CN114514955B - Composite coated potassium diformate microcapsule and preparation process thereof - Google Patents
Composite coated potassium diformate microcapsule and preparation process thereof Download PDFInfo
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Abstract
The invention discloses a composite coated potassium diformate microcapsule and a preparation method thereof, wherein the composite coated potassium diformate microcapsule comprises the following raw materials in parts by weight: 1-5 parts of potassium diformate, 5-10 parts of microcrystalline cellulose, 2-5 parts of chitosan, 2-6 parts of tetraethyl silicate, 0.1-1 part of calcium chloride, 100-150 parts of sodium alginate solution, 50-70 parts of ethanol solution, 50-100 parts of acetic acid solution and 1-3 parts of ammonia water. The encapsulation rate of the potassium diformate can reach more than 94.3%, the potassium diformate is kept complete in the stomach and is dissolved and released in the intestinal tract, the influence on digestion, absorption and metabolism of mineral elements is reduced, the slow-release stability is high, the antibacterial rate can reach more than 96.6%, the potassium diformate utilization efficiency is high, and the use dosage can be effectively reduced.
Description
Technical Field
The invention relates to the technical field of potassium diformate microencapsulation, in particular to a composite coated potassium diformate microcapsule and a preparation process thereof.
Background
The consumption of the antibiotics for feeding is more than 10 ten thousand tons each year, which accounts for more than 30 percent of the global consumption. However, as the feed antibiotics are not used normally for a long time, the bacterial drug resistance situation is more and more severe, the animal-derived bacterial drug resistance rate is continuously increased, the risk of exceeding the standard of antibacterial drug residues is aggravated, the animal food safety is seriously affected, and the human health is greatly threatened. Thus, the disablement of feeding antibiotics has become a global consensus of industry and society. The national debate policies of the european union, japan, korea, etc. prohibit the use of antibiotic growth promoters in feeds. The agricultural rural department of China also has high-density related policies and plans of 'limiting/disabling' antibiotics, and prescribes that all growth-promoting medicinal feed additives and varieties except traditional Chinese medicines are withdrawn from 2020. From this, the feed antibiotic substitution product has great market demand prospect in the livestock breeding industry in the future.
Potassium diformate was first developed by BASF corporation and approved for use in 2001 by the european union, the first non-antibiotic feed additive approved by the european union for replacement of antibiotic growth promotion. At present, feed additives based on potassium diformate developed by BASF have been approved by the european community, swiss, norway for widespread use as growth promoters in piglet, finishing pig and sow feeds. In 2005, potassium diformate was approved as a new feed additive for pig feed in China. Clinical application research results show that the potassium diformate serving as a non-antibiotic growth promoter is safe and nontoxic in animals, has no residue, can not generate drug resistance, has no harm to ecological environment, and can be completely degraded. Therefore, the potassium diformate has good commercial value and application prospect as a feed antibiotic substitute.
Potassium diformate is a short-chain organic acid, and can be absorbed by intestinal epithelial cells through passive diffusion after entering the intestinal tract, so as to provide energy for metabolism of the intestinal epithelial cells and maintenance of intestinal health. Potassium diformate can release protons through the cell wall of bacteria into the cytoplasm, and bacteria need to consume large amounts of ATP to excrete protons in order to maintain the balance of intracellular pH, depleting their energy, ultimately leading to bacterial death. Potassium diformate is used as a first non-antibiotic antibacterial growth promoter, and has generally accepted the effects of inhibiting bacteria, promoting growth, regulating intestinal microecological environment, preventing diarrhea of animals and the like.
Currently, the majority of potassium diformates that are common in the market are unprocessed or simply mixed products. CN 101502299B discloses a feed additive for tilapia, the raw materials include potassium diformate, silicon dioxide, beta-cyclodextrin or cyclodextrin derivative of eucommia active substance or lactose or dextromethorphan inclusion compound, sodium 5-nitro guaiacol, vitamin C, betaine; CN 102172266B discloses an additive for improving feed intake of lactating sows and application thereof, which is prepared by compounding potassium diformate, gamma-aminobutyric acid, cysteamine salt, active yeast and enzyme-producing probiotics; the processing technology of the potassium diformate is still in a simple and extensive state, and the most common processing technology of the potassium diformate at present is to add carriers such as silicon dioxide and the like for simple mixing or to carry out crude coating on the potassium diformate for convenient storage, and the use effect of the potassium diformate is greatly reduced by the extensive processing technology.
