Phosphorus- rich NANO sponge

Abstract

The present invention relates to a phosphorus-rich nano sponge comprising a porous matrix having an average size of less than 1000 nm and stabilized with a surface-active agent wherein the porous matrix is held together by ionic linkages of one or more of transition metals selected from iron, copper, titanium, vanadium, nickel, cobalt, post transition metals selected from zinc, cadmium, aluminum, tin, lead, bismuth, alkaline earth metals selected from calcium, magnesium, barium and strontium, metalloids selected from silicon, boron and tellurium, alkali metals selected from potassium, sodium and lithium, lanthanides selected from cerium, gadolinium, europium, or mixed metals. The phosphorus-rich nano sponge is selectively enriched for sustained and targeted delivery of molecular payloads.

Description

[0001] PHOSPHORUS- RICH NANO SPONGE

[0002] FIELD OF INVENTION

[0003] The present invention relates to the field of advanced materials, specifically a phosphorus-rich nano structure material, nano sponge. This nano sponge features a phosphorus- rich porous matrix having an average size of less than 1000 nanometers and exists in a semi-crystalline, amorphous, or mixed crystal state. The unique phosphorus- rich nano sponge structure is reinforced or held together by ionic linkages of one or more of transition metals, post transition metals, alkaline earth metals, metalloids, alkali metals, lanthanides or mixed metals. This nano sponge can deliver essential molecules, growth hormones, and protective agents, aiding the survival and resilience of microbes, plants, and animals. This innovation is particularly significant for applications requiring highly stable and efficient phosphorus delivery systems.

[0004] BACKGROUND AND PRIOR ART OF THE INVENTION

[0005] Nano sponge structures are synthesized through organic, inorganic, or composite preparation methods. They are porous in structure, pores being nanometers in size, and can therefore be targeted to absorb targeted molecules. Nanostructure with a spongy architecture is often used in medicine as targeted drug delivery systems, detoxification methods, or as a way of damage control after an injury. They can also be used in environmental applications to clean up ecosystems by performing tasks like purifying water or metal deposits. Their small size allows them to move quickly through media like water or blood, efficiently finding and attacking unwanted matter. Nano sponges are often synthetically manufactured but oftentimes include natural materials to improve their efficiency when injected into the body. Nanostructures due to their smaller size allow less disruption into the system in which it is implemented therefore imposing less risk of failure or detrimental effects.

[0006] In his article titled, “Significance of Phosphate Nano-Fertilizers Foliar Application: A Brief Real-Field Study of Quantitative, Physiological Parameters, and Agro-Ecological Diversity in Sunflower”, David Ernst says, one of the challenges in agriculture is to ensure an adequate supply of bioavailable phosphorus for plants in phosphorus- deficient soils. A promising alternative lies in the utilization of phosphate nanofertilizers (NFs) through spray applications. In a study, phosphate-based NFs, including nano-hydroxyapatite (nano-Hap), a mixture of nano-calcium zinc phosphate and macrosized parascholzite (nano / macro-ZnPhos) when applied at reduced concentrations, elicited a statistically significant elevation in quantitative parameters and seasonal physiological responses in sunflower. The parameters analyzed included head diameter, dry head weight, seed yield per hectare, nutritional seed oil-content, etc. as well as the physiological normalized difference vegetation index (NDVI), stomatai conductance index, and crop water stress index (CWSI).

[0007] AU2011262310A1- highlights a macronutrient sustained release composition for plant locus comprising a nanocomposite wherein a nitrogen containing macronutrient compound is adsorbed on the surface of hydroxyapatite phosphate nanoparticles, intercalated within the interlayer spacing of a nano clay particle. The nanocomposite containing the adsorbed macronutrient compounds is slowly released in a sustained manner when contacted with an acidic soil.

[0008] WO2023199355A1- describes a method for synthesis of nano plant nutrients- comprising plant nutrient and natural polymers like chitosan for improving the bioavailability of macro and micronutrients to plants. WO2016189521A2- Fertilizer compositions based on a substituted calcium phosphate and / or calcium carbonate compound. The application refers to fertilizing compositions comprising inorganic particles of calcium phosphate compound substituted with micro and macro elements and surface functionalized with at least one organic compound containing at least one hydroxyl group and at least one micro or macro nutritional element and / or comprising a substituted and possibly surface functionalized calcium carbonate compound and a process for preparing particles of calcium phosphate compound and calcium carbonate compound.

