An adhesive emulsifier based on protein amyloid aggregates, and a method for preparing and using the same

Abstract

The application provides an adhesive emulsifier based on protein amyloid aggregates and a preparation method and application thereof, and belongs to the technical field of new materials and emulsifier preparation; the adhesive emulsifier is a core-shell structure composite material, the core is an arbitrary structure nanometer material, and the shell is a nanometer film formed by protein amyloid aggregates; the adhesive emulsifier can be firmly adsorbed on the oil-water interface to enhance the stability of the emulsion; the adhesive emulsifier can be used for preparing nanoemulsion and nanoemulsion herbicide; the nanoemulsion herbicide can be firmly adhered to the leaf surface of weeds, resist wind and rain erosion, and achieve the purpose of reducing application and increasing efficiency; and in addition to emulsifying the oil-water interface, the adhesive emulsifier can also efficiently emulsify the gas-liquid interface, and has great application potential in the preparation of other nano pesticides (such as sterilization and insect killing), cosmetics, intelligent food, biological medicine and other fields.

Description

Technical Field

[0001] This invention belongs to the field of new materials and emulsifier preparation technology, specifically relating to an adhesive emulsifier based on protein amyloid aggregates, its preparation method, and its application. Background Technology

[0002] Herbicide application is the most efficient method for controlling weeds in farmland and a crucial guarantee for increasing the yield of most cash crops. However, during herbicide application, because the herbicide droplets cannot effectively penetrate, deposit, and adhere to the surface of target plants, most of the herbicide solution is lost through bouncing, rolling, evaporation, and aggregation, resulting in low weed control efficiency and causing environmental pollution to the atmosphere, water bodies, and soil. It also leads to biodiversity hazards such as pesticide residues in agricultural products, non-target beneficial organisms, and humans, as well as a waste of pesticide resources. To achieve reduced application and increased efficiency of herbicides and prevent the loss of active ingredients due to wind and rain erosion, it is necessary to design and optimize herbicide formulations to enhance their adhesion to weed leaves and their resistance to wind and rain erosion.

[0003] Nanoemulsion herbicides are colloidal systems with particle sizes ranging from 20 to 1000 nm, composed of herbicide active ingredients, solvent oil, water, emulsifiers, and small amounts of other adjuvants (antifreeze agents, emulsifying aids, thickeners, and defoamers, etc.). Compared with traditional emulsifiable concentrates and wettable powders, nanoemulsion herbicides have a series of advantages, including low interfacial tension and low active ingredient usage, high kinetic stability, good leaf spreadability, high adhesion, high penetration and absorption, low herbicide loss and degradation, low biohazard, and low environmental residue and pollution. They have broad application potential in agriculture, serving as an effective measure for the green control of crop pests and an important support for achieving increased agricultural production and income, as well as a green and low-carbon economic transformation. However, the development of nanoemulsion herbicides faces many technical challenges, particularly the development of intelligent, green nanoemulsion herbicide formulations based on biological raw materials that possess high adhesion, resistance to wind and rain erosion, stable quality, and are suitable for widespread application. This has become a key bottleneck in the current promotion of the industrialization of nanoemulsion herbicides.

[0004] In recent years, researchers have conducted extensive research on the preparation of nanoemulsion herbicides. Based on their phase composition, herbicide properties, and application range, they are mainly classified into oil-in-water (O / W) nanoemulsions for controlling the release of lipid-soluble pesticides, water-in-oil (W / O) nanoemulsions for controlling the release of water-soluble pesticides, and bicontinuous nanoemulsions, which fall between the two. Water-in-oil (W / O) and bicontinuous nanoemulsions typically consume large amounts of highly toxic organic solvents, and most herbicide molecules are lipid-soluble organic compounds. Therefore, developing water-based, component-neutral, and highly adhesive environmentally friendly oil-in-water (O / W) nanoemulsion formulations has become the mainstream development trend in herbicide formulations. However, current research still faces the following challenges: 1) Most existing nanoemulsions are prepared using surfactants as emulsifiers, but the synthesis and application of surfactants can easily cause environmental pollution. Therefore, it is urgent to develop a high-efficiency emulsifier based on biological raw materials and green biodegradable to stabilize nanoemulsions; 2) To improve the adhesion properties of substances at the interface, the common strategy is to use dopamine or tannic acid to modify the surface of the substances. However, both dopamine and tannic acid are hydrophilic materials, lack interfacial activity (amphiphilicity), and cannot be adsorbed at the oil-water interface. Therefore, it is urgent to develop a high-efficiency emulsifier with excellent interfacial activity and general adhesion at the surface of the substance. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides an adhesive emulsifier based on protein amyloid aggregates, its preparation method, and its application. The adhesive emulsifier is a core-shell structured composite material, where the core is an arbitrary structured nanomaterial and the shell is a nanofilm formed from protein amyloid aggregates. In this adhesive emulsifier, the core nanomaterial provides a carrier for the protein amyloid aggregates, preventing precipitation due to self-aggregation. The adhesion of the protein amyloid aggregates to the surface of the core nanomaterial significantly improves the interfacial activity of the composite material, enabling this novel core-shell structured emulsifier to firmly adsorb onto the oil-water interface, thereby enhancing the stability of the emulsion. This adhesive emulsifier demonstrates great potential in the preparation of nanoemulsions and nanoemulsion herbicides. The prepared nanoemulsion herbicides exhibit excellent adhesion, firmly adhering to weed leaves and resisting wind and rain erosion, achieving the goal of reducing application while increasing efficiency.

[0006] To achieve the above-mentioned technical objectives, the present invention employs the following technical means.

[0007] The present invention first provides an adhesive emulsifier based on protein amyloid aggregates. The adhesive emulsifier is a core-shell structured composite material, wherein the core is a nanomaterial of arbitrary structure and the shell is a nanofilm formed by protein amyloid aggregates. The nanofilm has a thickness of 1 to 50 nm and is formed by protein amyloid aggregates with a particle size of 1 to 10 nm.

[0008] This invention also provides a method for preparing the above-mentioned adhesive emulsifier based on protein amyloid aggregates, specifically including the following steps:

[0009] (1) The nanomaterial dispersion was added dropwise to the protein aqueous solution under stirring conditions, and the mixture was stirred and mixed evenly to obtain a mixture;

[0010] (2) Tris(2-carboxyethyl)phosphine hydrochloride aqueous solution was added dropwise to the mixture under stirring conditions and reacted. After the reaction was completed, the adhesive emulsifier based on protein amyloid aggregates was obtained.

