CN112642371A - Preparation method of thin-wall large-scale soft microcapsule based on bubble method - Google Patents
Preparation method of thin-wall large-scale soft microcapsule based on bubble method Download PDFInfo
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- CN112642371A CN112642371A CN202011434309.3A CN202011434309A CN112642371A CN 112642371 A CN112642371 A CN 112642371A CN 202011434309 A CN202011434309 A CN 202011434309A CN 112642371 A CN112642371 A CN 112642371A
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- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000003094 microcapsule Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims abstract description 22
- 229920002518 Polyallylamine hydrochloride Polymers 0.000 claims abstract description 19
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 claims abstract description 17
- 108091003079 Bovine Serum Albumin Proteins 0.000 claims abstract description 15
- 229940098773 bovine serum albumin Drugs 0.000 claims abstract description 15
- 238000005119 centrifugation Methods 0.000 claims description 23
- 239000006228 supernatant Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002775 capsule Substances 0.000 abstract description 16
- 230000007547 defect Effects 0.000 abstract description 5
- 229940079593 drug Drugs 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 4
- 238000004945 emulsification Methods 0.000 abstract description 4
- 230000035699 permeability Effects 0.000 abstract description 4
- 238000001338 self-assembly Methods 0.000 abstract description 3
- 239000005518 polymer electrolyte Substances 0.000 abstract description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000008358 core component Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229920000867 polyelectrolyte Polymers 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 2
- 229920001448 anionic polyelectrolyte Polymers 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
- A61J3/00—Devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms
- A61J3/07—Devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms into the form of capsules or similar small containers for oral use
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
- B01J13/046—Making microcapsules or microballoons by physical processes, e.g. drying, spraying combined with gelification or coagulation
Abstract
The invention discloses a preparation method of a thin-wall large-scale soft microcapsule based on a bubble method, which belongs to the technical field of biological medicines and comprises the following steps: 1) uniformly dispersing bovine serum albumin microbubbles with negative charges on the surface; 2) and sequentially assembling the polyallylamine hydrochloride solution and the sodium polystyrene sulfonate solution layer by layer on the surface of the micro-bubbles to leave the thin-wall large-scale soft micro-capsules. The invention overcomes the defects that the polymer electrolyte capsule has small size (<15um) and the additional nucleolysis treatment can influence the further use of the capsule; meanwhile, the defects that the large-size capsules prepared by an emulsion method including a micro-flow control method have wall thickness and permeability which are difficult to control are overcome; according to the preparation method of the thin-wall large-scale soft microcapsule based on the bubble method, the thin-wall large-scale capsule prepared by the layer-by-layer self-assembly method is simple and convenient to operate, the preparation time is short, and the required equipment is simple.
Description
Technical Field
The invention belongs to the technical field of biological medicines, and particularly relates to a preparation method of a thin-wall large-scale soft microcapsule based on a bubble method.
Background
With the wide application of the microcapsule in the fields of biomedicine, cosmetics, food and the like, for example, the microcapsule can be used as a drug carrier to realize the function of controllable release of drugs.
Nowadays, various methods for preparing microcapsules have been developed, in which polyelectrolyte capsules prepared by dropping a cationic polyelectrolyte solution into an anionic polyelectrolyte solution are limited in size and hardly exceed 15 um. Meanwhile, the concentration of residues in the inner core of the capsule is temporarily higher due to the core dissolving operation, osmotic pressure is generated, so that the capsule is expanded, the polyelectrolyte capsule is subjected to high mechanical pressure, and the further use of the capsule is influenced by the core residues.
Although the emulsion method including the microfluidic method can be used for preparing large-size capsules, the capsule walls are too thick and usually larger than 20um, and the capsule permeability is difficult to regulate and control, so that the application of the emulsion method in the fields of biological medicines and the like is limited.
Therefore, the thin-wall large-scale soft microcapsule which is free of template dissolving operation and has adjustable permeability overcomes the defects of the two microcapsules, and has wide application prospect in the fields of biomedicine and the like in the future.
Disclosure of Invention
The purpose of the invention is as follows: in order to solve the problems in the prior art, the invention discloses a preparation method of a thin-wall large-scale soft microcapsule based on a bubble method.
The technical scheme is as follows: in order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a thin-wall large-scale soft microcapsule based on a bubble method comprises the following steps:
1) uniformly dispersing bovine serum albumin microbubbles with negative charges on the surface;
2) and sequentially assembling the polyallylamine hydrochloride solution and the sodium polystyrene sulfonate solution layer by layer on the surface of the micro-bubbles to leave the thin-wall large-scale soft micro-capsules.
