CN101966441A - Polydopamine microcapsules and preparation method thereof - Google Patents

Polydopamine microcapsules and preparation method thereof Download PDF

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CN101966441A
CN101966441A CN 201010275929 CN201010275929A CN101966441A CN 101966441 A CN101966441 A CN 101966441A CN 201010275929 CN201010275929 CN 201010275929 CN 201010275929 A CN201010275929 A CN 201010275929A CN 101966441 A CN101966441 A CN 101966441A
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dopamine
pss
capsule
preparation
micro
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姜忠义
张蕾
石家福
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Tianjin University
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Tianjin University
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Abstract

The invention relates to polydopamine microcapsules and a preparation method thereof. The polydopamine microcapsules are prepared from dopamine serving as a raw material and calcium carbonate particles serving as templates in a mass ratio of 0.1:1-10:1. The preparation method comprises the following steps of: preparing the calcium carbonate particles serving as the templates; adsorbing the dopamine on the templates so as to form polydopamine membranes on the templates by the self-polymerization of the dopamine; reacting for a certain period of time; and removing a calcium carbonate kernel by using ethylene diamine tetraacetic acid disodium after the polydopamine membranes on the templates reaches a certain thickness. For the microcapsules prepared by the method, a preparation process is simple and is convenient to operate, an acid-base catalyst and an organic solvent are saved, the raw material is readily available, the thickness of each membrane is easy to control through the assembly of different layers, the size of each particle is controllable, stability and repeatability are high and a wide application range is achieved.

