CN113351125A - Citrus essential oil microcapsule and preparation method and application thereof - Google Patents
Citrus essential oil microcapsule and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a citrus essential oil microcapsule and a preparation method and application thereof, belonging to the technical field of corrosion prevention and comprising the following steps: mixing chitosan quaternary ammonium salt with sodium alginate, acetic acid and water to obtain a composite wall material solution; and mixing with the citrus essential oil and the composite emulsifier to obtain emulsion, carrying out complex coacervation reaction, mixing with calcium chloride, and carrying out crosslinking curing to obtain the citrus essential oil microcapsule. The citrus essential oil is a natural bactericide, has high-efficiency, broad-spectrum and safe antibacterial action, the prepared microcapsule has small particle size, high embedding rate and drug-loading rate and excellent antibacterial performance, and can slowly release the core material to play the antibacterial action and prolong the antibacterial action time in the use process. The results of the examples show that the citrus essential oil microcapsule prepared by the invention has the average particle size of 340nm, the embedding rate of 89.3 percent and the drug-loading rate of 44.65 percent, has excellent bacteriostatic performance on various bacteria and has better bacteriostatic performance in a longer time.
Description
Technical Field
The invention relates to the technical field of corrosion prevention, and particularly relates to a citrus essential oil microcapsule as well as a preparation method and application thereof.
Background
Cosmetics occupy an important position in people's daily life, and in order to ensure stable performance of products, antimicrobial substances, i.e., preservatives, must be added. With the progress of scientific research, the society has more and more deeply researched the preservative, and a plurality of traditional preservatives are proved to have certain negative effects and can influence the human health, so that the preservative product without additive is popular in the market.
The non-volatile components of the plant essential oil contain active substances with excellent antioxidant, antiviral, antibacterial and anti-inflammatory effects, and are widely applied to the fields of cosmetics, daily chemicals and the like due to the nature and safety of the active substances. However, the plant essential oil causes inconvenience in storage and transportation due to its own volatility and instability of effective components, and also limits its application range. The microcapsule technology is a new high-tech technology developed in recent years, well solves the problem of application of the plant essential oil, and greatly expands the development of the plant essential oil industry. However, the microcapsules prepared in the prior art have larger particle size and lower embedding rate, so that the performance improvement is limited, for example, the particle size of the microcapsules prepared in the research on the preparation and performance of the microcapsules of three plant essential oils is more than 1.91 μm, and the maximum embedding rate is only 66%.
Therefore, how to reduce the particle size of the microcapsule and improve the embedding rate of the microcapsule so as to improve the antibacterial performance of the microcapsule becomes a difficult problem in the prior art.
Disclosure of Invention
The invention aims to provide a citrus essential oil microcapsule as well as a preparation method and application thereof. The citrus essential oil microcapsule prepared by the invention has the advantages of small particle size, high embedding rate and drug-loading rate and excellent antibacterial performance.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a preparation method of a citrus essential oil microcapsule, which comprises the following steps:
(1) mixing chitosan quaternary ammonium salt with sodium alginate, acetic acid and water to obtain a composite wall material solution;
(2) mixing the composite wall material solution obtained in the step (1) with the citrus essential oil and the composite emulsifier, and emulsifying to obtain an emulsion;
(3) mixing the emulsion obtained in the step (2) with alkali, and carrying out complex coacervation reaction to obtain an orange essential oil microcapsule primary product;
(4) and (4) mixing the orange essential oil microcapsule primary product obtained in the step (3) with calcium chloride, and carrying out cross-linking curing reaction to obtain the orange essential oil microcapsule.
Preferably, the mass ratio of the chitosan quaternary ammonium salt to the sodium alginate in the step (1) is (0.2-5): 1.
Preferably, the total mass concentration of the chitosan quaternary ammonium salt and the sodium alginate in the composite wall material solution in the step (1) is 0.2-3%.
Preferably, the mass ratio of the citrus essential oil to the composite wall material solution in the step (2) is (0.5-2): 100.
Preferably, the composite emulsifier in the step (2) comprises tween-80 and span-80, and the mass ratio of the composite emulsifier to the composite wall material solution is (0.1-0.5): 100.
Preferably, the pH value of the complex coacervation reaction in the step (3) is 5.0-10.0.
Preferably, the mass ratio of the calcium chloride to the orange essential oil microcapsule primary product in the step (4) is (0.1-2): 100.