[0009] For example, an application highlights that conventional fertilizers only increase the growth of maize plants with higher phosphorus uptake of plant tissues; however, an application along with poultry manure even enhances the iron fraction (Ojo et al., 2015). The application of calcium phosphate nanoparticles to the plant system has proven to be efficient in promoting plant growth. For instance, the application of CaPC>4 NPs demonstrated root proliferation, harmonious growth elevation, and vitality development properties along with an improvement in colonization of endosymbiotic arbuscular mycorrhizal fungi in maize (Rane et al., 2015). Another study conducted on rice concluded that calcium phosphate nanoparticles impacted growth and antioxidant activity in a dose-reliant way. It is found that calcium phosphate nanoparticles interact with plants and inflict physiological changes (Upadhyaya et al., 2017).

[0010] US20130104612 Al describes a phosphate compound with organic source and mineral acid focusing on chemical modification of the phosphate compound through the addition of an organic source, a filler organic carbon for slow and gradual release of nutrients. A study titled, “Polyvinylidene fluoride -a-zirconium phosphate nanoparticles based mixed matrix membranes for removal of heavy metal ions”-by Abdulkarem et al focuses on novel poly (vinylidene fluoride) -alpha-zirconium phosphate (a- ZrP) mixed matrix membranes prepared via the phase inversion method. Membranes with different content of a-ZrP nanoparticles loadings (0.25, 0.50, 0.75, or 1.00 wt%) were fabricated, and the impact of a-ZrP NP loading was evaluated w.r.t the membrane’s morphology, functionality, surface charge, and hydrophilicity.

[0011] Nano-iron phosphates show high removal rates for lead, cadmium, and copper in soil leachates of different pH (Guoqiang Wang et. Al., 2023). In the soil remediation experiments, the analysis shows that the acid-soluble, reducible and oxidizable fractions of lead, cadmium, and copper in the soil were effectively converted into a more stable residual fraction. The study reveals a prospect for the application of nano phosphate composites in the remediation of contaminated soil.

[0012] However, all above-mentioned documents report only a single nutrient payload within nanocarriers. Hence, there is a longstanding and significant need to increase nutrient uptake efficiency by developing carrier molecules or structures that can deliver multiple nutrients, elements, and organic nutrition to plant and animal systems. This will help meet sustainability goals as well aid in supplying to the growing demand for food supply among the ever-increasing population. There is strong need for an effective nano carrier for delivery of multiple elements that are nontoxic, easy to handle, helps conserve natural resources, and provides consistent efficacy.

[0013] The discussion of documents, materials, devices, articles and the like included in this specification are solely for the purpose of providing a context for the present invention. It is not suggested or represented that any or all these form part of the prior art or were common general knowledge in the field relevant to the present invention as it existed before the priority date of each claim of this application.

[0014] OBJECTIVES OF THE INVENTION

[0015] • To create a phosphorus-rich nano sponge comprising a porous matrix having an average size less than 1000 nanometers for efficient nutrient delivery.

[0016] • To design a phosphorous-rich nano sponge with a semi-crystalline and amorphous porous matrix, stabilized by surface -active agents for better performance.

[0017] • To strengthen the phosphorus- rich porous matrix using ionic bonds / linkages of one ormore of elements like transition metals, post transition metals, alkaline earth metals, metalloids, alkali metals, lanthanides or mixed metals.

[0018] • To deliver important molecular payloads like polysaccharides, proteins, lipids, vitamins, free sugars, minerals and their compounds, plant nutrients, nitrates, amino acids, growth hormones, and plant protective agents to nurture the growth of microbes, plants, and animals.

[0019] • To ensure that the phosphorus-rich nano sponge forms a colloidal dispersion when mixed with a solvent and stabilized by a surface-active agent making it easy to apply-

[0020] • To create a slow-release system that gradually releases molecular payloads and bioavailable phosphorus over at least 20 days, providing continuous nourishment and protection.

[0021] • To develop a phosphorus-rich nano sponge that can adhere to living and nonliving surfaces including those of plants and animals. • To make a phosphorus- rich nano sponge that can deliver phosphorus along with other plant nutrients through foliar and root zone application.

[0022] • To make a phosphorus- rich nano sponge that can catalyze reactions within its porous matrix.

[0023] • To make a phosphorus- rich nano sponge that can adsorb and absorb pollutants from contaminated water and soil.

[0024] • To make a phosphorus- rich nano sponge that can be used as a coating agent resistant to corrosion under varying conditions of temperatures and acidity.

[0025] SUMMARY OF THE INVENTION

[0026] The invention relates to a novel phosphorus-rich nano sponge designed for efficient delivery of beneficial molecules in various biological systems. The phosphorus-rich nano sponge comprises a phosphorus-rich porous matrix with an average particle size of less than 1000 nm and stabilized with a surface -active agent. The unique structure of the porous matrix is maintained or held together by ionic linkages of one or more of transition metals selected from one or more of iron, copper, titanium, vanadium, nickel, cobalt, post transition metals selected from one or more of zinc, cadmium, aluminum, tin, lead, bismuth, alkaline earth metals selected from one or more of calcium, magnesium, barium and strontium, metalloids selected from one or more of silicon, boron and tellurium, alkali metals selected from one or more of potassium, sodium and lithium, lanthanides selected from one or more of cerium, gadolinium, europium, or mixed metals.