Description

Poly-dopamine micro-capsule and preparation method
Technical field
The present invention relates to the preparation of macromolecular material, is a kind of poly-dopamine micro-capsule and preparation method, is specially biological poly-dopamine micro-capsule of preparation and the preparation method down of inspiring.
Background technology
Nowadays micro-capsule is used to fields such as the embedding protection of microreactor, pharmaceutical carrier, cell and enzyme and gene transfection more and more.Traditional microcapsule preparation method mainly contains three kinds: (1) chemical method is meant the method that the chemical reaction encystation takes place in liquid phase.Currently used chemical method mainly contains 2 kinds, i.e. interface polycondensation and chemical radiation.Though can obtain the micro-capsule of size than homogeneous, its size often is difficult to regulate.(2) physical-chemical process, this law is encystation in liquid phase, promptly in the mixture of core-clad material and capsule material, add another kind of material or adopt other suitable methods that the solubility of capsule material is reduced and condense upon capsule core material around, form a cenotype and separate out, so be called phase separation method again.The equipment that is characterized in is simple, and the macromolecular material wide material sources are applicable to the microencapsulation of multiple medicine, and shortcoming is micro-capsule adhesion, gathering, the process poor controllability.(3) physics and Mechanical Method mainly are the physical changes by microcapsule capsule wall material, carry out micro-capsule preparation, poor controllability in conjunction with certain mechanical processing tools.(4) self-assembly method layer by layer, this is a kind of emerging method, can carry out layer assembly by Electrostatic Absorption or covalent method at template surface, and the wall thickness and the release characteristics of micro-capsule are realized accuracy controlling.
The bivalves of occurring in nature self can be secreted a kind of albumen can adhere to various surfaces such as boats and ships, rock.This reaction condition temperature is closed, and adhesion is strong.Studies show that the oxidation of DOPA plays most important effect in liquid attachment proteins generation crosslinked action solidification process.Dopamine is a kind of nerve conduction material, transmits the chemical substance of pulse with helping cell, and it and DOPA are similar, under the weak base condition auto polymerization can take place, and have the function of mimic biology binding proteins.Dopamine has suitable hydrophily and good biocompatibility, has multi-functional group (amino and catechol base is the catechu phenolic group again) simultaneously.In addition, dopamine is easy to be coated in kinds of surface, and this makes that utilizing dopamine to prepare micro-capsule becomes possibility.This bioadhesive process prepares micro-capsule, easy and simple to handle, has avoided the use of acid base catalysator, organic solvent, the preparation condition gentleness, and particle size can be wider by size control, the scope of application of control template.
Summary of the invention
The object of the present invention is to provide a kind of poly-dopamine micro-capsule and preparation method.Inspiring down based on biology, is the preparation that raw material carries out micro-capsule with the dopamine.At template surface absorption dopamine, utilize the characteristics of dopamine auto polymerization under the weak base condition earlier, form a strata dopamine film, again template is removed at last at template surface.Preparation condition gentleness of the present invention, the preparation raw material is easy to get, and preparation is simple, and the thickness by the concentration and the polymerization time of dopamine are regulated and control film is also than being easier to.
A kind of poly-dopamine micro-capsule provided by the invention is to be template with the calcium carbonate microparticle, and dopamine is a raw material, is to be prepared in 0.1: 1~10: 1 to form processing step according to the quality proportioning of dopamine and calcium carbonate template:
Contain the calcium chloride solution of kayexalate (PSS) and the calcium carbonate CaCO that sodium carbonate liquor prepared in reaction PSS mixes 3(PSS) colloidal particles; CaCO 3Compound with PSS, be expressed as: CaCO 3(PSS).
This particulate is disperseed with the dissolving of Tris-HCl cushioning liquid, and add dopamine, at CaCO 3(PSS) microparticle surfaces adsorbs dopamine and makes the dopamine auto polymerization obtain the particulate of nucleocapsid structure;
The particulate of nucleocapsid structure and disodium ethylene diamine tetraacetate (EDTA) solution stirring reaction, water washing, centrifugation; Repeat above process, remove calcium carbonate and obtain the poly-dopamine micro-capsule of self assembly, store standby in the water.Average grain diameter is 3-5 μ m.
The preparation method of a kind of poly-dopamine micro-capsule provided by the invention may further comprise the steps:
