CN106984247B - A kind of preparation method for the polymer microcapsule carrying hydrophilic material - Google Patents
A kind of preparation method for the polymer microcapsule carrying hydrophilic material Download PDFInfo
- Publication number
- CN106984247B CN106984247B CN201710329901.9A CN201710329901A CN106984247B CN 106984247 B CN106984247 B CN 106984247B CN 201710329901 A CN201710329901 A CN 201710329901A CN 106984247 B CN106984247 B CN 106984247B
- Authority
- CN
- China
- Prior art keywords
- hydrophilic material
- water
- hydrogel
- oil
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/001—Preparation for luminescence or biological staining
- A61K49/0013—Luminescence
- A61K49/0017—Fluorescence in vivo
- A61K49/005—Fluorescence in vivo characterised by the carrier molecule carrying the fluorescent agent
- A61K49/0056—Peptides, proteins, polyamino acids
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/001—Preparation for luminescence or biological staining
- A61K49/0063—Preparation for luminescence or biological staining characterised by a special physical or galenical form, e.g. emulsions, microspheres
- A61K49/0069—Preparation for luminescence or biological staining characterised by a special physical or galenical form, e.g. emulsions, microspheres the agent being in a particular physical galenical form
- A61K49/0089—Particulate, powder, adsorbate, bead, sphere
- A61K49/0091—Microparticle, microcapsule, microbubble, microsphere, microbead, i.e. having a size or diameter higher or equal to 1 micrometer
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K51/00—Preparations containing radioactive substances for use in therapy or testing in vivo
- A61K51/02—Preparations containing radioactive substances for use in therapy or testing in vivo characterised by the carrier, i.e. characterised by the agent or material covalently linked or complexing the radioactive nucleus
- A61K51/04—Organic compounds
- A61K51/08—Peptides, e.g. proteins, carriers being peptides, polyamino acids, proteins
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K51/00—Preparations containing radioactive substances for use in therapy or testing in vivo
- A61K51/02—Preparations containing radioactive substances for use in therapy or testing in vivo characterised by the carrier, i.e. characterised by the agent or material covalently linked or complexing the radioactive nucleus
- A61K51/04—Organic compounds
- A61K51/08—Peptides, e.g. proteins, carriers being peptides, polyamino acids, proteins
- A61K51/081—Peptides, e.g. proteins, carriers being peptides, polyamino acids, proteins the protein being an albumin, e.g. human serum albumin [HSA], bovine serum albumin [BSA], ovalbumin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K51/00—Preparations containing radioactive substances for use in therapy or testing in vivo
- A61K51/12—Preparations containing radioactive substances for use in therapy or testing in vivo characterised by a special physical form, e.g. emulsion, microcapsules, liposomes, characterized by a special physical form, e.g. emulsions, dispersions, microcapsules
- A61K51/1262—Capsules
- A61K51/1265—Microcapsules
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/0002—Galenical forms characterised by the drug release technique; Application systems commanded by energy
- A61K9/0009—Galenical forms characterised by the drug release technique; Application systems commanded by energy involving or responsive to electricity, magnetism or acoustic waves; Galenical aspects of sonophoresis, iontophoresis, electroporation or electroosmosis
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
- A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
- A61K9/5005—Wall or coating material
- A61K9/5021—Organic macromolecular compounds
- A61K9/5036—Polysaccharides, e.g. gums, alginate; Cyclodextrin
- A61K9/5042—Cellulose; Cellulose derivatives, e.g. phthalate or acetate succinate esters of hydroxypropyl methylcellulose
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
- A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
- A61K9/5005—Wall or coating material
- A61K9/5021—Organic macromolecular compounds
- A61K9/5052—Proteins, e.g. albumin
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Epidemiology (AREA)
- Pharmacology & Pharmacy (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Biomedical Technology (AREA)
- Dispersion Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Molecular Biology (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention discloses a kind of preparation methods of polymer microcapsule for carrying hydrophilic material, the polymer microcapsule is a kind of using the cross linking membrane of polymer molecule building as shell, the fine structure material for the oily Xiang Weihe for being loaded with hydrophilic material, preparation method are as follows: high-intensitive ultrasonic radiation is carried out to the water phase of the oily Xiang Yuhan polymer molecule containing hydrophilic material, so that a step realizes the preparation for being loaded with the polymer microcapsule of hydrophilic material.The method of the present invention is fast and convenient, high-efficiency environment friendly, raw material sources are extensive, and it is strong to encapsulate ability, is widely portable to the load of a variety of hydrophilic materials.In addition, some characteristics based on polymer microcapsule, such as the reduction responsiveness of cross linking membrane, hydrophilic and hydrophobic etc., the controlled release of hydrophilic material may be implemented.Therefore, the present invention is meaningful for simply and efficiently preparing microstructure support and the synchronous secure package for realizing hydrophilic material.
