CN101693181B - Silicon oxide and protamine microcapsule and preparation method thereof - Google Patents
Silicon oxide and protamine microcapsule and preparation method thereof Download PDFInfo
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- CN101693181B CN101693181B CN2009100708090A CN200910070809A CN101693181B CN 101693181 B CN101693181 B CN 101693181B CN 2009100708090 A CN2009100708090 A CN 2009100708090A CN 200910070809 A CN200910070809 A CN 200910070809A CN 101693181 B CN101693181 B CN 101693181B
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Abstract
The invention relates to a silicon oxide and protamine microcapsule and a preparation method thereof. The silicon oxide and protamine microcapsule is prepared by using a calcium carbonate particulate as a template and sodium silicate and protamine as raw materials, wherein the mass ration of the sodium silicate to the protamine is 1:1-7:1. The preparation method comprises the following steps: firstly preparing the calcium carbonate particulate with negative charges as the template; interacting the protamine with positive charges and the calcium carbonate particulate with negative charges and alternately absorbing to the template; inducing the forming of silicon oxide by using the biomineralizing function of the protamine when three to five double-layers are generated on the template; removing the inner core of the calcium carbonate by EDTA-2Na. The invention is gentle in reaction conditions during the preparation of the silicon oxide and protamine microcapsule. The prepared silicon oxide and protamine microcapsule has the advantages of gentle reaction condition, size controllability, good stability, and excellent repeatability.
Description
Technical field
The present invention relates to a kind of silicon oxide and protamine microcapsule and preparation method thereof, specifically is the method for preparing that silicon oxide and protamine hydridization prepare microcapsule.
Background technology
Nowadays microcapsule is used to the field such as embedding protection and gene transfection of microreactor, pharmaceutical carrier, cell and enzyme more and more.Traditional microcapsule preparation method mainly contains three kinds: (1) chemical method, chemical method are 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 these class methods can access the microcapsule 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 capsule core material and capsule material, add another kind of material or adopt other appropriate method that the dissolubility 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 microcapsule adhesion, accumulative problem, and condition is difficult to control etc. in the technical process.(3) physics and Mechanical Method, these class methods mainly are the physical changes through microcapsule capsule wall material, carry out the microcapsule preparation in conjunction with certain mechanical processing tools.The method is comparatively difficult to the control of the physicochemical properties of microcapsule.
Adopt the microcapsule of covalent layer-by-layer self-assembling technique preparation then to have characteristics such as high-modulus, high stability, wherein be can be to the physical and chemical performance accuracy controlling on surface for biggest advantage.At first be the regulation and control to film thickness, the regulation and control of thickness can be regulated through several aspects: the assembled material that (1) is selected for use; (2) number of plies of assembling can be followed the tracks of assembling process through elliptical polarization technology or ultraviolet etc., and the thickness of film can be linear growth along with the increase of the number of plies; (3) assembling condition, under the different assembling conditions, the thickness that obtains is often different.For example the ionic strength in the solution can influence the thickness of every tunic of assembling strongly; Temperature and solvent polarity etc. are all influential to thickness.Through with upper type, can be at several dusts accuracy controlling thickness in the scope of several nanometers.Next is the regulation and control to the surface chemistry performance.The material that can be used for static self assembly layer by layer is except that synthetic polyelectrolyte; Other charged species can be used for constructing multilayer film like natural macromolecular (like protein and nucleic acid), virus, inorganic nano-particle (comprise receive gold, quantum dot, fullerene, CNT etc.), resin-like macromole and multivalence organic ion such as dye molecule etc.
Summary of the invention
The object of the present invention is to provide a kind of silicon oxide and protamine microcapsule and preparation method thereof, is the preparation that raw material carries out microcapsule with silicon oxide-protamine.Through at interval adsorbing sodium silicate and protamine makes sodium silicate and protamine adsorb each other through electrostatic interaction; In the assembling process under the inducing action of protamine sodium silicate can generate silicon oxide, thereby reach the purpose of formation by silicon oxide and protamine layer assembly microcapsule.Preparation condition of the present invention is gentle, and the preparation raw material is easy to get, and preparation is simple, and the thickness through the assembling of the different numbers of plies being regulated and control film is also than being easier to.
