CN114250125B

CN114250125B - Plant source porous micron particle and preparation method and application thereof

Info

Publication number: CN114250125B
Application number: CN202011013738.3A
Authority: CN
Inventors: 冯亮; 张雨; 赵旭辉
Original assignee: Henan Chengcheng Technology Development Co ltd; Dalian Institute of Chemical Physics of CAS
Current assignee: Henan Chengcheng Technology Development Co ltd; Dalian Institute of Chemical Physics of CAS
Priority date: 2020-09-24
Filing date: 2020-09-24
Publication date: 2022-09-06
Anticipated expiration: 2040-09-24
Also published as: CN114250125A

Abstract

The application discloses a plant-derived porous microparticle, which is obtained by performing a cross-linking reaction on wheat protein. The plant source porous micron particles are micron-sized, the pore size is nano-sized, the particles are uniform, the specific surface area is high, the adsorption effect on pesticide residues is good, the raw materials are derived from plants, and the plant source porous micron particles are natural and harmless and can be directly applied to the related field of fruit and vegetable cleaning without a complex purification process.

Description

Plant source porous micron particle and preparation method and application thereof

Technical Field

The application relates to a plant source porous micron particle, a preparation method and an application thereof, and belongs to the field of daily chemical cleaning agents.

Background

In recent years, porous materials have attracted much attention in the fields of chemical engineering, functional materials, environmental protection, and the like because of their advantages in porosity, specific surface area, adsorption performance, and the like. However, the synthesis of most materials involves either toxic chemicals or organic solvents, which limits the use of porous materials in food, medicine, household chemicals, etc. In order to ensure the use safety of the porous material, natural extracts are selected from precursors used for preparing the material, solvents and cross-linking agents in the preparation process, and the like for synthesis.

Wheat gliadin and glutenin are the main storage proteins of wheat seeds, the content of the gliadin and glutenin accounts for about 85 percent of the total amount of wheat seed protein, and the gliadin and glutenin are the main components for forming wheat gluten. The wheat gliadin is a single peptide chain with small molecular weight, forms a spherical structure through intramolecular disulfide bonds, hydrogen bonds and hydrophobic effects, and comprises glutamic acid, glutamine, proline, glycine, phenylalanine, cysteine, methionine and the like. Glutenin is a heterogeneous macromolecular polymer, is connected by intramolecular and intermolecular disulfide bonds, is fibrous, is easy to aggregate, is soluble in dilute acid or dilute alkali, and comprises cysteine, glutamine, methionine, serine, isoleucine and the like.

Oleuropein belongs to natural iridoid molecules, widely exists in fruits and leaves of olive trees, is easy to obtain, has strong antibacterial and antiviral properties, and also has strong antioxidant capacity. Oleuropein can generate cross-linking reaction with amino in protein, and is a biological cross-linking agent with great development potential.

The plant-derived proteins wheat gliadin and glutenin are used for preparing porous micron particles under the action of a plant-derived cross-linking agent oleuropein and the application of the porous micron particles in the field of fruit and vegetable cleaning is not reported at present.

Disclosure of Invention

According to one aspect of the application, the plant source porous micron particles are provided, raw materials used by the plant source porous micron particles are plant sources, and are natural, non-toxic and harmless, so that the plant source porous micron particles can be applied to the fields related to fruit and vegetable cleaning without a complex purification process after synthesis.

The plant source porous micron particles are obtained by performing a cross-linking reaction on wheat protein.

Optionally, the wheat protein comprises gliadin and/or glutenin.

Optionally, the particle size of the plant-derived porous microparticle is 5.4-10.9 μm.

Optionally, the plant-derived porous microparticle has a pore size of 0.2-10 nm.

Optionally, the plant-derived porous microparticles have a pore size of 1-18 nm.

Optionally, the specific surface area of the plant-derived porous microparticle is 400-600 m ² /g。

Optionally, the plant-derived porous microparticles have a specific surface area of 400-506.9 m ² /g。

Optionally, the specific surface area of the plant-derived porous microparticle is 506.9-600 m ² /g。

According to an aspect of the present application, there is provided a method for preparing a porous microparticle of plant origin as defined in any one of the preceding claims, said method comprising the steps of: and (3) carrying out crosslinking reaction on the wheat protein under the action of a crosslinking agent and a plant source emulsifier to obtain the plant source porous micron particles.