Description
Technical field
The invention belongs to the crossing domains of chemical industry, materialogy and biological medicine, and in particular to a kind of load hydrophily material
The preparation method of the polymer microcapsule of material.
Background technique
Microcapsules are using encystation substance by solid, liquid, gas entrapment or the micron order with core-shell structure sealed up for safekeeping
Or submicron order coating.Exist due to having structured particularity, the variability of performance and the robustness of delivered payload capability, microcapsules
The fields such as medicine, biology, food, chemical industry, agricultural are all widely used, also always a forward position of scientific research and heat
Point.Currently, the preparation method of microcapsules has very much, for example aqueous phase separation method, physics self-assembly method, monomer polymerization method, chemistry are handed over
Connection method, extrusion, template auxiliary law, etc., and microcapsules are also varied to the assembly strategy of material, LBL self-assembly, change
Combination, swelling, solvent volatilization etc. can realize the load to target material.Although the technology of preparing of microcapsules is many kinds of,
Feature is totally different, but operating process is mostly comparatively laborious, and reaction time consumption is also long, and be easily introduced impurity etc., this pole
The earth limits their practicability.
In the 1990s, American scientist Suslick et al. is successfully prepared for egg using high-intensitive ultrasonic radiation
White matter class microcapsules, and propose a kind of new method for preparing microcapsules --- phonochemistry method.Phonochemistry method not only has behaviour
Make simple, efficient quick, it is environmentally protective the advantages that, and can directly encapsulate target material while synthesizing microcapsules.
Although preparing the document for carrying oil microcapsule about phonochemistry method both at home and abroad has very much, so far, there has been no utilize phonochemistry
Method preparation carries the domestic and foreign literature and patent report of the microcapsules of hydrophilic material.
Summary of the invention
The purpose of the present invention is to the deficiencies of above-mentioned existing method, and it is micro- to provide a kind of polymer for carrying hydrophilic material
The preparation method of capsule.The preparation method can be realized while completing polymer microcapsule preparation to load hydrophilic material
Oily phase encapsulation, and can be encapsulated with a step and be loaded with the oily phases of a variety of hydrophilic materials.
The specific technical solution of the present invention is as follows:
The first aspect of the invention provides a kind of preparation method of polymer microcapsule for carrying hydrophilic material.It is described
Method include: that ultrasonic radiation is carried out by water phase to the oily Xiang Yuhan polymer molecule containing hydrophilic material, ultimately form
Using the cross linking membrane of polymer molecule building as shell, the microcapsules for the oily Xiang Weihe for carrying hydrophilic material;Wherein, described containing hydrophilic
Property material oil be mutually to be prepared by the following method to obtain: hydrophilic material is dissolved or is distributed to hydrogel in flowable state
In, the hydrogel containing hydrophilic material is then distributed to by the oily phase containing water-in-oil emulsifier by high-speed stirred, thus shape
At the oily phase containing hydrophilic material.
Further, specifically includes the following steps:
(1) polymer molecule is soluble in water, form the water phase containing polymer molecule;Hydrophilic material is dissolved or dispersed
To in the hydrogel of flowable state, then the hydrogel containing hydrophilic material is distributed to containing water-in-oil type cream by high-speed stirred
The oily phase of agent forms the oily phase containing hydrophilic material;
(2) water phase of the oily Xiang Yuhan polymer molecule containing hydrophilic material is added into reaction flask according to setting ratio,
It is then immersed in water-bath;Ultrasonic probe is placed in oil/water two-phase interface, carries out high-intensitive ultrasonic radiation;
(3) after reaction, cooling carried out to reaction solution, be centrifuged, be washed out lower sediment thing, finally obtained to polymerize
The cross linking membrane of object molecule construction be shell, carry hydrophilic material oily Xiang Weihe microcapsules.
In step (1) of the invention, the polymer that the proportion and content of each raw material carry hydrophilic material to synthesis is micro-
Capsule has more important influence.In order to be effectively constructed crosslinked polymer film, stablize the water that package is loaded with water wetted material
Gel, therefore the concentration of polymer molecule needs in right amount;Hydrogel can not only steadily load hydrophilic material, and can be in micro- glue
Intracapsular portion plays a supporting role, therefore the hydrogel containing hydrophilic material mutually needs body appropriate with the oil containing water-in-oil emulsifier
Product ratio;The content of water-in-oil emulsifier needs in right amount, experiments verify that, when the content of emulsifier is higher, solution can be made
Viscosity becomes larger, and droplet distribution effect is deteriorated, and the size in turn resulting in microcapsules is larger, influences its stability, and when emulsifier contains
When measuring lower, the hydrogel for carrying hydrophilic material cannot be fully wrapped, the formation of microcapsules is unfavorable for.It is preferred, therefore, that
The proportion and content of each raw material are as described below: content of the polymer molecule in water phase is 5-100mg/mL;Described
Content of the hydrophilic material in hydrogel is 1 μ g/mL-20mg/mL;The hydrogel and oil-containing packet containing hydrophilic material
The volume ratio of the oily phase of water type emulsifier is 1:3-1:30;The water-in-oil emulsifier is 5-200mg/ in the content of oily phase
mL。
In step (1) of the invention, stirring helps for the hydrogel for containing hydrophilic material to be quickly and evenly distributed to
In oily phase containing water-in-oil emulsifier, it is preferred, therefore, that the mixing speed is 500-1000rpm.
