Granules for delayed release of active ingredients to plants or seeds

Abstract

A particle for delayed release of an active ingredient to a plant or seed wherein the particle consists of a composite material comprising an active ingredient component and a clay component, the active ingredient component comprises a microbial cell extract or a mixture of at least one type of amino acid and one or more negatively charged ions and / or neutral molecules wherein the mixture comprises at least one type of positively charged amino acid, and the clay component comprises a montmorillonite clay mineral. The clay component forms a layered stack in the composite material, and the active ingredient component is interposed between individual clay layers in the stack.

Description

Technical Field

[0001] This disclosure relates to particles for delayed release of an active ingredient into plants or seeds, the use of such particles for delayed release of an active ingredient into plants or seeds, and methods for producing such particles. Background Technology

[0002] Controlled releases of plant growth enhancers (such as fertilizers, biostimulants, plant growth regulators, and pesticides) formulated with non-biodegradable polymers can cause persistent pollution with unknown consequences for animal and human health. Repeated application of such formulations can lead to the accumulation of microplastics, impacting local soil biodiversity and function. In the event of a fire, these plastics can release secondary compounds with unknown toxicity.

[0003] US20060135368A1 discloses controlled-release nitrogen particles that are dispersible in water. These particles may contain methylene urea and bentonite binder components. These particles disperse upon contact with water from the treated area itself, irrigation, or natural precipitation. These particles retain their size and shape during handling and application to the desired area and decompose or break down into smaller particles within 12 hours after contact with water.

[0004] CN112409077A, CN107056468B, and US2011 / 0296885A1 disclose various contellations for combining montmorillonite clay with urea to produce controlled-release nitrogen fertilizers. More efficient plant treatment can be achieved if the release of inputs in pellets / granules can be matched to the plant's nutrient requirements, or if more optimal timed release can be obtained. Summary of the Invention

[0005] One object of this disclosure is to provide granules for delaying the release of an active ingredient into plants or seeds.

[0006] This invention is defined by the appended independent claims. Non-limiting embodiments appear in the independent claims, drawings, and the following description.

[0007] According to a first aspect, there is provided a particle for delayed release of an active ingredient to a plant or seed, the particle being composed of a composite material comprising an active ingredient component and a clay component, wherein 5 to 99 wt.% of the composite material is composed of the clay component, wherein 1 to 95 wt.% of the composite material is composed of the active ingredient component, and the weight ratio of the clay component to the active ingredient component in the composite material is 1:20 to 99:1, wherein the active ingredient component comprises a microbial cell extract or a mixture comprising at least one type of amino acid and one or more negatively charged ions and / or neutral molecules, wherein the mixture comprises at least one type of positively charged amino acid, wherein the clay component comprises montmorillonite clay mineral, and the composite material comprises at least 5 wt.% montmorillonite clay mineral, and wherein the clay component forms a layered stack in the composite material, and the active ingredient component is intercalated between the individual clay layers in the stack.

[0008] Clay is an ideal naturally occurring component of agricultural soils because of its ability to retain moisture and nutrients.

[0009] Montmorillonite-type clays possess a layered structure, in which each individual clay layer or sheet consists of an octahedral sheet (O) predominantly composed of aluminum, iron, or magnesium sandwiched between two tetrahedral silica sheets (T). The montmorillonite TOT layers have a negative anionic surface charge and exhibit a combined characteristic of swelling and expansion along the normal direction when exposed to water, primarily due to the counteracting cation hydration present between the negatively charged TOT layers. Due to its layered structure and negative surface charge, montmorillonite-containing clays can possess high specific surface area and high cation exchange capacity.

[0010] The clay component forms a layered stack in the composite material, and at least a portion of the active ingredient component is intercalated or interposed between the individual clay layers in the stack. The active ingredient component can also be disposed on the edges of the clay layers, the outer surface of the stacked clay layers, etc.

[0011] The stacking of clay layers may be caused by a combination of electrostatic forces and van der Waals forces.

[0012] The active ingredient component comprises a microbial cell extract or a mixture comprising at least one type of amino acid and one or more negatively charged ions and / or neutral molecules, wherein the mixture comprises at least one type of positively charged amino acid. The active ingredient (i.e., the microbial cell extract or the mixture of at least one type of amino acid and one or more negatively charged ions and / or neutral molecules, wherein the mixture comprises at least one type of positively charged amino acid) may constitute at least 80%, 85%, 90%, or at least 95% of the active ingredient component. The remainder may be a binder or other substance, such as a harmless inert ballast.

[0013] The active ingredient component may contain more or less ionic components. The active ingredient component contains components that are ionic enough to interact with the clay minerals in the clay component.

[0014] Microbial cell extracts (such as yeast extracts) are complex mixtures of the cellular contents of microbial cells (such as yeast cells), including proteins, peptides, amino acids, metabolites, ions, carbohydrates, and lipids. It comprises a complex mixture of cations, anions, and neutral molecules in both inorganic and organic forms. Most nitrogen exists in the form of free amino acids and peptides, which carry both positive and negative charges depending on the different pKa values ​​of the various organic molecules and the pH. In turn, the release profile of the components of a yeast extract from the particles will depend on charge and size.