Meng Xiangjian construction and sustained-release antibacterial property of potassium diformate microcapsule [ J ]. Fine chemical engineering, 2013, volume 36, 11 th stage: 2253-2257 discloses that the sustained-release microcapsule is prepared by adopting a complex coacervation method by taking zeolite molecular sieve as a carrier and carrying potassium diformate and chitosan and sodium alginate as shell materials, wherein the mechanical and stability properties of the microcapsule are improved to a certain extent, but the encapsulation efficiency is 68.33%, the encapsulation efficiency is limited, the sustained-release property is unstable, and the antibacterial rate can only reach 85% at most.
Other mature technologies do not exist in China yet to solve the problems of potassium diformate, how to microencapsulate the potassium diformate, further improve the encapsulation rate of the potassium diformate, reduce the influence on digestion, absorption and metabolism of mineral elements, improve the slow-release stability, increase the antibacterial rate and reduce the dosage, and become the technical problems to be solved at present.
Disclosure of Invention
Based on the technical problems in the background technology, the invention provides a composite coated potassium diformate microcapsule and a preparation process thereof.
The invention provides a composite coated potassium diformate microcapsule, which comprises the following raw materials in parts by weight: 1-5 parts of potassium diformate, 5-10 parts of microcrystalline cellulose, 2-5 parts of chitosan, 2-6 parts of tetraethyl silicate, 0.1-1 part of calcium chloride, 100-150 parts of sodium alginate solution, 50-70 parts of ethanol solution, 50-100 parts of acetic acid solution and 1-3 parts of ammonia water.
Preferably, the acidity of the potassium diformate is > 34.55%.
Microcrystalline cellulose has a particle size of 20-200 μm, is free flowing, has strong fluidity but no fiber property, contains linear polysaccharide bonded by beta-1, 4-glucosidic bond as main component, and is free flowing, very fine, short rod-like or powdery porous granule prepared by hydrolyzing natural cellulose with dilute acid to limit polymerization degree.
Preferably, the microcrystalline cellulose has a particle size of 20-40 μm and a limiting degree of polymerization of 15-145.
Preferably, chitosan has a degree of deacetylation of > 90%.
Preferably, the concentration of the sodium alginate solution is 1-2.5wt%.
Preferably, the viscosity of the sodium alginate is 1.06-1.12Pa.s.
Preferably, the concentration of the ethanol solution is 40-60wt%.
Preferably, the concentration of the acetic acid solution is 1-2v/v%.
The preparation method of the composite coated potassium diformate microcapsule comprises the following steps:
s1, adding microcrystalline cellulose into an ethanol solution, adding ammonia water, uniformly stirring, dropwise adding tetraethyl silicate in a stirring state, stirring at room temperature for 10-30h, sequentially washing with ethanol and water, freeze-drying, then adding into a sintering furnace for calcination, wherein the calcination temperature is 300-400 ℃, and air-cooling to room temperature to obtain silicon dioxide composite microspheres;
s2, adding the potassium diformate into water, and uniformly stirring, wherein the weight ratio of the potassium diformate to the water is 1-5:40-60, adding silicon dioxide composite microspheres into the mixture, stirring the mixture for 2-4 hours at the temperature of 40-50 ℃, carrying out ultrasonic treatment for 1-2 hours at the ultrasonic frequency of 10-16kHz, centrifuging, washing, and drying in an oven at the temperature of 40-50 ℃ to obtain a potassium diformate core material;
s3, adding chitosan into the acetic acid solution, uniformly stirring at the temperature of 40-50 ℃, adding calcium chloride, and uniformly stirring to obtain a wall material solution;
s4, adding the potassium diformate core material into the sodium alginate solution, uniformly stirring at the temperature of 30-40 ℃, dropwise adding the wall material solution into the solution at the high stirring speed of 1000-2000r/min, continuously stirring for 1-2h, washing with distilled water, and drying in an oven at the temperature of 40-50 ℃ to obtain the composite coated potassium diformate microcapsule.