Further, the step 1) is specifically that after uniformly mixing the bovine serum albumin solution and the glucose according to the volume ratio of 1:10, heating the mixture in a constant-temperature water bath kettle, and obtaining the bovine serum albumin microbubbles with negative charges on the surface by a bubble preparation method.
Further, the method for preparing bubbles includes an ultrasonic method or a syringe method.
Further, the step 2) comprises the following steps:
2.1) uniformly dispersing the prepared original microbubbles, adding a polyallylamine hydrochloride solution with positive charges, soaking for reaction, centrifuging, removing the supernatant, and cleaning to obtain the assembled microbubbles;
2.2) immersing the assembled micro-bubbles into a sodium polystyrene sulfonate solution with negative charges for a period of time, performing immersion reaction, and then centrifuging and removing the supernatant;
2.3) repeating the process for a plurality of times, adsorbing the polyallylamine hydrochloride and the polystyrene sodium sulfonate layer by layer through electrostatic action, thereby obtaining the micro-bubbles of which the surfaces are coated with a plurality of layers of the polyallylamine hydrochloride and the polystyrene sodium sulfonate, and finally, because the micro-bubbles of which the cores are air are unstable, the air bubbles are slowly dissolved along with the time extension, and the thin-wall large-scale soft micro-capsules are left after the air bubbles are completely dissolved.
Further, in the steps 2.1) -2.2), the centrifugation speed is 30-50 RCF, and the centrifugation time is 1-2 min.
Further, the concentration of the polyallylamine hydrochloride solution is 1-5 mg/mL; the concentration of the sodium polystyrene sulfonate solution is 1-5 mg/mL.
Further, in the steps 2.1) -2.2), the soaking reaction time is 2-3 min.
Further, in the step 2.3), the thickness of the thin-wall large-scale soft microcapsule is 5-10nm, and the diameter is 10-50 um.
Has the advantages that: compared with the prior art, the invention overcomes the defects that the polymer electrolyte capsule has small size (<15um), and the additional nucleolysis treatment can influence the further use of the capsule; meanwhile, the defects that the large-size capsules prepared by an emulsion method including a micro-flow control method have wall thickness and permeability which are difficult to control are overcome; the thin-wall large-scale capsule prepared by the layer-by-layer self-assembly method is simple and effective, simple and convenient to operate, short in preparation time and simple in required equipment.
Drawings
Figure 1 is a micrograph of the thin-walled large-scale soft microcapsules left after the bubbles dissolved.
Detailed Description
The invention is further described with reference to the following figures and specific examples.
A preparation method based on a bubble method for thin-wall large-scale soft microcapsules comprises the steps of uniformly dispersing Bovine Serum Albumin (BSA) microbubbles with negative charges on the surface in a solution, sequentially assembling polyallylamine hydrochloride solution and polystyrene sodium sulfonate solution to the surfaces of the microbubbles layer by a layer-by-layer self-assembly method, and leaving the thin-wall large-scale polymer soft microcapsules after being dissolved slowly with time due to instability of the microbubbles; the method comprises the following steps:
1) uniformly mixing a bovine serum albumin solution and glucose in proportion, heating in a constant-temperature water bath kettle, and obtaining original Bovine Serum Albumin (BSA) microbubbles with air as a core component and negative charges on the surface by using a bubble preparation method (including an ultrasonic method, a syringe method and other methods for preparing microbubbles);
2) then uniformly dispersing the prepared original microbubbles, adding a polyallylamine hydrochloride solution with positive charges, and reacting for 2-3 min, wherein the concentration of the polyallylamine hydrochloride solution is 1-5 mg/mL; centrifuging to remove the lower clear liquid, and then washing with deionized water for multiple times (3-5 times), wherein the centrifugation speed is 30-50 RCF, and the centrifugation time is 1-2 min;
3) then immersing the polystyrene sodium sulfonate into a polystyrene sodium sulfonate solution with negative charges for a period of time, wherein the concentration of the polystyrene sodium sulfonate solution is 1-5 mg/mL; similarly, soaking for 2-3 min, then centrifuging and removing the lower clear liquid, wherein the centrifugation speed and the centrifugation time are the same as above;
4) repeating the process for many times, adsorbing the PAH and the PSS layer by layer through electrostatic action, thereby obtaining micro bubbles with the surface coated with multiple layers of the PAH and the PSS, and finally, because the micro bubbles with the core being air are unstable, the bubbles slowly dissolve along with the time extension, and when the bubbles are completely dissolved, the thin-wall large-scale soft microcapsule with the thickness of 5-10nm and the diameter of 10-50um is left.