[0015] A mixture of at least one type of amino acid and one or more negatively charged ions and / or neutral molecules (wherein the mixture contains at least one type of positively charged amino acid) is a mixture containing arginine, lysine and / or histidine and one or more negatively charged ions (e.g., phosphate, sulfate, nitrate or phytic acid and / or one or more neutral molecules (e.g., serine, threonine, glutamine or asparagine)).

[0016] Clay layers can be stacked to form primary particles; primary particles can be stacked together to form larger particles. This is likely due to a combination of ionic and van der Waals forces. Particles can have any shape (e.g., spherical, flake-like, or cylindrical) and any size (e.g., nanometer, micrometer, millimeter, or centimeter scale), and are suitable for provision at or near plants. In one instance, particles may have an average diameter of 0.01–4 mm. Particles may consist solely of composite materials, or, for example, 80–100% of the particles may be composed of composite materials. The remainder may be, for example, coatings, adhesives, etc.

[0017] It should be noted that embodiments of the present invention are not limited to particles and composite materials having specific characteristics (e.g., shape, size, distance, etc.).

[0018] The composite material contains 5 to 99 wt.% clay component, calculated based on the total weight of the clay component excluding active ingredients. The composite material may contain 5-99 wt.%, 10-99 wt.%, 20-99 wt.%, 30-99 wt.%, 40-99 wt.%, 50-99 wt.%, 60-99 wt.%, 70-99 wt.%, 80-99 wt.%, 90-99 wt.%, 5-90 wt.%, 5-80 wt.%, 5-70 wt.%, 5-60 wt.%, 5-50 wt.%, 5-40 wt.%, 5-30 wt.%, 5-20 wt.%, 5-10 wt.%, 10-80 wt.%, or 20-50 wt.% clay component.

[0019] The composite material contains 1 to 95 wt.% of active ingredient components, calculated based on the percentage of active ingredient components in the total weight of the composite material. The composite material may contain 1-95 wt.%, 1-90 wt.%, 1-80 wt.%, 1-70 wt.%, 1-60 wt.%, 1-50 wt.%, 1-40 wt.%, 1-30 wt.%, 1-20 wt.%, 1-10 wt.%, 10-95 wt.%, 20-95 wt.%, 30-95 wt.%, 40-95 wt.%, 50-95 wt.%, 60-95 wt.%, 70-95 wt.%, 80-95 wt.%, 90-95 wt.%, 20-90 wt.% or 50-80 wt.% of active ingredient components.

[0020] The ratio of clay component to active ingredient component is 1:20 to 99:1, 1:10 to 99:1, 1:5 to 99:1, 1:2 to 99:1, 1:1 to 99:1; 2:1 to 99:1, 5:1 to 99:1, 10:1 to 99:1, 20:1 to 99:1, 30:1 to 99:1, 40:1 to 99:1, 50:1 to 99:1, 60:1 to 99:1, 70:1 to 99:1, 80:1 to 99:1, 1:20 to 99:1. 0:1, 1:20 to 80:1, 1:20 to 70:1, 1:20 to 60:1, 1:20 to 50:1, 1:20 to 40:1, 1:20 to 30:1, 1:20 to 20:1, 1:20 to 10:1, 1:20 to 5:1, 1:20 to 2:1, 1:20 to 1:1, 1:20 to 1:2, 1:20 to 1:5, 1:20 to 1:10, 1, 1:10 to 5:1, 1:2 to 2:1, or 1:5 to 1:1.

[0021] In one embodiment, the particles are composed of a composite material, wherein 10-80 wt.% of the composite material is composed of a clay component and 20-90 wt.% of the composite material is composed of an active ingredient component, and the weight ratio of the clay component to the active ingredient component in the composite material is 1:20 to 20:1.

[0022] Montmorillonite clay minerals can be montmorillonite, beidillite, chlorodiatomite, soapstone, lithium soapstone, vermiculite, hectorite, Stevensite, zinc soapstone, or any combination thereof.

[0023] Bentonite clay, which is mainly composed of montmorillonite, can be used.

[0024] The clay component includes montmorillonite clay mineral, and the composite material includes at least 5 wt.% montmorillonite clay mineral, or the composite material may contain 5-99 wt.%, 10-99 wt.%, 20-99 wt.%, 30-99 wt.%, 40-99 wt.%, 50-99 wt.%, 60-99 wt.%, 70-99 wt.%, 80-99 wt.%, 90-99 wt.%, 5-90 wt.%, 5-80 wt.%, 5-70 wt.%, 5-60 wt.%, 5-50 wt.%, 5-40 wt.%, 5-30 wt.%, 5-20 wt.%, 5-10 wt.%, 10-80 wt.%, or 20-50 wt.% montmorillonite clay mineral.