Preferably, in S1, the silica composite microsphere has a diameter of 100 to 500 μm.
Preferably, in S1, the mixture is added into a sintering furnace for calcination, and in the specific calcination process, the mixture is heated to 200-250 ℃ from room temperature at a speed of 1-5 ℃ per minute under the protection of nitrogen, is kept for 10-30min, is continuously heated to 300-400 ℃ at a speed of 10-15 ℃ per minute, and is kept for 10-20min.
The technical effects of the invention are as follows:
(1) The microcrystalline cellulose is of a short rod-shaped or porous particle structure, silicon dioxide is deposited on the surface of the microcrystalline cellulose, and the microcrystalline cellulose is carbonized through calcination to form a nano microsphere structure taking the silicon dioxide as a shell and containing porous carbon sphere cores, and meanwhile, a large number of holes are formed in the silicon dioxide shell, and the porous carbon sphere cores can be used as support carriers of the silicon dioxide shell, so that the stability of the shell structure is effectively ensured;
(2) In the carbonization process of microcrystalline cellulose, the size is reduced, the shrinkage rate of the microsphere formed by combining nano silicon dioxide particles at the outer layer is smaller than that of a porous carbon sphere center, so that a core and a shell are separated, the diameter of a silicon dioxide composite microsphere can be shrunk to 100-500 mu m, potassium diformate is fully adsorbed into the silicon dioxide composite microsphere by adding the silicon dioxide composite microsphere into a potassium diformate solution, and the adsorption capacity is extremely large and the adsorption stability is good by the dual action of the porous carbon sphere center and a silicon dioxide microsphere shell;
(3) The invention disperses the silicon dioxide composite microsphere in the potassium diformate solution, the potassium diformate enters the porous carbon sphere in the microsphere through the microsphere pore canal, under the acidic condition, the chitosan forms-NH 3 + And is combined with carboxyl of sodium alginate to form polymerThe electrolyte membrane and the potassium diformate core material are coated, the encapsulation rate of the potassium diformate can reach 94.3%, the potassium diformate is kept complete in the stomach and dissolved in the intestinal tract to release the potassium diformate, the influence on digestion, absorption and metabolism of mineral elements is reduced, the slow-release stability is high, the antibacterial rate can reach 93%, the potassium diformate utilization efficiency is high, and the use dosage of the potassium diformate can be effectively reduced.
(4) According to the invention, the silica composite microsphere is prepared by a specific process, double synergistic adsorption of potassium diformate is realized, the prepared silica composite microsphere is extremely high in stability and not easy to break, meanwhile, the slow release performance in intestinal tracts is good, the dissolution rate of potassium diformate is controllable, the acting time in the intestinal tracts is effectively prolonged, the bioavailability is improved, and the use dosage is reduced.
Drawings
FIG. 1 is a graph showing the pH change of potassium diformate microcapsules obtained in example 5 of the present invention at various times when immersed in simulated gastric fluid and simulated intestinal fluid.
FIG. 2 is a graph showing the change in the antibacterial activity of the samples of potassium diformate microcapsules obtained in example 5 of the present invention and comparative examples 1 to 2 over time.
Detailed Description
The technical scheme of the invention is described in detail through specific embodiments.
Example 1
A preparation process of a composite coated potassium diformate microcapsule comprises the following steps:
s1, adding 5kg of microcrystalline cellulose into 50kg of ethanol solution with the concentration of 40wt%, adding 1kg of ammonia water, uniformly stirring, dropwise adding 2kg of tetraethyl silicate in a stirring state, stirring for 10 hours at room temperature, washing for 1 time with ethanol, washing for 1 time with water, freeze-drying, then adding into a sintering furnace for calcination, heating to 200 ℃ from room temperature at the speed of 1 ℃/min under the protection of nitrogen, preserving heat for 10min, continuously heating to 300 ℃ at the speed of 10 ℃/min, preserving heat for 10min, and air-cooling to room temperature to obtain silicon dioxide composite microspheres;
the grain diameter of the microcrystalline cellulose is 20-40 mu m, and the limit polymerization degree is 15-145;
the diameter of the silicon dioxide composite microsphere is 100-500 mu m, and the wall thickness is 15-45 mu m;
s2, adding 1kg of potassium diformate into 40kg of water, uniformly stirring, adding silicon dioxide composite microspheres into the mixture, stirring the mixture for 2 hours at the temperature of 40 ℃, carrying out ultrasonic treatment for 1 hour, centrifuging the mixture, washing the mixture, and drying the mixture in an oven at the temperature of 40 ℃ for 2 hours to obtain a potassium diformate core material;
s3, adding 2kg of chitosan into 50kg of acetic acid solution with the concentration of 1v/v%, uniformly stirring at the temperature of 40 ℃, adding 0.1kg of calcium chloride, and uniformly stirring to obtain a wall material solution;
s4, adding the potassium diformate core material into 100kg of sodium alginate solution with the concentration of 1wt%, uniformly stirring at the temperature of 30 ℃, dropwise adding the wall material solution into the solution at the high stirring speed of 1000r/min, continuously stirring for 1h, washing with distilled water for 2 times, and drying in an oven at the temperature of 40 ℃ for 10h to obtain the composite coated potassium diformate microcapsule.