Optionally, the mass of the cross-linking agent is 4-10% of the wheat protein.

Optionally, the cross-linking agent comprises oleuropein.

Optionally, the plant source emulsifier comprises one or more of lecithin, phytosterol, and tea saponin.

Optionally, the conditions of the crosslinking reaction are: reacting for 1-24 h at 40-60 ℃.

Optionally, the method comprises the steps of:

(S1) mixing the wheat protein and the plant source emulsifier to obtain a mixture;

(S2) adding a cross-linking agent into the mixture to perform a cross-linking reaction to obtain the plant-derived porous microparticles;

optionally, the mass-to-volume ratio (mg/ml) of the cross-linking agent to the mixture is (13-50): (50-200).

Optionally, the mass-to-volume ratio (mg/ml) of the cross-linking agent to the mixture is (13-30): (50-200).

Optionally, the mass-to-volume ratio (mg/ml) of the cross-linking agent to the mixture is (30-50): (50-200).

Optionally, the mass-to-volume ratio (mg/ml) of the cross-linking agent to the mixture is (13-30): (100-200).

Optionally, the mass-to-volume ratio (mg/ml) of the cross-linking agent to the mixture is (13-30): (50-100).

Optionally, the step (S1) includes the steps of:

(s1a) dissolving gliadin in an alcoholic solution to obtain an aqueous phase I;

(s1b) dissolving glutenin in an alkaline solution to obtain an aqueous phase II;

(s1c) dispersing a plant-derived emulsifier in a vegetable oil to obtain oil phase I;

(s1d) adding aqueous phase I and aqueous phase II to oil phase I to obtain a mixture.

Optionally, the alcohol in the alcohol solution comprises ethanol.

Optionally, the alcohol solution has a concentration of 60% to 80%.

Optionally, the alcohol solution is at a concentration of 70%.

Optionally, the alkali of the alkaline solution is selected from one or more of sodium hydroxide, sodium bicarbonate and sodium carbonate.

Optionally, the pH value of the alkali solution is 9-10.

Optionally, the pH of the alkali solution is 9 to 9.5.

Optionally, the pH value of the alkali solution is 9.5-10.

Optionally, the vegetable oil is selected from one or more of soybean oil, corn oil, sunflower oil in combination.

Optionally, the mass fraction of gliadin in the water phase I is 2% to 4%.

Optionally, the mass fraction of gliadin in the water phase I is 2% to 3%.

Optionally, the mass fraction of gliadin in the water phase I is 3% to 4%.

Optionally, the mass fraction of glutenin in the water phase II is 2% to 4%.

Optionally, the mass fraction of glutenin in the water phase II is 2% to 3%.

Optionally, the mass fraction of glutenin in the water phase II is 3% to 4%.

Optionally, the mass fraction of the plant-derived emulsifier in the oil phase I is 0.1% to 0.3%.

Optionally, the mass fraction of the plant-derived emulsifier in the oil phase I is 0.1-0.2%.

Optionally, the mass fraction of the plant-derived emulsifier in the oil phase I is 0.2-0.3%.

Optionally, the volume ratio (ml/ml) of the water phase I to the water phase II is (1-3): (5-10).

Optionally, the volume ratio (ml/ml) of the water phase I to the water phase II is (1-2): (5-10).

Optionally, the volume ratio (ml/ml) of the water phase I to the water phase II is (1-2): (9-10).

Optionally, the volume ratio (ml/ml) of the water phase I to the water phase II is (1-2): (5-9).

Optionally, the volume ratio (ml/ml) of the sum of the volumes of the water phase I and the water phase II to the oil phase I is (1-3): (10-20).

Optionally, the volume ratio (ml/ml) of the sum of the volumes of the water phase I and the water phase II to the oil phase I is (1-3): 10.

optionally, the volume ratio (ml/ml) of the sum of the volumes of the water phase I and the water phase II to the oil phase I is (1-2): 10.

optionally, the volume ratio (ml/ml) of the sum of the volumes of the water phase I and the water phase II to the oil phase I is (2-3): 10.

optionally, (s1d) is specifically: and (3) respectively dropwise adding the water phase I and the water phase II into the oil phase I at 40-60 ℃, and uniformly stirring, wherein the stirring is top stirring, and the stirring speed is 200-2000 rpm.