In step (2) of the invention, oil/water volume ratio, reaction temperature, ultrasonic radiation can all influence to carry hydrophilic material
Polymer microcapsule synthesis and its particle size range, it is preferred, therefore, that the temperature of the water-bath is 20-50 DEG C;It is preferred that
, the volume ratio of the water phase containing polymer molecule and the oily phase containing hydrophilic material is 2:1-20:1;Preferably, described
The power of ultrasonic radiation be 100-600W/cm2, the time of ultrasonic radiation is 2-15min.
In step (3) of the invention, cooling be conducive to stablize polymer microcapsule, and be centrifuged, wash can extract and
Purified polymer microcapsules, it is preferred, therefore, that the cooling temperature of the reaction solution is 5-15 DEG C, the revolving speed of centrifugation is 1000-
5000rpm, the number of washing are 2-6 times.
The second aspect of the invention provides a kind of polymer of load hydrophilic material being prepared using the above method
Microcapsules.The polymer microcapsule of the load hydrophilic material is spherical in shape or elliposoidal, partial size are 500nm-10 μm, structure
Including shell and core, wherein the shell is the cross linking membrane constructed by polymer molecule, and the core is to be loaded with hydrophily
The oily phase of material.
In the present invention, the shell of the polymer microcapsule is that chemical crosslinking or hydrophobic effect occur by polymer molecule
Made of answering, it is preferred, therefore, that the polymer molecule is polyglutamic acid, cellulose macromolecule, starch polymer, antibiosis
Fibroin, and one of the protein containing multiple sulfydryls or polypeptide.Wherein, it is preferred that the egg containing multiple sulfydryls
White matter or polypeptide be hemoglobin, bovine serum albumin(BSA), human serum albumins, creatine kinase, ovalbumin, metallothionein,
Phytochelatin.
In the present invention, the core of the polymer microcapsule is by hydrogel, water-in-oil emulsifier, hydrophily material
Material is mutually made with oil.
In the present invention, hydrogel is not particularly limited, can steady load hydrophilic material, but be based on
Hydrogel of the invention needs to be emulsified using emulsifier, so as to be dispersed stably in it in oily phase, it is therefore preferable that
, the hydrogel is aquagel, cellulose aquagel, dextran hydrogel, Sodium Alginate Hydrogel Films, gelatin water-setting
One of glue, polyacrylamide hydrogel, polyvinyl alcohol hydrogel, polyacrylic acid hydrogel.
In the present invention, hydrogel needs are dispersed stably in oily phase by water-in-oil emulsifier, it is therefore preferable that
, the water-in-oil emulsifier is Span60, sorbitan monooleate, the different tristearin of anhydrous sorbitol
Acid esters, glycerin monostearate, lecithin, sucrose ester, propylene glycol monolaurate, diethylene glycol monoleate, diethylene glycol
One of monostearate, stearic alcohol ether -2, rilanit special, oleyl alcohol ether -2, PEG-4 dioleate.
In the present invention, the hydrophilic material is water-soluble inorganic salts, dyestuff, drug, large biological molecule, magnetism
One of material, nano material are a variety of;The oil is mutually animal oil, vegetable oil, microbial oil, mineral oil, silicone oil
One of class and the immiscible organic solvent of water.
The third aspect of the invention provides a kind of polymer microcapsule of above-mentioned load hydrophilic material in material delivery
Application.For example, polymer microcapsule can be used as drug delivery system, reach when the hydrophilic material of load is drug
The effect of delivery and slow releasing pharmaceutical;When the hydrophilic material of load is magnetic material, polymer microcapsule can be used as magnetic Jie
Material is led, achievees the purpose that targeting and treatment;When the hydrophilic material of load is for fluorescer or containing the salt of isotope, polymer
Microcapsules can be used as the tracer factor, achieve the purpose that tracking and label.