1) compound concentration is the calcium chloride solution of 0.2~0.5M, and to wherein adding kayexalate (PSS), making its concentration is 2~3mg/mL; The sodium carbonate liquor of molar concentrations such as preparation and calcium chloride, after filtering respectively, respectively get 15~25mL calcium chloride solution and isopyknic sodium carbonate liquor, under the rotating speed of 1000~1200rpm, sodium carbonate liquor is added in the calcium chloride solution, reaction 15~30s, leave standstill 15~30min, obtain containing the dispersion soln of carbonic acid calcium precipitate.
2) be centrifugal 3min in the centrifuge of 3000rpm with the gained dispersion soln at rotating speed, wash with water after centrifugal, repeated centrifugation-water-washing process secondary, supernatant is removed in the back, CaCO 3(PSS) particulate.
3) compound concentration is the Tris-HCl cushioning liquid of 0.01~0.1M, and regulating its PH is 6.0~10.0.
4) dopamine is dissolved in the Tris-HCl cushioning liquid for preparing, is made into the solution of 0.2~20mg/mL.
5) with Tris-HCl cushioning liquid washed twice CaCO 3(PSS) particulate, particle concentration are 1% (w/w), and be centrifugal, and product adds the dopamine solution of step 4), makes CaCO 3(PSS) disperse stirring at room 3~48h again; Centrifugation repeats with Tris-HCl cushioning liquid washed twice.
7) with the EDTA solution washing of 0.05~0.5M, the 3000rpm centrifugation repeats 3-5 time, thoroughly removes calcium carbonate, gets micro-capsule after the stoning, and with water washing three times, the micro-capsule preparation so far finishes.
The invention provides a kind of poly-dopamine micro-capsule and preparation method.At first prepare calcium carbonate microparticle as template, dopamine is adsorbed on the template, will utilizes the auto polymerization effect of dopamine then, on template, form poly-dopamine film, after poly-dopamine film has suitable mechanical strength, remove the calcium carbonate kernel with disodium ethylene diamine tetraacetate.The micro-capsule of the present invention preparation, easy and simple to handle, avoided the use of acid base catalysator, organic solvent, raw material is easy to get, preparation is simple, by to assembling the different numbers of plies to the THICKNESS CONTROL of film also than being easier to, granular size is controlled, good stability, favorable repeatability, applied widely.
Description of drawings
Fig. 1 is dopamine microballoon ESEM (SEM) photo of embodiment 1 preparation.
Fig. 2 is dopamine microballoon ESEM (SEM) photo of embodiment 2 preparations.
Fig. 3 is dopamine microballoon ESEM (SEM) photo of embodiment 3 preparations.
Fig. 4 is dopamine microballoon ESEM (SEM) photo of embodiment 4 preparations.
Fig. 5 is microballoon ESEM (SEM) photo of Comparative Examples 1 preparation.
The specific embodiment
Embodiment 1
The kayexalate (PSS) of 30mg is dissolved in the calcium chloride solution (concentration is 0.2M) after 15mL filters, the sodium carbonate liquor that adds the 0.2M after 15mL filters to this solution, in being the electromagnetic agitation machine of 1000rpm, rotating speed reacts 15s, open electromagnetic agitation after closing electromagnetic agitation and leaving standstill 15min, reaction solution is stirred, get 5mL and add in the centrifuge tube, get 4 pipes altogether.With 4 pipe suspensions rotating speed be in the centrifuge of 3000rpm behind the centrifugal 3min with the deionized water washing, secondary is operated in repeated centrifugation-washing.
The Tris-HCl cushioning liquid of preparation 0.01M, regulating its PH is 6.5, the dopamine solution of preparation 2mg/mL.With dopamine solution join stir 48h in the calcium carbonate after the cleaning after, the centrifugal collection solids of 3000rpm 3min add 5mL Tris-HCl cushioning liquid to each centrifuge tube, rock particle is disperseed again.At rotating speed is centrifugal 3min in the centrifuge of 3000rpm, and Tris-HCl cushioning liquid is washed, and repeated centrifugation-buffer solution is washed secondary, and supernatant is removed in the back.Disodium ethylene diamine tetraacetate (EDTA) solution of preparation 0.05M adds 5mL in every centrifuge tube, concussion reaction 30min, and the centrifugal 3min of 3000rpm removes supernatant.Above process repeats 3-5 time, thoroughly to remove calcium carbonate, gets micro-capsule after the stoning, and with water washing three times, just can make particle diameter is the poly-dopamine micro-capsule of 3-5 μ m.
Embodiment 2
The kayexalate (PSS) of 45mg is dissolved in the calcium chloride solution (concentration is 0.3M) after 15mL filters, the sodium carbonate liquor that adds the 0.3M after 15mL filters to this solution, in being the electromagnetic agitation machine of 1000rpm, rotating speed reacts 20s, open electromagnetic agitation after leaving standstill 20min, reaction solution is mixed, get 5mL and add in the centrifuge tube, get 4 pipes altogether.Is to spend deionised water behind the centrifugal 3min in the centrifuge of 3000rpm with 4 pipe suspensions at rotating speed, and secondary is operated in repeated centrifugation-washing.