Optionally, (s1d) is specifically: and (3) respectively dropwise adding the water phase I and the water phase II into the oil phase I at 40-50 ℃, and uniformly stirring, wherein the stirring is top stirring, and the stirring speed is 500-800 rpm.

Optionally, (s1d) is specifically: and (3) respectively dropwise adding the water phase I and the water phase II into the oil phase I at 50-60 ℃, and uniformly stirring, wherein the stirring is top stirring, and the stirring speed is 500-2000 rpm.

Optionally, the reaction temperature of the (S2) is 40-60 ℃, and the reaction time is 1-24 h.

Optionally, the reaction temperature of the (S2) is 40-60 ℃, and the reaction time is 12-24 h.

Optionally, the reaction temperature of the (S2) is 40-50 ℃, and the reaction time is 12-20 h.

Optionally, the reaction temperature of the (S2) is 50-60 ℃, and the reaction time is 20-24 h.

Optionally, the reaction of (S2) is performed under stirring conditions, the stirring is overhead stirring, and the stirring speed is 200-2000 rpm.

Optionally, the reaction of (S2) is performed under stirring conditions, the stirring is overhead stirring, and the stirring speed is 800-1600 rpm.

Optionally, the reaction of (S2) is performed under stirring conditions, the stirring is overhead stirring, and the stirring speed is 1000-1600 rpm.

Optionally, the reaction of (S2) is performed under stirring conditions, the stirring is overhead stirring, and the stirring speed is 800-1000 rpm.

Optionally, the method further comprises the steps of standing, taking out the lower aqueous phase clear solution, freezing and drying after the (S2) reaction is finished.

According to one aspect of the application, an application of the plant-derived porous microparticle or the plant-derived porous microparticle prepared by the preparation method in preparation of a fruit and vegetable cleaning agent is provided.

According to one aspect of the application, the fruit and vegetable washing effervescent tablet is characterized by comprising the plant-derived porous micro-particles or the plant-derived porous micro-particles prepared by the preparation method.

According to one aspect of the application, a preparation method of the fruit and vegetable washing effervescent tablet is provided, and is characterized by comprising the following steps: and mixing the plant source porous micro-granules with an effervescent tablet disintegrating agent, and tabletting to obtain the fruit and vegetable cleaning effervescent tablet.

Optionally, the preparation of the effervescent tablet disintegrant comprises the preparation of an acidic soft material and an alkaline soft material.

Optionally, the soft acidic material is formed by sodium chloride, starch and citric acid under the action of a binder.

Optionally, the alkaline soft material is formed by sodium chloride, starch and sodium carbonate under the action of a binder.

Optionally, the effervescent tablet disintegrating agent is formed by sieving, drying and mixing the prepared acidic soft material and the prepared alkaline soft material.

The beneficial effects that this application can produce include:

1) the application provides a porous micron granule of botanical source, particle size is the micron order, the aperture is the nanometer, and the granule is even, has higher specific surface area, has good adsorption to pesticide residue etc. and used raw materials derive from the plant, and is natural harmless, need not complicated purification process and can directly be applied to fruit vegetables and wash relevant field.

2) According to the preparation method of the plant-derived porous micron particles, by scientific selection and proportion regulation of the protein precursor, the cross-linking agent and the emulsifying agent and optimization of the mixing/reaction sequence, the reaction temperature and the stirring speed of the raw materials, the finally obtained plant-derived porous micron particles are uniform and have large specific surface area, and harmful substances such as pesticide residues can be adsorbed and removed.

3) The fruit and vegetable cleaning effervescent tablet provided by the application is simple in preparation method, can be obtained by mixing and tabletting the plant source porous micro-particles and the effervescent tablet disintegrating agent, and is safe and efficient.

Drawings

FIG. 1 is a graph of N of plant-derived porous microparticles prepared in example 1 of the present application ₂ Adsorption-desorption curves.

