CN105418959A - Preparation method of protamine-silicon oxide porous hybridization micro-capsules - Google Patents
Preparation method of protamine-silicon oxide porous hybridization micro-capsules Download PDFInfo
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Abstract
The invention discloses a preparation method of protamine-silicon oxide porous hybridization micro-capsules. Calcium carbonate microspheres are adopted as a template, and protamine-silicon oxide hybridization micro-capsules are prepared in situ in agarose gel by means of a biomimetic mineralization method. The calcium carbonate microspheres are added into an agarose solution, and agarose molecules are assembled to form fiber on the calcium carbonate microspheres along with decrease of temperature to obtain the agarose gel with scattered calcium carbonate microspheres. Then, biomimetic mineralization is implemented on the surfaces of the calcium carbonate microspheres to form a protamine-silicon oxide hybridization capsule wall, and meanwhile the fiber on the surface of calcium carbonate is embedded into the protamine-silicon oxide hybridization capsule wall. Then, heating is performed to remove the agarose gel, and an ethylene diamine tetraacetic acid disodium solution is utilized for removing the calcium carbonate microspheres to obtain the protamine-silicon oxide porous hybridization micro-capsules. According to the preparation method, the prepared raw materials are cheap and easy to obtain, the preparation conditions are mild, the preparation technology is simple and easy to implement, and regulation of the microsphere morphology and the capsule wall structure can be achieved by changing the frequency of biomimetic mineralization in the preparation process.
Description
Technical field
The present invention relates to the preparation method of a kind of protamine-silicon oxide porous hybrid micro-capsule, belong to the technology of preparing of porous material.
Background technology
Hybridized microcapsule, owing to having unique nucleocapsid structure, hydridization cyst wall, high specific surface area and shorter mass transfer distance, has been widely used in the structure of new catalyst.Its hollow core kernel can be used for carrying active substance, and hydridization cyst wall can realize the exchange of material.At present, a series of chemistry and physico-chemical process, comprise LBL self-assembly, sol-gel, molecular self-assembling, biomimetic mineralization, Pickering emulsification, interfacial polymerization etc. and prepare for the design of hybridized microcapsule.But the cyst wall duct of hybridized microcapsule prepared by aforesaid method forms primarily of particle packing, and structure is comparatively fine and close, creates larger resistance to mass transfer.At present, the preparation method of porous material mainly contains hard template method and soft template method, but the removal of template needs to realize by calcining or extracting usually, and process is complicated, condition is harsh.Therefore, develop a kind of simple, gentle porous hybrid microcapsule preparation method and there is important value and active demand.
Summary of the invention
The object of the present invention is to provide the preparation method of protamine-silicon oxide porous hybrid micro-capsule.Raw materials of the present invention is cheap, be easy to get, and preparation is simple.
The preparation method of a kind of protamine-silicon oxide porous hybrid micro-capsule that the present invention proposes, comprises the following steps:
Step one, to concentration be 0.2 ~ 0.4M calcium chloride solution in add sodium polystyrene sulfonate, be made into the solution A that sodium polystyrene sulfonate concentration is 1 ~ 3mg/mL; The sodium carbonate solution of the volumetric molar concentrations such as preparation and calcium chloride solution, under 800 ~ 1200r/min rotating speed, sodium carbonate solution is poured into rapidly in isopyknic solution A, reaction 25 ~ 30s, leaves standstill 8 ~ 10min, centrifugation under the rotating speed of 3000r/min, deionized water wash is used after removing supernatant liquor, repeated centrifugation-washing, to supernatant liquor not containing PSS, obtains the calcium carbonate microspheres of sodium polystyrene sulfonate doping;
