Disclosure of Invention
The invention aims to solve the technical problems of poor moisture retention and sterilization stability of the existing ultrasonic coupling agent, and provides a sterilization gel, a preparation method thereof, an ultrasonic coupling agent based on the sterilization gel, and a preparation method and an application thereof.
The sterilization gel comprises the following components in percentage by mass: 6% -8%, ethyl acrylate: 50% -70%, butyl acrylate: 20% -30%, AEO-15:1% -3%, sodium dodecyl sulfate: 1% -2%, persulfate: 3% -5%, tannic acid: 5% -10%, chitosan quaternary ammonium salt: 2% -8% of the composition.
Further defined, the persulfate is ammonium persulfate, potassium persulfate, or sodium persulfate.
The preparation method of the sterilization gel of the invention comprises the following steps:
step 1: adding chitosan into isopropanol, stirring, heating to 70-80 ℃ in a water bath, adding 2, 3-epoxypropyltrimethylammonium chloride aqueous solution for three times, reacting for 8-10h, and then performing alcohol precipitation, suction filtration, washing and vacuum drying to obtain chitosan quaternary ammonium salt;
and 2, step: adding acrylic acid, ethyl acrylate, butyl acrylate, AEO-15 and sodium dodecyl sulfate into deionized water, uniformly mixing, stirring, heating to 50-70 ℃, then adding persulfate, tannic acid and chitosan quaternary ammonium salt, continuously heating to 80-90 ℃, reacting for 1h, cooling, adding into a calcium chloride solution, demulsifying, and carrying out vacuum drying on precipitates to obtain the sterilized gel.
Further defined, the ratio of the mass of chitosan to the volume of isopropanol in step 1 is 2g: (4-6) mL.
Further defined, the ratio of the mass of chitosan to the volume of 2, 3-epoxypropyltrimethylammonium chloride aqueous solution in step 1 is 2g: (7-9) mL, wherein the concentration of the 2, 3-epoxypropyltrimethylammonium chloride aqueous solution is 0.4-0.6 mg/mL.
Further limiting, in step 1, the volume ratio of each time when the addition is divided into three times is 2.
Further limiting, the mass fraction of the calcium chloride solution in the step 1 is 8-12%.
The ultrasonic coupling agent based on the sterilization gel comprises the following components in percentage by mass: and (3) sterilizing gel: 0.5% -1.2%, polyethylene glycol 1000:0.4% -1.4%, glycerol: 8% -12%, triethanolamine: 0.5% -0.8% and the balance of deionized water.
The preparation method of the ultrasonic coupling agent provided by the invention comprises the following steps:
the method comprises the following steps: dissolving the sterilized gel in deionized water to obtain a gel solution;
step two: mixing glycerol andpolyethylene glycol 1000 uniformly to obtain a mixed solution;
step three: and (3) uniformly mixing the solution obtained in the first step and the solution obtained in the second step, adding triethanolamine, adjusting the pH value to 6-7, and stirring in vacuum for 20 minutes to obtain the ultrasonic coupling agent.
The ultrasonic couplant is used for ultrasonic detection.
Compared with the prior art, the invention has the advantages that:
the ultrasonic couplant can reduce the friction between the probe and the human body during ultrasonic examination, so that the probe can flexibly and slidably probe, the discomfort of the human body caused by the friction is reduced, a better detection effect is achieved, and a reliable and accurate detection and diagnosis image is obtained. In addition, the antibacterial moisture-retaining agent has excellent moisture-retaining property, antibacterial property and use stability, and has the following specific advantages:
1) The gel and the ultrasonic coupling agent based on the gel have certain moisturizing effect by utilizing a large amount of amino and hydroxyl on a chitosan molecular chain, and the positively charged quaternary ammonium groups in the quaternized chitosan molecules can promote the mutual combination between the chitosan molecules and thallus cell wall negative ions, so that thallus is dead, and the antibacterial performance of the quaternized chitosan molecular gel is superior to that of chitosan and other chitosan derivatives.