Preferably, the temperature of the crosslinking curing reaction in the step (4) is 0-4 ℃, and the time of the crosslinking curing reaction is 1-3 h.
The invention provides a citrus essential oil microcapsule prepared by the preparation method of the technical scheme.
The invention also provides application of the citrus essential oil microcapsule in cosmetics.
The invention provides a preparation method of a citrus essential oil microcapsule, which comprises the following steps: mixing chitosan quaternary ammonium salt with sodium alginate, acetic acid and water to obtain a composite wall material solution; mixing the obtained composite wall material solution with the citrus essential oil and the composite emulsifier, and emulsifying to obtain an emulsion; mixing the obtained emulsion with alkali, and performing complex coacervation reaction to obtain an orange essential oil microcapsule primary product; and mixing the obtained orange essential oil microcapsule primary product with calcium chloride, and carrying out cross-linking curing reaction to obtain the orange essential oil microcapsule. The invention takes the citrus essential oil as the core material, the citrus essential oil is a natural bactericide, has high-efficiency, broad-spectrum and safe antibacterial action, the chitosan quaternary ammonium salt and the sodium alginate are used for preparing the wall material, the obtained microcapsule has small particle size, higher embedding rate and drug-loading rate and excellent antibacterial performance, and the core material can be slowly released to play the antibacterial action in the using process, so that the antibacterial action time is prolonged. The results of the examples show that the citrus essential oil microcapsule prepared by the invention has the average particle size of 340nm, the embedding rate of 89.3 percent and the drug-loading rate of 44.65 percent, has excellent bacteriostatic performance on various bacteria and has better bacteriostatic performance in a longer time.
Drawings
Fig. 1 is a particle size distribution diagram of citrus essential oil microcapsules prepared in example 5 of the present invention.
Detailed Description
The invention provides a preparation method of a citrus essential oil microcapsule, which comprises the following steps:
(1) mixing chitosan quaternary ammonium salt with sodium alginate, acetic acid and water to obtain a composite wall material solution;
(2) mixing the composite wall material solution obtained in the step (1) with the citrus essential oil and the composite emulsifier, and emulsifying to obtain an emulsion;
(3) mixing the emulsion obtained in the step (2) with alkali, and carrying out complex coacervation reaction to obtain an orange essential oil microcapsule primary product;
(4) and (4) mixing the orange essential oil microcapsule primary product obtained in the step (3) with calcium chloride, and carrying out cross-linking curing reaction to obtain the orange essential oil microcapsule.
In the present invention, the sources of the components are not particularly limited, unless otherwise specified, and commercially available products known to those skilled in the art may be used.
The invention mixes chitosan quaternary ammonium salt with sodium alginate, acetic acid and water to obtain the composite wall material solution.
In the invention, the chitosan quaternary ammonium salt is a chitosan derivative, improves the water solubility of chitosan while keeping the original biological characteristics and chemical characteristics of chitosan, has certain antibacterial performance, can be combined with sodium alginate to form a wall layer, and is gradually dissolved in the use process, so that the microcapsule has a slow release effect.
In the invention, the sodium alginate is used as a raw material of the wall material, and is combined with the chitosan quaternary ammonium salt to form the wall layer after a subsequent crosslinking reaction, so that the tightness and the strength of the wall layer are improved.
In the invention, the mass ratio of the chitosan quaternary ammonium salt to the sodium alginate is preferably (0.2-5): 1, more preferably (0.5-4.5): 1, more preferably (1.0-4): 1, and most preferably (2.0-3.0): 1.
The invention limits the mass ratio of the chitosan quaternary ammonium salt to the sodium alginate in the range, can improve the embedding rate and the drug-loading rate of the microcapsule, and further improves the antibacterial effect of the microcapsule.
In the invention, the total mass concentration of the chitosan quaternary ammonium salt and the sodium alginate in the composite wall material solution is preferably 0.2-3%, more preferably 0.5-2.5%, more preferably 1.0-2.0%, and most preferably 1.5%.
According to the invention, the total mass concentration of the quaternary ammonium salt of chitosan and the sodium alginate in the composite wall material solution is limited within the range, so that the quaternary ammonium salt of chitosan and the sodium alginate can be fully dissolved, and the subsequent reaction can be favorably carried out.