[0011] Preferably, in step (1), the nanomaterial includes any one of cellulose nanofibers, cellulose nanocrystals, lithium magnesium silicate nanosheets, or nano-silica particles.

[0012] Preferably, the cellulose nanofibers have a diameter of 4-10 nm and a length of 1-5 μm, and their final concentration in the mixture is 0.1-6 mg / mL;

[0013] The cellulose nanocrystals have a diameter of 4–10 nm and a length of 100–500 nm, and their final concentration in the mixture is 1–30 mg / mL.

[0014] The magnesium lithium silicate nanosheets have a thickness of 1-3 nm, a lateral dimension of 25-50 nm, and a final concentration of 1-30 mg / mL in the mixture.

[0015] The nano-silica particles have a particle size of 20–50 nm and a final concentration of 1–30 mg / mL in the mixture.

[0016] Preferably, in step (1), the protein includes one or more of lysozyme, bovine serum albumin, insulin, and α-lactalbumin; the final concentration of the protein aqueous solution in the mixture is 1-30 mg / mL.

[0017] Preferably, in step (2), the final concentration of tris(2-carboxyethyl)phosphine hydrochloride in the mixture is 1-100 mmol / L; the pH value of the aqueous solution of tris(2-carboxyethyl)phosphine hydrochloride is 3-10;

[0018] The reaction conditions are 25–40°C for 1–24 hours.

[0019] This invention also provides the application of the above-mentioned adhesive emulsifier based on protein amyloid aggregates in the preparation of nanoemulsions.

[0020] The present invention also provides a nanoemulsion containing the above-mentioned adhesive emulsifier based on protein amyloid aggregates.

[0021] Preferably, the aqueous phase of the nanoemulsion comprises deionized water containing the aforementioned adhesive emulsifier based on protein amyloid aggregates, and the oil phase comprises any one of olive oil, methyl oleate, n-hexane, ethyl acetate, paraffin oil, oleic acid, n-decane, and dodecane; the particle size of the nanoemulsion is 200–900 nm. Preferably, the water-to-oil volume ratio of the nanoemulsion is 9:1 to 5:5.

[0022] The emulsification method for the nanoemulsion is ultrasonic emulsification. During emulsification, the probe-type ultrasonic instrument (ultrasonic cell disruptor) operates at a frequency of 20-25 kHz and an ultrasonic power of 300 W / cm². 2 The total duration of ultrasound is 2-10 minutes (with a 2-second pause after every 2 seconds of ultrasound). During the ultrasound emulsification process, the emulsion system is placed in an ice bath to prevent overheating. The lifespan of the prepared emulsion is greater than 6 months.

[0023] This invention also provides the application of the above-mentioned nanoemulsion or the above-mentioned adhesive emulsifier based on protein amyloid aggregates in emulsifying oil-water interfaces or gas-liquid interfaces. The oil-water interface and gas-liquid interface include those used in the fields of nanopesticides, cosmetics, smart foods, and biomedicine.

[0024] The present invention also provides a nano herbicide, the nano herbicide comprising:

[0025] (1) the above-mentioned nanoemulsion or the above-mentioned adhesive emulsifier based on protein amyloid aggregates; and

[0026] (2) Herbicidal active ingredients.

[0027] This invention also provides the application of the above-mentioned nanoemulsion herbicide in weed control.

[0028] Preferably, the weeds include one or more of the following: *Hedysarum heterotropoides*, *Capsella bursa-pastoris*, *Galium affine*, *Euphorbia helioscopia*, *Veronica persica*, *Achyranthes bidentata*, *Chenopodium album*, *Cirsium japonicum*, *Cirsium setosum*, *Polygonum aviculare*, *Stellaria media*, *Vaccaria segetalis*, *Geranium wilfordii*, *Gnaphalium affine*, *Gnaphalium affine*, *Vaccaria segetalis*, *Alternanthera philoxeroides*, *Amaranthus chinensis*, *Solanum nigrum*, *Lysimachia christinae*, *Portulaca oleracea*, *Amaranthus retroflexus*, *Hylocereus undatus*, and *Humulus scandens*. Compared with the prior art, the beneficial effects of this invention are:

[0029] This invention innovatively prepares an adhesive emulsifier based on protein amyloid aggregates. The adhesive emulsifier is a core-shell structured composite material, with the shell being a nanofilm formed by protein amyloid aggregates, while the core can be any structured nanomaterial. The material is widely available, inexpensive, green, and pollution-free. Furthermore, the adhesive emulsifier is prepared using water as a green solvent under mild reaction conditions, avoiding the use, generation, and emission of toxic and harmful substances, making it suitable for industrial-scale mass production.

[0030] The core and shell of the adhesive emulsifier based on protein amyloid aggregates described in this invention have a synergistic effect. On the one hand, the core nanomaterial provides a carrier for the protein amyloid aggregates, preventing them from precipitating due to self-aggregation. On the other hand, the deposition of protein amyloid aggregates on the surface of the core nanomaterial significantly improves the interfacial activity and adhesion of the novel emulsifier, enabling this core-shell structured emulsifier to be firmly adsorbed at the oil-water interface, thereby enhancing the stability of the emulsion and its adhesion to leaf surfaces. This novel emulsifier exhibits broad-spectrum emulsification properties for the oil phase and is suitable for emulsifying olive oil, methyl oleate, n-hexane, ethyl acetate, paraffin oil, oleic acid, n-decane, and dodecane, etc. The prepared nanoemulsion can remain stable for more than 6 months.

[0031] This invention uses an adhesive emulsifier based on protein amyloid aggregates as the aqueous phase to dissolve herbicides in the oil phase, thereby preparing nanoemulsion herbicides. Compared with traditional emulsifiable concentrates and wettable powders, adhesive nanoemulsion herbicides have a series of advantages, including low surfactant usage, high kinetic stability, good leaf spreadability, high permeability and absorption, low herbicide loss and degradation, low biohazard, and low environmental residue and pollution. Furthermore, the biomimetic adhesion based on protein amyloid transformation endows the nanoemulsion herbicides with excellent adhesiveness, allowing them to firmly adhere to weed leaves and resist wind and rain erosion. The prepared nanoemulsion herbicides adhere firmly to weed leaves, with a retention rate of ≥85% on the leaves after rainwater washing, and a weed kill rate of ≥99%. Under the same killing effect, the amount of original herbicide can be reduced by more than 70%, achieving the goal of reducing application while increasing efficiency.