[0027] The phosphorus-rich nano sponge is designed to encapsulate and deliver a wide range of molecular payloads, highly effective in enhancing the survival, reproduction, and resilience of microbial, plant, and animal life forms.

[0028] In an aspect, the phosphorus-rich nano sponge comprises a porous matrix having an average particle size of less than 1000 nm and stabilized with a surface-active agent, wherein the porous matrix is held together by ionic linkages of one or more of transition metals selected from one or more of iron, copper, titanium, vanadium, nickel, cobalt, post transition metals selected from one or more of zinc, cadmium, aluminum, tin, lead, bismuth, alkaline earth metals selected from one or more of calcium, magnesium, barium and strontium, metalloids selected from one or more of silicon, boron and tellurium, alkali metals selected from one or more of potassium, sodium and lithium, lanthanides selected from one or more of cerium, gadolinium, europium, or mixed metals; and a molecular payload selected from polysaccharides, proteins, lipids, vitamins, free sugars, minerals and their compounds, plant nutrients, nitrates, amino acids, growth hormones, or plant protecting agents.

[0029] A key feature of the invention is the ability of the phosphorus-rich nano sponge to reconstitute into a colloidal dispersion when mixed with a solvent and stabilized with a surface-active agent, facilitating easy application and uniform distribution. Additionally, the phosphorus-rich nano sponge is engineered as a slow-release formulation, capable of releasing molecular payload and bioavailable phosphorus over along duration, ensuring sustained availability of essential molecular payload for optimal growth and development. This innovative approach to molecular payload delivery has significant implications for agriculture, biotechnology, and environmental management, offering a controlled, efficient, and versatile solution for enhancing biological productivity and health.

[0030] STATEMENT OF THE INVENTION

[0031] The present invention relates to a phosphorus-rich nano sponge designed for efficient delivery of beneficial molecules to diverse biological systems. The phosphorus-rich nano sponge comprises of a phosphorus- rich porous matrix and possesses an average particle size of less than 1000 nm, existing in a semi -crystalline, amorphous, mixed state of crystals, and stabilized with a surface-active agent. The internal structure of porous matrix is maintained or held together by ionic linkages of one or more of transition metals, post transition metals, alkaline earth metals, metalloids, alkali metals, lanthanides or mixed metals.

[0032] The phosphorus-rich nano sponge of the present invention enables the encapsulation and delivery of a wide range of molecular payloads, including polysaccharides, proteins, lipids, vitamins, free sugars, minerals and their compounds, plant nutrients, nitrates, amino acids, growth hormones, and plant-protecting agents. The nano sponge is designed for direct application that allows for rapid absorption by plants, enhancing the efficiency and effectiveness of delivery of molecular payloads compared to traditional fertilizers or pesticides.

[0033] The phosphorus-rich nano sponge provides primary plant nutrients in sufficient quantities, promoting greater root and shoot ratios, enhanced photosynthesis, improved nutrient uptake, better water retention, and optimized crop canopy. These improvements collectively lead to increased crop yields.

[0034] Moreover, when applied at very low doses directly to seeds, the phosphorus-rich nano sponge significantly increases the seedling vigor index, demonstrating its ability to promote rapid and robust seedling germination and establishment.

[0035] Additionally, the invention offers an environmentally safe and nutritionally efficient formulation with a customizable composition that can be optimized to provide specific nutritional remediation through a single application, minimizing the need for multiple products without compromising nutrient efficacy.

[0036] BRIEF DESCRIPTION OF DRAWINGS:

[0037] For a more complete understanding of the features and advantages of the present invention, reference is now made to the detailed description of the invention along with the accompanying figures and in which:

[0038] Figure 1 illustrates Transmission electron micrograph of phosphorus-rich nano sponge. Figure 2 illustrates Transmission electron micrograph of a cluster of phosphorus-rich nano sponges prepared according to Example 1.

[0039] Figure 3 illustrates Energy dispersive spectrograph and elemental mapping of phosphorous- rich nano sponge prepared according to Example 1.

[0040] Figure 4 illustrates Size distribution of phosphorus-rich nano sponge prepared according to Example 1 in a suspension as obtained from dynamic light scattering analysis.

[0041] Figure 5 illustrates Zeta potential of phosphorus rich nano sponge prepared according to Example 1 in a suspension.

[0042] Figure 6 illustrates Shoot and root length of mung bean seeds treated with control (water (A)) and phosphorus- rich nano sponge prepared according to Example 1 (B).