Step 2, Xiang Shuizhong add the agarose of certain mass, after heating for dissolving, are made into the solution B that agarose concentration is 1% ~ 3%w/v; The calcium carbonate microspheres of sodium polystyrene sulfonate doping obtained for step one is added in solution B, mixes, naturally cooling, obtain the sepharose of the calcium carbonate microspheres being dispersed with sodium polystyrene sulfonate doping;
Step 3, compound concentration 1-3mg/mL are protamine solution; Compound concentration is the sodium silicate solution of 0.01 ~ 0.03M, and the pH of regulator solution is 7.0 ~ 8.0;
Step 4, first the sepharose that step 2 obtains is dipped into 5-15min in the obtained protamine solution of step 3, is dipped in deionized water after taking-up and cleans; Then, the sepharose subsequently after this cleaning is dipped into 5-15min in the obtained sodium silicate solution of step 3, is dipped in water after taking-up and cleans; Operation steps 41 ~ 2 times;
Step 5, the heating for dissolving sepharose after step 4 process, centrifugation under the rotating speed of 3000r/min, removes supernatant liquor, uses deionized water repeated washing, thoroughly remove agarose, retains microballoon;
Step 6, preparation disodium ethylene diamine tetraacetate concentration are the solution C of 0.03 ~ 0.05M, and the pH of regulator solution C is 5.0 ~ 6.0; According to mass ratio 20:1 by solution C and step 5 thus obtained microsphere Homogeneous phase mixing, rock 5 ~ 10min; Centrifugation under the rotating speed of 3000r/min, removes supernatant liquor, repeats above-mentioned centrifugal separation processes, thoroughly to remove calcium carbonate; Afterwards, with deionized water wash, repeated centrifugation-water washing process, to supernatant liquor not containing disodium ethylene diamine tetraacetate, obtains protamine-silicon oxide porous hybrid micro-capsule.
Compared with prior art, the preparation method of a kind of protamine-silicon oxide porous hybrid micro-capsule that the present invention proposes, raw materials is cheap, be easy to get, preparation condition is gentle, preparation is simple, by changing the number of times of biomimetic mineralization in preparation process, the regulation and control of micro-capsule pattern and cyst wall structure can be realized.
Accompanying drawing explanation
Fig. 1 is scanning electron microscope (SEM) photo of protamine-silicon oxide porous hybrid micro-capsule prepared by embodiment 1;
Fig. 2 is scanning electron microscope (SEM) photo of protamine-silicon oxide porous hybrid micro-capsule prepared by embodiment 2;
Fig. 3 is scanning electron microscope (SEM) photo of protamine-silicon oxide hybridized microcapsule prepared by comparative example 1;
Fig. 4 is scanning electron microscope (SEM) photo of protamine-silicon oxide hybridized microcapsule prepared by comparative example 2.
Embodiment
Be described in further detail technical solution of the present invention below in conjunction with the drawings and specific embodiments, described specific embodiment only explains the present invention, not in order to limit the present invention.
The invention discloses the preparation method of a kind of protamine-silicon oxide porous hybrid micro-capsule, be template with calcium carbonate microspheres, utilize the method for biomimetic mineralization, prepared protamine-silicon oxide hybridized microcapsule at sepharose situ.Calcium carbonate microspheres joins in agarose solution, and along with the reduction of temperature, agarose molecules forms fiber in calcium carbonate microspheres assembling, obtains the sepharose being dispersed with calcium carbonate microspheres.Subsequently, implement biomimetic mineralization on calcium carbonate microspheres surface, define protamine-silicon oxide hydridization cyst wall, the embedded fiber of calcium carbonate surface has been arrived in protamine-silicon oxide hydridization cyst wall simultaneously.Remove sepharose with post-heating, utilize disodium ethylene diamine tetra-acetic acid solution to remove calcium carbonate microspheres, obtain protamine-silicon oxide porous hybrid micro-capsule.