Detailed Description

The present application will be described in detail with reference to examples, but the present application is not limited to these examples.

Unless otherwise specified, the raw materials in the examples of the present application were all purchased commercially.

Example 1.

The method for preparing the plant source porous micron particles comprises the following steps:

(S1): (s1a) dissolving gliadin in 70% ethanol to prepare water phase I with mass fraction of 2%; (s1b) dissolving glutenin in sodium bicarbonate solution with pH of 10 to prepare water phase II with mass fraction of 4%; (s1c) dispersing lecithin in soybean oil to prepare an oil phase I with the mass fraction of 0.1%; (s1d) at 60 ℃, mixing the water phase I and the water phase II according to the volume ratio of 1: 5 into the oil phase I drop by drop, and finally, the volume ratio of the water phase to the oil phase is 3: 10, the volume of the whole mixing system is 100ml, the mixture is continuously stirred at the rotating speed of 500rpm in the mixing process, and a mixture is obtained after the mixture is completely mixed;

(S2): adding 50mg of cross-linking agent oleuropein into the mixture, continuously stirring at 60 ℃ for cross-linking reaction for 24h, stirring at 1600rpm, standing, taking out the lower-layer aqueous phase clear liquid, and freeze-drying for 12h to obtain the plant-derived porous micron particles.

And (3) respectively measuring the particle size distribution, the pore size and the specific surface area of the prepared plant source porous micron particles by using a micron laser particle size analyzer and a pore size and specific surface area analyzer. The test result of the particle size distribution shows that the prepared plant source porous micron particles are 5.4-10.9 microns in size distribution and uniform in particle size. The pore diameter test result shows that the pore diameter of the particles is 1-8 nm. According to the plant source porous microparticle pair N ₂ The specific surface area of the plant-derived porous microparticles is 506.9m ² /g。

Example 2.

(S1): (s1a) dissolving gliadin in 70% ethanol to prepare a water phase I with the mass fraction of 4%; (s1b) dissolving glutenin in sodium hydroxide solution with pH of 9 to prepare water phase II with mass fraction of 3%; (s1c) dispersing phytosterol in corn oil to prepare an oil phase I with the mass fraction of 0.3%; (s1d) at 40 ℃, respectively adding the water phase I and the water phase II into the reactor according to the volume ratio of 1: 10 into the oil phase I drop by drop, and finally leading the volume ratio of the water phase to the oil phase to be 1: 10, the volume of the whole mixing system is 50ml, the stirring is continuously carried out at the rotating speed of 800rpm in the mixing process, and a mixture is obtained after the whole mixing process;

(S2): adding 13mg of cross-linking agent oleuropein into the mixture, continuously stirring at 40 ℃ for carrying out cross-linking reaction for 12 hours, keeping the stirring speed at 800rpm, taking out the lower-layer aqueous phase clear liquid, and freeze-drying for 12 hours to obtain the plant-derived porous micron particles.

Example 3.

(S1): (s1a) dissolving gliadin in 70% ethanol to prepare water phase I with the mass fraction of 3%; (s1b) dissolving glutenin in sodium carbonate alkali solution with pH of 9.5 to prepare water phase II with mass fraction of 2%; (s1c) dispersing tea saponin in sunflower seed oil to prepare an oil phase I with the mass fraction of 0.2%; (s1d) at 50 ℃, respectively adding the water phase I and the water phase II into a reactor at a volume ratio of 2: 9 is dripped into the oil phase I drop by drop, and finally the volume ratio of the water phase to the oil phase is 2: 10, the volume of the whole mixing system is 200ml, the mixture is continuously stirred at the rotating speed of 500rpm in the mixing process, and a mixture is obtained after the mixture is completely mixed;

(S2): adding 30mg of cross-linking agent oleuropein into the mixture, continuously stirring at 50 ℃ for cross-linking reaction for 20h, stirring at 1000rpm, standing, taking out the lower-layer aqueous phase clear liquid, and freeze-drying for 12h to obtain the plant-derived porous micron particles.

Example 4.