[0025] At least 50% of the clay component may consist of montmorillonite clay minerals, and at least 60%, at least 70%, at least 80%, at least 90%, or 50-100%, 60-100%, 70-100%, 80-100%, or 90-100% may contain montmorillonite clay minerals. The remaining clay component may consist of non-montmorillonite accessory minerals commonly found in clay, such as silicates, magnesium oxides, aluminum oxides, manganese oxides, iron oxides, sand, and / or silt.

[0026] In one embodiment, the composite material comprises 10-80 wt.% or 20-50 wt.% clay component, with the remainder being active ingredient component.

[0027] The described particles retain their size and shape during handling and application to the desired area. Upon contact with water or moisture, the clay layer of the particle's clay component re-swells and peels off as water enters the interlayer space. This allows the active ingredient to dissolve and diffuse out of the particle, enabling the active ingredient component to reach the intended area or plant. Particles containing a non-layered mixture of clay and active ingredient release their active ingredient immediately and almost completely upon contact with water / moisture. On the other hand, the aforementioned particles, where the active ingredient is intercalated between clay layers in a stack, exhibit a more delayed, controlled, and buffered release of the active ingredient from the particle upon contact with water / moisture / soil, providing an alternative to non-biodegradable polymers. By adjusting the amount of clay component, the amount of active ingredient component, and the ratio between the clay and active ingredient components in the composite material, the particles can be adapted to different requirements and conditions, such as the time required for complete release of the active ingredient.

[0028] The active ingredient component is thoroughly mixed with the clay to form a homogeneous phase. Therefore, the amount of active ingredient component inserted into the clay particles is mainly determined by the ratio of the active ingredient component to the clay. The amount of active ingredient component inserted into the particles is not limited and can be at least 40 wt.% or at least 50 wt.% of the total particle weight (as measured by XRD).

[0029] The aforementioned particles exhibit a combined effect of delayed and staggered / multi-stage release rates. The nitrogen source in the microbial cell extract is primarily in organic form, such as 20 different protein amino acids. Each amino acid has a unique isoelectric point and therefore carries a unique charge depending on the pH. These 20 different amino acids will be released at unique rates based on their charge and size. Delayed and staggered / multi-stage controlled release rates are beneficial because they help match available nutrients with the nutrient requirements for healthy and stress-tolerant growth, thereby reducing losses and increasing efficiency. Delayed and staggered / multi-stage release is compatible with biosensitive processes such as seed germination, where small changes in osmotic potential around the seed can inhibit germination, allowing particles to be precisely placed near the seeds in the seed furrow at a reduced rate compared to broadcast application.

[0030] An active ingredient component comprising at least one type of amino acid and one or more negatively charged ions and / or neutral molecules (wherein the mixture contains at least one type of positively charged amino acid clay particles) will produce similar results because the release rate of organic nitrogen and other nutrients will be delayed and staggered / multi-stage in a manner similar to that of microbial cell extracts, thus matching plant needs.

[0031] If similar clay particles were instead formed from clay and urea as an active ingredient, this would result in a limited amount of urea inserted, at most about 35 wt.% of the total particle weight (as measured by XRD). Urea is a low-charge neutral molecule with a molecular weight of 60.06 g / mol and a nitrogen content of 46%. Urea contains no phosphates, potassium, or any other plant nutrients, and its density is no more than 1.3 g / cm³. 3 Excess urea that is not inserted will recrystallize outside the clay particles.

[0032] When using urea as fertilizer, most of the nitrogen in urea can be absorbed and utilized by plants after being hydrolyzed by free urease in the soil to form ammonia. It is well known that ammonia derived from urea can damage root tips, exhibiting characteristic symptoms of leaf tip burn, or inhibit seed germination if applied too close. Therefore, broadcast fertilization, i.e., spreading the fertilizer evenly on the soil surface, reduces the effective concentration at the seed site. Furthermore, unembedded and recrystallized urea outside the clay particles can be released into the plants immediately and at a highly concentrated rate, which may harm the plants rather than promote their growth and germination, as mentioned above. The release rate of urea is not affected by ion association, and the concentration of urea in the soil will increase according to a single, rapid release rate function. If the particles are placed near the seeds, the release rate of both inserted and uninserted urea in this way is incompatible with sensitive biological processes such as seed germination, meaning that such particles cannot be used for precise placement in the sowing furrow and must be broadcast at a high total rate or banded away from the sowing furrow.

[0033] The active ingredient component and / or clay component may contain phytic acid.

[0034] Phytic acid is a six-fold dihydrogen phosphate ester of inositol (specifically, the muscle-type isomer), also known as inositol hexaphosphate (IP6) or inositol polyphosphate. It is found in many seeds and grains, and non-ruminant animals lack the enzymes (phytases) necessary to break it down, thus hindering digestion. Phytic acid also binds to proteins, amino acids, and ions. Therefore, phytic acid is considered an "anti-nutritional" in animal feed and food because it restricts the digestion and absorption of nutrients. This property can be used as a means of delaying the release of organic and inorganic active ingredients (such as fertilizers) in plant production systems.