[0032] The adhesive emulsifier described in this invention possesses interfacial activity and can be adsorbed at the gas-liquid interface. Therefore, its addition can also increase the adhesion of water-soluble drugs and suspended particles to the target surface. Thus, it can exert excellent emulsifying effects at other gas-liquid or oil-water interfaces. It is not limited to herbicides, but also has enormous application potential in the preparation of other nanopesticides (such as sterilizers and insecticides), cosmetics, smart foods, and biomedicine. Attached Figure Description

[0033] Figure 1 The effect of LZ concentration on the surface tension of the gas-liquid interface.

[0034] Figure 2 The effect of LAP concentration on surface tension when PTL concentration is 10 mg / mL.

[0035] Figure 3 This is a transmission electron microscope image of PTL-LAP in Example 1.

[0036] Figure 4 The effect of PTL modification on the apparent contact angle of the material.

[0037] Figure 5 The effect of PTL-LAP as an emulsifier on the stability of nanoemulsions.

[0038] Figure 6 The effect of isooctyl ester content on the stability of nanoemulsion herbicides.

[0039] Figure 7 The wettability of the adhesive nanoemulsion herbicide on the surface of lotus leaves.

[0040] Figure 8 High-speed camera images of different droplets impacting the surface of a lotus leaf.

[0041] Figure 9 This study investigates the wetting effect of adhesive nanoemulsion herbicides on the leaves of weeds such as thistle, tufted grass, wild strawberry, and shepherd's purse.

[0042] Figure 10 This is a high-speed photograph of droplets of PTL-LAP-stabilized adhesive nanoemulsion herbicide impacting the leaves of weeds.

[0043] Figure 11 The retention rate of the adhesive nanoemulsion herbicide on the leaves of shepherd's purse after being washed away by rainwater. Detailed Implementation

[0044] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, but the scope of protection of the present invention is not limited thereto. Unless otherwise specified, the raw materials used in the following embodiments are all prior art and can be obtained by commercial purchase or by existing conventional methods.

[0045] Example 1:

[0046] In this embodiment, an adhesive emulsifier (PTL-LAP) based on LZ amyloid aggregates (PTL) was prepared using lysozyme (LZ) and lithium magnesium silicate nanosheets (LAP) as raw materials. The physicochemical properties of PTL-LAP, the stability of the prepared nanoemulsion and nanoemulsion herbicide, the leaf surface adhesion and rainwater erosion resistance of the nanoemulsion herbicide, and the weed killing rate of the nanoemulsion herbicide were studied.

[0047] S1. Preparation of an adhesive emulsifier based on LZ amyloid aggregates (PTL-LAP):

[0048] (1) Add 5 mL of lithium magnesium silicate nanosheet (LAP) dispersion dropwise to 5 mL of lysozyme (LZ) solution, stirring continuously during the dropwise addition process to ensure that the two substances are fully mixed. The stirring time is 2 hours and the stirring speed is 300 rpm to obtain the mixture.

[0049] (2) Add 100 μL of tris(2-carboxyethyl)phosphine hydrochloride aqueous solution with pH 5 dropwise to the mixture obtained in step (1) under magnetic stirring at a stirring speed of 300 rpm. After stirring and mixing evenly, react at 25°C for 12 hours to cause the protein to undergo amyloid transformation and adhere to the LAP surface, thereby forming an adhesive emulsifier (PTL-LAP) based on LZ amyloid aggregates.

[0050] Figure 1 The effect of LZ concentration on the surface tension of the gas-liquid interface is shown. It can be seen that the surface tension gradually decreases with increasing LZ concentration. When the LZ concentration reaches 10 mg / mL, the surface tension drops to about 47 mN / m, and the decrease in surface tension slows down with further increases in LZ concentration.

[0051] Figure 2 The effect of LAP concentration on surface tension when PTL concentration is 10 mg / mL. Figure 2 It is known that at the same concentration (10 mg / mL), PTL can reduce the surface tension to approximately 42 mN / m, indicating that under the same conditions, PTL has stronger interfacial activity than LZ, and the interfacial activity of PTL-LAP increases with increasing LAP concentration within a certain range. When the LAP concentration reaches 1 mg / mL, PTL-LAP can reduce the surface tension to approximately 37 mN / m. Due to the hydrophilic properties of LAP, further increasing the LAP concentration leads to a decrease in the interfacial activity of PTL-LAP, manifested as an increase in surface tension.

[0052] Figure 3 The image shows a transmission electron microscope (TEM) image of PTL-LAP. It can be seen from the image that after LZ undergoes amyloid transformation, a thin film forms around the sheet-like LAP. This indicates that PTL-LAP has a core-shell structure, with LAP as the core and PTL as the shell.

[0053] Figure 4 The effect of LZ amyloid aggregate (PTL) modification on the apparent contact angle of the material is shown in the figure. As can be seen from the figure, the contact angle of the glass substrate is approximately 16°; when a layer of LAP is uniformly coated on the glass surface, the apparent contact angle of LAP is measured to be approximately 40°, indicating that LAP is a hydrophilic material; when a layer of LZ is uniformly adsorbed on the glass surface, the apparent contact angle of LZ is measured to be approximately 65°; in comparison, the apparent contact angle of PTL-LAP is approximately 80°, indicating that PTL significantly improves the hydrophobicity and interfacial activity of LAP after adsorption on the LAP surface, allowing the novel emulsifier PTL-LAP to be firmly adsorbed at the interface for stabilizing multiphase systems such as emulsions and foams.

[0054] S2. Preparation and stability study of nanoemulsions:

[0055] In this step, a nanoemulsion was prepared based on the PTL-LAP prepared in step S1, and the effect of PTL-LAP on the stability of the nanoemulsion was investigated. The specific steps are as follows:

[0056] Using olive oil as the oil phase and an aqueous dispersion of PTL-LAP (PTL concentration of 10 mg / mL and LAP concentration of 1 mg / mL) as the aqueous phase, different volume ratios of the aqueous and oil phases were mixed and ultrasonically emulsified to obtain the nanoemulsion. The probe-type ultrasonic instrument (ultrasonic cell disruptor) used during emulsification operated at a frequency of 20 kHz and an ultrasonic power of 300 W / cm². 2 The total duration of ultrasound is 5 minutes (with a 2-second pause after every 2 seconds of ultrasound). During the ultrasound emulsification process, the emulsion system is placed in an ice bath to prevent the system from overheating.

[0057] The stability of the nanoemulsions with different oil-to-water ratios prepared above was investigated, and the results are as follows: Figure 5 As shown. By Figure 5 It can be seen that as the oil phase ratio increases, the initial particle size of the emulsion increases, and the uniformity deteriorates. Specifically, when the oil-to-water ratio increases to 4:6, the emulsion breaks down in approximately 10 days. Figure 5 Only the average droplet size for the first two months is shown; the stability of the remaining emulsions was examined and found to be maintained for more than six months.