In the present invention, the water is preferably distilled water. In the invention, the distilled water can avoid the adverse effect of impurities in the water on the performance of the microcapsule.
In the present invention, the acetic acid is used to dissolve the chitosan quaternary ammonium salt. The amount of the acetic acid used in the present invention is not particularly limited, and the amount of the acetic acid used in dissolving the chitosan quaternary ammonium salt, which is well known to those skilled in the art, may be used.
The operation of mixing the chitosan quaternary ammonium salt with the sodium alginate, the acetic acid and the water is not particularly limited, and the technical scheme of mixing materials, which is well known by the technical personnel in the field, is adopted. In the invention, the mixture of the chitosan quaternary ammonium salt, sodium alginate, acetic acid and water is preferably as follows: mixing acetic acid and part of water to obtain an acetic acid solution with the mass concentration of 1%, and adding chitosan quaternary ammonium salt to obtain a chitosan quaternary ammonium salt solution; mixing sodium alginate with the rest part of water to obtain a sodium alginate solution; and then mixing the chitosan quaternary ammonium salt solution with the sodium alginate solution to obtain a composite wall material solution. The mixing mode of the invention can ensure that the chitosan quaternary ammonium salt and the sodium alginate are mixed more uniformly and fully.
After the composite wall material solution is obtained, the composite wall material solution is mixed with the citrus essential oil and the composite emulsifier for emulsification to obtain the emulsion.
In the invention, the mass ratio of the citrus essential oil to the composite wall material solution is preferably (0.5-2): 100, more preferably (0.8-1.8): 100, more preferably (1.0-1.6): 100, and most preferably (1.2-1.4): 100.
In the invention, the citrus essential oil is used as a core material, and the citrus essential oil is a natural bactericide and has high-efficiency, broad-spectrum and safe antibacterial action. The invention limits the mass ratio of the citrus essential oil to the composite wall material solution within the range, can improve the balance of the intermolecular interaction between the core material and the wall material and the strength of electrostatic interaction, further reduces the particle size of the microcapsule, and improves the embedding rate and the drug-loading rate.
In the present invention, the complex emulsifier preferably comprises tween-80 and span-80. In the invention, the mass ratio of the Tween-80 to the span-80 is preferably (0.5-2): 1, and more preferably (1.0-1.5): 1. According to the invention, the mass ratio of the tween-80 to the span-80 is limited within the range, so that the system can be fully emulsified to form uniform and stable emulsion.
In the invention, the mass ratio of the composite emulsifier to the composite wall material solution is preferably (0.1-0.5): 100, more preferably (0.2-0.4): 100, and most preferably 0.3: 100. The invention limits the mass ratio of the composite emulsifier to the composite wall material solution within the range, and can fully emulsify the system to form stable emulsion.
The operation of mixing the composite wall material solution, the citrus essential oil and the composite emulsifier is not particularly limited, and the technical scheme of mixing materials, which is well known to a person skilled in the art, is adopted.
In the present invention, the emulsification is preferably performed under stirring, and the stirring is preferably mechanical stirring; the stirring speed is preferably 10000-30000 rpm; the emulsifying time is preferably 1-5 min, and more preferably 3 min; the emulsifying temperature is preferably 20-30 ℃. The present invention limits the emulsifying rate, temperature and time within the above ranges, enables the components to be fully emulsified, and improves the stability of the emulsion.
After the emulsion is obtained, the emulsion is mixed with alkali for complex coacervation reaction to obtain the orange essential oil microcapsule initial product.
In the invention, the alkali is used for adjusting the pH value of the system so as to be beneficial to the complex coacervation reaction. In the present invention, the pH value of the complex coacervation reaction is preferably 5.0 to 10.0, more preferably 6.0 to 9.0, and most preferably 7.0 to 8.0. In the present invention, the kind and amount of the base are not particularly limited, and the pH of the system may be in the above range. In the present invention, the alkali is preferably a sodium hydroxide solution, and the mass concentration of the sodium hydroxide solution is preferably 5%.
According to the invention, the pH value of the complex coacervation reaction is limited in the range, so that the electrostatic interaction between the chitosan quaternary ammonium salt and the sodium alginate is complete, the chitosan quaternary ammonium salt and the sodium alginate are coacervated into the microcapsule on the surface of the citrus essential oil, and the embedding rate and the drug loading rate of the microcapsule are further improved.