[0035] According to the second aspect, the use of the aforementioned particles for delaying the release of active ingredients into plants or seeds is provided.

[0036] Granules or aggregates thereof, in granule or pellet form, can be applied to the soil, incorporated into the soil, mixed into potting mix, placed near seeds at sowing, or placed near the roots when planting seedlings to delay the release of the active ingredients. These granules can be applied to seeds in powder form. They can also be sprayed onto leaves as a suspended powder.

[0037] According to a third aspect, a method for producing particles for delayed-release active ingredients is provided, the method comprising the following steps: - Pre-swell in an aqueous solvent a clay component consisting of at least 50% montmorillonite clay minerals. - The pre-swollen clay component is mixed with an active ingredient component comprising a microbial cell extract or a mixture comprising at least one type of amino acid and one or more negatively charged ions and / or neutral molecules, wherein the mixture comprises at least one type of positively charged amino acid, wherein 5 to 99 wt.% of the mixture, by dry weight, consists of the clay component, wherein 1 to 95 wt.% of the mixture, by dry weight, consists of the active ingredient component, and the weight ratio of the clay component to the active ingredient component in the mixture is 1:20 to 99:1. - Dry the mixture, This results in the formation of particles containing layered stacks of clay components, with active ingredients interspersed between the individual clay layers in the stack.

[0038] The amounts and ratios of the clay and active ingredient components used in this method can be varied for particulate composites as described above.

[0039] After mixing the pre-swollen clay component with the active ingredient component, the mixture can be dried during or after extrusion.

[0040] The active ingredient component can be mixed with phytic acid before being mixed with the clay component.

[0041] The amount of phytic acid mixed with the active ingredient component can be such that the ratio of phytic acid to the active ingredient component is 1:100 to 1:10 (w / w or mole:mole).

[0042] Mixing active ingredient components with phytic acid can be used as a means to bind active ingredients and slow down the release rate of active ingredients from particles.

[0043] Alternatively or additionally, the pre-swollen clay component may be mixed with phytic acid before the clay component is mixed with the active ingredient component.

[0044] The amount of phytic acid mixed with the clay component can be such that the ratio of phytic acid to clay component is 1:1000 to 1:100 (w / w or mole: mole).

[0045] Phytic acid can adsorb onto clay, giving it a greater negative charge and ensuring it peels off into separate clay layers. Adding phytic acid acts as a diluent (reducing viscosity), which is useful in the production process as a way to reduce the amount of water needed for effective dispersion and mixing, and also lowers the drying costs of the mixture.

[0046] According to the fourth aspect, a plant or seed treatment composition comprising the aforementioned particles is provided.

[0047] The composition may comprise particles in the form of aggregates, granules, or pellets. The composition may also be in powder form. Alternatively, the composition may be a suspension, such as a sprayable suspension. The composition can be applied to soil, incorporated into soil, added to potting mix, placed near seeds at sowing, or placed near the roots when planting seedlings to delay the release of the active ingredient. In addition to particles, the composition may contain other components, such as binders (e.g., carboxymethyl cellulose). Such components may, for example, comprise less than or about 2% of the composition by dry weight. Attached Figure Description

[0048] Figure 1 The diagram schematically illustrates a possible structure for a composite material containing particles for delayed release of an active ingredient into plants or seeds. A clay component is arranged within a stack of clay layers, with the active ingredient component interspersed between the individual clay layers.

[0049] Figure 2 This schematically illustrates how active ingredients can be inserted between clay layers in a granular composite material (left side of the figure). Average basal spacing (d) 001 (Greater than 2 nm or about 2 nm, ranging from 1.2 nm to 4.1 nm.) Figure 2 The right side shows the clay layers, where the active ingredients were not inserted between the clay layers. Basement spacing (d) 001 The average is less than 2 nm.

[0050] Figure 3 Release rate profiles for two types of particles (Materials 1 and 2) are shown. Material 1 comprises particles of pre-swollen montmorillonite mixed with yeast extract at a 1:1 ratio. Material 2 comprises particles of non-pre-swollen / dehydrated montmorillonite mixed with yeast extract at the same 1:1 ratio.

[0051] Figure 4 The main steps of a method for producing particles for delayed release of active ingredients are illustrated schematically.

[0052] Figure 5The following powder XRD data are shown: (a) montmorillonite clay intercalated with urea, exhibiting XRD patterns at 4.9°2 due to ordered and limited lamellar expansion. The (001) diffraction peak is displayed at the corresponding d. 001 (a) Montmorillonite clay intercalated with yeast extract, showing no (001) diffraction peak due to unrestricted and disordered swelling; (b) Natural montmorillonite clay, showing a peak at 7.4° 2 due to water absorption at ambient relative humidity. The (001) diffraction peak is displayed at the corresponding d. 001 For approximately 12.4 Å, (d) pure urea in powder form at 22.2°, 24.6°, 29.3° and 31.6° 2 The (110), (101), (111), and (200) diffraction peaks of crystalline urea are shown. The peaks indicated by i-iv are minor mica phase, montmorillonite (hk0) reflection, quartz phase, and feldspar phase.