Example 2
A preparation process of a composite coated potassium diformate microcapsule comprises the following steps:
s1, adding 10kg of microcrystalline cellulose into 70kg of ethanol solution with the concentration of 60wt%, adding 3kg of ammonia water, uniformly stirring, dropwise adding 6kg of tetraethyl silicate in a stirring state, stirring for 30 hours at room temperature, washing 3 times with ethanol, washing 3 times with water, freeze-drying, then adding into a sintering furnace for calcination, heating to 250 ℃ from room temperature at the speed of 5 ℃/min under the protection of nitrogen, preserving heat for 30min, continuously heating to 400 ℃ at the speed of 15 ℃/min, preserving heat for 20min, and air-cooling to room temperature to obtain silicon dioxide composite microspheres;
the grain diameter of the microcrystalline cellulose is 20-40 mu m, and the limit polymerization degree is 15-145;
the diameter of the silicon dioxide composite microsphere is 100-500 mu m, and the wall thickness is 15-45 mu m;
s2, adding 5kg of potassium diformate into 60kg of water, uniformly stirring, adding silicon dioxide composite microspheres into the mixture, stirring the mixture for 4 hours at the temperature of 50 ℃, carrying out ultrasonic treatment for 2 hours at the ultrasonic frequency of 16kHz, centrifuging, washing, and drying the mixture in an oven at the temperature of 50 ℃ for 6 hours to obtain a potassium diformate core material;
s3, adding 5kg of chitosan into 100kg of acetic acid solution with the concentration of 2v/v%, uniformly stirring at the temperature of 50 ℃, adding 1kg of calcium chloride, and uniformly stirring to obtain a wall material solution;
s4, adding the potassium diformate core material into 150kg of sodium alginate solution with the concentration of 2.5wt%, uniformly stirring at the temperature of 40 ℃, dropwise adding the wall material solution into the solution at the high stirring speed of 2000r/min, continuously stirring for 2h, washing for 4 times with distilled water, and drying in an oven at the temperature of 50 ℃ for 20h to obtain the composite coated potassium diformate microcapsule.
Example 3
A preparation process of a composite coated potassium diformate microcapsule comprises the following steps:
s1, adding 6kg of microcrystalline cellulose into 55kg of 45wt% ethanol solution, adding 1.2kg of ammonia water, uniformly stirring, dropwise adding 3kg of tetraethyl silicate in a stirring state, stirring for 15 hours at room temperature, washing for 1 time with ethanol, washing for 2 times with water, freeze-drying, adding into a sintering furnace for calcination, heating to 220 ℃ from room temperature at a speed of 1.5 ℃/min under the protection of nitrogen, preserving heat for 15min, continuously heating to 320 ℃ at a speed of 12 ℃/min, preserving heat for 12min, and air-cooling to room temperature to obtain silicon dioxide composite microspheres;
the grain diameter of the microcrystalline cellulose is 20-40 mu m, and the limit polymerization degree is 15-145;
the diameter of the silicon dioxide composite microsphere is 100-500 mu m, and the wall thickness is 15-45 mu m;
s2, adding 3kg of potassium diformate into 42kg of water, uniformly stirring, adding silicon dioxide composite microspheres into the mixture, stirring the mixture for 2.5 hours at the temperature of 42 ℃, carrying out ultrasonic treatment for 1.2 hours at the ultrasonic frequency of 12kHz, centrifuging, washing, and drying the mixture in an oven at the temperature of 42 ℃ for 3 hours to obtain a potassium diformate core material;
s3, adding 2.5kg of chitosan into 60kg of acetic acid solution with the concentration of 1.2v/v%, uniformly stirring at the temperature of 42 ℃, adding 0.2kg of calcium chloride, and uniformly stirring to obtain a wall material solution;
s4, adding the potassium diformate core material into 120kg of sodium alginate solution with the concentration of 1.2wt%, uniformly stirring at the temperature of 32 ℃, dropwise adding the wall material solution into the solution at the high stirring speed of 1200r/min, continuously stirring for 1.2h, washing for 2 times with distilled water, and drying in an oven at the temperature of 41 ℃ for 12h to obtain the composite coated potassium diformate microcapsule.