[0058] S3. Preparation and performance evaluation of nanoemulsion herbicides:

[0059] This step uses the nanoemulsion prepared in step S2 as a carrier to encapsulate the herbicide active ingredient isooctyl ester in the oil phase, thus preparing a nanoemulsion herbicide. The specific preparation method is as follows:

[0060] (1) Dissolve isooctyl ester in olive oil under magnetic stirring, wherein the mass fraction of isooctyl ester in olive oil is 10%-80%;

[0061] (2) Olive oil containing isooctyl ester (oil phase) was added to an aqueous phase containing PTL-LAP (water-oil volume ratio of 8:2), and ultrasonic emulsification was performed to obtain a nanoemulsion herbicide. The emulsification method was ultrasonic emulsification, and the probe-type ultrasonic instrument (ultrasonic cell disruptor) used had a working frequency of 20 kHz and an ultrasonic power of 300 W / cm². 2 The total duration of ultrasound is 5 minutes (with a 2-second pause after every 2 seconds of ultrasound). During the ultrasound emulsification process, the emulsion system is placed in an ice bath to prevent the system from overheating.

[0062] The stability of nanoemulsion herbicides containing different mass fractions of isooctyl ester was investigated, and the results are as follows: Figure 6 As shown. Figure 6The effect of isooctyl ester content on the stability of nanoemulsion herbicides is shown in the figure. As the isooctyl ester content increases, the initial particle size of the emulsion increases, and the uniformity deteriorates. When the concentration of isooctyl ester in olive oil is ≥60%, the nanoemulsion herbicide demulsifies in approximately 15 days; the stability of other nanoemulsion herbicides can be maintained for more than 6 months. Figure 6 (Only the average droplet size for the first two months is shown).

[0063] Figure 7 To assess the wettability of adhesive nanoemulsion herbicides on lotus leaf surfaces, such as... Figure 7 As shown, the contact angle of water on the lotus leaf surface is approximately 150°, demonstrating the superhydrophobic properties of the lotus leaf surface. The contact angle of the nanoemulsion herbicide prepared using LZ+LAP as an emulsifier on the lotus leaf surface is approximately 130°, which is lower than that of water. In contrast, the contact angle of the nanoemulsion herbicide stabilized by PTL-LAP on the lotus leaf surface is reduced to approximately 80°, indicating that the presence of PTL-LAP significantly increases the wettability of the nanoemulsion herbicide on the lotus leaf surface, which is beneficial for the spread of the nanoemulsion herbicide droplets on the lotus leaf surface.

[0064] Figure 8 High-speed photographs of different droplets impacting the surface of lotus leaves show that, compared with water droplets and LZ+LAP-stabilized emulsions, the adhesive nanoemulsion herbicide prepared using PTL-LAP as an emulsifier adheres firmly to the surface of the superhydrophobic lotus leaf after impact, without rebounding. This indicates that the presence of PTL-LAP significantly increases the adhesion of droplets to the lotus leaf surface.

[0065] Figure 9 This study investigated the wetting effect of adhesive nanoemulsion herbicides on the leaves of weeds such as thistle, tuft of grass, wild strawberry, and shepherd's purse. As shown in the figure, compared with water, the adhesive nanoemulsion herbicide stabilized by PTL-LAP can significantly reduce the contact angle of droplets on the weed leaves, indicating that the presence of PTL-LAP can significantly increase the wettability of nanoemulsion herbicides on the weed surface.

[0066] Figure 10 This is a high-speed photographic image of PTL-LAP-stabilized adhesive nanoemulsion herbicide droplets impacting the weed leaf surface. The image shows that the adhesive nanoemulsion herbicide droplets adhere firmly to the weed leaf surface during impact without bouncing, indicating that the presence of PTL-LAP significantly increases the adhesion of the nanoemulsion herbicide to the weed surface.

[0067] Figure 11The retention rate of adhesive nanoemulsion herbicides on shepherd's purse leaves after rainwater runoff is shown. The retention rate of nanoemulsion herbicides prepared using LZ+LAP as emulsifiers on the leaf surface decreased significantly with rainwater runoff. In contrast, the retention rate of PTL-LAP-stabilized nanoemulsion herbicides on the leaf surface remained relatively stable with rainwater runoff, consistently above 90%, demonstrating that the presence of PTL-LAP significantly increases the adhesion of droplets to the leaf surface and their resistance to rainwater erosion.

[0068] In addition, the weed control experiment targeting shepherd's purse showed that the weed control rate of this adhesive nanoemulsion herbicide was ≥99%. Under the same control rate conditions, it can save more than 70% of the amount of raw material used, thus achieving the goal of reducing application and increasing efficiency.

[0069] Example 2:

[0070] In this embodiment, an adhesive emulsifier (PTB-CNF) based on BSA amyloid aggregates (PTB) was prepared using bovine serum albumin (BSA) and cellulose nanofibers (CNF) as raw materials. The physicochemical properties of PTB-CNF, the stability of the prepared nanoemulsion and nanoemulsion herbicide, the leaf adhesion and rainwater erosion resistance of the nanoemulsion herbicide, and the weed killing rate were studied.

[0071] S1. Preparation of an adhesive emulsifier based on BSA amyloid aggregates (PTB-CNF):

[0072] (1) Add 5 mL of LCNF dispersion dropwise to 5 mL of BSA solution, stirring constantly during the addition process to ensure thorough mixing of the two substances. Stir for 2 hours at a stirring speed of 300 rpm to obtain a mixture.

[0073] (2) Add 100 μL of tris(2-carboxyethyl)phosphine hydrochloride aqueous solution with pH 5 dropwise to the mixture obtained in step (1) under magnetic stirring at a stirring speed of 300 rpm. After stirring and mixing evenly, react at 25°C for 12 hours to cause the protein to undergo amyloid transformation and adhere to the CNF surface, thereby forming an adhesive emulsifier (PTB-CNF) based on BSA amyloid aggregates.

[0074] In this process, BSA undergoes an amyloid transformation, forming a thin film composed of PTB nanoparticles around the fibrous CNF. Therefore, PTB-CNF has a core-shell structure, with CNF as the core and PTB as the shell. Compared to BSA, PTB-CNF exhibits stronger interfacial activity, reducing the surface tension between air and water to 30-40 mN / m. After PTB surface modification, the apparent contact angle of PTB-CNF is approximately 80°, indicating that PTB significantly improves the hydrophobicity and interfacial activity of the material surface, allowing the material to firmly adhere to the interface for stabilizing multiphase systems such as emulsions and foams.