In the present invention, the complex coacervation reaction is preferably carried out under stirring, which is preferably mechanical stirring; the stirring speed is preferably 400-600 rpm; the time of the complex coacervation reaction is preferably 10-100 min, and more preferably 30-50 min; the temperature of the complex coacervation reaction is preferably 40-60 ℃, and more preferably 50 ℃. In the present invention, the complex coacervation reaction is preferably carried out under water bath conditions.
According to the invention, the rate, temperature and time of the complex coacervation reaction are limited within the above ranges, so that the chitosan quaternary ammonium salt and the sodium alginate can be fully coacervated into the microcapsule on the surface of the citrus essential oil, and the embedding rate and the drug-loading rate of the microcapsule are further improved.
In the invention, in the complex coacervation process, the chitosan quaternary ammonium salt and the sodium alginate are combined and deposited on the surface of the citrus essential oil through electrostatic interaction to form a microcapsule structure.
After the initial citrus essential oil microcapsule product is obtained, the initial citrus essential oil microcapsule product is mixed with calcium chloride, and crosslinking curing reaction is carried out to obtain the citrus essential oil microcapsule.
In the invention, the mass ratio of the calcium chloride to the citrus essential oil microcapsule primary product is preferably (0.1-2): 100, more preferably (0.5-1.5): 100, and even more preferably 1.0: 100. In the invention, the calcium chloride is used as a cross-linking agent and has a cross-linking reaction with carboxyl in a complex coacervation system, so that a network cross-linking structure is formed, and the tightness and strength of a microcapsule wall layer are improved. In the invention, the calcium chloride is safe and nontoxic, and can avoid toxic substance residues in the microcapsule, thereby ensuring the use safety of the microcapsule. According to the invention, the mass ratio of the calcium chloride to the primary orange essential oil microcapsule is limited within the range, so that the sodium alginate can be fully crosslinked to form a crosslinked structure.
In the present invention, the crosslinking curing reaction is preferably carried out under stirring, and the stirring is preferably mechanical stirring; the stirring speed is preferably 400-600 rpm; the time of the crosslinking curing reaction is preferably 1-3 h, and more preferably 2 h; the temperature of the crosslinking curing reaction is preferably 0-4 ℃, and more preferably 1-3 ℃. In the present invention, the crosslinking curing reaction is preferably performed under ice bath conditions.
The invention limits the temperature and time of the crosslinking curing reaction in the range, can fully carry out the crosslinking curing reaction, further improves the embedding rate and the drug loading rate of the microcapsule, and prolongs the action time of the microcapsule.
In the invention, in the crosslinking and curing reaction process, sodium alginate is subjected to curing crosslinking under the action of calcium ions, so that the tightness and strength of the wall layer are improved, and a stable microcapsule structure is formed.
After the crosslinking and curing reaction is finished, the product of the crosslinking and curing reaction is preferably filtered and dried to obtain the citrus essential oil microcapsule.
In the present invention, the filtration is preferably suction filtration.
In the present invention, the drying is preferably spray drying. In the present invention, the spray drying is preferably performed in a spray dryer, the inlet temperature of the spray dryer is preferably 180 to 200 ℃, and the outlet temperature of the spray dryer is preferably 80 to 90 ℃.
The invention takes the citrus essential oil as the core material, the citrus essential oil is a natural bactericide, has high-efficiency, broad-spectrum and safe antibacterial action, takes the chitosan quaternary ammonium salt and the sodium alginate as the wall material, controls the use amount of each component, the reaction temperature, the reaction time and other process parameters of each step, and the prepared microcapsule has small particle size, higher embedding rate and drug-loading rate and excellent antibacterial performance, and can slowly release the core material to play the antibacterial action and prolong the antibacterial action time in the use process.
The invention provides a citrus essential oil microcapsule prepared by the preparation method of the technical scheme.
The citrus essential oil microcapsule prepared by the invention has the advantages of small particle size, high embedding rate and drug-loading rate and excellent antibacterial performance.
The invention also provides application of the citrus essential oil microcapsule in cosmetics.