Example 4
A preparation process of a composite coated potassium diformate microcapsule comprises the following steps:
s1, adding 8kg of microcrystalline cellulose into 60kg of 55wt% ethanol solution, adding 2.5kg of ammonia water, uniformly stirring, dropwise adding 5kg of tetraethyl silicate in a stirring state, stirring for 20 hours at room temperature, washing for 2 times with ethanol, washing for 3 times with water, freeze-drying, then adding into a sintering furnace for calcination, heating to 240 ℃ from room temperature at a speed of 4 ℃/min under the protection of nitrogen, preserving heat for 25min, continuously heating to 360 ℃ at a speed of 14 ℃/min, preserving heat for 18min, and air-cooling to room temperature to obtain silicon dioxide composite microspheres;
the grain diameter of the microcrystalline cellulose is 20-40 mu m, and the limit polymerization degree is 15-145;
the diameter of the silicon dioxide composite microsphere is 100-500 mu m, and the wall thickness is 15-45 mu m;
s2, adding 5kg of potassium diformate into 45kg of water, uniformly stirring, adding silicon dioxide composite microspheres into the mixture, stirring the mixture for 3 hours at 48 ℃, performing ultrasonic treatment for 1.5 hours at an ultrasonic frequency of 15kHz, centrifuging, washing, and drying the mixture in an oven at 46 ℃ for 5 hours to obtain a potassium diformate core material;
s3, adding 4kg of chitosan into 80kg of acetic acid solution with the concentration of 1.8v/v%, uniformly stirring at 46 ℃, adding 0.8kg of calcium chloride, and uniformly stirring to obtain a wall material solution;
s4, adding the potassium diformate core material into 140kg of sodium alginate solution with the concentration of 2.2wt%, uniformly stirring at the temperature of 36 ℃, dropwise adding the wall material solution into the solution at the high stirring speed of 1800r/min, continuously stirring for 1.8h, washing 3 times with distilled water, and drying in an oven at the temperature of 48 ℃ for 18h to obtain the composite coated potassium diformate microcapsule.
Example 5
A preparation process of a composite coated potassium diformate microcapsule comprises the following steps:
s1, adding 6kg of microcrystalline cellulose into 54kg of ethanol solution with the concentration of 50wt%, adding 2.5kg of ammonia water, uniformly stirring, dropwise adding 3kg of tetraethyl silicate in a stirring state, stirring for 15 hours at room temperature, washing for 2 times with ethanol, washing for 2 times with water, freeze-drying, then adding into a sintering furnace for calcination, heating to 220 ℃ from room temperature at the speed of 2 ℃/min under the protection of nitrogen, preserving heat for 20min, continuously heating to 350 ℃ at the speed of 12 ℃/min, preserving heat for 15min, and air-cooling to room temperature to obtain silicon dioxide composite microspheres;
the grain diameter of the microcrystalline cellulose is 20-40 mu m, and the limit polymerization degree is 15-145;
the diameter of the silicon dioxide composite microsphere is 100-500 mu m, and the wall thickness is 15-45 mu m;
s2, adding 4kg of potassium diformate into 50kg of water, uniformly stirring, adding silicon dioxide composite microspheres into the mixture, stirring the mixture for 3 hours at the temperature of 45 ℃, performing ultrasonic treatment for 1.2 hours at the ultrasonic frequency of 12kHz, centrifuging, washing, and drying the mixture in an oven at the temperature of 45 ℃ for 4 hours to obtain a potassium diformate core material;
s3, adding 3.2kg of chitosan into 60kg of acetic acid solution with the concentration of 1.2v/v%, uniformly stirring at the temperature of 45 ℃, adding 0.2kg of calcium chloride, and uniformly stirring to obtain a wall material solution;
s4, adding the potassium diformate core material into 125kg of sodium alginate solution with the concentration of 2.1wt%, uniformly stirring at the temperature of 35 ℃, dropwise adding the wall material solution into the solution at the high stirring speed of 1500r/min, continuously stirring for 1.5h, washing 3 times with distilled water, and drying in an oven at the temperature of 45 ℃ for 15h to obtain the composite coated potassium diformate microcapsule.