[0075] S2. Preparation and stability study of nanoemulsions:

[0076] In this step, a nanoemulsion was prepared based on the PTB-CNF prepared in step S1, and the effect of PTB-CNF on the stability of the nanoemulsion was investigated. The specific steps are as follows:

[0077] Using olive oil as the oil phase and a PTB-CNF aqueous dispersion (PTB concentration of 20 mg / mL and CNF concentration of 2 mg / mL) as the aqueous phase, different volume ratios of the aqueous and oil phases were mixed and ultrasonically emulsified to obtain the nanoemulsion. The probe-type ultrasonic instrument (ultrasonic cell disruptor) used during emulsification operated at a frequency of 20 kHz and an ultrasonic power of 300 W / cm². 2 The total duration of ultrasound is 5 minutes (with a 2-second pause after every 2 seconds of ultrasound). During the ultrasound emulsification process, the emulsion system is placed in an ice bath to prevent the system from overheating.

[0078] Investigations revealed that as the oil phase ratio increased (from 1:9 to 4:6), the initial particle size of the nanoemulsion increased from about 200 nm to about 500 nm, but all prepared nanoemulsions remained stable for more than 6 months.

[0079] S3. Preparation and performance evaluation of nanoemulsion herbicides:

[0080] This step uses the nanoemulsion prepared in step S2 as a carrier to encapsulate the herbicide active ingredient isooctyl ester in the oil phase, thus preparing a nanoemulsion herbicide. The specific preparation method is as follows:

[0081] (1) Dissolve isooctyl ester in olive oil under magnetic stirring, wherein the mass fraction of isooctyl ester in olive oil is 10%-80%;

[0082] (2) Olive oil containing isooctyl ester (oil phase) was added to an aqueous phase containing PTB-CNF (water-oil volume ratio 8:2), and ultrasonic emulsification was performed to obtain a nanoemulsion herbicide. The emulsification method was ultrasonic emulsification, and the probe-type ultrasonic instrument (ultrasonic cell disruptor) used had a working frequency of 20 kHz and an ultrasonic power of 300 W / cm². 2 The total duration of ultrasound is 5 minutes (with a 2-second pause after every 2 seconds of ultrasound). During the ultrasound emulsification process, the emulsion system is placed in an ice bath to prevent the system from overheating.

[0083] Investigations revealed that the initial particle size of the emulsion increased with increasing isooctyl ester content. When the concentration of isooctyl ester in olive oil exceeded 40%, the instability of the nanoemulsion herbicide intensified; the stability of other nanoemulsion herbicides remained for more than 6 months.

[0084] The wettability of adhesive nanoemulsion herbicides on lotus leaf surfaces was studied. Compared with the control group, the contact angle of the PTB-CNF-stabilized nanoemulsion herbicide on the lotus leaf surface decreased to approximately 80°, indicating that the amyloid transformation of BSA significantly increases its wettability on the lotus leaf surface. Furthermore, the adhesive nanoemulsion herbicide did not bounce upon impact with the lotus leaf surface, demonstrating that the presence of PTB-CNF significantly increases the adhesion of the nanoemulsion herbicide to the lotus leaf surface.

[0085] A study on the wetting of weed leaves of adhesive nanoemulsion herbicides on weeds such as thistle, tufted clover, wild strawberry, and shepherd's purse revealed that the use of PTB-CNF-stabilized nanoemulsion herbicides significantly reduced the contact angle of droplets on weed leaves, indicating that the presence of PTB-CNF greatly increased the wettability of nanoemulsion herbicides on weed surfaces. Furthermore, the adhesive nanoemulsion herbicide droplets adhered firmly to the weed leaf surface upon impact, without bouncing, demonstrating that the presence of PTB-CNF significantly enhanced the adhesion of the nanoemulsion herbicides to weed leaves.

[0086] The retention rate of the PTB-CNF-stabilized nanoemulsion herbicide on the leaf surface remained relatively stable above 80% despite rainwater runoff, demonstrating that the presence of PTB-CNF significantly increases the adhesion of the nanoemulsion herbicide to the leaf surface and its resistance to rainwater erosion. This adhesive nanoemulsion herbicide achieved a kill rate of ≥99% against shepherd's purse, saving over 70% of the original herbicide dosage under the same kill rate conditions, thus achieving the goal of reducing application while increasing efficacy.

[0087] Example 3:

[0088] In this embodiment, an adhesive nanoemulsion herbicide was prepared using PTB-CNF as an adhesive emulsifier, methyl oleate as the oil phase, and cyhalofop-butyl as the herbicide. The stability of the prepared nanoemulsion and nanoemulsion herbicide, the leaf surface adhesion and rainwater erosion resistance of the nanoemulsion herbicide, and the weed killing rate were studied.

[0089] S1. The preparation of the adhesive emulsifier (PTB-CNF) based on BSA amyloid aggregates is the same as in Example 2.

[0090] S2. Preparation and stability study of nanoemulsions:

[0091] In this step, a nanoemulsion was prepared based on the PTB-CNF prepared in step S1, and the effect of PTB-CNF on the stability of the nanoemulsion was investigated. The specific steps are as follows:

[0092] Using methyl oleate as the oil phase and a PTB-CNF aqueous dispersion (PTB concentration of 20 mg / mL and CNF concentration of 2 mg / mL) as the aqueous phase, different volume ratios of the aqueous and oil phases were mixed and ultrasonically emulsified to obtain the nanoemulsion. The probe-type ultrasonic instrument (ultrasonic cell disruptor) used during emulsification operated at a frequency of 20 kHz and an ultrasonic power of 300 W / cm². 2 The total duration of ultrasound is 5 minutes (with a 2-second pause after every 2 seconds of ultrasound). During the ultrasound emulsification process, the emulsion system is placed in an ice bath to prevent the system from overheating.

[0093] Investigations revealed that as the oil phase ratio increased (from 1:9 to 4:6), the initial particle size of the emulsion gradually increased, but all prepared emulsions remained stable for more than 6 months.

[0094] S3. Preparation and performance evaluation of nanoemulsion herbicides:

[0095] This step uses the nanoemulsion prepared in step S2 as a carrier to encapsulate the herbicide active ingredient, cyhalofop-butyl, in the oil phase, thus preparing a nanoemulsion herbicide. The specific preparation method is shown below:

[0096] (1) Dissolve cyhalofop-butyl in methyl oleate under magnetic stirring, wherein the mass fraction of cyhalofop-butyl in methyl oleate is 1%-30%.

