MXPA99008200A - Plant fertilizer compositions containing phosphonate and phosphate salts, and derivatives thereof - Google Patents

Abstract

A fertilizer composition for plants containing phosphonate and phosphate salts, and derivatives thereof is disclosed. The composition provides a single product which may be employed to stimulate the growth response in plants.

Description

PLANT FERTILIZER COMPOSITIONS CONTAINING PHOSPHONATE AND PHOSPHATE SALTS AND DERIVATIVES THEREOF CROSS REFERENCE FOR RELATED APPLICATION The present invention is a continuation in part of the application with co-pending serial number 08 / 705,594 issued on August 30, 1996.

BACKGROUND OF THE INVENTION The present invention relates broadly to fungal compositions, and methods of use, which provide improved efficacy in the control of parasitic fungi in plants. More particularly, the compositions and methods of use of the invention include fungicidically effective amounts of phosphate, preferably in the form of mono, di, tri or dipotassium phosphate (KH2PO4, K2HPO4) and phosphonate, preferably the mono-phosphonate form or dipotassium (KH2PO3, K2HPO3), in aqueous solution. According to another aspect of the present invention, the compositions and methods of use of the invention include effective amounts of phosphate growth response, preferably in the form of mono or dipotassium phosphate (KH2PO4, K2HPO4) and phosphonate, preferably of the form of mono or dipotassium phosphonate (KH2PO3, K2HPO3), in aqueous solution. Phosphorus is a major essential element in plant nutrition because it governs energy production reactions, including those that are oxidative and photophosphorylating and the production of adenosine diphosphate (ADP) and adenosine triphosphate (ATP). The energy-rich phosphate bonds of ADP and ATP provide the energy for several of the physiological reactions that occur to plants. The phosphorus element appears in two general forms to which the present invention refers, phosphonate and phosphate. The term "phosphonate", sometimes also referred to as "phosphite", refers to salts (organic or inorganic) of phosphonic acid or phosphorous acid. The phosphonic and phosphorous acids have the formula H3PO3 and a molecular weight of 82.00. Their structures starting from the International Union of Pure and Applied Chemistry are shown below: OH OH H P = O HO OH OH Phosphonic Acid Phosphorous Acid CA: 13598-36-2 CA: 10294-56-1 The term "phosphate" refers to the salts (organic or inorganic) of the phosphoric acid having the formula H3PO4, a molecular weight of 98, and has the following structure: O I I G - P - OH OH Phosphoric acid CA: 7664-38-2 Previously, various phosphonate compounds have been proposed as useful in the fungicidal and fertilizer compositions for application to plants, see, for example, Patents of E.U.A. Nos. 4,075,324 and 4,119,724 to Thizy, which describes phosphorous acid, its inorganic and organic salts, as a plant fungicide; Patent of E.U.A. No. 4,139,616 to Dueret, which discloses fungicidal compositions based on phosphorous acid esters and salts thereof; Patent of E.U.A. No. 4,542,023 to Lacroix et al., Which describes the organophosphorus derivatives by having a systematic and fungistatic contact and fungicidal activity; the Patents of E.U.A. Nos. 4,698,334 and 4,806,445 and 5,169,646 to Horriere et al. Describe fungicidal compositions based on alkyl phosphonates; the Patents of E.U.A. Nos. 4,935,410 and 5,070,083 to Barlet disclose aluminum tris-alkyl-phosphonate compositions fungicides; the Patent of E.U.A. No. 5,514,200 to Lovatt, which describes acid formulations containing phosphorus fertilizer for plants. (The teachings of the above U.S. Patents are incorporated herein by reference). It has been found that the above references describing phosphonate compositions are effective to protect plants, and particularly vineyards, citrus and fruit trees and tropical plants, against fungal attack. Once assimilated, the phosphonates have been shown to boost the phyto-immune system. Induced phosphonate stimulation of the phyto-immune system is triggered by the induction of ethylene production, followed by a rapid accumulation of phytoalexins at the site of infection. Phosphonates have also been shown to have a detrimental effect on the growth of phycomycetes. See, Pegg, K.G. and deBoer, RF, "Proceedings of the Phosphonic Acid Work Shop," Australiasian Plant Pathology, Vol. 19 (4) 1990. According to said development of the present invention, however, it has recently been discovered that phosphonates they exacerbate non-target ascomycete fungi, and other fungi that produce a eifitotic break much greater than infections that occur without phosphonate treatment. This phenomenon is known as pathological acerpathy. Previously, phosphates were not observed as a solution to the pathological accretion of ascomycete fungal infections. This is due to the fact that phosphates are mainly observed as fertilizers with only limited or even detrimental fungal properties. For example, the Patent of E.U.A. 5,514,200 teaches that phosphate fertilizers inhibit the beneficial symbiosis between the roots of the plant and mycorrhizal fungi, and also promote bacterial and fungal growth in the rhizosphere, including the growth of pathogenic fungi and other small organisms that originate in the soil (Col. 2, lines 18-28). The phosphates have also been considered as a competitive inhibitor for the assimilation of the phosphonate, thus inhibiting the ability of the phosphonates to protect against attack by fungi. See, Pegg, K.G. and deBoer, RF, "Proceedings of the Phosphonic (Phosphorous) Acid Work Shop," Australiasian Plant Pathology, Vol. 19 (4), pp. 17 and 144, 1990. Furthermore, phosphonates and phosphates are believed to be "biological aliens". ", with the presence of phosphonates or their esters, exerting little or no influence on the enzyme reaction involving phosphates. Robertson, H.E. and Boyer, P.D., "The Biological Inactivity of Glucose 6 Phosphonate, Inorganic Phosphites and Other Phosphites," Archives of Biochemistry and Biophysics, 62 pp. 380-395 (1956). Accordingly, the successful requirements for a phosphonate-based fungicide depend on the elimination of pathological phosphonate-induced pathology from ascomycete fungal infections. In addition, the prior art teaches that phosphates and phosphonates are "biological strangers" is relevant to the lack of teaching of use of a composition of any agricultural use.