Test example I
1.2g of the composite coated potassium diformate microcapsule obtained in example 5 was placed in 200mL of hydrochloric acid solution (simulated gastric fluid system) with pH=2.0 and 200mL of PBS buffer solution (simulated intestinal system) with pH=7.2, respectively, and stirred at a constant temperature of 37 ℃ at a speed of 80r/min, and the pH value of the solution was detected at regular time.
The results are shown in FIG. 1. As can be seen from fig. 1: the composite coated potassium diformate microcapsule obtained in example 5 was immersed in simulated gastric fluid and the pH value of the composite coated potassium diformate microcapsule was raised to 3, and the applicant hypothesizes that the composite coated potassium diformate microcapsule obtained in example 5 was stably present in simulated gastric fluid because the sodium alginate and chitosan are adopted as wall materials in example 5, and the wall materials (particularly chitosan) react under acidic conditions, so that the pH value is raised, and then the pH value is not changed any more, which means that the microcapsule wall materials in example 5 are not broken, and the potassium diformate is not released.
The composite coated potassium diformate microcapsule obtained in the embodiment 5 is soaked in simulated intestinal juice, the microcapsule wall material is broken in alkaline environment, so that the potassium diformate is released, but the pH value is not greatly reduced later, and the applicant believes that the embodiment 5 adopts the silicon dioxide composite microsphere to protect the potassium diformate, so that the potassium diformate is slowly released in the intestinal environment, the effect of long-acting effect on the intestinal tract is achieved, and the potassium diformate can reach the end section of the intestinal tract along with the peristaltic movement of the intestinal tract.
Comparative example 1
A preparation process of coated potassium diformate microcapsule comprises the following steps:
(i) Adding 4kg of potassium diformate into 50kg of water, uniformly stirring, adding a zeolite molecular sieve, wherein the adding amount of the zeolite molecular sieve is the same as that of the silica composite microsphere in the embodiment 5, stirring for 3 hours at the temperature of 45 ℃, carrying out ultrasonic treatment for 1.2 hours, carrying out ultrasonic frequency for 12kHz, centrifuging, washing, and drying in an oven at the temperature of 45 ℃ for 4 hours to obtain a potassium diformate core material;
(ii) Adding 3.2kg of chitosan into 60kg of acetic acid solution with the concentration of 1.2v/v%, uniformly stirring at the temperature of 45 ℃, adding 0.2kg of calcium chloride, and uniformly stirring to obtain a wall material solution;
(iii) Adding the potassium diformate core material into 125kg of sodium alginate solution with the concentration of 2.1wt%, uniformly stirring at the temperature of 35 ℃, dripping the wall material solution into the solution at the high stirring speed of 1500r/min, continuously stirring for 1.5h, washing 3 times with distilled water, and drying in an oven at the temperature of 45 ℃ for 15h to obtain the coated potassium diformate microcapsule.