[0043] Figure 7 illustrates Seedling vigour index of mung bean seeds treated with control (water (A)) and phosphorus- rich nano sponge prepared according to Example 1 (B). DETAILED DESCRIPTION OF THE INVENTION

[0044] The making and using of various embodiments of the present invention are discussed in detail below. It should be appreciated that the present invention provides many applicable inventive concepts that can be embodied in a wide variety of contexts. The embodiments discussed herein are merely illustrative of specific ways to make and use the invention and do not delimit the scope of the invention.

[0045] To facilitate the understanding of this invention, a number of terms are defined below. Terms defined herein have meanings as commonly understood by a person of ordinary skill in the areas relevant to the present invention. Terms such as "a", "an" and "the" are not intended to refer to only a singular entity but include the general class of which a specific example may be used for illustration. The terminology herein is used to describe specific embodiments of the invention, but their usage does not delimit the invention, except as outlined in the claims.

[0046] The term “nano” as used herein, refers to the particle of matter having size in a range from 1 to 1000 nanometers (nm) in diameter. The present invention relates to a phosphorus- rich nano sponge comprising a porous matrix having an average size of less than 1000 nm and stabilized with a surface -active agent, wherein the porous matrix is held together by ionic linkages of one or more of transition metals selected from one or more of iron, copper, titanium, vanadium, nickel, cobalt, post transition metals selected from one or more of zinc, cadmium, aluminum, tin, lead, bismuth, alkaline earth metals selected from one or more of calcium, magnesium, barium and strontium, metalloids selected from one or more of silicon, boron and tellurium, alkali metals selected from one or more of potassium, sodium and lithium, lanthanides selected from one or more of cerium, gadolinium, europium, or mixed metals. Preferably, the metal is selected from but not limited to calcium nitrate tetrahydrate, calcium chloride or mixture thereof.

[0047] The phosphorus-rich nano sponge is a semi-crystalline, amorphous or mixed state of crystal.

[0048] The phosphorus- rich nano sponge is used to deliver molecules that are beneficial for survival, reproduction, and resilience of microbial, plant, fungal and animal life forms.

[0049] In an embodiment the phosphorus- rich nano sponge additionally comprises molecular payloads for targeted delivery and are selected from polysaccharides, proteins, lipids, vitamins, free sugars, minerals and their compounds, plant nutrients, nitrates, amino acids, growth hormones, or plant protecting agents for the survival, reproduction, and resilience of microbial, plant and animal life forms.

[0050] In a preferred embodiment, the phosphorus-rich nano sponge comprises a porous matrix having an average particle size of less than 1000 nm and stabilized with a surface-active agent, wherein the porous matrix is held together by ionic linkages of one or more of transition metals selected from one or more of iron, copper, titanium, vanadium, nickel, cobalt, post transition metals selected from one or more of zinc, cadmium, aluminum, tin, lead, bismuth, alkaline earth metals selected from one or more of calcium, magnesium, barium and strontium, metalloids selected from one or more of silicon, boron and tellurium, alkali metals selected from one or more of potassium, sodium and lithium, lanthanides selected from one or more of cerium, gadolinium, europium, or mixed metals; and a molecular payload selected from polysaccharides, proteins, lipids, vitamins, free sugars, minerals and their compounds, plant nutrients, nitrates, amino acids, growth hormones, or plant protecting agents.

[0051] The surface active agent comprises ionic / non-ionic surfactants selected from sodium alkyl sulfates such as sodium dodecyl sulphate, sodium alkylbenzene sulfonates, sodium alkyl ether sulfates, sodium lauryl sulfoacetate, sodium dodecyl benzene sulfonates, quaternary ammonium compounds, imidazolinium derivatives, ammonium carboxylates, alkyl trimethyl ammonium salts such as cetyltrimethylammonium bromide and dodecyl trimethylammonium chloride, alkyl benzyl dimethylammonium salts, polyoxymethylene alkyl esters, fatty alcohol polyglycol ethers, glyceryl esters, sorbitan esters such as polyoxyethylene sorbitan monolaurate (Tween 20), polyethylene sorbitol ester (Tween 80), Polyethyleneglycol-[4-(l,l,3,3-tetramethylbutyl)phenyl]-ether (Triton X-100), polyethylene glycol, Pluronic F68 / F127, trisodium citrate, sodium oleate, sodium polyacrylate, sodium lignosulfonate, sodium hexametaphosphate, tetrasodium pyrophosphate, polyvinylpyrrolidone or their combinations. The surface-active agent prevents sedimentation or precipitation of the porous matrix.

[0052] In an embodiment, the phosphorus-rich nano sponge as described above comprising the porous matrix is reinforced or held together by ionic linkages and by covalent linkages of esters, ethers, alkaline phosphates, phosphate anhydrides and aromatic compounds.