[0097] (2) Methyl oleate (oil phase) containing cyhalofop-butyl was added to an aqueous phase containing PTB-CNF (water-oil volume ratio 8:2), and ultrasonic emulsification was performed to obtain a nanoemulsion herbicide. The emulsification method was ultrasonic emulsification, and the probe-type ultrasonic instrument (ultrasonic cell disruptor) used had a working frequency of 20 kHz and an ultrasonic power of 300 W / cm². 2 The total duration of ultrasound is 5 minutes (with a 2-second pause after every 2 seconds of ultrasound). During the ultrasound emulsification process, the emulsion system is placed in an ice bath to prevent the system from overheating.

[0098] According to the investigation, the initial particle size of the nanoemulsion is between 200-500 nm, and the emulsion can remain stable for more than 6 months.

[0099] The wettability of adhesive nanoemulsion herbicides on lotus leaf surfaces was studied. Compared with the control group, the contact angle of the PTB-CNF-stabilized nanoemulsion herbicide on the lotus leaf surface decreased to approximately 80°, indicating that the presence of PTB-CNF significantly increases the wettability of the nanoemulsion herbicide on the lotus leaf surface. Furthermore, the adhesive nanoemulsion herbicide did not bounce upon impact with the lotus leaf surface, demonstrating that the presence of PTB-CNF significantly increases the adhesion of the nanoemulsion herbicide to the lotus leaf surface.

[0100] A study on the wetting of weed leaves of adhesive nanoemulsion herbicides on weeds such as barnyardgrass and Echinochloa crus-galli revealed that the use of PTB-CNF-stabilized nanoemulsion herbicides significantly reduced the contact angle of droplets on weed leaves, indicating that the presence of PTB-CNF greatly increased the wettability of nanoemulsion herbicides on weed surfaces. Furthermore, the adhesive nanoemulsion herbicide droplets adhered firmly to the weed leaf surface upon impact, without bouncing, demonstrating that the presence of PTB-CNF significantly enhanced the adhesion of the nanoemulsion herbicides to weed leaves.

[0101] The retention rate of the PTB-CNF-stabilized nanoemulsion herbicide on the leaf surface remained relatively stable above 80% despite rainwater runoff, demonstrating that the presence of PTB-CNF significantly increases the adhesion of the nanoemulsion herbicide to the leaf surface and its resistance to rainwater erosion. This adhesive nanoemulsion herbicide achieved a kill rate of ≥99% against shepherd's purse, saving over 70% of the original herbicide dosage under the same kill rate conditions, thus achieving the goal of reducing application while increasing efficacy.

[0102] Example 4:

[0103] In this embodiment, an adhesive nanoemulsion herbicide was prepared using PTL-LAP as an adhesive emulsifier, methyl oleate as the oil phase, and cyhalofop-butyl as the herbicide. The stability of the prepared nanoemulsion and nanoemulsion herbicide, the leaf surface adhesion and rainwater erosion resistance of the nanoemulsion herbicide, and the weed killing rate were studied.

[0104] In this embodiment, an adhesive nanoemulsion herbicide was prepared using PTB-CNF as an adhesive emulsifier, methyl oleate as the oil phase, and cyhalofop-butyl as the herbicide. The stability of the prepared nanoemulsion and nanoemulsion herbicide, the leaf surface adhesion and rainwater erosion resistance of the nanoemulsion herbicide, and the weed killing rate were studied.

[0105] S1. The preparation of the adhesive emulsifier (PTL-LAP) based on LZ amyloid aggregates is the same as in Example 1.

[0106] S2. Preparation and stability study of nanoemulsions:

[0107] In this step, a nanoemulsion was prepared based on the PTL-LAP prepared in step S1, and the effect of PTL-LAP on the stability of the nanoemulsion was investigated. The specific steps are as follows:

[0108] Using methyl oleate as the oil phase and a PTL-LAP aqueous dispersion (PTL concentration of 10 mg / mL and LAP concentration of 1 mg / mL) as the aqueous phase, different volume ratios of the aqueous and oil phases were mixed and ultrasonically emulsified to obtain the nanoemulsion. The probe-type ultrasonic instrument (ultrasonic cell disruptor) used during emulsification operated at a frequency of 20 kHz and an ultrasonic power of 300 W / cm².2 The total duration of ultrasound is 5 minutes (with a 2-second pause after every 2 seconds of ultrasound). During the ultrasound emulsification process, the emulsion system is placed in an ice bath to prevent the system from overheating.

[0109] Investigations revealed that as the oil phase ratio increased (from 1:9 to 4:6), the initial particle size of the emulsion gradually increased, but all prepared emulsions remained stable for more than 6 months.

[0110] S3. Preparation and performance evaluation of nanoemulsion herbicides:

[0111] This step uses the nanoemulsion prepared in step S2 as a carrier to encapsulate the herbicide active ingredient, cyhalofop-butyl, in the oil phase, thus preparing a nanoemulsion herbicide. The specific preparation method is shown below:

[0112] (1) Dissolve cyhalofop-butyl in methyl oleate under magnetic stirring, wherein the mass fraction of cyhalofop-butyl in methyl oleate is 1%-30%.

[0113] (2) Methyl oleate (oil phase) containing cyhalofop-butyl was added to an aqueous phase containing PTB-CNF (water-oil volume ratio 8:2), and ultrasonic emulsification was performed to obtain a nanoemulsion herbicide. The emulsification method was ultrasonic emulsification, and the probe-type ultrasonic instrument (ultrasonic cell disruptor) used had a working frequency of 20 kHz and an ultrasonic power of 300 W / cm². 2 The total duration of ultrasound is 5 minutes (with a 2-second pause after every 2 seconds of ultrasound). During the ultrasound emulsification process, the emulsion system is placed in an ice bath to prevent the system from overheating.

[0114] According to the investigation, the initial particle size of the nanoemulsion is between 200-500 nm, and the emulsion can remain stable for more than 6 months.

[0115] The wettability of adhesive nanoemulsion herbicides on lotus leaf surfaces was studied. Compared with the control group, the contact angle of the PTL-LAP-stabilized nanoemulsion herbicide on the lotus leaf surface decreased to approximately 80°, indicating that the presence of PTL-LAP significantly increases the wettability of the nanoemulsion herbicide on the lotus leaf surface. Furthermore, the adhesive nanoemulsion herbicide did not bounce upon impact with the lotus leaf surface, demonstrating that the presence of PTL-LAP significantly increases the adhesion of the nanoemulsion herbicide to the lotus leaf surface.