[0053] Figure 6 A photograph of corn seeds placed in soil with a moisture content of 14% is shown. Five days after sowing, control seeds (without fertilizer) (a) showed normal germination, while seeds (b) fertilized with montmorillonite clay and urea granules (c1) placed next to seeds (b) did not germinate.

[0054] Figure 7 Photographs of corn seeds placed in soil with a moisture content of 14% are shown. Five days after sowing, both the control seed (without fertilizer) (a) and the seed (b) fertilized with montmorillonite clay and yeast extract granules (c1) placed next to the seed (b) showed normal germination. Detailed Implementation

[0055] The following describes a method for producing granules that can be used to delay the release of active ingredients, such as fertilizers, soil nutrients, biostimulants, and / or pesticides, onto plants or seeds.

[0056] The particles are composed of a composite material comprising an active ingredient component and a clay component. 5 to 99 wt.% of the composite material consists of the clay component, of which 1 to 95 wt.% consists of the active ingredient component, and the weight ratio of clay component to active ingredient component in the composite material is 1:20 to 99:1. The clay component comprises montmorillonite clay mineral, and the composite material contains at least 5 wt.% montmorillonite clay mineral. Due to the layered structure of montmorillonite-type clay, the clay component forms layered stacks within the composite material, and at least a portion of the active ingredient component is inserted or sandwiched between the individual clay layers within the stacks. This active ingredient component comprises microbial cell extracts or a mixture containing at least one type of amino acid and one or more negatively charged ions and / or neutral molecules, wherein the mixture contains at least one type of positively charged amino acid. The active ingredient component can also be arranged on the edges of the clay layers, on the outer surface of the stacked clay layers, etc. The degree of stacking of the clay layers (i.e., the number of stacks and the number of layers in each stack) can be determined by transmission electron microscopy and / or XRD (X-ray diffraction analysis).

[0057] Figure 1 The possible structure of such a composite material is schematically illustrated. A clay component is arranged in a stack of clay layers (black lines), and an active ingredient component (dotted areas) is interspersed between the individual clay layers. The thickness of each individual clay layer can be approximately 1 nm, while the other two dimensions are approximately 30–1000 nm. The average distance between the clay layers in the stack of the composition can be at least 1.0 nm or at least 3 nm. However, these thicknesses and distances can deviate from these ranges and depend on the active ingredient component and the active ingredient used, as well as the amount and ratio of the clay component and the active ingredient component in the composite material.

[0058] Figure 2 This schematically illustrates how active ingredients can be inserted between clay layers in a composite material (left side of the figure). Average basal spacing (d) 001 The wavelength is greater than 2 nm or approximately 2 nm, ranging from 1.2 nm to 4.1 nm. The right side of the figure shows the clay layers where the active ingredient was not intercalated between the clay layers. Average basal spacing (d) 001) Less than 2 nm. The space between the inner surfaces of adjacent clay flakes and clay layers is a sandwich layer, which can be occupied by materials (e.g., active ingredients). The sum of the distance and the flake thickness is "d". 001 "The interplanar spacing (plate spacing) can be measured using X-ray diffraction. The specific surface area of ​​composite materials can be greater than 700 m²." 2 / g, and can have a large aspect ratio, such as greater than 50.

[0059] In composite materials, most or at least a portion of the clay layers may not be arranged as a stack (i.e., non-aggregate (dispersed) clay layers), but rather exist as a single monolith or as edge-to-edge ion-associations (cardboard house structure), or as no more than two face-to-face clay layers, with no active components in the interlayer spaces. However, this cardboard house structure may be primarily present in wet / hydrated particles, and may collapse when the particles dry.

[0060] The number of stacks in composite materials and particles depends on factors such as the amount of clay in the composition and the size of the particles. There can be varying numbers of individual clay layers (also known as tactoids / aggregates) within the stacks, for example, from at least 2 to up to 100 clay layers or more. The stacks of clay layers in the composite material can be disordered, curved, and of varying sizes. The degree of stacking of clay layers / sheets (i.e., the number of layers per stack) can be determined by transmission electron microscopy and / or XRD.

[0061] generally, Figure 4 The method schematically illustrated includes pre-swelling a clay component 100, consisting of at least 50% montmorillonite clay minerals, in an aqueous solvent. Prior to pre-swelling, the clay component may be pretreated in various ways, such as enriching the clay component with sodium. Pre-swelling may be carried out, for example, in water, distilled water, a buffer solution, or water with a salt content of up to 0.3 M. In the pre-swelling step 100, the clay component, typically added in dry powder form, is mixed with the aqueous solvent at a ratio of 5% to 50% (w / v). The mixing of the clay component and the solvent may be carried out, for example, by stirring or by mixing during incubation or subsequently incubating for at least 4 hours, at least 8 hours, or up to 48 hours or longer, to ensure complete swelling and exfoliation of the clay layer.