2) The invention introduces tannic acid on the basis of quaternized chitosan, so that the ultrasonic couplant based on the gel can generate stable phenoxy free radicals in organisms through dehydrogenation reaction, and the process combines the free radicals such as active oxygen to play the characteristic of antioxidation while consuming oxygen, thereby playing a role in protecting biological tissues. In addition, the tannin can also effectively inhibit the formation of a staphylococcus aureus biomembrane, and has remarkable antibacterial property.
3) The sterilization gel has a stable network structure, and on one hand, a first chemical network structure is formed through intermolecular hydrogen bonding between amino groups of the chitosan quaternary ammonium salt and hydroxyl groups of tannic acid; on the other hand, acrylic acid, ethyl acrylate, butyl acrylate and the like generate a large number of carboxyl groups under the action of an initiator and an emulsifier, meanwhile, the carboxyl groups and a large number of hydroxyl groups in the chemical network structure form a second chemical network through intermolecular hydrogen bonding, and the stable gel network can combine a large amount of free water, so that the moisture retention of the gel and the ultrasonic couplant based on the gel are greatly improved.
4) The complex use of the chitosan quaternary ammonium salt and the tannic acid not only endows the gel and the ultrasonic coupling agent based on the gel with excellent moisture retention, but also improves the stability of the chitosan quaternary ammonium salt and the tannic acid in the use process through a stable gel network, so that the antibacterial performance is improved in a synergistic manner, the cross infection is avoided, and the long-acting performance of the antibacterial performance is ensured.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The experimental procedures used in the following examples are conventional unless otherwise specified. The materials, reagents, methods and apparatus used, unless otherwise specified, are conventional and commercially available to those skilled in the art.
Example 1: the preparation method of the ultrasonic couplant of the embodiment is carried out according to the following steps:
the components of the sterilizing gel and the mass percentage content thereof are as follows: 6% of acrylic acid, 60% of ethyl acrylate, 20% of butyl acrylate, 1% of AEO-15, 1% of sodium dodecyl sulfate, 3% of potassium persulfate, 5% of tannic acid and 4% of chitosan quaternary ammonium salt.
Preparation of sterilized gel:
step 1: adding 2g of chitosan into 5 mL of isopropanol, stirring, heating to 75 ℃ in a water bath, adding 8 mL of 2, 3-epoxypropyltrimethylammonium chloride aqueous solution with the concentration of 0.5 mg/mL in a total amount for three times according to the volume ratio of 2;
and 2, step: adding 6% of acrylic acid, 60% of ethyl acrylate, 20% of butyl acrylate, 1% of AEO-15 and 1% of sodium dodecyl sulfate into deionized water according to mass fraction, uniformly mixing, transferring the solution into a four-neck flask provided with a stirrer, a reflux condenser tube and a constant-pressure separating funnel, stirring and heating to 60 ℃, then adding 3% of potassium persulfate, 5% of tannic acid and 4% of chitosan quaternary ammonium salt, continuously heating to 85 ℃ and reacting for 1h, cooling, then adding into a calcium chloride solution with the mass fraction of 10% for demulsification, collecting and cleaning white precipitate, and then vacuum drying for 8h at 80 ℃ to obtain the sterilized gel.
The ultrasonic coupling agent comprises the following components in percentage by mass: 0.5% of the above sterilized gel, 1% ofpolyethylene glycol 1000, 10% of glycerol, 0.5% of triethanolamine and 88% of deionized water.
Preparing an ultrasonic coupling agent:
the method comprises the following steps: dissolving 0.5% of the sterilized gel in deionized water according to mass fraction, and stirring at 35 ℃ until the sterilized gel is completely dissolved to obtain a gel solution;
step two: uniformly mixing 10% of glycerol and 1% ofpolyethylene glycol 1000 to obtain a mixed solution;
step three: and (3) uniformly mixing the gel solution obtained in the step one with the mixed solution obtained in the step two, adding 0.5% of triethanolamine, adjusting the pH value to 7, and then placing the mixture in a vacuum stirrer to stir in vacuum for 20 minutes to obtain the ultrasonic coupling agent.