The application of the citrus essential oil microcapsule in the cosmetics is not particularly limited, and the technical scheme of the application of the citrus essential oil microcapsule in the cosmetics, which is well known to those skilled in the art, can be adopted.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Dissolving chitosan quaternary ammonium salt in acetic acid aqueous solution with the mass concentration of 1% to obtain chitosan quaternary ammonium salt solution; dissolving sodium alginate in distilled water to obtain sodium alginate solution;
(2) mixing the chitosan quaternary ammonium salt solution with the sodium alginate solution to obtain a composite wall material solution (the mass ratio of the chitosan quaternary ammonium salt to the sodium alginate is 1:1, and the total mass concentration of the chitosan quaternary ammonium salt and the sodium alginate in the composite wall material solution is 2%);
(3) adding the citrus essential oil, the tween-80 and the span-80 into the composite wall material solution obtained in the step (2), and emulsifying at 30000rpm and 25 ℃ for 3min to obtain an emulsion (the mass ratio of the citrus essential oil to the composite wall material solution is 1:100, the mass ratio of the tween-80 to the span-80 is 1:1, and the mass ratio of the total mass of the tween-80 and the span-80 to the composite wall material solution is 0.1: 100);
(4) reducing the stirring speed to 500rpm, adding 5% sodium hydroxide solution to adjust the pH of the system to 5.0, and reacting for 90min under the condition of water bath at 40 ℃ to obtain a primary citrus essential oil microcapsule;
(5) and (3) removing the water bath, cooling to 0-4 ℃ in an ice bath, adding calcium chloride, curing and crosslinking for 2h (the mass ratio of the calcium chloride to the primary orange essential oil microcapsule is 0.6:100), stopping stirring, performing suction filtration, and drying the filtrate by using a spray dryer, wherein the inlet temperature of the spray dryer is 180-200 ℃, and the outlet temperature of the spray dryer is 80-90 ℃ to obtain the powdery orange essential oil microcapsule.
Example 2
Replacing the mass ratio of the citrus essential oil to the composite wall material solution in the step (3) in the example 1 by 2:100, and obtaining powdery citrus essential oil microcapsules by using the same parameters as those in the example 1.
Example 3
Replacing the mass ratio of the citrus essential oil to the composite wall material solution in the step (3) in the example 1 with 2:100, replacing the mass ratio of the tween-80 to the span-80 with 1:2, replacing the mass ratio of the total mass of the tween-80 and the span-80 to the composite wall material solution with 0.3:100, and obtaining the powdery citrus essential oil microcapsule with the other parameters being the same as those in the example 1.
Example 4
The emulsification rate in step (3) of example 3 was replaced with 25000rpm, and the other parameters were the same as those of example 3, to obtain powdery citrus essential oil microcapsules.
Example 5
(1) Dissolving chitosan quaternary ammonium salt in acetic acid aqueous solution with the mass concentration of 1% to obtain chitosan quaternary ammonium salt solution; dissolving sodium alginate in distilled water to obtain sodium alginate solution;
(2) mixing the chitosan quaternary ammonium salt solution with the sodium alginate solution to obtain a composite wall material solution (the mass ratio of the chitosan quaternary ammonium salt to the sodium alginate is 1:1, and the total mass concentration of the chitosan quaternary ammonium salt and the sodium alginate in the composite wall material solution is 2%);
(3) adding the citrus essential oil, the tween-80 and the span-80 into the composite wall material solution obtained in the step (2), and emulsifying at 25000rpm and 25 ℃ for 3min to obtain an emulsion (the mass ratio of the citrus essential oil to the composite wall material solution is 2:100, the mass ratio of the tween-80 to the span-80 is 1:2, and the mass ratio of the total mass of the tween-80 and the span-80 to the composite wall material solution is 0.3: 100);
(4) reducing the stirring speed to 500rpm, adding 5% sodium hydroxide solution to adjust the pH of the system to 6.0, and reacting for 50min under the condition of water bath at 40 ℃ to obtain a primary citrus essential oil microcapsule;
(5) and (3) removing the water bath, cooling to 0-4 ℃ in an ice bath, adding calcium chloride, curing and crosslinking for 2h (the mass ratio of the calcium chloride to the primary orange essential oil microcapsule is 0.3:100), stopping stirring, performing suction filtration, and drying the filtrate by using a spray dryer, wherein the inlet temperature of the spray dryer is 180-200 ℃, and the outlet temperature of the spray dryer is 80-90 ℃ to obtain the powdery orange essential oil microcapsule.