Embodiment 1
Step one, to concentration be 0.3M calcium chloride solution in add sodium polystyrene sulfonate (PSS), be made into the solution A that PSS concentration is 3mg/mL; The sodium carbonate solution of the volumetric molar concentrations such as preparation and calcium chloride solution, under 800r/min rotating speed, sodium carbonate solution is poured into rapidly in isopyknic solution A, reaction 30s, leaves standstill 10min, centrifugation under the rotating speed of 3000r/min, deionized water wash is used after removing supernatant liquor, repeated centrifugation-washing, to supernatant liquor not containing PSS, obtains the calcium carbonate microspheres (PSS-dopedCaCO of sodium polystyrene sulfonate doping
3microballoon);
Step 2, Xiang Shuizhong add the agarose of certain mass, after heating for dissolving, are made into the solution B that agarose concentration is 1%w/v; By PSS-dopedCaCO
3microballoon adds in solution B, mixes, naturally cooling, obtains being dispersed with PSS-dopedCaCO
3the sepharose of microballoon;
Step 3, compound concentration 3mg/mL are protamine solution; Compound concentration is the sodium silicate solution of 0.03M, and the pH of regulator solution is 7.0;
Step 4, sepharose is dipped into 15min in protamine solution, sepharose is dipped in deionized water cleans subsequently; By 15min in soak to sodium silicate solution, sepharose is dipped in water cleans subsequently;
Step 5, heating for dissolving sepharose, centrifugation under the rotating speed of 3000r/min, removes supernatant liquor, uses deionized water repeated washing, thoroughly to remove agarose;
Step 6, preparation disodium ethylene diamine tetraacetate (EDTA) concentration are the solution C of 0.05M, and the pH of regulator solution C is 6.0; According to mass ratio 20:1 by solution C and step 5 thus obtained microsphere Homogeneous phase mixing, rock 10min; Centrifugation under the rotating speed of 3000r/min, removes supernatant liquor, repeats above-mentioned step with centrifugal separation, thoroughly to remove calcium carbonate; With deionized water wash, repeated centrifugation-washing, to supernatant liquor not containing EDTA, obtains protamine-silicon oxide porous hybrid micro-capsule.Obtain the hybridized microcapsule that particle diameter is 4-6 micron, rich surface contains porous, after freeze-drying, micro-capsule subsides.Fig. 1 is embodiment
1scanning electron microscope (SEM) photo of the protamine ~ silicon oxide porous hybrid micro-capsule of preparation.
Embodiment 2
The present embodiment 2 is substantially identical with embodiment 1 step, with its unlike: to the process operation 2 times of step 4, finally obtain particle diameter be 4-6 micron, rich surface containing the protamine-silicon oxide hybridized microcapsule of porous, after freeze-drying, micro-capsule keeps spherical.Fig. 2 is scanning electron microscope (SEM) photo of protamine-silicon oxide porous hybrid micro-capsule prepared by embodiment 2.
Comparative example 1
Step one, to concentration be 0.3M calcium chloride solution in add sodium polystyrene sulfonate (PSS), be made into the solution A that PSS concentration is 3mg/mL; The sodium carbonate solution of the volumetric molar concentrations such as preparation and calcium chloride solution, under 800r/min rotating speed, sodium carbonate solution is poured into rapidly in isopyknic solution A, reaction 30s, leaves standstill 10min, centrifugation under the rotating speed of 3000r/min, deionized water wash is used after removing supernatant liquor, repeated centrifugation-washing, to supernatant liquor not containing PSS, obtains the calcium carbonate microspheres (PSS-dopedCaCO of sodium polystyrene sulfonate doping
3microballoon);
Step 2, compound concentration 3mg/mL are protamine solution; Compound concentration is the sodium silicate solution of 0.03M, and the pH of regulator solution is 7.0;
Step 3, according to mass ratio 20:1 by protamine solution and PSS-dopedCaCO
3microballoon mixes, and rocks 10min; Centrifugation under the rotating speed of 3000r/min, removes supernatant liquor, washes-centrifugal 2 ~ 3 times; The microballoon obtained is mixed with sodium silicate solution, rocks 10min; Centrifugation under the rotating speed of 3000r/min, removes supernatant liquor, washes-centrifugal 2 ~ 3 times;
Step 4, preparation disodium ethylene diamine tetraacetate (EDTA) concentration are the solution C of 0.05M, and the pH of regulator solution C is 6.0; According to mass ratio 20:1 by solution C and step 3 thus obtained microsphere Homogeneous phase mixing, rock 10min; Centrifugation under the rotating speed of 3000r/min, removes supernatant liquor, repeats above-mentioned steps, thoroughly to remove calcium carbonate; With deionized water wash, repeated centrifugation-washing, to supernatant liquor not containing EDTA, obtains protamine-silicon oxide porous hybrid micro-capsule.Obtain the hybridized microcapsule that particle diameter is 4-6 micron, surface does not have obvious duct, after freeze-drying, micro-capsule subsides.Fig. 3 is scanning electron microscope (SEM) photo of protamine-silicon oxide hybridized microcapsule prepared by comparative example 1.