Comparative example 2
A preparation process of coated potassium diformate microcapsule comprises the following steps:
(i) Adding 4kg of potassium diformate into 50kg of water, uniformly stirring, adding mesoporous silica microspheres, stirring at 45 ℃ for 3 hours, performing ultrasonic treatment for 1.2 hours, performing centrifugation and washing, and drying in an oven at 45 ℃ for 4 hours to obtain a potassium diformate core material, wherein the adding amount of the mesoporous silica microspheres is the same as that of the silica composite microspheres in the embodiment 5;
(ii) Adding 3.2kg of chitosan into 60kg of acetic acid solution with the concentration of 1.2v/v%, uniformly stirring at the temperature of 45 ℃, adding 0.2kg of calcium chloride, and uniformly stirring to obtain a wall material solution;
(iii) Adding the potassium diformate core material into 125kg of sodium alginate solution with the concentration of 2.1wt%, uniformly stirring at the temperature of 35 ℃, dripping the wall material solution into the solution at the high stirring speed of 1500r/min, continuously stirring for 1.5h, washing 3 times with distilled water, and drying in an oven at the temperature of 45 ℃ for 15h to obtain the coated potassium diformate microcapsule.
Test example II
1.2g of each group (potassium diformate microcapsules obtained in example 5 and comparative examples 1 to 2) of samples were placed in PBS buffer solution with pH=7.2, and the samples were placed in a constant temperature water bath at 37℃and stirred under a magnetic stirrer with a rotation speed of 80r/min, so that the potassium diformate in the microcapsules was sufficiently released. Sucking 5mL of slow release liquid in a centrifuge tube with a mark at intervals of 0.5h by using a pipetting gun, centrifuging for 30min in a centrifuge with a speed of 5000r/min, diluting for 30 times by using distilled water, performing absorbance test on each diluted slow release liquid by using an atomic absorption spectrophotometer, and converting into the content of potassium diformate in each slow release liquid, thereby calculating the encapsulation rate.
Encapsulation efficiency = content of potassium diformate in microspheres/initial potassium diformate dose x 100%
The results are as follows:
| test item | Encapsulation efficiency% |
| Example 5 | 94.3 |
| Comparative example 1 | 69.4 |
| Comparative example 2 | 66.2 |
As can be seen from the table above: the encapsulation efficiency of the potassium diformate microcapsule obtained in example 5 was the highest, and comparative example 1 was slightly inferior to example 5, and the applicant believes that this is due to the limited adsorption capacity of zeolite molecular sieve to potassium diformate, whereas example 5 uses silica composite microspheres to adsorb potassium diformate, and the silica composite microspheres have large loading and high stability, so that the encapsulation efficiency reaches 94.3%.
Test example III
Each group of potassium diformate microcapsule samples was added to the PBS buffer solution of ph=7.2 used in test example 2 at an addition amount of 4%, 2mL was added to a test tube containing 8mL of the medium, 100 μl of the bacterial suspension of escherichia coli which had been cultured to the logarithmic phase was further added, and the mixture was treated at a water bath 37 ℃ at a stirring speed of 220r/min, and absorbance at a wavelength of 630nm was measured with a visible spectrophotometer at 1h, 2h, 3h, 4h, 6h, 8h, 10h, 12h, 15h, 18h, respectively, and the antibacterial ratio was calculated as shown in fig. 2, according to the following formula.
Antibacterial ratio= (OD 1 -OD)/OD×100％
OD is absorbance of the sample; OD (optical density) 1 Is absorbance of the microcapsule-free bacteria-containing culture solution.