The principle of the present invention: hydrogel can steadily load hydrophilic material, and water-in-oil emulsifier can make to carry
The hydrogel of hydrophilic material is dispersed stably in oily phase, to form the oily phase for carrying hydrophilic material;Utilize ultrasonic wave
Acoustic cavitation effect, can promote the polymer molecule in oil/water interface that chemical crosslinking or hydrophobic effect occurs, be built into stabilization
Cross linking membrane, while will be dispersed in the encapsulation of the hydrophilic material in oily phase, formed it is a kind of using crosslinked polymer film as shell, carry parent
The oil of water-based material is mutually the microcapsules of core.
Compared with prior art, technical solution of the present invention has the following beneficial effects: the method for the present invention operating process letter
List, reaction time consumption is short, raw material sources are extensive, synthesis cost is low, and encapsulation ability is strong, and it is micro- can quickly and efficiently to prepare polymer
Capsule;The method of the present invention is completed to can be realized the envelope to the oily phase for carrying hydrophilic material while polymer microcapsule preparation
Dress, and the oily phase for being loaded with a variety of hydrophilic materials can be encapsulated with a step;Using some characteristics of polymer microcapsule, for example, it is poly-
Reduction responsiveness or the hydrophilic and hydrophobic etc. for closing object cross linking membrane, may be implemented the controlled release of packed hydrophilic material.
Specific embodiment
In order to enable those skilled in the art can clearly understand technical solution of the present invention, following tool will be combined
The embodiment of the body technical solution that the present invention will be described in detail.
Embodiment 1
Bovine serum albumin(BSA) (500mg) is dissolved in deionized water (10mL), Bovine Serum Albumin in Aqueous Solution is made into;It will
NaCl (10mg) is dissolved into the aquagel (10mL) in flowable state, is then gathered shell by high-speed stirred (500rpm)
Syrup gel is evenly dispersed into (V in the soybean oil containing sorbitan monooleate (20mg/mL)Hydrogel:VOily phase=1:5), shape
At the oily phase containing NaCl;Bovine Serum Albumin in Aqueous Solution and the soybean oil containing NaCl are added into reaction flask by 3:1 by volume,
And it places it in water-bath (40 DEG C);Ultrasonic probe is placed in oil/water two-phase interface, carries out high-intensitive ultrasonic radiation (200W/
cm2, 10min);After reaction, cooling (10 DEG C), centrifugation (1000rpm) are carried out to reaction solution, and washs lower sediment thing (3
It is secondary), finally obtain it is a kind of using bovine serum albumin(BSA) cross linking membrane as shell, be loaded with the soybean oil of NaCl as the microcapsules of core.In optics
Under microscope, microcapsules are spherical in shape or ellipsoid;By laser particle size analyzer, the average grain diameter for measuring microcapsules is about 4.5 μ
m;By conductivity measuring instrument, measuring and calculating microcapsules is 51.1% to the rate that contains of NaCl.
Embodiment 2
Hemoglobin (300mg) is dissolved in deionized water (10mL), haemoglobin aqueous solution is made into;By rhodamine B (50
μ g) it is dissolved into the aquagel (10mL) in flowable state, then pass through high-speed stirred (600rpm) for chitosan water-setting
Glue is evenly dispersed into (V in the soybean oil containing sorbitan monooleate (20mg/mL)Hydrogel:VOily phase=1:10), formation contains
There is the oily phase of rhodamine B;Haemoglobin aqueous solution and the soybean oil containing rhodamine B are added into reaction flask by 3:1 by volume, and
It places it in water-bath (30 DEG C);Ultrasonic probe is placed in oil/water two-phase interface, carries out high-intensitive ultrasonic radiation (200W/
cm2, 10min);After reaction, cooling (5 DEG C), centrifugation (1000rpm) are carried out to reaction solution, and washs lower sediment thing (4
It is secondary), finally obtain it is a kind of using hemoglobin cross linking membrane as shell, be loaded with the soybean oil of rhodamine B as the microcapsules of core.It is aobvious in optics
Under micro mirror, microcapsules are spherical in shape or ellipsoid;By laser particle size analyzer, the average grain diameter for measuring microcapsules is about 5.0 μm;
Under laser confocal microscope, the hydrogel that discovery is loaded with rhodamine B is distributed in microcapsules;Pass through ultraviolet-visible spectrum
Instrument, measuring microcapsules is 62.7% to the rate that contains of rhodamine B.