[0062] To determine whether the pre-swelling method has resulted in complete or adequate swelling of the clay component, a simple method is to measure the volume of the clay component before and after swelling. If the wet volume of the swollen clay is four times or more the volume of the dry clay (before mixing with the solvent), the pre-swelling step has produced adequately swollen clay. Another method to measure the degree of clay swelling is to rotate the solid and measure the volume while the clay undergoes swelling. Typically, the clay should swell to a uniform consistency, and the average basal distance between layers should be at least 2 nm. The pre-swelling step 100 can be performed at room temperature or a higher temperature (e.g., 20–50 °C).

[0063] Subsequently, the pre-swollen clay component is mixed with the active ingredient component using methods such as kneading or stirring 101. The mixture consists of 5 to 99 wt.% clay component by dry weight, and 1 to 95 wt.% active ingredient component by dry weight, with a clay component to active ingredient component weight ratio of 1:20 to 99:1. Mixing step 101 can be carried out at room temperature or higher temperatures (e.g., 20-80°C). Following the mixing step, a culture step of up to 24 hours or longer can be performed to ensure sufficient diffusion of the yeast extract within the exfoliated montmorillonite interlayers. This can be measured using XRD. Sufficient diffusion does not necessarily mean that the active ingredient component completely and uniformly penetrates into the clay interlayer space. While complete diffusion is ideal, sufficient mixing means that the active ingredient component is sufficiently residing in the interlayer space, resulting in a reduced rate of release of the active ingredient from the particles. In heterogeneous structures, some (at least 5% of the total volume of the particulate composite) of the active ingredient component is inserted, with the remainder retained in the composite as unincorporated active ingredient component.

[0064] The mixture may then be extruded, dried 102, and possibly crushed into smaller particles.

[0065] XRD measurements were used to compare the structures of clay particles containing urea and clay particles containing yeast extract. Figure 5 The XRD data in the samples showed the following powder XRD data: (a) montmorillonite clay intercalated with urea (material 3), due to ordered and limited layered expansion, at 4.9° 2 The (001) diffraction peak is displayed at the corresponding d. 001 (a) Montmorillonite clay intercalated with yeast extract (Material 1) did not show a (001) diffraction peak at 18 Å, and (b) natural montmorillonite clay, due to water absorption at ambient relative humidity, showed a peak at 7.4° 2. The (001) diffraction peak is displayed at the corresponding d. 001 For approximately 12.4 Å, (d) pure urea in powder form at 22.2°, 24.6°, 29.3° and 31.6° 2 The diffraction peaks of crystalline urea (110), (101), (111), and (200) are shown at the position.

[0066] The peaks indicated by i-iv are minor mica phases, montmorillonite (hk0) reflections, quartz phases, and feldspar phases.

[0067] For the clay-yeast extract composite particles, XRD results showed that the swelling of the montmorillonite layer was disordered or unrestricted, because the (001) peak of the clay peak disappeared in the presence of yeast extract. This means that the large-scale insertion of yeast extract is unrestricted and is determined only by the ratio of yeast extract to clay.

[0068] The release pattern of the active ingredient from layered particles containing yeast extract was compared with that from particles containing a non-layered mixture of the same clay and active ingredient. Release of the active ingredient from the non-layered particles containing yeast extract was immediate and almost complete. In contrast, release from the clay particles containing intercalated yeast extract was delayed.

[0069] This indicates that, compared to the same amount of active ingredient and clay as a mixture (where clay layers are stacked into aggregates with an average basal distance of less than 2 nm), the inserted active ingredient is retained to a greater extent during long periods and multiple elution cycles. Release of the active ingredient held between each individual clay layer is delayed because it requires the material to first swell, followed by the release of ions from cation and anion exchange sites on the surface and edges of the clay layers, respectively.

[0070] Depending on the expected results of active ingredient application, the release rate can be varied to ensure the active ingredient remains available at optimal levels over a longer period. Increasing the clay-to-active-ingredient ratio can further delay release or reduce peak concentration, thereby prolonging the treatment's effectiveness.

[0071] Furthermore, the biological relevance of using clay granules containing yeast extract as fertilizer was compared with that of using clay granules containing urea. The biological relevance of using clay granules containing yeast extract as fertilizer was also compared with not using any fertilizer at all. After 5 days, the germination status of the seeds was visually inspected.

[0072] Figure 6 The image shows corn seeds placed in soil with a moisture content of 14%. Five days after sowing, control seeds (without fertilizer) (a) showed normal germination, while seeds (b) fertilized with montmorillonite clay and urea granules (c1) placed next to seeds (b) did not germinate. Clearly, the urea-containing clay granules inhibited germination, while all control seeds germinated normally.

[0073] Clearly, urea does not interact with the charged montmorillonite surface or edges via ionic bonds and is released at a rate sufficient to generate stress and inhibit germination. Urea loaded at levels exceeding the insertion limit is most likely to be released first, allowing urease-mediated ammonia production and causing associated toxicity. To some extent, plants can remove ammonia toxicity through metabolism into amino acids. With the breaking of seed dormancy and the restoration of metabolic capacity, it is particularly sensitive to ammonia toxicity. Amino acids (such as those in yeast extracts) can be directly absorbed and efficiently metabolized.