As can be seen from fig. 2: in the embodiment 5, the silicon dioxide composite microspheres are adopted to adsorb the potassium diformate, so that the potassium diformate is slowly released in the intestinal tract, the long-acting sterilization and bacteriostasis are realized, and the antibacterial rate is steadily increased within 16 hours and can reach 93 percent at most; in comparative example 1, zeolite molecular sieve is adopted to adsorb potassium diformate, but the antibacterial time is short, the antibacterial rate is only stable, the highest antibacterial rate can reach 82%, but the antibacterial rate is continuously reduced after 6 hours, and the continuous antibacterial in intestinal tracts is difficult to maintain; in comparative example 1, mesoporous silica microspheres were used to protect potassium diformate, but the adsorption stability was poor and the amount of adsorbent was limited.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (8)
1. The composite coated potassium diformate microcapsule is characterized by comprising the following raw materials in parts by weight: 1-5 parts of potassium diformate, 5-10 parts of microcrystalline cellulose, 2-5 parts of chitosan, 2-6 parts of tetraethyl silicate, 0.1-1 part of calcium chloride, 100-150 parts of sodium alginate solution, 50-70 parts of ethanol solution, 50-100 parts of acetic acid solution and 1-3 parts of ammonia water;
the preparation method comprises the following steps:
s1, adding microcrystalline cellulose into an ethanol solution, adding ammonia water, uniformly stirring, dropwise adding tetraethyl silicate in a stirring state, stirring at room temperature for 10-30h, sequentially washing with ethanol and water, freeze-drying, then adding into a sintering furnace for calcination, wherein the calcination temperature is 300-400 ℃, and air-cooling to room temperature to obtain silicon dioxide composite microspheres;
s2, adding the potassium diformate into water, and uniformly stirring, wherein the weight ratio of the potassium diformate to the water is 1-5:40-60, adding silicon dioxide composite microspheres into the mixture, stirring the mixture for 2-4 hours at the temperature of 40-50 ℃, carrying out ultrasonic treatment for 1-2 hours at the ultrasonic frequency of 10-16kHz, centrifuging, washing, and drying in an oven at the temperature of 40-50 ℃ to obtain a potassium diformate core material;
s3, adding chitosan into the acetic acid solution, uniformly stirring at the temperature of 40-50 ℃, adding calcium chloride, and uniformly stirring to obtain a wall material solution;
s4, adding the potassium diformate core material into the sodium alginate solution, uniformly stirring at the temperature of 30-40 ℃, dropwise adding the wall material solution into the solution at the high stirring speed of 1000-2000r/min, continuously stirring for 1-2h, washing with distilled water, and drying in an oven at the temperature of 40-50 ℃ to obtain the composite coated potassium diformate microcapsule.
2. The composite coated potassium diformate microcapsule according to claim 1, wherein the microcrystalline cellulose has a particle size of 20-40 μm and a limiting degree of polymerization of 15-145.
3. The composite coated potassium diformate microcapsule according to claim 1, characterized in that the concentration of sodium alginate solution is 1-2.5wt%.
4. The composite coated potassium diformate microcapsule according to claim 1, characterized in that the concentration of the ethanol solution is 40-60wt%.
5. The composite coated potassium diformate microcapsule according to claim 1, wherein the concentration of acetic acid solution is 1-2v/v%.
6. A method of preparing a composite coated potassium diformate microcapsule according to any one of claims 1 to 5, comprising the steps of:
s1, adding microcrystalline cellulose into an ethanol solution, adding ammonia water, uniformly stirring, dropwise adding tetraethyl silicate in a stirring state, stirring at room temperature for 10-30h, sequentially washing with ethanol and water, freeze-drying, then adding into a sintering furnace for calcination, wherein the calcination temperature is 300-400 ℃, and air-cooling to room temperature to obtain silicon dioxide composite microspheres;
s2, adding the potassium diformate into water, and uniformly stirring, wherein the weight ratio of the potassium diformate to the water is 1-5:40-60, adding silicon dioxide composite microspheres into the mixture, stirring the mixture for 2-4 hours at the temperature of 40-50 ℃, carrying out ultrasonic treatment for 1-2 hours at the ultrasonic frequency of 10-16kHz, centrifuging, washing, and drying in an oven at the temperature of 40-50 ℃ to obtain a potassium diformate core material;
s3, adding chitosan into the acetic acid solution, uniformly stirring at the temperature of 40-50 ℃, adding calcium chloride, and uniformly stirring to obtain a wall material solution;
s4, adding the potassium diformate core material into the sodium alginate solution, uniformly stirring at the temperature of 30-40 ℃, dropwise adding the wall material solution into the solution at the high stirring speed of 1000-2000r/min, continuously stirring for 1-2h, washing with distilled water, and drying in an oven at the temperature of 40-50 ℃ to obtain the composite coated potassium diformate microcapsule.
7. The method of preparing composite coated potassium diformate microcapsule according to claim 6, wherein in S1, the diameter of the silica composite microsphere is 100-500 μm.
8. The method for preparing the composite coated potassium diformate microcapsule according to claim 6, wherein in S1, the mixture is added into a sintering furnace to be calcined, and in the specific calcination process, the mixture is heated to 200-250 ℃ from room temperature at a speed of 1-5 ℃/min under the protection of nitrogen, is kept for 10-30min, and is continuously heated to 300-400 ℃ at a speed of 10-15 ℃/min, and is kept for 10-20min.
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