The invention is further explained below with reference to examples and figures. The following examples are provided only for illustrating the present invention and are not intended to limit the scope of the present invention.
Example 1:
uniformly mixing bovine serum albumin solution and glucose, heating in a constant-temperature water bath kettle, and carrying out ultrasonic treatment by an ultrasonic cell disruptor to obtain microbubbles with air as a core component. Then uniformly dispersing the microbubbles, adding a polyallylamine hydrochloride solution with positive charges, and reacting for 2-3 min, wherein the concentration of the polyallylamine hydrochloride solution is 3 mg/mL; and after the supernatant is removed by centrifugation, washing the supernatant for multiple times (3-5 times) by using deionized water, wherein the centrifugation speed is 30-50 RCF, and the centrifugation time is 1-2 min. Then the sodium polystyrene sulfonate is immersed into the sodium polystyrene sulfonate solution with negative charges for a period of time, and the concentration of the sodium polystyrene sulfonate solution is 3 mg/mL. Similarly, soaking for 2-3 min, then centrifuging and sucking off the lower clear liquid, wherein the centrifugation speed and the centrifugation time are the same as above. Repeating the process for many times to obtain microbubbles adsorbing PAH and PSS layer by layer through electrostatic action, and finally, as the microbubbles with air as the core are unstable, the bubbles are slowly dissolved along with the time extension, and thin-wall large-scale soft microcapsules with the thickness of 5-10nm and the diameter of 10-50um are left after the bubbles are completely dissolved.
Figure 1 is a micrograph of thin-walled large-scale soft microcapsules left after dissolution of the bubbles.
Example 2:
uniformly mixing bovine serum albumin solution and glucose, heating in a constant-temperature water bath kettle, and carrying out ultrasonic treatment by an ultrasonic cell disruptor to obtain microbubbles with air as a core component. Then uniformly dispersing the microbubbles, adding a polyallylamine hydrochloride solution with positive charges, and reacting for 2-3 min, wherein the concentration of the polyallylamine hydrochloride solution is 1 mg/mL; and after the supernatant is removed by centrifugation, washing the supernatant for multiple times (3-5 times) by using deionized water, wherein the centrifugation speed is 30-50 RCF, and the centrifugation time is 1-2 min. Then the sodium polystyrene sulfonate is immersed into the sodium polystyrene sulfonate solution with negative charges for a period of time, and the concentration of the sodium polystyrene sulfonate solution is 1 mg/mL. Similarly, soaking for 2-3 min, then centrifuging and sucking off the lower clear liquid, wherein the centrifugation speed and the centrifugation time are the same as above. Repeating the process for many times to obtain microbubbles adsorbing PAH and PSS layer by layer through electrostatic action, and finally, as the microbubbles with air as the core are unstable, the bubbles are slowly dissolved along with the time extension, and thin-wall large-scale soft microcapsules with the thickness of 5-10nm and the diameter of 10-50um are left after the bubbles are completely dissolved.
Example 3:
uniformly mixing bovine serum albumin solution and glucose, heating in a constant-temperature water bath kettle, and carrying out ultrasonic treatment by an ultrasonic cell disruptor to obtain microbubbles with air as a core component. Then uniformly dispersing the microbubbles, adding a polyallylamine hydrochloride solution with positive charges, and reacting for 2-3 min, wherein the concentration of the polyallylamine hydrochloride solution is 5 mg/mL; and after the supernatant is removed by centrifugation, washing the supernatant for multiple times (3-5 times) by using deionized water, wherein the centrifugation speed is 30-50 RCF, and the centrifugation time is 1-2 min. Then the sodium polystyrene sulfonate is immersed into the sodium polystyrene sulfonate solution with negative charges for a period of time, and the concentration of the sodium polystyrene sulfonate solution is 5 mg/mL. Similarly, soaking for 2-3 min, then centrifuging and sucking off the lower clear liquid, wherein the centrifugation speed and the centrifugation time are the same as above. Repeating the process for many times to obtain microbubbles adsorbing PAH and PSS layer by layer through electrostatic action, and finally, as the microbubbles with air as the core are unstable, the bubbles are slowly dissolved along with the time extension, and thin-wall large-scale soft microcapsules with the thickness of 5-10nm and the diameter of 10-50um are left after the bubbles are completely dissolved.