Example 2: the preparation method of the ultrasonic couplant of the embodiment is carried out according to the following steps:
the components of the sterilizing gel and the mass percentage content thereof are as follows: 7% of acrylic acid, 52% of ethyl acrylate, 25% of butyl acrylate, 1.5% of AEO-15, 1.5% of sodium dodecyl sulfate, 4% of sodium persulfate, 6% of tannic acid and 3% of chitosan quaternary ammonium salt.
Preparation of sterilized gel:
step 1: adding 2g of chitosan into 5 mL of isopropanol, stirring, heating to 75 ℃ in a water bath, adding 8 mL of 2, 3-epoxypropyltrimethylammonium chloride aqueous solution with the concentration of 0.5 mg/mL in a total amount for three times according to the volume ratio of 2;
step 2: adding 7% of acrylic acid, 52% of ethyl acrylate, 25% of butyl acrylate, 1.5% of AEO-15 and 1.5% of sodium dodecyl sulfate into deionized water according to mass fraction, uniformly mixing, transferring the solution into a four-neck flask provided with a stirrer, a reflux condenser and a constant-pressure separating funnel, stirring and heating to 60 ℃, then adding 4% of sodium persulfate, 6% of tannic acid and 3% of chitosan quaternary ammonium salt, continuously heating to 85 ℃ and reacting for 1h, cooling, then adding into a 10% of calcium chloride solution according to mass fraction for demulsification, collecting and cleaning white precipitate, and then carrying out vacuum drying for 8h at 80 ℃ to obtain the sterilized gel.
The ultrasonic coupling agent comprises the following components in percentage by mass: 0.7% of the above sterilized gel, 0.6% ofpolyethylene glycol 1000, 10% of glycerol, 0.7% of triethanolamine and 88% of deionized water.
Preparing an ultrasonic coupling agent:
the method comprises the following steps: dissolving 0.7% of the sterilized gel in deionized water according to mass fraction, and stirring at 35 ℃ until the sterilized gel is completely dissolved to obtain a gel solution;
step two: uniformly mixing 10% of glycerol and 0.6% ofpolyethylene glycol 1000 to obtain a mixed solution;
step three: and (3) uniformly mixing the gel solution obtained in the step one with the mixed solution obtained in the step two, adding 0.7% triethanolamine, adjusting the pH value to 7, and then placing the mixture into a vacuum stirrer to stir in vacuum for 20 minutes to obtain the ultrasonic couplant.
Example 3: the preparation method of the ultrasonic couplant of the embodiment is carried out according to the following steps:
the components of the sterilizing gel and the mass percentage content thereof are as follows: 7% of acrylic acid, 55% of ethyl acrylate, 20% of butyl acrylate, 1.5% of AEO-15, 1.5% of sodium dodecyl sulfate, 4% of ammonium persulfate, 6% of tannic acid and 5% of chitosan quaternary ammonium salt.
Preparation of sterilized gel:
step 1: adding 2g of chitosan into 5 mL of isopropanol, stirring, heating in a water bath to 75 ℃, adding 8 mL of 2, 3-epoxypropyltrimethylammonium chloride aqueous solution with the total concentration of 0.5 mg/mL for three times according to the volume ratio of 2;
step 2: adding 7% of acrylic acid, 55% of ethyl acrylate, 20% of butyl acrylate, 1.5% of AEO-15 and 1.5% of sodium dodecyl sulfate into deionized water according to mass fraction, uniformly mixing, transferring the solution into a four-neck flask provided with a stirrer, a reflux condenser tube and a constant-pressure separating funnel, stirring and heating to 60 ℃, then adding 4% of ammonium persulfate, 6% of tannic acid and 5% of chitosan quaternary ammonium salt, continuously heating to 85 ℃ and reacting for 1h, cooling, then adding into a 10% of calcium chloride solution according to mass fraction for demulsification, collecting and cleaning white precipitate, and then carrying out vacuum drying for 8h at 80 ℃ to obtain the sterilized gel.