The citrus essential oil microcapsules prepared in example 5 were tested for particle size distribution and the results are shown in figure 1. As can be seen from figure 1, the citrus essential oil microcapsules prepared by the method have the advantages that the particle size is normally distributed, the particle size is uniform, the particle size ranges from 200 nm to 700nm, and the average particle size is 340 nm.
The average particle size of the citrus essential oil microcapsules prepared in examples 1 to 4 was tested, and the average particle size of example 1 was 237nm, the average particle size of example 2 was 364nm, the average particle size of example 3 was 597nm, and the average particle size of example 4 was 191 nm.
The embedding rate and drug loading of the citrus essential oil microcapsules prepared in examples 1 to 5 were tested: the embedding rate of the citrus essential oil microcapsule prepared in example 1 was 83.5%, and the drug loading was 27.8%; the embedding rate of the citrus essential oil microcapsule prepared in example 2 is 83.7%, and the drug loading is 41.85%; the embedding rate of the citrus essential oil microcapsule prepared in example 3 is 84.3%, and the drug loading is 42.15%; the embedding rate of the citrus essential oil microcapsule prepared in example 4 is 85.2%, and the drug loading rate is 42.6%; the embedding rate of the citrus essential oil microcapsule prepared in example 5 was 89.3%, the drug loading rate was 44.65%, and both the embedding rate and the drug loading rate were high.
The citrus essential oil microcapsules prepared in examples 1-5 are used as test samples, and the bacteriostatic activity of the microcapsules is qualitatively tested as follows: sterilizing filter paper (6mm), nutrient agar (for culturing Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa) and tiger red agar (for culturing Candida albicans and Aspergillus niger), pouring sterilized culture medium into sterile plate, solidifying, and inoculating to obtain culture medium with concentration of 1 × 107CFU/mL, the inoculated medium was placed in a prepared filter paper sheet (filter paper sheet preparation: placing in a sample solution, fully soaking for 12h, and drying treatment), cultured at 35 ℃ for 36h (bacteria), cultured at 28 ℃ for 48h (fungi), observed, and sterile water was used as a blank control, and the results are listed in Table 1.
TABLE 1 bacteriostatic Activity of Citrus essential oil microcapsules prepared in examples 1-5
Note: + shows that the substance has a diameter of inhibition zone larger than the experimental range, -shows that the substance has no inhibition zone;
and (3) judging standard: the high sensitivity is obtained when the inhibition zone is larger than or equal to 15mm, the medium sensitivity is obtained when the inhibition zone is 10-15 mm, the low sensitivity is obtained when the inhibition zone is 7-9 mm, and the insensitivity is obtained when the inhibition zone is not present.
As can be seen from Table 1, the products prepared by the present invention have excellent bacteriostatic activity against both bacteria and fungi.
The citrus essential oil microcapsules prepared in example 5, chitosan quaternary ammonium salt, sodium alginate and citrus essential oil were used as test samples according to the same test method, and the bacteriostatic activity thereof was qualitatively tested, and the results are shown in table 2.
Table 2 bacteriostatic activity of citrus essential oil microcapsules, chitosan quaternary ammonium salt, sodium alginate and citrus essential oil prepared in example 5
Note: + shows that the substance has a diameter of inhibition zone larger than the experimental range, -shows that the substance has no inhibition zone;
and (3) judging standard: the high sensitivity is obtained when the inhibition zone is larger than or equal to 15mm, the medium sensitivity is obtained when the inhibition zone is 10-15 mm, the low sensitivity is obtained when the inhibition zone is 7-9 mm, and the insensitivity is obtained when the inhibition zone is not present.
As can be seen from table 2, the bacteriostatic activity of the citrus essential oil microcapsule prepared by the invention is greater than that of the chitosan quaternary ammonium salt and the citrus essential oil which are used independently, and the chitosan quaternary ammonium salt and the citrus essential oil have synergistic effect, so that the bacteriostatic activity of the citrus essential oil microcapsule is improved.
Quantitative analysis MIC experiment, taking the citrus essential oil microcapsule, chitosan quaternary ammonium salt, sodium alginate and citrus essential oil prepared in example 5 as test samples, quantitatively testing the MIC value of the minimum inhibitory concentration: the results of the observation of the test samples diluted with the sterilized nutrient broth (used for culturing Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa) and the Sa's medium (used for culturing Candida albicans and Aspergillus niger) by the two-fold dilution method, inoculated into the dilution, cultured at 35 ℃ for 36 hours (bacteria) and at 28 ℃ for 48 hours (fungi), are shown in Table 3.