Embodiment 3
Hemoglobin (300mg) is dissolved in deionized water (10mL), haemoglobin aqueous solution is made into;By phosphoric acid phenylpropyl alcohol piperazine
Woods (50 μ g) is dissolved into the polyvinyl alcohol hydrogel (10mL) in flowable state, then passes through high-speed stirred (500rpm) for poly- second
Enol hydrogel is evenly dispersed into (V in the chicken fat containing sorbitan monooleate (50mg/mL)Hydrogel:VOily phase=1:10),
Form the oily phase containing benproperine phosphate;Haemoglobin aqueous solution and phosphoric acid benzene are added into reaction flask by 5:1 by volume
The chicken fat of third piperazine woods, and place it in water-bath (40 DEG C);Ultrasonic probe is placed in oil/water two-phase interface, carries out high intensity
Ultrasonic radiation (300W/cm2, 5min);After reaction, cooling (10 DEG C), centrifugation (1500rpm) are carried out to reaction solution, and washed
Wash lower sediment thing (5 times), finally obtain it is a kind of using hemoglobin cross linking membrane as shell, be loaded with the chicken fat of benproperine phosphate as core
Microcapsules.Under an optical microscope, microcapsules are spherical in shape or ellipsoid;By laser particle size analyzer, microcapsules are measured
Average grain diameter is about 3.2 μm;By ultraviolet-visible spectrometer, measure microcapsules is to the rate that contains of benproperine phosphate
65.9%.
Embodiment 4
Bovine serum albumin(BSA) (300mg) is dissolved in deionized water (10mL), Bovine Serum Albumin in Aqueous Solution is made into;By phosphorus
Sour benproperine (50 μ g) is dissolved into the polyvinyl alcohol hydrogel (10mL) in flowable state, then passes through high-speed stirred
Polyvinyl alcohol hydrogel is evenly dispersed into the oil of the golden dragonfish containing sucrose fatty ester (50mg/mL) by (600rpm)
(VHydrogel:VOily phase=1:10), form the oily phase containing benproperine phosphate;It is pure that ox blood is added into reaction flask by 5:1 by volume
The golden dragonfish of protein solution and phosphoric acid benproperine oil, and place it in water-bath (30 DEG C);By ultrasonic probe be placed in oil/
Water two-phase interface carries out high-intensitive ultrasonic radiation (300W/cm2, 5min);After reaction, cooling (10 are carried out to reaction solution
DEG C), centrifugation (1000rpm), and wash lower sediment thing (3 times), finally obtain it is a kind of using bovine serum albumin(BSA) cross linking membrane as shell,
The golden dragonfish oil for being loaded with benproperine phosphate is the microcapsules of core.Under an optical microscope, microcapsules are spherical in shape or ellipsoid;It is logical
Laser particle size analyzer is crossed, the average grain diameter for measuring microcapsules is about 3.1 μm;By ultraviolet-visible spectrometer, microcapsules are measured
The rate that contains to rhodamine B is 63.5%.
Embodiment 5
Methylcellulose (100mg) is dissolved in deionized water (10mL), methylated cellulose aqueous solution is made into;By phosphoric acid benzene
Third piperazine woods (50 μ g) is dissolved into the polyvinyl alcohol hydrogel (10mL) in flowable state, and then passing through high-speed stirred (700rpm) will
Polyvinyl alcohol hydrogel is evenly dispersed into (V in the hydroxy silicon oil containing sucrose fatty ester (50mg/mL)Hydrogel:VOily phase=1:
20) the oily phase containing benproperine phosphate, is formed;10:1 is added methylated cellulose aqueous solution and contains into reaction flask by volume
The hydroxy silicon oil of benproperine phosphate, and place it in water-bath (25 DEG C);Ultrasonic probe is placed in oil/water two-phase interface, into
High-intensitive ultrasonic radiation (the 300W/cm of row2, 5min);After reaction, cooling (15 DEG C), centrifugation are carried out to reaction solution
(2000rpm), and wash lower sediment thing (4 times), finally obtain one kind using methylcellulose cross linking membrane as shell, be loaded with phosphoric acid benzene
The hydroxy silicon oil of third piperazine woods is the microcapsules of core.Under an optical microscope, microcapsules are spherical in shape or ellipsoid;Pass through laser particle size
Analyzer, the average grain diameter for measuring microcapsules is about 2.2 μm;By ultraviolet-visible spectrometer, microcapsules are measured to rhodamine B
Contain rate be 52.2%.