Claims (8)
1. A preparation method of a thin-wall large-scale soft microcapsule based on a bubble method is characterized by comprising the following steps:
1) uniformly dispersing bovine serum albumin microbubbles with negative charges on the surface;
2) and sequentially assembling the polyallylamine hydrochloride solution and the sodium polystyrene sulfonate solution layer by layer on the surface of the micro-bubbles to leave the thin-wall large-scale soft micro-capsules.
2. The method for preparing the thin-wall large-scale soft microcapsule based on the bubble method according to claim 1, wherein the step 1) is specifically that after uniformly mixing a bovine serum albumin solution and glucose, heating the mixture in a constant-temperature water bath kettle, and obtaining the bovine serum albumin microbubbles with negative charges on the surface by a bubble preparation method.
3. The method for preparing the thin-walled large-scale soft microcapsule based on the bubble method as claimed in claim 2, wherein the method for preparing the bubbles comprises an ultrasonic method or a syringe method.
4. The method for preparing the thin-walled large-scale soft microcapsule based on the bubble method as claimed in claim 1, wherein the step 2) comprises the following steps:
2.1) uniformly dispersing the prepared original microbubbles, adding a polyallylamine hydrochloride solution with positive charges, soaking for reaction, centrifuging, removing the supernatant, and cleaning to obtain the assembled microbubbles;
2.2) immersing the assembled micro-bubbles into a sodium polystyrene sulfonate solution with negative charges for a period of time, performing immersion reaction, and then centrifuging and removing the supernatant;
2.3) repeating the above process for a plurality of times to obtain the microbubbles with the surface coated with a plurality of layers of polyallylamine hydrochloride and sodium polystyrene sulfonate, and leaving the thin-wall large-scale soft microcapsules after the bubbles are completely dissolved.
5. The preparation method of the thin-wall large-scale soft microcapsule based on the bubble method according to claim 4, wherein in the steps 2.1) -2.2), the centrifugation speed is 30-50 RCF, and the centrifugation time is 1-2 min.
6. The method for preparing thin-walled large-scale soft microcapsules based on the bubble method according to claim 4, wherein in the steps 2.1) -2.2), the concentration of the polyallylamine hydrochloride solution is 1-5 mg/mL; the concentration of the sodium polystyrene sulfonate solution is 1-5 mg/mL.
7. The method for preparing the thin-walled large-scale soft microcapsule based on the bubble method as claimed in claim 4, wherein in the steps 2.1) -2.2), the soaking reaction time is 2-3 min.
8. The method for preparing the thin-wall large-scale soft microcapsule based on the bubble method according to claim 4, wherein in the step 2.3), the thickness of the thin-wall large-scale soft microcapsule is 5-10nm, and the diameter is 10-50 um.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6110444A (en) * | 1994-03-01 | 2000-08-29 | Nycomed Imaging As | Gas-containing microcapsules useful as contrast agents for diagnostic imaging |
| CN101785764A (en) * | 2010-03-19 | 2010-07-28 | 浙江大学 | Method for improving blood compatibility of microcapsule |
| CN104257510A (en) * | 2014-08-28 | 2015-01-07 | 东南大学 | Preparation method of functional nano-microcapsule mask based on layer-by-layer self assembly |
| CN105153386A (en) * | 2015-10-19 | 2015-12-16 | 南京工程学院 | Preparation method and application of hollow melamine formaldehyde resin microspheres |
-
2020
- 2020-12-10 CN CN202011434309.3A patent/CN112642371A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6110444A (en) * | 1994-03-01 | 2000-08-29 | Nycomed Imaging As | Gas-containing microcapsules useful as contrast agents for diagnostic imaging |
| CN101785764A (en) * | 2010-03-19 | 2010-07-28 | 浙江大学 | Method for improving blood compatibility of microcapsule |
| CN104257510A (en) * | 2014-08-28 | 2015-01-07 | 东南大学 | Preparation method of functional nano-microcapsule mask based on layer-by-layer self assembly |
| CN105153386A (en) * | 2015-10-19 | 2015-12-16 | 南京工程学院 | Preparation method and application of hollow melamine formaldehyde resin microspheres |
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