BRIEF DESCRIPTION OF THE INVENTION The present invention solves problems described above, and provides an improved antifungal composition for plants which contains, as active ingredients, fungicidically active amounts of phosphonates and phosphates. In accordance with the present invention, it has been found that the application to a plant of an inventive phosphonate / phosphate composition substantially eliminates the acercomation of ascomycete fungi, while at the same time providing a means to control phycomycetes and ascomycetes. and other mushrooms with a unique product. Thus, an object of the present invention is to provide a fungal composition for the protection of plants against fungal infection, especially phycomycetes and ascomycetes. Another object of the invention is to provide said antifungal protection with a unique product that does not cause in the application a pathological acercoma infection of ascomycetes. Another object of the invention is to provide a method of treating plants and provide an antifungal protection in plants against the attack of phycomycetes, ascomycetes and other fungi and bacteria. Still another object of the invention is to provide an antifungal composition for the treatment of plants that is environmentally safe, economical in its use and that has a low mammalian toxicity.

These and other objects of the invention are achieved by the invention described below. According to the invention, antifungal compositions for the protection of plants, especially citrus and fruit trees and vineyards against the attack of fungi, preferably contain an active material and a fungicide-effective amount of at least one first salt formula selected from the group consisting of KH2PO3, K2HPO3, and K3PO3, and at least one second salt selected from the group consisting of KH2PO4, K2HPO and K3PO4, in a mixture with an agriculturally acceptable carrier. The composition preferably comprises an aqueous solution wherein each salt is present in a solution of about 20 millimoles to about 50 vol / vol%. According to another aspect of the invention, the amount of the first salt is one part by weight and the amount of the second salt is between 0.001 and 1, 000 parts by weight. Phosphonate salts useful in the practice of the invention also include those organic and inorganic salts shown by U.S. Pat. Nos. 4,075,324 and 4,119,724 to Thizy et al., (See, eg, Col. 1, in .51-69 to Col. 2, in. 1-4). The present invention, in another aspect, has also been found to be effective as a growth stimulator or fertilizer for plants, and solves the problems in the art with respect to the effective fertilizers encountered. In this way, the present invention provides a means to apply a unique product to plants that is an effective fungicide and an effective fertilizer. It is therefore an object of said aspect of the invention to present a composition and method of use that functions as a fertilizer for plants. Another object of said aspect of the invention is to function as a fertilizer that provides substantial growth response results. Another object of said aspect of the invention is to function as a fertilizer that is ecologically compatible with humans, that is economical and that is efficient. These and other objects, features and advantages of the invention will become more apparent with reference to the specification and appended claims.