A kind of silicon oxide provided by the invention and protamine microcapsule are to be template with the calcium carbonate microparticle, and sodium silicate and protamine are raw material, are to be prepared from processing step in 1: 1～7: 1 according to the quality proportioning of sodium silicate and protamine:
The calcium chloride solution and the adulterated calcium carbonate CaCO of sodium carbonate liquor prepared in reaction PSS that contain kayexalate (PSS)
3(PSS) colloidal particles; CaCO
3Compound with PSS, be expressed as: CaCO
3(PSS).
This microgranule is disperseed with the dissolving of protamine solution, and hatching is assembled into the particle of protamine layer, and then continues to disperse with sodium silicate solution hatching; Repeat above process, at CaCO
3(PSS) microparticle surfaces alternately adsorbs the colloidal particle that protamine and sodium silicate obtain nucleocapsid structure;
The colloidal particle of nucleocapsid structure and the reaction of EDTA solution stirring, water washing, centrifugalize; Repeat above process, remove calcium carbonate and derive from silicon oxide and the protamine microcapsule that assembles, store subsequent use in the water.
The step that the method for preparing of a kind of silicon oxide provided by the invention and protamine microcapsule comprises:
1) configuration concentration is the calcium chloride solution of 0.2～0.5mol/l, and to wherein adding kayexalate (PSS), making its concentration is 2～3mg/l; The sodium carbonate liquor of molar concentrations such as configuration 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, reacted 15～25 seconds; Left standstill 15～25 minutes, and obtained the dispersion soln of carbonated calcium deposit.
2) be in the centrifuge of 3000rpm centrifugal three minutes with the gained dispersion soln at rotating speed, centrifugal back is with washing, repeated centrifugation-water-washing process secondary, supernatant is removed in the back, CaCO
3(PSS) microgranule.
3) configuration concentration is the sodium silicate solution of 0.02～0.04mol/l, and using hydrochloric acid to regulate its PH is 7.0～8.0.
4) protamine is dissolved in the NaCl solution of 0.5mol/l, is made into the solution of 0.5～2.0mg/mL, using hydrochloric acid and sodium hydroxide to regulate its PH is 6.5～7.0.
5) twice CaCO of water washing
3(PSS) microgranule, particle concentration is 1%w/w, and is centrifugal, product adds the protamine solution of step 4), makes CaCO
3(PSS) disperse again, hatching 15～30min, during slight vibration centrifuge tube calcium carbonate particle is disperseed; Centrifugalize repeats twice of water washing.
6) microgranule joins the sodium silicate solution of step 3); Particle is disperseed again; Hatching 15～30min, during slightly vibration, be centrifugal in the centrifuge of 3000rpm at rotating speed then; Repeat to wash twice, make the microcapsule that one deck protamine, one deck silicon oxide assemble on the surface of calcium carbonate microspheres.
7) repeating step 5) and step 6) at least twice, make protamine and sodium silicate and adsorb at interval and form the microcapsule that the covalency self assembly forms.The ratio in each step is 1: 1.
8) with EDTA solution and the water washing of 0.05～0.15mol/l, the 3000rpm centrifugalize repeats 3-5 time, thoroughly removes calcium carbonate, gets microcapsule after the enucleation, and with water washing three times, the microcapsule preparation so far finishes.
The invention provides a kind of silicon oxide and protamine microcapsule and preparation method thereof.At first preparation have negative charge calcium carbonate microparticle as template, positively charged protamine and electronegative sodium silicate through electrostatic interaction, are adsorbed on the template alternately.After three to five bilayers are arranged on the template, utilize the biomineralization function of protamine to induce the formation of silicon oxide, remove the calcium carbonate kernel with disodiumedetate at last.The present invention prepares raw material and is easy to get, and preparation is simple, through to assembling the different numbers of plies to the THICKNESS CONTROL of film also than being easier to microcapsule controlled amount, good stability, favorable repeatability.