TABLE 3 minimum inhibitory concentration values (MIC) for citrus essential oil microcapsules, chitosan quaternary ammonium salt, sodium alginate and citrus essential oil prepared in example 5
Note: means that the substance was not detected within the range of the lowest inhibitory concentration
As can be seen from Table 3, the citrus essential oil microcapsule prepared by the invention has excellent bacteriostatic performance, the MIC values of the citrus essential oil microcapsule are smaller than those of the chitosan quaternary ammonium salt and the citrus essential oil which are independent, and the chitosan quaternary ammonium salt and the citrus essential oil have synergistic effect, so that the bacteriostatic performance of the citrus essential oil microcapsule is improved.
Irritation test
Fertilized chick embryos (chick embryos weight is 50g-60g, SPF chick embryos are preferably selected) of white-Lai Hangzhou chick and other varieties are incubated at the temperature of 37.5 +/-0.5 ℃, the relative humidity is 55-70 percent, and the egg turning frequency is 3 times/h-6 times/h. And (5) checking eggs by using an egg candler after the eggs are incubated to the 8 th day, discarding unfertilized and inactive chicken embryos, selecting the chicken embryos with well developed blood vessels, and marking the positions of air chambers on the surfaces of the eggshells. The test was started on day 9. Carefully peeling off the eggshell part of the air chamber by dental bending, dripping a few drops of physiological saline on the surface of the eggshell membrane to fully wet the eggshell membrane, pouring out the eggshell membrane, and carefully removing the eggshell membrane by using a forceps to ensure that the exposed allantoic membrane is intact and does not suffer any damage. 0.3ml/0.3g of the test substance was applied directly to the CAM. (negative control: 0.9% by mass of sodium chloride solution; positive control: 0.1mol/L of sodium hydroxide; solvent control: deionized water; reference substance control: 0.05% -0.3% by mass of methyl paraben diluted with deionized water; sample: 50% by mass of non-bacteriostatic component in the citrus essential oil microcapsule obtained in example 5 and the content of preservative added in general cosmetics, concentration gradient of the citrus essential oil microcapsule sample is 0.2% -3% by mass of deionized water). Spread as far as possible to ensure coverage of at least 50%. After 3min of action, the CAM surface was rinsed gently with double distilled water, the rinsing was completed within 30s, the liquid was decanted, the degree of change of each toxic effect was immediately observed under a stereomicroscope, and the results are given in Table 4.
TABLE 4 chick embryo chorioallantoic membrane test Table
As can be seen from Table 4, the citrus essential oil microcapsule prepared by the invention has relatively lower irritation than a chemical preservative, namely methyl paraben, and is friendly to human skin.
Application example 1
The citrus essential oil microcapsules prepared in example 5 were used for the preparation of O/W moisturizing emulsions, with the formulations as in table 5.
TABLE 5O/W moisturizing emulsion formulations
The preparation process comprises the following steps:
preparing 1% carbomer aqueous solution in advance for later use;
respectively heating the phase A and the phase B to 80 ℃, fully mixing and uniformly stirring;
slowly adding phase B into phase A, stirring, and homogenizing at 1000r/min for 5min before cooling;
when the temperature of the AB mixed part is reduced to 55 ℃, the phase C is added.
The citrus essential oil microcapsules prepared in example 5 were used for the preparation of O/W moisturizing creams, with the formulation as in table 6.
TABLE 6O/W moisturising cream formulations
The preparation process comprises the following steps:
preparing 1% carbomer aqueous solution in advance for later use;
respectively heating the phase A and the phase B to 80 ℃, fully mixing and uniformly stirring;
slowly adding phase B into phase A, stirring, and homogenizing at 1000r/min for 5min before cooling; adding phase C when the temperature of the AB mixed part is reduced to 55 DEG C
30g of the emulsion and cream prepared in application example 1 were taken in a sterilized Erlenmeyer flask, and 0.3mL of a mixed solution having a concentration of 1X 10 was inoculated6CFU/mL of a mixed bacterial suspension of Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa; another inoculation was performed at a mixed concentration of 1X 10 in a volume of 0.3mL4CFU/mL of mixed fungus suspension of Candida albicans and Aspergillus niger spores; in addition, a portion of the cosmetic without preservative was set for blank comparison. Uniformly mixing the components by using a vortex oscillator, standing the mixture in a dry and ventilated place, storing the mixture at room temperature (20-25 ℃), testing the colony count of each sample every 7 days within 28 days of inoculation, transferring 1mL of sample, diluting the sample to a proper concentration by using a sterile physiological saline log, calculating the microbial content in the sample by using a plate counting method, and testing each group for three times in parallel, wherein the specific results are shown in tables 7-10.