DETAILED DESCRIPTION OF THE PREFERRED MODALITIES The following examples are set forth for preferred concentrations and techniques for formulating them, as well as methods of application and use and test results demonstrating the effectiveness of the inventive concentration in plants that are protected against attack by ascomycete fungi and phytomicept. It will be understood, however, that said examples are presented by way of illustration only and should not be taken as limiting the general scope of the invention. Said specific components tested in the examples were prepared and applied in the following manner.

Preparation method A. Aqueous solution of potassium phosphonate (KH9PO3) - H3PO3 was produced by hydrolysis of phosphorus trichloride according to the reaction: PCI3 + 3H2O > H3PO3 + 3HCI. The HCl was removed by dragging under reduced pressure and the phosphonic acid (H3PO3) was sold as a 70% acid solution. The phosphonic acid was then neutralized in aqueous solution by potassium hydroxide according to the reaction: H3P? 3 + KOH > KH2P? 3 + H2? at about pH 6.5 and to produce 0-22-20 liquid weighing 5.22 kg / 3.18 liters. Said solution is commercially available and sold under the trade name "Phos-Might" by Foliar Nutrients, Inc., Cairo, GA 31728. B. Aqueous solution of potassium phosphate (K? HPO?). Monopotassium phosphate (0-51.5-34) is reacted with 45% potassium hydroxide in aqueous solution to produce dipotassium phosphate by the following reaction: Said solution is commercially available and sold under the trade name "K-Phos" by Foliar Nutrients, Inc., Cairo, Ga 31724. HK2PO4 + KOH > K2HPO4 + H2O with a density product of 1394 at 20 ° C and a pH solution of 7.6 which produces a 0-18-20 analysis.

C. Solution KH9PO3 / K2HPO4. Various amounts of each compound (K2HPO3; KH2PO3; K2HPO4; or KH2PO4) in aqueous solution are combined at rates ranging from 20 millimoles to 5 vol / vol, depending on the host crop and the pathogen complex and infection level.

Method of application The preferable method of application is foliar, either by land or aerial equipment, but is not limited to the method only. Injection or dirt applications, for example, can also be effective depending on specific crops and pathogens. The inventive compositions have utility in fruit crops, agronomic crops, ornamentals, trees, grasses, vegetables, grains and floricultural crops, as well as some aquatic crops including watercress. The fungal properties of the compounds according to the invention are several, but they are particularly interesting in the case described in the following examples: Examples 1-5 exemplify a portion of said applications. In Examples 1-4, fungal treatments were applied to ornaments, citrus and vegetables. In each of the examples 1-4, the treatments were applied in a 3.18 liter solution by means of a packing sprinkler, maintained at 42 kg / cm2, in sufficient quantities of water to achieve full coverage. All treatments were applied to the appropriate number of experimental units assigned in a randomized complete block design (RCB) repeated four times. Example number 5 was a pre-harvest fungal sprinkling evaluation in "Nova" tangents. As used in the examples, "percent infection" refers to the percentage of leaves that show a fungal lesion. "Phytotoxicity" refers to the number of crops that hurt the leaves that fall from the plant after the application of the solution. The ascomiseto mushrooms were tested in examples 1 to 5 and all members of the ascomiseto family.

EXAMPLE NO. 1 Fungicide trial against powdery mildew of the Cherry Trail Trail Nursev, Keystone Hts "Florida The compounds according to the invention were studied for the effect on powdery mildew (Oidium Spp.), Which is responsible for the foliar infections in the cherry tree. The solutions of potassium phosphate and potassium phosphate were applied in the compositions as described in table 1 below. An average of 5 containers of 15 cm per experimental unit with 4 replicates was considered in a randomized complete block design ("RCB"). The solutions were applied to the cherry tree (Cornis Florida Var. "Weaver"). The application of the compositions was made on April 25, 1996, May 8, 1996 and May 23, 1996. The effects of the various compositions were subjected to the regime on May 30, 1996. Table 1 shows that when a Potassium phosphonate solution (which does not contain a considerable amount of phosphate) is applied to the cherry tree, the pathological accretion of the ascomycete fungus occurs in 100% of the leaves of the cherry tree, in contrast to the control, which shows only 30% of infection. The inventive composition combining potassium phosphate and potassium phosphonate showed a complete elimination of the phenomenon of pathological acerbination, and in fact, the amount of infection was reduced to approximately 20%.