The Tris-HCl cushioning liquid of preparation 0.02M, regulating its pH is 7.5, the dopamine solution of preparation 5mg/mL.With dopamine solution join stir 24h in the calcium carbonate after the cleaning after, the centrifugal collection solids of 3000rpm 3min add 5mL Tris-HCl cushioning liquid to each centrifuge tube, vibration disperses particle again.At rotating speed is centrifugal 3min in the centrifuge of 3000rpm, and Tris-HCl cushioning liquid is washed, and repeated centrifugation-buffer solution is washed secondary, and supernatant is removed in the back.Disodium ethylene diamine tetraacetate (EDTA) solution of preparation 0.1M adds 5mL in every centrifuge tube, oscillating reactions 30min, and the centrifugal 3min of 3000rpm removes supernatant.Above process repeats 3-5 time, thoroughly to remove calcium carbonate, gets micro-capsule after the stoning, with water washing three times, thereby makes the poly-dopamine micro-capsule that particle diameter is 3-5 μ m.(please revise for several sections like this back)
Embodiment 3
The kayexalate (PSS) of 36mg is dissolved in the calcium chloride solution (concentration is 0.4M) after 15mL filters, the sodium carbonate liquor that adds the 0.4M after 15mL filters to this solution, in being the electromagnetic agitation machine of 1000rpm, rotating speed reacts 30s, open electromagnetic agitation after closing electromagnetic agitation and leaving standstill 25min, reaction solution is stirred, get 5mL and add in the centrifuge tube, get 4 pipes altogether.With 4 pipe suspensions rotating speed be in the centrifuge of 3000rpm behind the centrifugal 3min with the deionized water washing, secondary is operated in repeated centrifugation-washing.
The Tris-HCl cushioning liquid of preparation 0.1M, regulating its PH is 8.5, the dopamine solution of preparation 8mg/mL.With dopamine solution join stir 8h in the calcium carbonate after the cleaning after, the centrifugal collection solids of 3000rpm 3min add 5mL Tris-HCl cushioning liquid to each centrifuge tube, rock particle is disperseed again.At rotating speed is centrifugal 3min in the centrifuge of 3000rpm, and Tris-HCl cushioning liquid is washed, and repeated centrifugation-buffer solution is washed secondary, and supernatant is removed in the back.Disodium ethylene diamine tetraacetate (EDTA) solution of preparation 0.2M adds 5mL in every centrifuge tube, concussion reaction 30min, and the centrifugal 3min of 3000rpm removes supernatant.Above process repeats 3-5 time, thoroughly to remove calcium carbonate, gets micro-capsule after the stoning, and with water washing three times, just can make particle diameter is the poly-dopamine micro-capsule of 3-5 μ m.
Embodiment 4
The kayexalate (PSS) of 42mg is dissolved in the calcium chloride solution (concentration is 0.5M) after 15mL filters, the sodium carbonate liquor that adds the 0.5M after 15mL filters to this solution, in being the electromagnetic agitation machine of 1000rpm, rotating speed reacts 25s, open electromagnetic agitation after closing electromagnetic agitation and leaving standstill 30min, reaction solution is stirred, get 5mL and add in the centrifuge tube, get 4 pipes altogether.With 4 pipe suspensions rotating speed be in the centrifuge of 3000rpm behind the centrifugal 3min with the deionized water washing, secondary is operated in repeated centrifugation-washing.
The Tris-HCl cushioning liquid of preparation 0.05M, regulating its PH is 9.0, the dopamine solution of preparation 10mg/mL.With dopamine solution join stir 6h in the calcium carbonate after the cleaning after, the centrifugal collection solids of 3000rpm 3min add 5mL Tris-HCl cushioning liquid to each centrifuge tube, rock particle is disperseed again.At rotating speed is centrifugal 3min in the centrifuge of 3000rpm, and Tris-HCl cushioning liquid is washed, and repeated centrifugation-buffer solution is washed secondary, and supernatant is removed in the back.Disodium ethylene diamine tetraacetate (EDTA) solution of preparation 0.5M adds 5mL in every centrifuge tube, concussion reaction 30min, and the centrifugal 3min of 3000rpm removes supernatant.Above process repeats 3-5 time, thoroughly to remove calcium carbonate, gets micro-capsule after the stoning, and with water washing three times, just can make particle diameter is the poly-dopamine micro-capsule of 3-5 μ m.
Comparative Examples 1
The kayexalate (PSS) of 50mg is dissolved in the calcium chloride solution (concentration is 0.33M) after 15mL filters, the sodium carbonate liquor that adds the 0.33M after 15mL filters to this solution, in being the electromagnetic agitation machine of 1000rpm, rotating speed reacts 30s, open electromagnetic agitation after closing electromagnetic agitation and leaving standstill 30min, reaction solution is stirred, get 5mL and add in the centrifuge tube, get 4 pipes altogether.With four pipe suspensions rotating speed be in the centrifuge of 3000rpm behind the centrifugal 3min with the deionized water washing, secondary is operated in repeated centrifugation-washing.
The Tris-HCl cushioning liquid of preparation 0.01M, regulating its PH is 8.5.With Tris-HCl cushioning liquid join stir 6h in the calcium carbonate after the cleaning after, the centrifugal collection solids of 3000rpm 3min add 5mLTris-HCl cushioning liquid to each centrifuge tube, rock particle is disperseed again.At rotating speed is centrifugal 3min in the centrifuge of 3000rpm, and Tris-HCl cushioning liquid is washed, and repeated centrifugation-buffer solution is washed secondary, and supernatant is removed in the back.