An application experiment in the field of cleaning fruits and vegetables is carried out on the plant source porous micron particles prepared in the embodiments 1-3. Firstly, the adsorption and removal performance of three plant-derived porous micron particles on five common pesticides including dichlorvos, dimethoate, cypermethrin, fenvalerate and deltamethrin is inspected by a static adsorption method. The experimental procedure was as follows: weighing 50mg of plant source porous micron particles, putting the plant source porous micron particles into a 50ml centrifuge tube, respectively adding a pesticide solution with the concentration of 1ppm, shaking for 10min, standing, taking supernatant, passing through a membrane, extracting by using an organic solvent, measuring the pesticide in the extract according to the gas chromatography conditions in GB/T5009.20-2003 (dichlorvos, dimethoate) and GB/T5009.146-2008 (cypermethrin, fenvalerate and deltamethrin), and calculating the corresponding adsorption removal rate, wherein the results are shown in Table 1.

TABLE 1 adsorption removal rate of three plant-derived porous microparticles on common pesticides%

Examples	Dichlorvos	Dimethoate	Cypermethrin	Fenvalerate	Deltamethrin
							1	73.8	89.3	90.3	85.6	87.5
2	88.4	83.5	85.7	89.7	79.7
						3	79.0	91.6	89.4	92.1	90.3

As can be seen from Table 1, the prepared plant-derived porous micro-particles have strong adsorption and removal effects on pesticides. The plant source porous micron particles are suitable for being applied to the fruit and vegetable cleaning process as a fruit and vegetable cleaning agent. Standard dichlorvos was added to cherry tomatoes so that the concentration of pesticide residues was 5mg/Kg, and the cleaning effect of the pesticide residues on the cherry tomatoes by adding different amounts of the plant-derived porous microparticles per liter of water was examined, taking the plant-derived porous microparticles prepared in example 1 as an example. The experimental procedure was as follows: adding 500g of cherry tomatoes into each liter of water, then respectively adding 0.2g, 0.5g and 1.0g of plant source porous micron particles, standing for 10 minutes, washing the cherry tomatoes with 500ml of water, extracting the washing liquid by using an organic solvent, measuring the extract by using gas chromatography, and calculating the corresponding pesticide adsorption removal rate, wherein the results are shown in table 2.

TABLE 2 cleaning effect of different amount of plant source porous micro-particles on cherry tomato pesticide residue

Amount of added microparticles, g	Dichlorvos removal rate%
		0.2	76.8
0.5	92.3
		1.0	95.8

From the data in the table and the cost, 0.5g of plant source porous micron particles are properly added into each liter of water, and the pesticide residue removal rate can reach more than 90 percent after cleaning.

Example 5.

The plant-derived porous micro-particles are prepared into effervescent tablets and applied to the field of fruit and vegetable cleaning, and the plant-derived porous micro-particles prepared in the example 1 are taken as an example. Mixing the plant source porous micron granules with an effervescent tablet disintegrating agent, and tabletting. Wherein, the effervescent tablet disintegrating agent comprises the preparation of an acidic soft material and an alkaline soft material. The acidic soft material is formed by 20% of sodium chloride, 10% of starch and 15% of citric acid under the action of a binder, the alkaline soft material is formed by 10% of sodium chloride, 20% of starch and 25% of sodium carbonate under the action of the binder, the acidic soft material and the alkaline soft material are prepared, then are sieved by a sieve of 18 meshes, are dried at 50 ℃, are granulated by a sieve of 18 meshes again, are mixed to form the effervescent tablet disintegrating agent, are mixed with the plant source porous micro-granules according to a ratio of 1:6 and are pressed, the tabletting condition is 50KN, and the mass of each effervescent tablet is 3 g. The prepared effervescent tablet is used for fruit and vegetable cleaning experiments, and the residual quantity of the cypermethrin in the apples is 3mg/Kg after standard addition is carried out on the apples by taking standard cypermethrin as an example. The experimental procedure was as follows: preparing 2 parts of 500g apples, respectively cleaning the apples with 1 liter of water, adding 1 effervescent tablet into 1 part of cleaning water of the apples, taking the other 1 part of the cleaning water as a control experiment, adding no effervescent tablet, standing for 10 minutes, respectively washing the 2 parts of apples with 500ml of water, retaining the washing liquid, extracting the washing liquid by using an organic solvent, measuring the extraction liquid by using gas chromatography, and calculating the removal rate of cypermethrin in the apples cleaned by adding the effervescent tablets to reach 93.6 percent, while the removal rate of cypermethrin in the control experiment is only 56.8 percent. Therefore, the effervescent tablet prepared from the plant-derived porous micron particles can effectively remove pesticide residues, and the prepared plant-derived porous micron particles can be applied to the field of cleaning of fruits and vegetables.

Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims

1. A plant source porous microparticle is characterized in that the plant source porous microparticle is obtained by performing a cross-linking reaction on wheat protein;

the wheat protein comprises gliadin and glutenin; the crosslinking reaction comprises a crosslinking agent;

the cross-linking agent comprises oleuropein.

2. The plant-derived porous microparticle according to claim 1, wherein the particle size of the plant-derived porous microparticle is 5.4-10.9 μm.

3. The plant-derived porous microparticle of claim 1, wherein the plant-derived porous microparticle has a pore size of 0.2 to 10 nm.

4. The plant-derived porous microparticle according to claim 1, wherein the specific surface area of the plant-derived porous microparticle is 400-600 m ² /g。

5. A preparation method of the plant-derived porous microparticles as claimed in any one of claims 1 to 4, characterized in that the preparation method comprises the following steps: and (3) performing a crosslinking reaction on the wheat protein under the action of a crosslinking agent and a plant source emulsifier to obtain the plant source porous micron particles.

6. The method according to claim 5, wherein the amount of the cross-linking agent is 4 to 10% by mass based on the wheat protein.

7. The method of claim 5, wherein the plant-derived emulsifier comprises one or more of lecithin, phytosterol, and tea saponin.

8. The method according to claim 5, wherein the conditions of the crosslinking reaction are: reacting for 1-24 h at 40-60 ℃.

9. The method for preparing according to claim 5, characterized in that it comprises the following steps:

(S2) adding a cross-linking agent into the mixture to perform a cross-linking reaction, so as to obtain the plant-derived porous microparticles.

10. The preparation method according to claim 9, wherein the mass-to-volume ratio (mg/ml) of the cross-linking agent to the mixture is (13-50): (50-200).

11. The method of claim 9, wherein the step (S1) includes the steps of:

(s1a) dissolving gliadin in an alcoholic solution to obtain aqueous phase I;

12. The method of claim 11, wherein the alcohol in the alcohol solution comprises ethanol.

13. The preparation method according to claim 11, wherein the alkali of the alkaline solution is selected from one or more of sodium hydroxide, sodium bicarbonate and sodium carbonate.

14. The method according to claim 11, wherein the alkaline solution has a pH of 9 to 10.

15. The method as claimed in claim 11, wherein the vegetable oil is selected from soybean oil, corn oil, and sunflower oil.

16. The method according to claim 11, wherein the mass fraction of gliadin in the aqueous phase I is 2% to 4%.

17. The method according to claim 11, wherein the aqueous phase II contains glutenin in an amount of 2 to 4% by mass.

18. The preparation method according to claim 11, wherein the mass fraction of the plant-derived emulsifier in the oil phase I is 0.1% to 0.3%.

19. The preparation method according to claim 11, wherein the volume ratio (ml/ml) of the water phase I to the water phase II is (1-3): (5-10).

20. The method according to claim 11, wherein the volume ratio (ml/ml) of the sum of the volumes of the water phase I and the water phase II to the oil phase I is (1-3): (10-20).

21. Application of the plant-derived porous micro-particles as claimed in any one of claims 1 to 4 or the plant-derived porous micro-particles prepared by the method as claimed in any one of claims 5 to 20 in preparation of fruit and vegetable cleaning agents.

22. An effervescent tablet for cleaning fruits and vegetables, which is characterized by comprising the plant-derived porous micro-particles according to any one of claims 1 to 4 or the plant-derived porous micro-particles prepared by the method according to any one of claims 5 to 20.

23. A method for preparing the fruit and vegetable washing effervescent tablet as claimed in claim 22, wherein the method comprises the following steps: and mixing the plant source porous micro-granules with an effervescent tablet disintegrating agent, and tabletting to obtain the fruit and vegetable cleaning effervescent tablet.