TABLE I REGIME TREATMENT / 318 *% FITOTOXICITY Its. INFECTION 1) 1% SOLUTION 0 0 POTASSIUM PHOSPHONATE 2) 1% SOLUTION 0 0 POTASSIUM PHOSPHATE 3) 1% SOLUTION 0 0 POTASSIUM PHOSPHONATE SOLUTION OF 1% 0 PHOSPHATE OF POTASSIUM 4) 2% SOLUTION 0 0 PHOSPHATE OF POTASSIUM 5) CONTROL - 30 0 EXAMPLE NO. 2 Test of fungicide against powdery oak mildew of Shumard Trail Ridge Nursery, Keystone Hts., Florida In example No. 2, the inventive compositions were tested for effectiveness against mildew thumbling (Phyllactinia corylea) that infects shumard oak (Quercus shumardii). In Example No. 2, an average of 10 containers of 9.5 liters per experimental unit with four replicates in a randomized complete block design was examined. When it was only applied to the potassium phosphonate solution, the percentage of infection increased by 40%, compared to 20% of infection in the control, indicating a pathological accretion of the ascomycete fungi. When applied in the inventive composition that includes potassium phosphonate and potassium phosphate, the infection was completely eliminated.

TABLE 2 REGIME TREATMENT / 318 *% PHYTO-TOXICITY Its. INFECTION 1) 1% SOLUTION 40 0 PHOSPHONATE OF POTASSIUM 2) 1% SOLUTION 0 0 PHOSPHATE OF POTASSIUM 3) 1% solution 10 0 PHOSPHONATE OF POTASSIUM + + 1% SOLUTION 0 PHOSPHATE OF POTASSIUM 4) 2% SOLUTION 0 0 PHOSPHATE OF POTASSIUM 5) CONTROL - 20 0 EXAMPLE No. 3 Fungicide test against citrus alternate Kerr Center, Vero Beach, Florida In Example No. 3, the inventive composition was tested for effectiveness on citrus trees (Alternaria citri) that were infected with the fungi. As used in the following table No. 3, "% of YLD refers to the percentage of young leaf fall, and"% of YFD "refers to the percentage of young fruit fall.% YLD and% YFD were determined by examining 4 terminals / tree with 4 repetitions in the randomized complete block design The date on which the compositions were applied was March 21, 1996. The compositions were subjected to regimen on April 2, 1996. When only Potassium phosphonate solutions were applied,% YLD and% YFD were increased from 6.2 and 1.5 to 23.9 and 37.9, respectively, indicating the pathological acerbination of the Ascomycete fungi.The application of the inventive composition not only eliminated the acerbity but showed improvement in the YLD and YFD.

TABLE 3 REGIME TREATMENT / 318 lts. *% Y.L.D. % Y.F.D. PHYTO-TOXICITY 1) SOLUTION 0.5% 5.2 3.8 0 POTASSIUM PHOSPHATE 2) SOLUTION 1% 2.5 2.5 0 POTASSIUM PHOSPHATE 3) SOLUTION 2% 1.5 1.0 0 POTASSIUM PHOSPHATE 4) SOLUTION 1% 23.9 37.5 0 POTASSIUM PHOSPHATE 5 ) SOLUTION 0.5% 2.2 3.7 0 OF PHOSPHATE OF POTASSIUM + + 0.5% PHOSPHONATE SOLUTION OF POTASSIUM 6) CONTROL - 6.2 1.5 0 EXAMPLE 4 Fungicide test against carrot / A / femar / a In example No. 4 the carrot containers were inoculated with Alternaria dauci fungi. The sizes of the containers were single rows X 76 meters X 4 repetitions in an RCB design. The dates on which they applied the compositions were on February 2, 9, 15, 22 and March 8, 14, 22 and 28, 1996. Fungal infections were submitted to the regime on April 5 and April 23, 1996. The second regimen was 25 days after the last fungicidal application. The test was carried out in Sanford, Florida. The application of inventive solutions that include potassium phosphonate and potassium phosphate improved the extent of infection that would otherwise occur in the control carrot. Although the solution that makes use of only the potassium phosphonate caused a slight improvement of the infection that occurs in the control, it was substantially less than that associated with the inventive composition. Also shown in Example No. 4 is a comparison of the effectiveness of the inventive composition to other fungicides, including Cu-Alexina and Fe-Alexina. Said test showed that the inventive composition is effective as well as the known fungicides, but without being environmentally toxic.