The ultrasonic coupling agent comprises the following components in percentage by mass: 1% of the above sterilized gel, 0.5% ofpolyethylene glycol 1000, 10% of glycerol, 0.7% of triethanolamine and 87.8% of deionized water.
Preparing an ultrasonic coupling agent:
the method comprises the following steps: dissolving 1% of the sterilized gel in deionized water according to mass fraction, and stirring at 35 ℃ until the sterilized gel is completely dissolved to obtain a gel solution;
step two: uniformly mixing 10% of glycerol and 0.5% ofpolyethylene glycol 1000 to obtain a mixed solution;
step three: and (3) uniformly mixing the gel solution obtained in the step one with the mixed solution obtained in the step two, adding 0.7% of triethanolamine, adjusting the pH value to 7, and then placing the mixture in a vacuum stirrer to stir in vacuum for 20 minutes to obtain the ultrasonic couplant.
Example 4: the preparation method of the ultrasonic couplant of the embodiment is carried out according to the following steps:
the components of the sterilizing gel and the mass percentage content thereof are as follows: 8% of acrylic acid, 50% of ethyl acrylate, 25% of butyl acrylate, 3% of AEO-15, 2% of sodium dodecyl sulfate, 4% of potassium persulfate, 6% of tannic acid and 2% of chitosan quaternary ammonium salt.
Preparation of sterilized gel:
step 1: adding 2g of chitosan into 5 mL of isopropanol, stirring, heating to 75 ℃ in a water bath, adding 8 mL of 2, 3-epoxypropyltrimethylammonium chloride aqueous solution with the concentration of 0.5 mg/mL in a total amount for three times according to the volume ratio of 2;
and 2, step: adding 8% of acrylic acid, 50% of ethyl acrylate, 25% of butyl acrylate, 3% of AEO-15 and 2% of sodium dodecyl sulfate into deionized water according to mass fraction, uniformly mixing, transferring the solution into a four-neck flask provided with a stirrer, a reflux condenser tube and a constant-pressure separating funnel, stirring and heating to 60 ℃, then adding 4% of potassium persulfate, 6% of tannic acid and 2% of chitosan quaternary ammonium salt, continuously heating to 85 ℃ and reacting for 1 hour, cooling, then adding into a calcium chloride solution with the mass fraction of 10%, demulsifying, collecting and cleaning white precipitate, and then vacuum drying for 8 hours at 80 ℃ to obtain the sterilized gel.
The ultrasonic coupling agent comprises the following components in percentage by mass: 1.2% of the above sterilized gel, 0.9% ofpolyethylene glycol 1000, 10% of glycerol, 0.6% of triethanolamine and 87.3% of deionized water.
Preparing an ultrasonic coupling agent:
the method comprises the following steps: dissolving 1.2% of the sterilized gel in deionized water according to mass fraction, and stirring at 35 ℃ until the sterilized gel is completely dissolved to obtain a gel solution;
step two: uniformly mixing 10% of glycerol and 0.9% ofpolyethylene glycol 1000 to obtain a mixed solution;
step three: and (3) uniformly mixing the gel solution obtained in the step one with the mixed solution obtained in the step two, adding 0.6% of triethanolamine, adjusting the pH value to 7, and then placing the mixture in a vacuum stirrer to stir in vacuum for 20 minutes to obtain the ultrasonic couplant.
Example 5: the preparation method of the ultrasonic couplant of the embodiment is carried out according to the following steps:
the components of the sterilizing gel and the mass percentage content thereof are as follows: 6% of acrylic acid, 50% of ethyl acrylate, 30% of butyl acrylate, 2% of AEO-15, 2% of sodium dodecyl sulfate, 3% of potassium persulfate, 5% of tannic acid and 2% of chitosan quaternary ammonium salt.