Embodiment 6
Human serum albumins (200mg) is dissolved in deionized water (10mL), human serum albumins aqueous solution is made into;It will
Fe3O4Magnetic nano-particle (50mg) is distributed in the polyvinyl alcohol hydrogel (10mL) in flowable state, then passes through high-speed stirred
Polyvinyl alcohol hydrogel is evenly dispersed into the hydroxy silicon oil containing sucrose fatty ester (80mg/mL) by (800rpm)
(VHydrogel:VOily phase=1:20), formation contains Fe3O4The oily phase of magnetic nano-particle;People is added into reaction flask by 10:1 by volume
Seralbumin aqueous solution with contain Fe3O4The hydroxy silicon oil of magnetic nano-particle, and place it in water-bath (20 DEG C);It will be ultrasonic
Probe is placed in oil/water two-phase interface, carries out high-intensitive ultrasonic radiation (400W/cm2, 3min);After reaction, to reaction solution
Cooling (5 DEG C), centrifugation (3000rpm) are carried out, and washs lower sediment thing (5 times), finally obtains one kind with human serum albumins
Cross linking membrane is shell, is loaded with Fe3O4The hydroxy silicon oil of magnetic nano-particle is the microcapsules of core.Under an optical microscope, microcapsules are in
Spherical or ellipsoid;By laser particle size analyzer, the average grain diameter for measuring microcapsules is about 1.7 μm;It, can by transmission electron microscope
Observe that the inside of microcapsules is dispersed with a large amount of Fe3O4Nanoparticle;It is tested by Magneto separate, discovery microcapsules can be with
The change of externally-applied magnetic field and displacement occurs.
Embodiment 7
Bovine serum albumin(BSA) (300mg) is dissolved in deionized water (10mL), Bovine Serum Albumin in Aqueous Solution is made into;It will
Fe3O4Magnetic nano-particle (30mg) is distributed in the polyvinyl alcohol hydrogel (10mL) in flowable state, then passes through high-speed stirred
Polyvinyl alcohol hydrogel is evenly dispersed into the hydroxy silicon oil containing sucrose fatty ester (100mg/mL) by (1000rpm)
(VHydrogel:VOily phase=1:15), formation contains Fe3O4The oily phase of magnetic nano-particle;Ox is added into reaction flask by 15:1 by volume
Seralbumin aqueous solution with contain Fe3O4The hydroxy silicon oil of magnetic nano-particle, and place it in water-bath (30 DEG C);It will be ultrasonic
Probe is placed in oil/water two-phase interface, carries out high-intensitive ultrasonic radiation (500W/cm2, 3min);After reaction, to reaction solution
Cooling (10 DEG C), centrifugation (4000rpm) are carried out, and washs lower sediment thing (4 times), finally obtains one kind with bovine serum albumin(BSA)
Cross linking membrane is shell, is loaded with Fe3O4The hydroxy silicon oil of magnetic nano-particle is the microcapsules of core.Under an optical microscope, microcapsules are in
Spherical or ellipsoid;By laser particle size analyzer, the average grain diameter for measuring microcapsules is about 1.4 μm;It, can by transmission electron microscope
Observe that the inside of organic microgel is dispersed with a large amount of Fe3O4Nanoparticle;It is tested by Magneto separate, discovery microcapsules can
Displacement occurs with the change of externally-applied magnetic field.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (7)
1. a kind of preparation method for the polymer microcapsule for carrying hydrophilic material, characterized in that the preparation method includes: logical
It crosses and ultrasonic radiation is carried out to the water phase of the oily Xiang Yuhan polymer molecule containing hydrophilic material, ultimately form with polymer molecule structure
The cross linking membrane built be shell, carry hydrophilic material oily Xiang Weihe microcapsules;Wherein, the oil containing hydrophilic material is mutually
It is prepared by the following method to obtain: hydrophilic material being dissolved or is distributed in the hydrogel in flowable state, then pass through high speed
Hydrogel containing hydrophilic material is distributed to the oily phase containing water-in-oil emulsifier by stirring, to be formed containing hydrophilic material
Oily phase;
Wherein, specifically includes the following steps:
(1) polymer molecule is soluble in water, form the water phase containing polymer molecule;Hydrophilic material is dissolved or is distributed to and is in
In the hydrogel of flowable state, then the hydrogel containing hydrophilic material is distributed to containing water-in-oil emulsifier by high-speed stirred
Oily phase, formed the oily phase containing hydrophilic material;
(2) water phase of the oily Xiang Yuhan polymer molecule containing hydrophilic material is added into reaction flask according to setting ratio, and will
It is placed in water-bath;Ultrasonic probe is placed in oil/water two-phase interface, carries out high-intensitive ultrasonic radiation;
(3) after reaction, cooling carried out to reaction solution, be centrifuged, be washed out lower sediment thing, finally obtained with polymer point
Son building cross linking membrane be shell, carry hydrophilic material oily Xiang Weihe microcapsules;
Wherein, the polymer molecule is one in polyglutamic acid, cellulose macromolecule, starch polymer and avidin
Kind.