[0053] In an embodiment, the phosphorus-rich nano sponge is used as a fertilizer, a catalytic aid for conducting chemical reactions within its porous matrix, an aid for adsorption and absorption of pollutants from contaminated waters and soil or coating agent for preventing corrosion of metal surfaces under varying temperatures and acidity. The phosphorus-rich nano sponge may be formulated as a powder, suspension, emulsion or colloidal dispersion.

[0054] In an embodiment, the phosphorus-rich nano sponge is used as an agri-input such as, a fertilizer and comprises calcium and molecular payloads. Calcium forms a matrix within the phosphorus- rich nano sponge, which along with sulphur and other plant nutrients and bio-chemicals as molecular payloads forms a stable suspension. The calcium content is in the range of about 0. 1 to 1.0% (w / w or w / v or v / v), phosphate / phosphorus is in the range of about 1.2 to 8% (w / w or w / v or v / v) and sulphur is in the range of about 0.1 to 1.0 % (w / w or w / v or v / v). According to an embodiment, the plant nutrient is a macro and micronutrient and is selected from but not limited to potassium, calcium, magnesium, sulphur, iron, manganese, boron, molybdenum, copper, zinc, nickel chlorine, cobalt. According to an embodiment the total concentration of one or all macro and micronutrients will not exceed 20% (both w / w or w / v or v / v), respectively. Preferably, the phosphorus-rich nano sponge comprises up to 16% of phosphate or phosphorus. However, those skilled in the art will appreciate that it is possible to utilize other elements and composition and sizes known in the art without departing from the scope of the claims of the present invention. The fertilizer formulation comprising the phosphorus- rich nano sponge is applied by drones, foliar spray, root dipping technique, fertigation, and advanced greenhouse technologies such as hydroponics, aeroponics and nutrient films. Preferably, the fertilizer formulation is applied as a foliar or soil fertilizer. The fertilizer formulation comprising phosphorus-rich nano sponge is sustainable, non-toxic, biodegradable, and environment friendly, leaving negligible chemical residue after application. Further, the phosphorus-rich nano sponge as a fertilizer formulation ensures greater root: shoot ratios, elevated photosynthesis, enhanced nutrient uptake and richer crop canopy. The formulation is facile, rapid, and provides for a stable shelf life. Moreover, it has potential to be customized as per crop requirement. The formulation can positively influence plant immunity when enriched with protective functional ingredients. Applying the fertilizer formulation directly on leaves increases leaf activity, directly impacting the plant’s water intake, which in turn encourages root growth. Consequently, it can also accelerate nutrient uptake from the soil, helping plants with nutrient deficiencies that require immediate intervention.

[0055] In another embodiment, the phosphorus-rich nano sponge comprises zinc and iron, which also forms a matrix within the phosphorus- rich nano sponge. This nano sponge is used as foliar fertilizer. Zinc is in the range of about 0.5 to 2.0% (w / w or w / v or v / v) and iron is in the range of about 0.5 to 2.0% (w / w or w / v or v / v), and phosphate / phosphorus is in the range of about 3.0 to 6.0% (w / w or w / v or v / v).

[0056] In another embodiment, when used as a corrosion resistant coating, the phosphorus-rich nano sponge comprises zinc in the range of about 1.0 to 5.0% (w / w or w / v or v / v).

[0057] In another embodiment, the phosphorus-rich nano sponge comprises iron that forms a matrix within the phosphorus- rich nano sponge with an average size of 300 to 500 nm. When the phosphorus-rich nano sponge comprising, iron is used for heavy metal removal from wastewater and as foliar fertilizer, iron is in the range of about 0.5 and 2.0% (w / w or w / v or v / v).

[0058] In another embodiment, the phosphorus-rich nano sponge is a bone mineralization or resorption preventing formulation for treating bone fractures or osteopenia, dental cavities. In one embodiment the nano sponge contains calcium bound to phosphate in the porous matrix by formation of ionic bonding or covalent bonding. In other embodiment bone morphogenetic proteins and growth factors such as IGF1, IGF2, FGF, PDGF are incorporated in the sponge to promote bone regeneration.

[0059] The invention also relates to a process for preparation of phosphorus-rich nano sponge, wherein the phosphorus rich nano sponge is prepared by reacting phosphorus precursors with salts of one or more of transition metals selected from one or more of iron, copper, titanium, vanadium, nickel, cobalt, post transition metals selected from one or more of zinc, cadmium, aluminum, tin, lead, bismuth, alkaline earth metals selected from one or more of calcium, magnesium, barium and strontium, metalloids selected from one or more of silicon, boron, and tellurium alkali metals selected from one or more of potassium, sodium, and lithium, lanthanides selected from one or more of cerium, gadolinium, europium, or mixed metals. Herein the phosphorus precursors are selected from any of the phosphorous salts, phosphates such as hydrogen phosphate, dihydrogen phosphate, orthophosphate selected from but not limited to phosphoric acid, tripolyphosphate, pyrophosphate, metaphosphate, phosphides such as alkali metal phosphides, alkaline earth phosphides, phosphonates such as alkyl phosphonates, bisphosphonates, phosphonates salts.