Preparation of sterilized gel:
step 1: adding 2g of chitosan into 5 mL of isopropanol, stirring, heating to 75 ℃ in a water bath, adding 8 mL of 2, 3-epoxypropyltrimethylammonium chloride aqueous solution with the concentration of 0.5 mg/mL in a total amount for three times according to the volume ratio of 2;
step 2: adding 6% of acrylic acid, 50% of ethyl acrylate, 30% of butyl acrylate, 2% of AEO-15 and 2% of sodium dodecyl sulfate into deionized water according to mass fraction, uniformly mixing, transferring the solution into a four-neck flask provided with a stirrer, a reflux condenser tube and a constant-pressure separating funnel, stirring and heating to 60 ℃, then adding 3% of potassium persulfate, 5% of tannic acid and 2% of chitosan quaternary ammonium salt, continuously heating to 85 ℃ and reacting for 1h, cooling, then adding into a calcium chloride solution with the mass fraction of 10% for demulsification, collecting and cleaning white precipitate, and then vacuum drying for 8h at 80 ℃ to obtain the sterilized gel.
The ultrasonic coupling agent comprises the following components in percentage by mass: 1.2% of the above sterilized gel, 0.9% ofpolyethylene glycol 1000, 9% of glycerol, 0.5% of triethanolamine and 88.4% of deionized water.
Preparing an ultrasonic coupling agent:
the method comprises the following steps: dissolving 1.2% of the sterilized gel in deionized water according to mass fraction, and stirring at 35 ℃ until the sterilized gel is completely dissolved to obtain a gel solution;
step two: uniformly mixing 9% of glycerol and 0.9% ofpolyethylene glycol 1000 to obtain a mixed solution;
step three: and (3) uniformly mixing the gel solution obtained in the step one with the mixed solution obtained in the step two, adding 0.5% of triethanolamine, adjusting the pH value to 7, and then placing the mixture in a vacuum stirrer to stir in vacuum for 20 minutes to obtain the ultrasonic coupling agent.
Detection test
The mass measurement: appropriate amounts of the finished products obtained in example 1, example 2, example 3, example 4 and example 5 were measured for mass by the following tests, and the results of the measurements are shown in FIG. 2.
Detection indexes are as follows:
(1) Appearance shape: the finished product was observed for appearance and texture.
(2) Stability test: 50g of finished product is taken and put into a sterilized transparent plastic bottle with a cover, the plastic bottle is filled with the finished product, the plastic bottle is placed at room temperature and kept away from light, and the appearance change and the pH value of the sample are regularly observed.
(3) Moisture retention test: taking 5 healthy adult rabbits, 2 rabbits per backShaving hair on the part with area of 2.5cm2 And after 24 hours, uniformly coating 0.5g of finished product on the shaved part, and observing the drying time after film coating.
(4) Irritation test: taking 5 healthy adult rabbits, shaving 2 parts of each back, each area is 2.5cm2 After 24h, 0.5g of finished product is uniformly coated on the shaved part, and the reaction of the coated part is observed after 24h.
(II) bacteriostatic experiment:
test solution preparation: 20g of the finished products obtained in example 1, example 2, example 3, example 4 and example 5 were taken and added with 0.9% sterile sodium chloride solution, and the mixture was diluted to 1:10 test solution for standby.
Determination of Minimum Inhibitory Concentration (MIC) and Minimum Bactericidal Concentration (MBC): MIC was determined by agar double dilution. Inoculating bacteria on the surface of a series of agar plates containing test solution, wherein the final concentration of the bacteria solution is 105 CFU/ml, aerobic bacteria are cultured for 18h at 37 ℃, fungi are cultured for 24h at 27 ℃, anaerobic bacteria are placed in an anaerobic incubator for incubation for 48h at 37 ℃, and the minimum concentration of the test reagent contained in the plate without bacterial growth is the minimum inhibitory concentration (MIC, mg/L). Staphylococcus aureus and Escherichia coli were used as the quality control strains in the experiments. The MIC was measured by broth double dilution, and then 0.1ml of culture solution without bacterial growth tube was applied to the surface of a drug-free agar plate, which was then pushed up with a sterile glass rod, and the lowest concentration of drug without bacterial growth was the lowest bactericidal concentration (MBC, mg/L) as measured under the same culture conditions as the MIC, and the results are shown in FIG. 3.