TABLE 4 REGIME TREATMENT / 318 LTS PROM% OF INFECTION 4/5/96 4/23/96 1) SOLUTION 1% 6.9 8.2 POTASSIUM PHOSPHATE 2) SOLUTION 1% 18.7 28.8 POTASSIUM PHOSPHONATE 3) SOLUTION 0.5% 8.9 10.7 POTASSIUM PHOSPHATE + 0.5% POTASSIUM PHOSPHATE SOLUTION 4) Cu-ALEXINA 0.508 kg ai 8.8 11.6 ) Fe-ALEXINA 0.508 kg ai 12.7 12.9 6) CONTROL 23.0 34.8 EXAMPLE No. 5 Pre-harvest spraying test from Citrus Kerr Center, Vero Beach, Florida In example No. 5, twenty-two fruits each of five trees tangelo nova, were selected and marked in a random manner. The fruits were rubbed with a nail file and then sprayed with the compositions described in table 5, with five treatments on the same day. Seven days later, the fruit was collected and stored for 2 weeks in sealed white plastic bags, then examined for the penicillium mold. The degree of infection was regimented using the following records: 0 = no infection, 1 = light infection (less than 30% coverage), 2 = severe infection (100% coverage). The degree of infection is the means of registration of 22 fruits.

TABLE 5 TREATMENT DEGREE GRADE OF # OF FRUITS FITOTOXICI DAD INFECTION 1) SOLUTION 1% 1 9 0 POTASSIUM PHOSPHANATE 2) SOLUTION 2% 0.91 12 0 POTASSIUM PHOSPHONATE 3) SOLUTION 1% 0 POTASSIUM PHOSPHATE 4) SOLUTION 0.5% 0.27 3 0 OF PHOSPHATE OF POTASSIUM + + 0.5% PHOSPHONATE SOLUTION OF POTASSIUM 5) CONTROL - 1.41 12 0 The above examples show that the inventive compositions are useful in the protection of plants against the attack of Phycomycete, Ascomycete and other fungi and bacteria with the application of a solution. It will also be appreciated that compositions for controlling such fungal diseases of Phycomycete and Ascomycete in plants may also contain phosphate and phosphonate compounds comprising a fungicidically effective amount of at least one first salt having the following formula: and a second salt having the following formula: O OR Wherein R1 is selected from the group consisting of H, K, an alkyl radical containing from 1 to 4 carbon atoms, substituted allogenous alkyl or nitrosubstituted alkyl radical, an alkynyl, a substituted alkenyl alkenyl, alkynyl, substituted alkenyl alkynyl, alkyl substituted alkoxy radical, ammonium substituted by alkyl and hydroxy alkyl radicals; R2 and R3 are selected from the group consisting of H and K; I am selected from the group consisting of K, alkaline earth metal cations, aluminum atom; ammonium cation; and n is an integer from 1 to 3, equal to the valence of Me. It will be appreciated that the foliar applications of the inventive compositions will be effective as a common agricultural practice for controlling root pathogens caused by Phytophthoran, Phythium, and foliar infections caused by Plasmopara. It will also be appreciated that the inventive compositions will have a biocidal activity and control of anthropod pests, and also have fertilizing effects, in plants (see for example, U.S. Patent Nos. 5,206,228, 5,133,891 and 5,514,200). According to another aspect of the invention, it has been found that compositions that include potassium phosphate and potassium phosphonate produce a substantial growth response in certain plants. In the following table 6 is illustrative: TABLE 6 NUTRITIONAL FOLIAR EVALUATIONS OF "K-PHOS" AND "PHOS" IN RHAPHIOLEPIS INDICA No. of rods / Rep TREATMENT REGIME A B C D PROM 1) 1% SOLUTION 22 13 20 15 17.5 PHOSPHANATE OF POTASSIUM 2) 1% SOLUTION 28 23 25 32 27.0 PHOSPHATE OF POTASSIUM 3) 1/2% SOLUTION 23 26 24 20.3 PHOSPHONATE OF POTASSIUM + + SOLUTION OF 1/2% PHOSPHATE OF POTASSIUM 4) 2% SOLUTION 24 38 32 24 29.5 PHOSPHATE OF POTASSIUM 5) CONTROL 3.8 Experimental units = containers of 9.5 x 9.5 liters x 4 repetitions with assigned treatments in a randomized complete block design. The application dates for the A-D treatments were approximately one, two, four and three weeks apart respectively (October 31, 1996).; November 7, 1996; November 20, 1996, December 19, 1996 and January 8, 1997 respectively, submitted to regimen on January 14, 1997. As can be seen from Table 6, the four nutritional treatments provided greater growth response to the control without treat, and K-FOS at 1% and 2% were superior to FOS-MIGHT at 1% and the combination of 1/2% of each of FOS-MIGHT + K-PHOS. The combination, however, produced response of growths substantially superior to that of the control, in fact in a similar place to the individual treatments of K-FOS or FOS-MIGHT. The growth response is higher is, compared to the control, can be expected when the inventive composition of aqueous solution of potassium phosphate salt and potassium phosphonate salt in which each salt is present in the solution of about .25% vol./vol. at about 3.0% vol./vol., and preferably between 1.5% vol./vol. and 2.0 vol./vol. It is believed that the unexpected growth response is due to the slow conversion of PO3 into the inventive composition of PO4 after application. Said composition also provides the additional benefit of also being fungicide.