[0074] Figure 7Corn seeds placed in soil with a moisture content of 14% are shown. Five days after sowing, both the control seed (without fertilizer) (a) and the seed (b) fertilized with montmorillonite clay and yeast extract granules (c2) placed next to the seed (b) showed normal germination. All seeds fertilized with the clay and yeast extract granules germinated normally, with radicle and cotyledon growth rates similar to the control.

[0075] like Figure 7 As shown, normal seed germination was observed near yeast extract particles inserted into the montmorillonite layer. This is due to the combined effect of delayed and staggered / multi-stage release rates and nutrient forms. The nitrogen source in the yeast extract is primarily in organic forms, such as 20 different protein amino acids. Each amino acid has a unique isoelectric point and therefore carries a unique charge depending on pH. This is the reason for the significant functional difference between the mixture of different amino acids in the yeast extract and a single nitrogen source from urea inserted into the montmorillonite layer. Because the release rate of urea is not affected by ion association, the soil concentration will increase according to a single, rapid release rate function. On the other hand, these 20 different amino acids will be released at unique rates according to their charge and size. Delayed and staggered control of release rates is beneficial because it helps to match available nutrients with the nutrient requirements for healthy and stress-tolerant growth, thereby reducing losses and improving efficiency.

[0076] Therefore, montmorillonite clay continues to function as a charge-ion exchange surface.

[0077] The use of yeast extract as an active ingredient in clay particle active ingredient components has been discussed above. Other microbial cell extracts or active ingredient components containing at least one type of amino acid and one or more negatively charged ions and / or neutral molecules (wherein the mixture contains at least one type of positively charged amino acid clay particles) will produce similar results because the release rate of organic nitrogen and other nutrients will be delayed and staggered / multi-stage in a similar manner to yeast extract, thus better matching plant needs.

[0078] experiment Particle formation of pre-swellable clay, Material 1 Pre-swelling bentonite clay, consisting of at least 50% montmorillonite clay minerals, was prepared by gently mixing 10% (w / v) of montmorillonite-rich bentonite clay with tap water and allowing it to stand at room temperature for >48 hours to ensure complete exfoliation of the montmorillonite layer. This yielded a pre-swelled clay compound, i.e., a viscous gel. Dry yeast extract powder (i.e., the active ingredient component) was added to bring the mixture to 20% (w / v) with a dry content ratio of 1:1 (clay component: yeast extract powder). The gel was intermittently hand-kneaded in a plastic bag and incubated in a 65°C water bath for 24 hours to ensure sufficient diffusion of the yeast extract within and between the exfoliated montmorillonite layers. The gel was then extruded through a 7 mm diameter hole to form a sausage-like shape and dried at 50°C. The dried material was then crushed into smaller particles with a particle size distribution of 1–4 mm.

[0079] Particle formation of non-pre-swellable clay, Material 2 (reference material) A reference material (Material 2) was prepared, wherein the final particles comprised a material composed of the same amount of the same yeast extract and the same clay component used in Material 1, aggregated together, such that the yeast extract was not intercalated between the clay layers, as confirmed by electron microscopy or XRD. Equal amounts of dry (unswollen) montmorillonite-rich bentonite and dry yeast extract powder were homogenized. The dry mixture was granulated by spraying a fine water mist to momentarily (within minutes) wet the surface and by agitating in a plastic bag until a particle size distribution of 1–4 mm was achieved. The granules were then immediately dried at 50°C. The amount of water added during granulation did not cause any swelling or peeling of the montmorillonite layers, thus preventing the yeast extract from diffusing between the layers.

[0080] Particle formation for XRD measurements Urea-containing clay particles (Materials 3) were produced using the same method as Material 1, by pre-swelling montmorillonite-rich bentonite. However, instead of introducing yeast extract, urea was mixed with a clay paste to achieve a mixture of 20% (w / v) and a dry content ratio of 1:1 (clay component: urea). The gel was intermittently hand-kneaded in a plastic bag and incubated in a 65°C water bath for 24 hours to ensure sufficient diffusion of the yeast extract within and between the exfoliated montmorillonite layers. The gel was then extruded through a 7 mm diameter hole to form a sausage-like shape and dried at 50°C. The dried material was then crushed into smaller particles with a particle size distribution of 1–4 mm.

[0081] Clay particles containing yeast extract were produced in the same manner as Material 1.

[0082] XRD measurement Use 3.5-35 2 Standard powder XRD measurements were performed using CuKα X-rays (1.542 Å).

[0083] The 1:1 (clay component: yeast extract) and 1:1 (clay component: urea) samples used for XRD measurements were prepared by pre-swelling montmorillonite-rich bentonite and then mixing it with dry yeast extract or urea, respectively, in the same manner as Materials 1 and 3. Instead of extruding the materials to form granules, the 1:1 (clay component: yeast extract) or 1:1 (clay component: urea) paste was uniformly spread on a glass slide and dried to form an oriented sample mount. These slides were then placed on a stage for XRD measurements.