[0060] In an embodiment the phosphorus-rich nano sponge is purified using filtration(ultrafiltration, microfiltration, ion exchange, decantation and centrifugation).

[0061] The synthesis / preparation of the phosphorus-rich nano sponge as described above includes following advantages: (i) simple synthesis method, requiring no complex and time-consuming steps (ii) versatile reconstituted formulation may be prepared from the phosphorus-rich nano sponge, and (iii) scalable potential for market applications. In an embodiment, the phosphorus-rich nano sponge is formulated into colloidal dispersion by mixing with a solvent and stabilized using a surface-active agent to give a reconstituted formulation. The solvent is selected from but not limited to water, polar organic solvents such as methanol, ethanol or mixtures thereof. The surface-active agent is described above. In an embodiment the reconstituted formulation additionally further comprises, sulphur containing compounds or salts such as zinc sulphate, potassium sulphate, ammonium sulphate, copper sulphate, magnesium sulphate, ferrous sulphate, manganese sulphate, barite, amino acids or vitamins including methionine, lipoic acid, cysteine, homocysteine, cystine, thiamine and biotin, glucosinolates and allylic sulphur, or sulphides such as galena, pyrite, blend, gypsum, chalcopyrite, dimethyl sulphide, sulphuric acid; biopolymers selected from chitosan, alginates, gelatine, dextran, collagen, sericin, casein, cellulose, starch, pectin, pullulan, keratin, hyaluronic acid, albumin, wheat gluten, poly lactic acid, poly caprolactone, poly vinyl alcoholgum arabic, lecithin, xanthum gum and saponins; crosslinker selected from glutaraldehyde, epoxy compound, amino acid diamines, epichlorohydrin, tannic acid, tri polyphosphates and tri metaphosphate, citric acid, borax, calcium chloride; reducing agents selected from hydrides, citrate, glucose, ascorbate, hydroxides, sulphite compounds, alkali metals, natural plant / biomass extracts; antifoaming agents selected from insoluble oils such as castor oil, silicone oil, alcohols such as cetostearyl alcohol, stearates, polydimethylsiloxanes and other silicone derivatives, ether and glycols; preservatives or anti-microbials selected from benzoates such as sodium benzoates, propionates including calcium propionates, sorbates such as potassium sorbate, sodium sorbate, nitrates and nitrites including sodium nitrite, propyl glycols, parabens such as methyl paraben, ethyl paraben, quaternary ammonium salts such as benzalkonium chloride, bronopol, sodium azide, phenols, chlorhexidine, cetrimide or combinations thereof to prevent microbial growth or act as preservative.

[0062] In another embodiment the phosphorus-rich nano sponge is formulated as a nano fertilizer which provides biosafe stable liquid compositions containing nano clusters of sulphur, phosphorous, calcium and having Ca:P:S (as P2O5) ratio of 2:7: 1, wherein the hydrodynamic diameter of the particles is less than 100 nm. The liquid nano fertilizer of the present invention is stable at least up to 50°C without gelling, phase separation and precipitation during storage. The liquid nano fertilizer is stable for at least 24 months at pH ranges between 4 and 7 during storage. The liquid nano fertilizer of the present invention containing nano clusters of calcium, phosphorous and sulphur, demonstrates increase vigour index of major crops such as paddy, and green gram upon seed treatment. Further, the said liquid nano fertiliser demonstrated a significant field efficacy with positive impact on growth of different crops such as rice, pearl millet, maize, wheat, soybean, onion, tomato as presented below.

[0063] Table 1 summarizes some of the characteristics of the liquid nano fertilizer of the present invention in comparison with the conventional phosphate fertilizer:

[0064] Table 1:

[0065] The present invention is further described with the help of the following examples, which are given by way of illustration, wherein all the parts, percentage and ratios are by weight unless otherwise indicated and therefore should not be construed to limit the scope of the invention in any manner.

[0066] EXAMPLES:

[0067] Example 1: phosphorus-rich nano sponge as Fertilizer (Nano P or Nano SSP) according to the present invention:

[0068] Ingredients of composition in weight percentage range or in other unit in following conditions:

[0069] A: Preparation of phosphorus-rich nano sponge to be used as a Fertilizer (Nano

[0070] Step 1: preparation of solution A

[0071] Phosphorus - rich nano matrix bound with calcium was obtained by treating calcium nitrate tetrahydrate with phosphoric acid.