Claims (2)

1. a poly-dopamine micro-capsule is characterized in that it is is template with the calcium carbonate microparticle, and dopamine is a raw material, is to be prepared in 0.1: 1~10: 1 to form processing step according to the quality proportioning of dopamine and calcium carbonate template:
Contain the calcium chloride solution of kayexalate (PSS) and the calcium carbonate CaCO that sodium carbonate liquor prepared in reaction PSS mixes 3(PSS) colloidal particles, CaCO 3Compound with PSS, be expressed as: CaCO 3(PSS);
This particulate is disperseed with the dissolving of Tris-HCl cushioning liquid, and add dopamine, at CaCO 3(PSS) microparticle surfaces adsorbs dopamine and makes the dopamine auto polymerization obtain the particulate of nucleocapsid structure;
The particulate of nucleocapsid structure and disodium ethylene diamine tetraacetate (EDTA) solution stirring reaction, water washing, centrifugation; Repeat above process, remove calcium carbonate and derive from the poly-dopamine micro-capsule that assembles.
2. the preparation method of a poly-dopamine micro-capsule is characterized in that it may further comprise the steps:
1) compound concentration is the calcium chloride solution of 0.2~0.5M, and to wherein adding kayexalate (PSS), making its concentration is 2~3mg/mL; The sodium carbonate liquor of molar concentrations such as preparation and calcium chloride, after filtering respectively, respectively get 15~25mL calcium chloride solution and isopyknic sodium carbonate liquor, under the rotating speed of 1000~1200rpm, sodium carbonate liquor is added in the calcium chloride solution, reaction 15~30s, leave standstill 15~30min, obtain containing the dispersion soln of carbonic acid calcium precipitate;
2) be centrifugal 3min in the centrifuge of 3000rpm with the gained dispersion soln at rotating speed, wash with water after centrifugal, repeated centrifugation-water-washing process secondary, supernatant is removed in the back, CaCO 3(PSS) particulate;
3) compound concentration is the Tris-HCl cushioning liquid of 0.01~0.1M, and regulating its PH is 6.0~10.0;
4) dopamine is dissolved in the Tris-HCl cushioning liquid for preparing, is made into the solution of 0.2~20mg/mL;
5) with Tris-HCl cushioning liquid washed twice CaCO 3(PSS) particulate, particle concentration are 1% (w/w), and be centrifugal, and product adds the dopamine solution of step 4), makes CaCO 3(PSS) disperse stirring at room 3~48h again; Centrifugation repeats with Tris-HCl cushioning liquid washed twice;
7) with the EDTA solution washing of 0.05~0.5M, the 3000rpm centrifugation repeats 3-5 time, thoroughly removes calcium carbonate, gets micro-capsule after the stoning, with water washing three times, prepares micro-capsule.
CN 201010275929 2010-09-09 2010-09-09 Polydopamine microcapsules and preparation method thereof Pending CN101966441A (en)

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CN109394701B (en) * 2018-11-14 2021-04-06 温州大学 Biomedical material for treating gastric ulcer and preparation method thereof
CN109913441A (en) * 2019-01-31 2019-06-21 北京化工大学 A kind of method of polymer microcapsule embedding immobilized enzyme
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CN117123197A (en) * 2023-09-25 2023-11-28 中南大学 Adsorbent with efficient water purifying capacity and preparation method and application thereof
CN117123197B (en) * 2023-09-25 2024-04-02 中南大学 Adsorbent with efficient water purifying capacity and preparation method and application thereof

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Application publication date: 20110209