2. the method as described in claim 1, characterized in that the hydrogel be aquagel, cellulose aquagel,
Dextran hydrogel, Sodium Alginate Hydrogel Films, gelatin hydrogel, polyacrylamide hydrogel, polyvinyl alcohol hydrogel, polypropylene
One of acid hydrogel;The water-in-oil emulsifier is Span60, sorbitan monooleate, mistake
Water sorbierite isostearate, glycerin monostearate, lecithin, sucrose ester, propylene glycol monolaurate, diethylene glycol list oil
One of acid esters, diethylene glycol monostearate, stearic alcohol ether -2, rilanit special, oleyl alcohol ether -2, PEG-4 dioleate;
The hydrophilic material is water-soluble inorganic salts, dyestuff, drug, large biological molecule, magnetic material, one in nano material
Kind is a variety of;The described oil be mutually animal oil, vegetable oil, microbial oil, mineral oil, silicone oil, with immiscible organic of water
One of solvent.
3. the method as described in claim 1, characterized in that in step (1), content of the polymer molecule in water phase
It is 5-100mg/mL;Content of the hydrophilic material in hydrogel is 1 μ g/mL-20mg/mL;Described contains hydrophily
The hydrogel of material and the volume ratio of the oily phase containing water-in-oil emulsifier are 1:3-1:30;The water-in-oil emulsifier exists
The content of oily phase is 5-200mg/mL;The mixing speed is 500-1000rpm.
4. the method as described in claim 1, characterized in that in step (2), the water phase containing polymer molecule with containing parent
The volume ratio of the oily phase of water-based material is 2:1-20:1;The temperature of the water-bath is 20-50 DEG C;The function of the ultrasonic radiation
Rate is 100-600W/cm2, the time of ultrasonic radiation is 2-15min.
5. the method as described in claim 1, characterized in that in step (3), the cooling temperature of the reaction solution is 5-15
DEG C, the revolving speed of centrifugation is 1000-5000rpm, and the number of washing is 2-6 times.
6. using the polymer microcapsule for the load hydrophilic material that method according to any one of claims 1 to 5 is prepared,
It is characterized in that the polymer microcapsule is spherical in shape or elliposoidal, partial size are 500nm-10 μm, structure includes shell and core
Core;Wherein, the shell is the cross linking membrane constructed by polymer molecule, and the core is to be loaded with the oily phase of hydrophilic material.
7. the polymer microcapsule as claimed in claim 6 for carrying hydrophilic material is as the application in material carrier.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710329901.9A CN106984247B (en) | 2017-05-11 | 2017-05-11 | A kind of preparation method for the polymer microcapsule carrying hydrophilic material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710329901.9A CN106984247B (en) | 2017-05-11 | 2017-05-11 | A kind of preparation method for the polymer microcapsule carrying hydrophilic material |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106984247A CN106984247A (en) | 2017-07-28 |
CN106984247B true CN106984247B (en) | 2019-11-12 |
Family
ID=59417688
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710329901.9A Active CN106984247B (en) | 2017-05-11 | 2017-05-11 | A kind of preparation method for the polymer microcapsule carrying hydrophilic material |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106984247B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP4036580A1 (en) * | 2021-02-01 | 2022-08-03 | Oxford University Innovation Limited | Drug loaded cavitation agent |
EP4035655A1 (en) * | 2021-02-01 | 2022-08-03 | Oxford University Innovation Limited | Immune modulating particles |
EP4036581A1 (en) * | 2021-02-01 | 2022-08-03 | Oxford University Innovation Limited | Cavitation agent |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112867475B (en) * | 2018-08-17 | 2024-03-22 | 加利福尼亚大学董事会 | Particle-containing droplet system with monodisperse fluid volumes |
CN111389315A (en) * | 2020-03-27 | 2020-07-10 | 南京芬之怡生物科技有限公司 | Green impurity-removing purifying agent and preparation method thereof |
CN112657438B (en) * | 2020-12-23 | 2023-01-24 | 西华师范大学 | Colloidal capsule for embedding small-molecule hydrophilic components and preparation method thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101357120A (en) * | 2008-09-04 | 2009-02-04 | 浙江大学 | Water-soluble drug sustained release microsphere agents and preparation method thereof |
CN103735531A (en) * | 2013-12-23 | 2014-04-23 | 吉林大学 | Preparation method for microcapsules with magnetic nanoparticles-containing capsule walls |
CN104622845A (en) * | 2015-01-02 | 2015-05-20 | 吉林大学 | Preparation method of chitosan microcapsules containing magnetic nano particles inside |
CN105267991A (en) * | 2015-11-03 | 2016-01-27 | 吉林大学 | Microcapsule with fluorescent tracing and reduction responsive drug release functions and its preparation method |
-
2017