[0072] Step 2: preparation of solution B

[0073] Solution B was prepared by mixing biopolymer starch solution with potassium sulphate solution, reducing agent, cross linking agent and trisodium citrate as surface-active agent.

[0074] Step 3: Preparation of nano fertilizer formulation

[0075] Measured quantities of Solution A and Solution B prepared according to steps 1 and 2 were mixed using stirrer at 10 to 50 rpm for 20 to 60 minutes to obtain the Nano P fertilizer formulation.

[0076] Step 4: Addition of antimicrobial agents

[0077] Weighed quantities of antimicrobials such as benzalkonium chloride and sodium benzoate were further added to the formulation obtained in step 3. Example 2: Characterization of the phosphorus-rich nano sponge (Nano P or

[0078] Nano SSP) prepared according to Example 1:

[0079] The characteristics of the phosphorus-rich nano sponge fertiliser (Nano P) with nano clusters of sulphur, calcium and phosphorous is presented in Table 2 below: Table 2:

[0080] Example 3: Field trials of the phosphorus-rich nano sponge fertilizer (Nano P or Nano SSP) prepared according to Example 1:

[0081] A. Seed germination study: A seed germination study comparing the impact of phosphorus-rich nano sponge fertilizer (Nano P) on shoot length (cm), root length (cm), germination (%) and seed vigour index on mung beans seeds as compared with control (water) was performed. The results of the study are presented in Table 3 below. Further the graphical representation of the root and shoot length has been demonstrated in Figures 6 and 7. Table 3:

[0082] As observed from Table 3 and Figures 6 and 7, the mung beans seed treated with Nano P fertilizer had a higher shoot and root length in comparison to the control. This shows that the phosphorus-rich nano sponge of the present invention significantly increases the seedling vigor index, demonstrating its ability to promote rapid and robust seedling germination and establishment.

[0083] B. Yield evaluation on pearl millet and maize crops: Farm Trials comparing impact of phosphorus-rich nano sponge fertilizer (Nano P) of

[0084] Example 1 along with conventional (PoP) or organic package of practice (Organic PoP) on the yields of pearl millet and maize over control (only PoP or Organic PoP) using recommended dose of conventional fertilizer was studied. The conventional PoP comprises Urea, SSP and Muriate of Potash (MoP). The results are present in Table 4 below: Table 4:

[0085] As observed from Table 4, treatment with Nano P of Example 1 along with conventional (PoP) or Organic PoP resulted in higher yield of pearl millet and maize crops as compared to crops treated only with conventional (PoP) or organic

[0086] PoP. This shows that the phosphorus-rich nano sponge of the present invention efficiently delivers molecular payloads leading to improved nutrient uptake thereby providing increased crop yields. C. Yield evaluation in rice crops by replacing the different dosages of conventional fertilizers (PoP) with Nano P of the present invention:

[0087] Farm Trials showing impact of phosphorus- rich nano sponge fertilizer (Nano P) along with different doses of conventional PoP fertilizer (0%, 25%, 50%, 75% and 100%) on yield of rice in comparison to control (only PoP) were performed and the results are presented in Table 5 below: Table 5:

[0088] Table 5 shows that the replacement of 100% PoP with Nano P resulted in an increase in the yields of rice. Further, the results show that substituting a portion of the PoP or supplementing PoP treatment with Nano P also significantly increased the yield of the rice crop. This indicates the potential of replacement, substitution or supplementation of the conventional PoP fertilizer with the phosphorus-rich nano sponge of the present invention, thereby providing a sustainable, non-toxic, biodegradable and environment friendly alternative while leaving a minimal chemical residue.

[0089] D. Yield evaluation of different crops on various plots or blocks:

[0090] Farm Trials showing impact of phosphorus- rich nano sponge fertilizer (Nano P) along with 100% PoP on the yield of different crops with respect to control (only PoP) were performed and the results are presented in Table 6 below: Table 6:

[0091] *LPT refers to Large Plot trial.

[0092] ARBD refers to Randomized block design.

[0093] * The numericals ‘2’, 3’, ‘4’ in column ‘trial design’ refers to the number of trials carried out in different plots / blocks for the same crop. Table 6 shows that treatment with the Nano P of Example 1 along with PoP resulted in a higher yield of all the tested crops in comparison to treatment with only PoP (Control). Thus, the phosphorus-rich nano sponge of the present invention is suitable for different varieties of crops.

[0094] Example 4:

[0095] Effect of the dosage of phosphorus-rich nano sponge fertilizer, that is Nano SSP prepared according to Example 1 of the present invention was compared with untreated control (crops treated only with water) on the yield of wheat crop. The results obtained are presented in Table 7:

[0096] Table 7

[0097] $UTC refers to Untreated Control. **refers to Critical Difference. *$refers to Standard Error.