[0116] A study on the wetting of weed leaves of adhesive nanoemulsion herbicides, including barnyardgrass and Echinochloa crus-galli, revealed that the use of PTL-LAP-stabilized nanoemulsion herbicides significantly reduced the contact angle of droplets on weed leaves, indicating that the presence of PTL-LAP greatly increased the wettability of nanoemulsion herbicides on weed surfaces. Furthermore, the adhesive nanoemulsion herbicide droplets adhered firmly to the weed leaf surface upon impact, without bouncing, demonstrating that the presence of PTL-LAP significantly enhanced the adhesion of the nanoemulsion herbicides to weed leaves.

[0117] The retention rate of the PTL-LAP-stabilized nanoemulsion herbicide on the leaf surface remained relatively stable above 90% despite rainwater runoff, demonstrating that the presence of PTL-LAP significantly increased the adhesion of the nanoemulsion herbicide to the leaf surface and its resistance to rainwater erosion. This adhesive nanoemulsion herbicide achieved a weed kill rate of ≥99%, saving over 70% of the original herbicide dosage under the same kill rate conditions, thus achieving the goal of reducing application while increasing efficiency.

[0118] Example 5:

[0119] In this embodiment, an adhesive emulsifier (PTB-Silica) based on BSA amyloid aggregates (PTB) was prepared using bovine serum albumin (BSA) and silica nanoparticles (Silica) as raw materials. The physicochemical properties of PTB-Silica, the stability of the prepared nanoemulsion and nanoemulsion herbicide, the leaf adhesion and rainwater erosion resistance of the nanoemulsion herbicide, and the weed killing rate were studied.

[0120] S1. Preparation of an adhesive emulsifier based on BSA amyloid aggregates (PTB-Silica):

[0121] (1) Add 5 mL of Silica dispersion dropwise to 5 mL of BSA solution, stirring constantly during the addition process to ensure thorough mixing of the two substances. Stir for 2 hours at a speed of 300 rpm to obtain the mixture.

[0122] (2) Add 100 μL of tris(2-carboxyethyl)phosphine hydrochloride aqueous solution with pH 5 dropwise to the mixture obtained in step (1) under magnetic stirring at a stirring speed of 300 rpm. After stirring and mixing evenly, react at 25°C for 12 hours to cause the protein to undergo amyloid transformation and adhere to the CNF surface, thereby forming an adhesive emulsifier (PTB-Silica) based on BSA amyloid aggregates.

[0123] Investigations revealed that after BSA undergoes amyloid transformation, a thin film composed of PTB nanoparticles forms around the silica. Therefore, PTB-Silica exhibits a core-shell structure, with silica as the core and PTB as the shell. Compared to BSA, PTB-Silica demonstrates stronger interfacial activity, reducing the surface tension between air and water to 30-40 mN / m. After PTB surface modification, the apparent contact angle of PTB-Silica is approximately 80°, indicating that PTB significantly enhances the hydrophobicity and interfacial activity of the material surface, enabling the material to firmly adhere to the interface and stabilize multiphase systems such as emulsions and foams.

[0124] S2. Preparation and stability study of nanoemulsions:

[0125] In this step, a nanoemulsion was prepared based on the PTB-Silica prepared in step S1, and the effect of PTB-Silica on the stability of the nanoemulsion was investigated. The specific steps are as follows:

[0126] Using olive oil as the oil phase and a PTB-Silica aqueous dispersion (PTB concentration of 10 mg / mL and Silica concentration of 1 mg / mL) as the aqueous phase, different volume ratios of the aqueous and oil phases were mixed and ultrasonically emulsified to obtain the nanoemulsion. The probe-type ultrasonic instrument (ultrasonic cell disruptor) used during emulsification operated at a frequency of 20 kHz and an ultrasonic power of 300 W / cm². 2 The total duration of ultrasound is 5 minutes (with a 2-second pause after every 2 seconds of ultrasound). During the ultrasound emulsification process, the emulsion system is placed in an ice bath to prevent the system from overheating.

[0127] Investigations revealed that as the oil phase ratio increased (from 1:9 to 4:6), the initial particle size of the emulsion increased from approximately 200 nm to approximately 500 nm, but all prepared emulsions remained stable for more than 6 months.

[0128] S3. Preparation and performance evaluation of nanoemulsion herbicides:

[0129] This step uses the nanoemulsion prepared in step S2 as a carrier to encapsulate the herbicide active ingredient isooctyl ester in the oil phase, thus preparing a nanoemulsion herbicide. The specific preparation method is as follows:

[0130] (1) Dissolve isooctyl ester in olive oil under magnetic stirring, wherein the mass fraction of isooctyl ester in olive oil is 10%-80%;

[0131] (2) Olive oil containing isooctyl ester (oil phase) was added to an aqueous phase containing PTB-Silica (water-oil volume ratio of 8:2) and ultrasonically emulsified to obtain a nanoemulsion herbicide. The emulsification method was ultrasonic emulsification, and the probe-type ultrasonic instrument (ultrasonic cell disruptor) used had a working frequency of 20 kHz and an ultrasonic power of 300 W / cm². 2 The total duration of ultrasound is 5 minutes (with a 2-second pause after every 2 seconds of ultrasound). During the ultrasound emulsification process, the emulsion system is placed in an ice bath to prevent the system from overheating.

[0132] Investigations revealed that the initial particle size of the emulsion increased with increasing isooctyl ester content. When the concentration of isooctyl ester in olive oil exceeded 40%, the instability of the nanoemulsion herbicide intensified; the stability of other nanoemulsion herbicides remained for more than 6 months.

[0133] The wettability of adhesive nanoemulsion herbicides on lotus leaf surfaces was studied. Compared with the control group, the contact angle of the PTB-Silica-stabilized nanoemulsion herbicide on the lotus leaf surface decreased to approximately 80°, indicating that the presence of PTB-Silica significantly increases the wettability of the nanoemulsion herbicide on the lotus leaf surface. Furthermore, the adhesive nanoemulsion herbicide did not bounce upon impact with the lotus leaf surface, demonstrating that the presence of PTB-Silica significantly increases the adhesion of the nanoemulsion herbicide to the lotus leaf surface.

[0134] A study on the wetting of leaves of weeds such as thistle, tufted clover, wild strawberry, and shepherd's purse using adhesive nanoemulsion herbicides revealed that the use of PTB-Silica-stabilized nanoemulsion herbicides significantly reduced the contact angle of droplets on weed leaves, indicating that the presence of PTB-Silica greatly increases the wettability of nanoemulsion herbicides on weed surfaces. Furthermore, the adhesive nanoemulsion herbicide droplets adhered firmly to the weed leaf surface upon impact, without bouncing, demonstrating that the presence of PTB-Silica significantly enhances the adhesion of the nanoemulsion herbicide to weed leaves.