[0084] Release rate test Release rate tests of the active ingredients in Materials 1 and 2 were conducted. This was done to demonstrate that the release of the active ingredients from the montmorillonite-based nanocomposite material could be delayed if the active ingredients were intercalated between clay layers.

[0085] The experiment was set up as follows: 50 mL plastic tubes with a 1.5 mm diameter orifice at the bottom were filled with washed and sieved sand to form a vertical cylinder. Equal amounts of Material 1 or Material 2 were uniformly mixed into their respective tubes. The sand / material mixture was brought to field capacity with deionized water over a series of time points. At each time point, 15 mL of deionized water, equivalent to the field capacity of the sand / material mixture, was introduced at the top of the tube and allowed to permeate under gravity, allowing for complete removal and renewal of the water in the column. The liquid drained from the orifice at the bottom of the column (eluent) was collected, and the conductivity of the eluent was measured. Blank tubes containing sand but without added material were used to measure and correct for the presence of small ions in the sand that might affect conductivity. Deionized water was continuously flowed through the tubes according to the schedule in Table 1. The conductivity of each continuous eluent was measured, providing a curve showing its change over time and volume.

[0086] Table 1 - A series of elution volumes over time, i.e., release rates Release rate curves of material 1 and material 2 ( Figure 3 The differences are as follows: The release of the active ingredient from material 2 is immediate and almost complete. In contrast, the release from material 1 is delayed, in which the active ingredient is effectively integrated into the montmorillonite interlayer.

[0087] Particle formation was used to compare clay particles fertilized with yeast extract and clay particles fertilized with urea. Yeast extract:clay particles with a ratio of 50:50 w / w were prepared in the same manner as Material 1.

[0088] Urea:clay particles with a urea:clay ratio of 50:50 w / w were prepared in the same manner as Material 3.

[0089] Six replicates were prepared for each sample.

[0090] Comparison of clay granules using yeast extract as fertilizer and clay granules using urea as fertilizer Fill 12 cm × 12 cm boards with soil containing 14% moisture (sufficient for normal seed germination). Place two corn seeds evenly spaced in the middle of each board and press them into the soil in the same direction, with the germ facing upwards, ensuring soil-seed contact. Then, place an equal amount (66 mg) of clay granules containing yeast extract or urea-containing clay granules directly in contact with one corn seed on each board. Include a reference seed on each board (no fertilizer granules are placed next to this seed). Wrap all boards in aluminum foil to protect them from light and place them vertically.

[0091] Five days later, visually inspect the seeds.

Claims

1. A particle for delayed release of an active ingredient into a plant or seed, the particle comprising a composite material comprising an active ingredient component and a clay component, wherein 5 to 99 wt.% of the composite material is composed of the clay component, wherein 1 to 95 wt.% of the composite material is composed of the active ingredient component, and the weight ratio of the clay component to the active ingredient component in the composite material is 1:20 to 99:1, wherein the active ingredient component comprises a microbial cell extract or a mixture comprising at least one type of amino acid and one or more negatively charged ions and / or neutral molecules, wherein the mixture comprises at least one type of positively charged amino acid, wherein the clay component comprises montmorillonite clay mineral, and the composite material comprises at least 5 wt.% of the montmorillonite clay mineral, and wherein the clay component forms a layered stack in the composite material, and the active ingredient component is intercalated between the individual clay layers in the stack.

2. The particles according to claim 1, wherein the montmorillonite clay mineral is montmorillonite, chlorometholite, saponite, hydropyrite, or any combination thereof.

3. The particles according to claim 1 or 2, wherein the active ingredient component and / or the clay component comprises phytic acid.

4. Use of the granules according to any one of claims 1-3 for delaying the release of an active ingredient into plants or seeds.

5. A method for producing particles for delayed-release active ingredients, the method comprising the following steps: - Pre-swell in an aqueous solvent a clay component (100) consisting of at least 50% montmorillonite clay minerals. - The pre-swelled clay component is mixed with the active ingredient component (101), wherein the active ingredient component comprises a microbial cell extract or a mixture comprising at least one amino acid and one or more negatively charged ions or neutral molecules, wherein the mixture comprises at least one type of positively charged amino acid, wherein 5 to 99 wt.% of the mixture is composed of the clay component on a dry weight basis, wherein 1 to 95 wt.% of the mixture is composed of the active ingredient component on a dry weight basis, and the weight ratio of the clay component to the active ingredient component in the mixture is 1:20 to 99:

1. - Dry the mixture (102), This forms particles containing a layered stack of clay components, wherein active ingredients are interspersed between the individual clay layers in the stack.

6. The method of claim 5, wherein the active ingredient component is mixed with phytic acid and then mixed with the clay component.

7. The method according to any one of claims 5-6, wherein the pre-swollen clay component is mixed with phytic acid, and then the clay component is mixed with the active ingredient component.

8. A plant or seed treatment composition comprising particles according to any one of claims 1-3.

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