[0098] As observed from Table 7, Nano SSP of the present invention gives a higher yield as compared to UTC, that is, crops treated only with water and further as the dosage of the Nano SSP increases the yield of the wheat crops also increases. All of the compositions and / or methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods of this invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the art that variations may be applied to the compositions and / or methods and in the steps or in the sequence of steps of the method described herein without departing from the concept, spirit and scope of the invention. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the invention as defined by the appended claims.

Claims

Claims :1 . A phosphorus- rich nano sponge comprising: a porous matrix having an average size of less than 1000 nm and stabilized with a surface-active agent wherein the porous matrix is held together by ionic linkages of one or more of transition metals selected from one or more of iron, copper, titanium, vanadium, nickel, cobalt, post transition metals selected from one or more of zinc, cadmium, aluminum, tin, lead, bismuth, alkaline earth metals selected from one or more of calcium, magnesium, barium and strontium, metalloids selected from one or more of silicon, boron and tellurium, alkali metals selected from one or more of potassium, sodium and lithium, lanthanides selected from one or more of cerium, gadolinium, europium, or mixed metals.

2. The phosphorus-rich nano sponge as claimed in claim 1 additionally comprising a molecular payload selected from polysaccharides, proteins, lipids, vitamins, free sugars, minerals and their compounds, plant nutrients, nitrates, amino acids, growth hormones, or plant protecting agents.

3. The phosphorous-rich nano sponge as claimed in claim 1 or 2, wherein the phosphorous-rich nano sponge is semi-crystalline, amorphous or mixed state of crystal.

4. A phosphorus-rich nano sponge comprising: a porous matrix having an average particle size of less than 1000 nm and stabilized with a surface-active agent, wherein the porous matrix is held together by ionic linkages of one or more of transition metals selected from one or more of iron,copper, titanium, vanadium, nickel, cobalt, post transition metals selected from one or more of zinc, cadmium, aluminum, tin, lead, bismuth, alkaline earth metals selected from one or more of calcium, magnesium, barium and strontium, metalloids selected from one or more of silicon, boron and tellurium, alkali metals selected from one or more of potassium, sodium and lithium, lanthanides selected from one or more of cerium, gadolinium, europium, or mixed metals; and a molecular payload selected from polysaccharides, proteins, lipids, vitamins, free sugars, minerals and their compounds, plant nutrients, nitrates, amino acids, growth hormones, or plant protecting agents.

5. The phosphorous-rich nano sponge as claimed in any one of the claims 1 to 4, wherein the phosphorus-rich nano sponge comprises up to 16% of phosphate or phosphorus.

6. The phosphorus-rich nano sponge as claimed in any one of the claims 1 to 5, wherein the porous matrix is held together additionally by covalent linkages of esters, ethers, alkaline phosphates, phosphate anhydrides and aromatic compounds.

7. The phosphorus-rich nano sponge as claimed in any one of the claims 1 to 6, wherein the phosphorous -rich nano sponge is formulated into colloidal dispersion by mixing with a solvent and stabilized using a surface -active agent.

8. The phosphorus rich nano sponge as claimed in any one of the claims 1 to 7, wherein the phosphorous-rich nano sponge is formulated as a slow-release formulation, releasing the molecular payloads along with bioavailable phosphorus over a duration9. The phosphorus- rich nano sponge as claimed in any one of the claims 1 to 8, wherein the phosphorus-rich nano sponge is formulated for delivery to microbial, plant, fungal or animal life forms.

10. The phosphorus-rich nano sponge as claimed in any one of the claims 1 to 7, wherein the phosphorus-rich nano sponge is used as a fertilizer, a catalytic aid for conducting chemical reactions within its porous matrix, an aid for adsorption and absorption of pollutants or coating agent for preventing corrosion of metal surfaces.

11. The phosphorus-rich nano sponge as claimed in claim 10, wherein the fertilizer is a foliar or soil fertilizer.

12. A colloidal dispersion comprising: a phosphorus- rich nano sponge comprising a porous matrix having an average size of less than 1000 nm and stabilized with a surface-active agent wherein the porous matrix is held together by ionic linkages of one or more of transition metals selected from one or more of iron, copper, titanium, vanadium, nickel, cobalt, post transition metals selected from one or more of zinc, cadmium, aluminum, tin, lead, bismuth, alkaline earth metals selected from one or more of calcium, magnesium, barium and strontium, metalloids selected from one or more of silicon, boron and tellurium, alkali metals selected from one or more of potassium, sodium and lithium, lanthanides selected from one or more of cerium, gadolinium, europium, or mixed metals; a solvent; and

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