Description of drawings
Fig. 1: the electron scanning micrograph in the Comparative Examples 1 after one deck microcapsule enucleation of preparation.
Fig. 2: the electron micrograph in the Comparative Examples 2 after three layers of microcapsule enucleation of preparation.
Fig. 3: embodiment 2 surperficial zeta potentials and number of plies graph of a relation.
The adsorption/desorption curve and the graph of pore diameter distribution of Fig. 4: embodiment 2 microcapsules.
The specific embodiment
Embodiment 1
The kayexalate (PSS) of 50mg is dissolved in the calcium chloride solution (concentration is 0.33mol/l) after 15ml filters; The sodium carbonate liquor that adds the 0.33mol/l after 15ml filters to this solution; In rotating speed is the electromagnetic agitation machine of 1000rpm, react 20s, close electromagnetic agitation and leave standstill after 15 minutes and open electromagnetic agitation, 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 after centrifugal 3 minutes with the deionized water washing, secondary is operated in repeated centrifugation-washing.
The sodium silicate solution of configuration 0.03mol/l, using hydrochloric acid to regulate its PH is 8; The protamine solution of configuration 2mg/ml, and to wherein adding 5844mg sodium chloride and regulating between its PH to 6.5-7.0 with hydrochloric acid and sodium hydroxide.
Add the protamine solution of 5ml 2mg/ml to each centrifuge tube, rock particle is disperseed again, hatching 15min, during slightly vibration, be in the centrifuge of 3000rpm centrifugal three minutes at rotating speed, washing, repeated centrifugation-washing secondary, back removal supernatant.
Add the 5ml sodium silicate solution to each centrifuge tube, rock particle is disperseed again, hatching 15min, during slightly vibration, be in the centrifuge of 3000rpm centrifugal three minutes at rotating speed, washing, repeated centrifugation-washing secondary, back removal supernatant.
Repeating step adds protamine and adds sodium silicate step 3 time.The EDTA solution of configuration 0.1mol/l 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 microcapsule after the enucleation, with water washing three times, just can make the protamine/silicon oxide LBL microcapsule by 3 bilayers.
The kayexalate (PSS) of 50mg is dissolved in the calcium chloride solution (concentration is 0.33mol/l) after 15ml filters; The sodium carbonate liquor that adds the 0.33mol/l after 15ml filters to this solution; In rotating speed is the electromagnetic agitation machine of 1000rpm, react 20s, close electromagnetic agitation and left standstill 15 minutes.Electromagnetic agitation is opened in the back, and reaction solution is stirred, and gets 5ml and adds in the centrifuge tube, gets 4 pipes altogether.With four pipe suspensions rotating speed be in the centrifuge of 3000rpm after centrifugal 3 minutes with the deionized water washing, secondary is operated in repeated centrifugation-washing.
The sodium silicate solution of configuration 0.03mol/, using hydrochloric acid to regulate its PH is 8; The protamine solution of configuration 2mg/ml, and to wherein adding 5844mg sodium chloride and regulating between its PH to 6.5-7.0 with hydrochloric acid and sodium hydroxide.
Add the protamine solution of 5ml 2mg/ml to each centrifuge tube, rock particle is disperseed again, hatching 15min, during slightly vibration, be in the centrifuge of 3000rpm centrifugal three minutes at rotating speed, washing, repeated centrifugation-washing secondary, back removal supernatant.
Add the 5ml sodium silicate solution to each centrifuge tube, rock particle is disperseed again, hatching 15min, during slightly vibration, be in the centrifuge of 3000rpm centrifugal three minutes at rotating speed, washing, repeated centrifugation-washing secondary, back removal supernatant.
Repeating step adds protamine and adds sodium silicate step 5 time, and the EDTA solution of configuration 0.1mol/l adds 5ml in every centrifuge tube, concussion reaction 30min, and the centrifugal 3min of 3000rpm removes supernatant.Above process repeats 4 times, thoroughly to remove calcium carbonate, gets microcapsule after the enucleation, with water washing three times, just can make 5 double-deck protamines/silicon oxide LBL microcapsule.