Table 7 preservative challenge experimental results for emulsion based bacteria
TABLE 8 Corrosion challenge test results for emulsion-based fungi
TABLE 9 antiseptic challenge test results for cream base bacteria
TABLE 10 antiseptic challenge test results for cream base fungi
Domestic reference to the evaluation criteria of the U.S. Personal Care Products Council (PCPC) preservation challenge test:
from the 7 th day, the bacteria or fungi is less than 10CFU/mL, and the preservative system has excellent bacteriostatic performance and is rated as A grade through a challenge test;
on 28 th day, the bacteria or fungi are 10-100 CFU/mL, the antiseptic system has good antibacterial performance, and the grade B is judged through challenge tests;
on 28 th day, bacteria or fungi are in the range of 100-1000 CFU/mL, the bacteriostatic performance of the preservative system is general, and the preservative system can conditionally pass a challenge test and is rated as C;
at 28 days, the bacteria or fungi are more than 1000CFU/mL, and the antiseptic system has poor bacteriostatic performance and can not pass the challenge test and is rated as D.
From tables 7 to 10, when no preservative is added, the number of bacteria and fungi in the cosmetics is in an increasing trend, and it can be seen that the blank formula has no preservative capability, the preservative effect can be enhanced with the increase of the addition of the citrus essential oil microcapsules when the addition of the citrus essential oil microcapsules is 0.3% in the cosmetic emulsion and cream, and is equivalent to the effect of the chemical preservative nipagin methyl ester in cosmetics, and the addition of the citrus essential oil microcapsules in the cosmetics is 0.3-0.6%, so that the efficient preservative capability can be achieved.
In conclusion, the citrus essential oil microcapsule prepared by the invention has the advantages of small particle size, high embedding rate and drug-loading rate and excellent antibacterial performance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of citrus essential oil microcapsules comprises the following steps:
(1) mixing chitosan quaternary ammonium salt with sodium alginate, acetic acid and water to obtain a composite wall material solution;
(2) mixing the composite wall material solution obtained in the step (1) with the citrus essential oil and the composite emulsifier, and emulsifying to obtain an emulsion;
(3) mixing the emulsion obtained in the step (2) with alkali, and carrying out complex coacervation reaction to obtain an orange essential oil microcapsule primary product;
(4) and (4) mixing the orange essential oil microcapsule primary product obtained in the step (3) with calcium chloride, and carrying out cross-linking curing reaction to obtain the orange essential oil microcapsule.
2. The preparation method of claim 1, wherein the mass ratio of the quaternary ammonium salt of chitosan to the sodium alginate in the step (1) is (0.2-5): 1.
3. The preparation method of claim 1, wherein the total mass concentration of the quaternary ammonium salt of chitosan and the sodium alginate in the composite wall material solution in the step (1) is 0.2-3%.
4. The preparation method according to any one of claims 1 to 3, wherein the mass ratio of the citrus essential oil to the composite wall material solution in the step (2) is (0.5-2): 100.
5. The preparation method according to any one of claims 1 to 3, wherein the composite emulsifier in the step (2) comprises Tween-80 and span-80, and the mass ratio of the composite emulsifier to the composite wall material solution is (0.1-0.5): 100.
6. The method according to claim 1, wherein the pH value of the complex coacervation reaction in step (3) is 5.0 to 10.0.
7. The preparation method according to claim 1, wherein the mass ratio of the calcium chloride to the citrus essential oil microcapsule primary product in the step (4) is (0.1-2): 100.
8. The preparation method according to claim 1, wherein the temperature of the crosslinking curing reaction in the step (4) is 0 to 4 ℃ and the time of the crosslinking curing reaction is 1 to 3 hours.
9. A citrus essential oil microcapsule prepared by the preparation method according to any one of claims 1 to 8.
10. Use of a citrus essential oil microcapsule according to claim 9 in cosmetics.
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