The descriptions above all the references cited herein are incorporated by reference.

Claims (13)

NOVELTY OF THE INVENTION CLAIMS

1. - A fertilizer composition for stimulating growth in plants, characterized in that it comprises an effective amount of growth stimulation of at least one first salt selected from a group consisting of K2HPO, KH PO3 and K3PO3, and a second salt selected at from a group consisting of K2HPO4, KH2PO4 and K3PO4.

2. The composition according to claim 1, further characterized in that said composition comprises an aqueous solution, wherein each of the first and second salts are present in solution of approximately .25% vol./vol. at approximately 5% vol./vol.

3. The composition according to claim 1, further characterized in that the amount of the first salt is one part by weight and the amount of the second salt is between 0.001 and 1, 000 parts by weight.

4. A plant growth stimulation method comprising: the application to plants, in effective amounts of growth stimulation, of at least one first salt selected from a group consisting of K2HPO3, KH2PO3 and K3PO3, and a second salt selected from a group consisting of K HPO, KH2PO4 and

5. - The method according to claim 4, further characterized in that the composition comprises an aqueous solution, wherein each of the first and second salts is present in solution of approximately .25% vol./vol. to approximately 5% vol./vol. 6. The method according to claim 4, further characterized in that the amount of the first salt is one part by weight and the amount of the second salt is between 0.001 and 1, 000 parts by weight. 7. A composition for fertilization comprising: an effective amount of stimulation of growth of at least one first salt that has the following formula: and a second salt having the following formula:

OR

OR

R3 wherein Ri is selected from the group consisting of H, K, an alkyl radical containing 1 to 4 carbon atoms, alkyl substituted with halogen or nitrosubstituted alkyl radical, an alkenyl, a halogen substituted alkenyl, alkenyl, halogen-substituted alkynyl, alkoxysubstituted alkyl radical, ammonium substituted by alkyl or hydroxyalkyl radicals; R2 and R3 are selected from a group consisting of H and K; I am selected from a group consisting of K, alkaline earth metal cations or aluminum atom, ammonium cation; and, n is an integer from 1 to 3 equal to the valence of Me. 8. The composition according to claim 7, further characterized in that it comprises an aqueous solution, wherein each of the first and second salts is present in a solution of approximately .25% vol./vol. at approximately 5% vol./vol.

9. The composition according to claim 7, further characterized in that the amount of the first salt is one part by weight and the amount of the second salt is between 0.001 and 1, 000 parts by weight.

10. - The composition according to claim 1, which is a fungicide. 11.- A fungicide / fertilizer composition comprising approximately .25% vol.? ol. at approximately 5% vol./vol. of a mixture of phosphite salt and phosphate salt. 12. A composition according to claim 10, further characterized in that the phosphite salt and the phosphate salt comprise about 1/2% by weight of the composition. 13. A composition according to claim 10, further characterized in that it is aqueous.