Comparative Examples one
The kayexalate (PSS) of 50mg is dissolved in the calcium chloride solution (concentration is 0.33mol/l) after 15ml filters; The sodium carbonate liquor that adds the 0.33mol/l after 15ml filters to this solution; In rotating speed is the electromagnetic agitation machine of 1000rpm, react 20s, close electromagnetic agitation and left standstill 15 minutes.Electromagnetic agitation is opened in the back, and reaction solution is stirred, and gets 5ml and adds in the centrifuge tube, gets 4 pipes altogether.With four pipe suspensions rotating speed be in the centrifuge of 3000rpm after centrifugal 3 minutes with the deionized water washing, secondary is operated in repeated centrifugation-washing.
The polyelectrolyte PSS and the albumen that will have opposite charges are dissolved in respectively in the 0.5MNaCl solution, respectively are made into the solution of 2mg/mL, and regulating pH is about 7.0.
Get certain amount of CaCO
3(PSS) microgranule places centrifuge tube (particle concentration is about 1%w/w), the water washed twice, and the centrifugal 3min of each washing back 3000rpm is to remove supernatant.In centrifuge tube, add the as above protamine solution of preparation, make CaCO
3(PSS) disperse again, hatching 15min, during slight vibration centrifuge tube calcium carbonate particle is disperseed; The centrifugal supernatant that goes adds the water washing calcium carbonate particle, repeats twice.Add PSS solution then in the particle that is assembled with one deck protamine, particle disperseed again, hatching 15min, during slightly vibration, the centrifugal then supernatant that goes is washed twice.
Repeat above process, at CaCO
3(PSS) microparticle surfaces alternately adsorbs protamine and PSS, assembles the colloidal particle that obtains nucleocapsid structure behind 5 bilayers.The EDTA enucleation that adds 0.02M in the colloidal particle of above nucleocapsid structure, reaction 30min, the centrifugal 3min of 3000rpm removes supernatant.Above process repeats 4 times, thoroughly to remove calcium carbonate, just can make 5 double-deck protamine/PSS LBL microcapsule.
Comparative Examples two
The kayexalate (PSS) of 50mg is dissolved in the calcium chloride solution (concentration is 0.33mol/l) after 15ml filters; The sodium carbonate liquor that adds the 0.33mol/l after 15ml filters to this solution; In rotating speed is the electromagnetic agitation machine of 1000rpm, react 20s, close electromagnetic agitation and left standstill 15 minutes.Electromagnetic agitation is opened in the back, and reaction solution is stirred, and gets 5ml and adds in the centrifuge tube, gets 4 pipes altogether.With four pipe suspensions rotating speed be in the centrifuge of 3000rpm after centrifugal 3 minutes with the deionized water washing, secondary is operated in repeated centrifugation-washing.
The sodium silicate solution of preparation 0.03mol/, using hydrochloric acid to regulate its PH is 8; The protamine solution of configuration 2mg/ml, and to wherein adding 5844mg sodium chloride and regulating between its PH to 6.5-7.0 with hydrochloric acid and sodium hydroxide.
Add the protamine solution of 5ml 2mg/ml to each centrifuge tube, rock particle is disperseed again, hatching 15min, during slightly vibration, be in the centrifuge of 3000rpm centrifugal three minutes at rotating speed, washing, repeated centrifugation-washing secondary, back removal supernatant.
Add the 5ml sodium silicate solution to each centrifuge tube, rock particle is disperseed again, hatching 15min, during slightly vibration, be in the centrifuge of 3000rpm centrifugal three minutes at rotating speed, washing, repeated centrifugation-washing secondary, back removal supernatant.
The EDTA solution of preparation 0.1mol/l adds 5ml in every centrifuge tube, concussion reaction 30min, and the centrifugal 3min of 3000rpm removes supernatant.Above process repeats 4 times, thoroughly to remove calcium carbonate, gets microcapsule after the enucleation, with water washing three times, just can make 1 double-deck protamine/sodium silicate LBL microcapsule.