- 2017-05-11 CN CN201710329901.9A patent/CN106984247B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101357120A (en) * | 2008-09-04 | 2009-02-04 | 浙江大学 | Water-soluble drug sustained release microsphere agents and preparation method thereof |
CN103735531A (en) * | 2013-12-23 | 2014-04-23 | 吉林大学 | Preparation method for microcapsules with magnetic nanoparticles-containing capsule walls |
CN104622845A (en) * | 2015-01-02 | 2015-05-20 | 吉林大学 | Preparation method of chitosan microcapsules containing magnetic nano particles inside |
CN105267991A (en) * | 2015-11-03 | 2016-01-27 | 吉林大学 | Microcapsule with fluorescent tracing and reduction responsive drug release functions and its preparation method |
Non-Patent Citations (1)
Title |
---|
多功能载药微胶囊的超声化学制备及其性能研究;李占锋;《吉林大学博士学位论文》;20160831;第126-141页 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP4036580A1 (en) * | 2021-02-01 | 2022-08-03 | Oxford University Innovation Limited | Drug loaded cavitation agent |
EP4035655A1 (en) * | 2021-02-01 | 2022-08-03 | Oxford University Innovation Limited | Immune modulating particles |
EP4036581A1 (en) * | 2021-02-01 | 2022-08-03 | Oxford University Innovation Limited | Cavitation agent |
WO2022162399A1 (en) * | 2021-02-01 | 2022-08-04 | Oxford University Innovation Limited | Immune modulating particles |
WO2022162396A1 (en) * | 2021-02-01 | 2022-08-04 | Oxford University Innovation Limited | Drug loaded cavitation agent |
WO2022162395A1 (en) * | 2021-02-01 | 2022-08-04 | Oxford University Innovation Limited | Cavitation agent |
Also Published As
Publication number | Publication date |
---|---|
CN106984247A (en) | 2017-07-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106984247B (en) | A kind of preparation method for the polymer microcapsule carrying hydrophilic material | |
Chen et al. | Calixarene‐based supramolecular AIE dots with highly inhibited nonradiative decay and intersystem crossing for ultrasensitive fluorescence image‐guided cancer surgery | |
Yang et al. | Drug delivery using nanoparticle-stabilized nanocapsules | |
Chen et al. | Rational synthesis of magnetic thermosensitive microcontainers as targeting drug carriers | |
Bollhorst et al. | Bifunctional submicron colloidosomes coassembled from fluorescent and superparamagnetic nanoparticles | |
EP3235512A1 (en) | Method using polyethylene glycol to prepare fibroin nano/microspheres, and application of method in controlled drug release | |
Wang et al. | Preloading of Hydrophobic Anticancer Drug into Multifunctional Nanocarrier for Multimodal Imaging, NIR‐Responsive Drug Release, and Synergistic Therapy | |
Gui et al. | Embedding fluorescent mesoporous silica nanoparticles into biocompatible nanogels for tumor cell imaging and thermo/pH-sensitive in vitro drug release | |
Zhang et al. | Porous microcapsules with tunable pore sizes provide easily controllable release and bioactivity | |
Zhang et al. | Magnetic colloidosomes fabricated by Fe3O4–SiO2 hetero-nanorods | |
Cheng et al. | YVO 4: Eu 3+ functionalized porous silica submicrospheres as delivery carriers of doxorubicin | |
Kumar et al. | Biocompatible PLGA-oil hybrid nanoparticles for high loading and controlled delivery of resveratrol | |
JP4982178B2 (en) | Microencapsulation system and its application | |
CN107096474A (en) | A kind of method that the preparation and encapsulating material of organic microgel are realized in synchronization | |
Xia et al. | A novel strategy to fabricate doxorubicin/bovine serum albumin/porous silicon nanocomposites with pH-triggered drug delivery for cancer therapy in vitro | |
Chansaenpak et al. | Aza-BODIPY based polymeric nanoparticles for cancer cell imaging | |
Beyer et al. | Assembly of biomacromolecule loaded polyelectrolyte multilayer capsules by using water soluble sacrificial templates | |
KR102407260B1 (en) | Method of producing nanoparticle-in-oil dispersion | |
Zhou et al. | Sonochemical synthesis of liquid-encapsulated lysozyme microspheres | |
Chen et al. | Polymerization-induced self-assembly of tea polyphenols into open-mouthed nanoparticles for active delivery systems and stable carbon bowls | |
Zubris et al. | Ease of synthesis, controllable sizes, and in vivo large animal lymph migration of polymeric nanoparticles | |
Li et al. | Superiority of amino-modified chiral mesoporous silica nanoparticles in delivering indometacin | |
Qiao et al. | Temperature‐Regulated Core Swelling and Asymmetric Shrinkage for Tunable Yolk@ Shell Polydopamine@ Mesoporous Silica Nanostructures | |
Dabbagh et al. | A new mechanism of thermal sensitivity for rapid drug release and low systemic toxicity in hyperthermia and thermal ablation temperature ranges | |
CN107875390B (en) | Drug-loaded micro-organic gel with shell containing ferroferric oxide as well as preparation method and application of drug-loaded micro-organic gel |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |