymer and 3.0 ppm of tannic acid exhibited inhibition rate of 50%.

[0176] Treatment composed of 1.0 ppm "T5" tetrapolymer and 4.0 ppm of tannic acid exhibited inhibition rate of 43%.

[0177] Treatment composed of 5.0 ppm of tannic acid (no T5) exhibited inhibition rate of 14%.

[0178] This example shows that the use of two inhibitors together is unexpectedly producing synergistic results compared to either one alone. By direct comparison, a total treatment of 5.0 ppm mixed tannic and T5 reached 50% inhibition, not far below the result achieved with 50 ppm, or 10X the rate of tannic alone. In another comparison of this data, the performance of 5.0 ppm total treatment was improved by more than 3X by using a mixture of inhibitors (13-14% vs. 50%). Inhibition was to be improved by about 20% to about 35%.

[0179] The suboptimal ratios unexpectedly resulted in significant performance decreases compared to optimal ratio. All mixtures performed better than either T5 or tannic alone. Other polyanionic polymers may have synergistic behavior as well, but only provided they contain at least about 1% by mole aliphatic sulfonate pendant groups. This synergistic effect was not found for maleic-itaconic copolymer. Example 3: Combination Composition

[0180] A mixture composed as described below is prepared as described.

[0181] Composition:

[0182] Tannic acid: 25% w/w actives

[0183] "T5" tetrapolymer: 25% w/w

[0184] Balance: water

[0185] To 2 L glass beaker equipped with suitable stirring and heating apparatus, 625 g of a 40% aqueous solution of T5 tetrapolymer made in accordance with U.S. Patent Appl. Pub. Nos. 2016/0272553 and 2017/0183492 was added, and stirred vigorously, then heated to maintain a temperature of 45 C. To this mixture, 277.8 g of a 90% actives tannic acid powder was added over about 30 minutes and allowed to fully dissolve. Subsequently, about 100 g of water was added to the solution to bring the total weight of beaker contents to 1000 g; the mixture was then cooled to room temperature and filtered.

Example 4: Long-term Stability

[0186] The composition of Example 4 was tested for long-term stability.

standing for four (4) months at room temperature in a sealed container, mixture was tested for tannic acid content using HPLC. No detectable tannic acid loss was found. A freshly made and a four month old sample of this composition were examined as air dried films deposited onto diamond crystal surface using FT-IR ATR technique over a range of 400 cm ¹ to 4000 cm , and no difference was found between the two samples. This confirms the lack of significant chemical changes in this composition over the time period tested under conditions employed.

[0187] It would have been expected that at low pH, which is used for many agricultural applications, mixtures of T5 in fully acid form with tannic acid would, at room temperature, degrade over the course of several days to weeks to a significant extent. We have found, unexpectedly, that compositions composed of 25% w/ w tannic acid, 25% w/w T5 in as polymerized form, and 50% w/w water did not exhibit measurable decomposition after standing at controlled room temperature over a time period of 4 (four) months. This is in contradiction to the expected significant levels of acid hydrolysis that esters should have undergone. Example 5: Coated Granular Urea Nitrogen Fertilizer Composition

[0188] The composition of Example 4 is applied to granular urea nitrogen fertilizer by adding 0.20 ml of the solution produced in Example 3 to 100 g of urea granules while vigorously agitating the granules in a container. The resulting coated urea is a useful agricultural composition for application to soil.

Example 6: Testing on Winter Wheat

[0189] Experimental Candidates testing on winter wheat with urea applied at emergence from spring dormancy. Testing was performed to determine if T5 + Tannic acid in UAN improves yield performance of winter wheat. Trials were performed at two location in Ohio and compared: (1) unfertilized check ; (2) fertilized check (UAN alone); (3) VLS 9201-06 (T5) (40% w/w solids) at 0.5% v/v with VLS 9230 (Tannic Acid) at 4% v/v in liquid UAN; (4) NutriSphere HV in UAN; and (5) Agrotain Ultra in UAN. Six replications per location per examined. The soil was a silt loam soil, with the wheat treated at Feekes 4 with a sidedress application of UAN. A total nitrogen rate of 85-90% of the recommended rate was used in order to induce a slight nitrogen deficiency.

Example 7: Testing on Maize Applied As a Sidedress

[0190] Experimental Candidates testing on maize with UAN applied at V4-6 stage as a sidedress. Testing was performed to determine if T5 Polymer and Tannic Acid combinations in UAN fertilizer improves yield performance of corn. Testing was done a 9 total locations in Iowa (2), Illinois (2), Indiana (2), Wisconsin (2), South Dakota (2), and Georgia and compared: (1) Unfertilized check; (2) Fertilized check (85-115 lbs N/A); (3) NutriSphere-HV at 18 fl oz/A in liquid UAN; (4) T5 Polymer (40% w/w solids) at 0.5% v/v + Tannic Acid at 4% v/v in liquid UAN; and (5) Agrotain Ultra (NBPT) at 0.2% v/v in liquid UAN. Five to six replications across each of the nine locations were examined. The test areas were treated at V4-6 with a sidedress application injected just below surface between crop rows or y-dropped near rows. T5 Polymer (40% w/w solids) at 0.5% v/v + Tannic Acid showed a significant improvement in crop yield over UAN alone across all nine locations.

Example 8: Testing on Maize Prior to Planting

[0191] Experimental Candidates testing on maize with urea applied prior to planting. Testing was performed to determine if T5 Polymer combined with Tannic Acid on UREA improves yield performance of maize. Testing was done a five total locations in Iowa, Illinois, Indiana, Wisconsin, and South Dakota and compared; (1) Unfertilized check; (2) Fertilized check; (3) T5 + Tannic Acid at 2 qt/ton on dry urea (46-0-0) ; (4) NutriSphere-QDO at 2 qt/ton on dry urea (46-0-0); and (5) Agrotain Ultra (NBPT) at 3 qt/ton on dry urea (46-0-0). Six replications across each of the five locations were examined. The test areas were treated preplant incorporated 1-4 weeks before planting. The locations were significantly different from each other. Therefore, the calculated LSD is not a reliable separation test.

[0192] All technical and scientific terms used herein have the same meaning.

Efforts have been made to ensure accuracy with respect to numbers used (e.g. amounts, temperature, etc.) but some experimental errors and deviations should be accounted for.

[0193] Throughout this specification and the claims, the words "comprise,"

"comprises," and "comprising" are used in a non-exclusive sense, except where the context requires otherwise. It is understood that embodiments described herein include

"consisting of and or "consisting essentially of embodiments.

[0194] As used herein, "and or" refers to and encompasses any and all possible combinations of one or more of the associated listed items, as well as the lack of combinations when interpreted in the alternative ("or").

[0195] As used herein, the term "about," when referring to a value is meant to encompass variations of, in some embodiments ± 50%, in some embodiments ± 20%, in some embodiments ± 10%, in some embodiments ± 5%, in some embodiments ± 1%, in some embodiments ± 0.5%, and in some embodiments ± 0.1% from the specified amount, as such variations are appropriate to perform the disclosed methods or employ the disclosed compositions.

[0196] Where a range of values is provided, it is understood that each intervening value, to the tenth of the unit of the lower limit, unless the context clearly dictates otherwise, between the upper and lower limit of the range and any other stated or intervening value in that stated range, is encompassed. The upper and lower limits of these small ranges which may independently be included in the smaller rangers is also encompassed, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included.

[0197] Many modifications and other embodiments set forth herein will come to mind to one skilled in the art to which this subject matter pertains having the benefit of the teachings presented in the foregoing descriptions and the associated drawings. Therefore, it is to be understood that the subject matter is not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the appended claims. Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.