Claims (1)
1. the method for preparing of silicon oxide and protamine microcapsule; This microcapsule is to be template with the calcium carbonate microparticle; Sodium silicate and protamine are raw material, are to be prepared from 1: 1～7: 1 according to the quality proportioning of sodium silicate and protamine, it is characterized in that it is through following steps:
1) compound concentration is the calcium chloride solution of 0.2～0.5mol/l, and to wherein adding kayexalate (PSS), making its concentration is 2～3mg/l; 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, reacted 15～25 seconds; Left standstill 15～25 minutes, and obtained the dispersion soln of carbonated calcium deposit;
2) be in the centrifuge of 3000rpm centrifugal three minutes with the gained dispersion soln at rotating speed, centrifugal back is with washing, repeated centrifugation-water-washing process secondary, supernatant is removed in the back, CaCO
3/ PSS microgranule;
3) compound concentration is the sodium silicate solution of 0.02～0.04mol/l, and using hydrochloric acid to regulate its pH is 7.0～8.0;
4) protamine is dissolved in the NaCl solution of 0.5mol/l, is made into the solution of 0.5～2.0mg/mL, using hydrochloric acid and sodium hydroxide to regulate its pH is 6.5～7.0;
5) twice CaCO of water washing
3/ PSS microgranule, particle concentration is 1%w/w, and is centrifugal, product adds the protamine solution of step 4), makes CaCO
3/ PSS disperses again, hatching 15～30min, during slight vibration centrifuge tube calcium carbonate particle is disperseed; Centrifugalize repeats twice of water washing;
6) microgranule joins the sodium silicate solution of step 3); Particle is disperseed again; Hatching 15～30min, during slightly vibration, be centrifugal in the centrifuge of 3000rpm at rotating speed then; Repeat to wash twice, make the microcapsule that one deck protamine, one deck silicon oxide assemble on the surface of calcium carbonate microspheres;
7) repeating step 5) and step 6) at least twice, make protamine and sodium silicate and adsorb at interval and form the microcapsule that the covalency self assembly forms; The ratio in each step is 1: 1;
8) with EDTA solution and the water washing of 0.05～0.15mol/l, the 3000rpm centrifugalize repeats 3-5 time, thoroughly removes calcium carbonate, gets microcapsule after the enucleation, and with water washing three times, the microcapsule preparation finishes.
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| CN105396522B (en) * | 2015-12-09 | 2018-01-12 | 天津大学 | A kind of wall thickness is the preparation method of nano level PAH silica hybridized microcapsule |
| CN105418959B (en) * | 2015-12-09 | 2018-08-10 | 天津大学 | The preparation method of protamine-silica porous hybrid micro-capsule |
| CN105483113A (en) * | 2015-12-09 | 2016-04-13 | 天津大学 | Preparation method of efficient and recyclable biocatalyst |
| CN108079914B (en) * | 2017-12-13 | 2021-02-09 | 温州生物材料与工程研究所 | Method for preparing polyamine compound microcapsules by one-step method |
| CN108707597A (en) * | 2018-06-06 | 2018-10-26 | 安徽工程大学 | A kind of cured phenylalanine mutase and its curing and application |
| CN109054846B (en) * | 2018-06-20 | 2021-01-22 | 上海工程技术大学 | Preparation method of soil conditioner based on layer-by-layer self-assembled microspheres |
| CN113926401A (en) * | 2021-10-20 | 2022-01-14 | 上海应用技术大学 | Organic-inorganic composite microcapsule and preparation method thereof |
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| CN101429503A (en) * | 2008-12-04 | 2009-05-13 | 天津大学 | Silicon oxide-protamine-PSS hybridisation microcapsule and preparation method thereof |
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Non-Patent Citations (1)
| Title |
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| Yanjun Jiang.Preparation of Protamine-Titania Microcapsules Through Synergy Between Layer-by-layer Assembly and Biomimetic Mineralization.《Advanced Functional Materials》.2008,第19卷第151页第2节至第155页第4节. * |
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