[0135] The retention rate of the PTB-Silica-stabilized nanoemulsion herbicide on the leaf surface remained relatively stable at over 80% despite rainwater runoff, demonstrating that the presence of PTB-Silica significantly increased the adhesion of the nanoemulsion herbicide to the leaf surface and its resistance to rainwater erosion. This adhesive nanoemulsion herbicide achieved a weed kill rate of ≥99%, saving over 70% of the original herbicide dosage under the same kill rate conditions, thus achieving the goal of reducing application while increasing efficiency.

[0136] Example 6:

[0137] Using the same method as in Example 1, this example prepared an adhesive emulsifier (PTI-CNF) based on INS amyloid aggregates (PTI) using insulin (INS) and cellulose nanofibers (CNF) as raw materials. The stability, leaf adhesion and rainwater erosion resistance of the prepared nanoemulsion herbicide, as well as the weed killing rate, were studied.

[0138] Experiments show that the stability of the PTI-CNF-based nanoemulsion herbicide can be maintained for more than 6 months. Furthermore, the retention rate of the PTI-CNF-stabilized nanoemulsion herbicide on the leaf surface remains relatively constant above 80% despite rainwater runoff, demonstrating that the presence of PTI-CNF significantly increases the adhesion of the nanoemulsion herbicide to the leaf surface and its resistance to rainwater erosion. This adhesive nanoemulsion herbicide achieves a kill rate of ≥99% against shepherd's purse, saving more than 70% of the original herbicide dosage under the same kill rate conditions, thus achieving the goal of reducing application while increasing efficacy.

[0139] Example 7:

[0140] Using the same method as in Example 1, this example prepared an adhesive emulsifier based on α-lactalbumin amyloid aggregates using α-lactalbumin and cellulose nanofibers (CNF) as raw materials. The stability, leaf adhesion, rain erosion resistance, and weed killing rate of the prepared nanoemulsion herbicide were studied.

[0141] Experiments show that the stability of the nanoemulsion herbicide prepared based on the adhesive emulsifier of α-lactalbumin amyloid aggregates can be maintained for more than 6 months. Furthermore, the retention rate of this stable nanoemulsion herbicide on the leaf surface remains relatively constant above 80% despite rainwater runoff, demonstrating that the presence of this adhesive emulsifier significantly increases the adhesion of the nanoemulsion herbicide to the leaf surface and its resistance to rainwater erosion. This adhesive nanoemulsion herbicide achieves a kill rate of ≥99% against shepherd's purse, saving more than 70% of the original herbicide dosage under the same kill rate conditions, thus achieving the goal of reducing application while increasing efficiency.

[0142] In summary, the preparation method of the novel emulsifier system based on protein amyloid aggregates described in this invention is simple, highly controllable, uses low-cost and widely available raw materials, and is easy to scale up for industrial production. Therefore, this novel emulsifier has great application potential in fields such as nanopesticides, cosmetics, smart foods, and biomedicine.

[0143] The embodiments described above are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments. Any obvious improvements, substitutions or modifications that can be made by those skilled in the art without departing from the essence of the present invention shall fall within the protection scope of the present invention.

Claims

1. A method for preparing an adhesive emulsifier based on protein amyloid aggregates, characterized in that, include: (1) The nanomaterial dispersion is added dropwise to the protein aqueous solution under stirring conditions and stirred until uniformly mixed to obtain a mixture; the nanomaterial includes any one of cellulose nanofibers, cellulose nanocrystals, lithium magnesium silicate nanosheets or nano silica particles; The protein includes one or more of lysozyme, bovine serum albumin, insulin, and α-lactalbumin; (2) Tris(2-carboxyethyl)phosphine hydrochloride aqueous solution was added dropwise to the mixture under stirring conditions and reacted. After the reaction was completed, the adhesive emulsifier based on protein amyloid aggregates was obtained.

2. The method for preparing the adhesive emulsifier based on protein amyloid aggregates according to claim 1, characterized in that, The cellulose nanofibers have a diameter of 4-10 nm and a length of 1-5 μm, and their final concentration in the mixture is 0.1-6 mg / mL. The cellulose nanocrystals have a diameter of 4-10 nm and a length of 100-500 nm, and their final concentration in the mixture is 1-30 mg / mL. The magnesium lithium silicate nanosheets have a thickness of 1-3 nm, a lateral dimension of 25-50 nm, and a final concentration of 1-30 mg / mL in the mixture. The particle size of the nano-silica particles is 20~50 nm, and their final concentration in the mixture is 1~30 mg / mL; The final concentration of the protein aqueous solution in the mixture is 1-30 mg / mL.

3. The method for preparing the adhesive emulsifier based on protein amyloid aggregates according to claim 1, characterized in that, In step (2), the final concentration of tris(2-carboxyethyl)phosphine hydrochloride in the mixed solution is 1-100 mmol / L; the pH value of the aqueous solution of tris(2-carboxyethyl)phosphine hydrochloride is 3-10; The reaction conditions are 25~40℃ for 1~24 hours.

4. The adhesive emulsifier based on protein amyloid aggregates prepared by the method according to any one of claims 1 to 3, characterized in that, The adhesive emulsifier is a core-shell structured composite material, wherein the core is a nanomaterial of arbitrary structure and the shell is a nanofilm formed by protein amyloid aggregates; the nanofilm has a thickness of 1~50 nm and is formed by protein amyloid aggregates with a particle size of 1~10 nm.

5. The application of the adhesive emulsifier based on protein amyloid aggregates as described in claim 4 in the preparation of nanoemulsions.

6. A nanoemulsion, characterized in that, The nanoemulsion contains the adhesive emulsifier based on protein amyloid aggregates as described in claim 4.

7. The nanoemulsion according to claim 6, characterized in that, The aqueous phase of the nanoemulsion includes deionized water containing the adhesive emulsifier based on protein amyloid aggregates as described in claim 5, and the oil phase includes any one of olive oil, methyl oleate, n-hexane, ethyl acetate, paraffin oil, oleic acid, n-decane, and dodecane. The particle size of the nanoemulsion is 200~900nm.

8. The application of the nanoemulsion of claim 6 or 7, or the adhesive emulsifier based on protein amyloid aggregates of claim 4, in the emulsification of oil-water interfaces or gas-liquid interfaces.

9. A nano-herbicide, characterized in that, The nano herbicide comprises: (1) The nanoemulsion of claim 6 or 7, or the adhesive emulsifier based on protein amyloid aggregates of claim 4; and (2) Herbicidal active ingredients.

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