Comparative example 2
This comparative example 2 is substantially identical with comparative example 1 step, with its unlike: the process that repeating step three describes once, finally obtains protamine-silicon oxide hybridized microcapsule that particle diameter is 4-6 micron, surface does not have obvious duct, after freeze-drying micro-capsule keep spherical.Fig. 4 is scanning electron microscope (SEM) photo of protamine-silicon oxide hybridized microcapsule prepared by comparative example 2.
To sum up, by above-described embodiment and comparative example, find successfully to have prepared the protamine-silicon oxide hybridized microcapsule with hierarchical porous structure in gel; In addition, the number of times undertaken by step 3 in step 4 in regulation and control embodiment and comparative example can realize the regulation and control of hybridized microcapsule structure; And increase the number of times that in embodiment, in step 4 and comparative example, step 3 is carried out further, less on the impact of micro-capsule pore passage structure.
Claims (1)
1. a preparation method for protamine-silicon oxide porous hybrid micro-capsule, is characterized in that, comprise the following steps:
Step one, to concentration be 0.2 ~ 0.4M calcium chloride solution in add sodium polystyrene sulfonate, be made into the solution A that sodium polystyrene sulfonate concentration is 1 ~ 3mg/mL; The sodium carbonate solution of the volumetric molar concentrations such as preparation and calcium chloride solution, under 800 ~ 1200r/min rotating speed, sodium carbonate solution is poured into rapidly in isopyknic solution A, reaction 25 ~ 30s, leaves standstill 8 ~ 10min, centrifugation under the rotating speed of 3000r/min, deionized water wash is used after removing supernatant liquor, repeated centrifugation-washing, to supernatant liquor not containing sodium polystyrene sulfonate, obtains the calcium carbonate microspheres of sodium polystyrene sulfonate doping;
Step 2, Xiang Shuizhong add the agarose of certain mass, after heating for dissolving, are made into the solution B that agarose concentration is 1% ~ 3%w/v; The calcium carbonate microspheres of sodium polystyrene sulfonate doping obtained for step one is added in solution B, mixes, naturally cooling, obtain the sepharose of the calcium carbonate microspheres being dispersed with sodium polystyrene sulfonate doping;
Step 3, compound concentration 1-3mg/mL are protamine solution; Compound concentration is the sodium silicate solution of 0.01 ~ 0.03M, and the pH of regulator solution is 7.0 ~ 8.0;
Step 4, first the sepharose that step 2 obtains is dipped into 5-15min in the obtained protamine solution of step 3, is dipped in deionized water after taking-up and cleans; Then, the sepharose subsequently after this cleaning is dipped into 5-15min in the obtained sodium silicate solution of step 3, is dipped in water after taking-up and cleans; Operation steps 41 ~ 2 times;
Step 5, the heating for dissolving sepharose after step 4 process, centrifugation under the rotating speed of 3000r/min, removes supernatant liquor, uses deionized water repeated washing, thoroughly remove agarose, retains microballoon;
Step 6, preparation disodium ethylene diamine tetraacetate concentration are the solution C of 0.03 ~ 0.05M, and the pH of regulator solution C is 5.0 ~ 6.0; According to mass ratio 20:1 by solution C and step 5 thus obtained microsphere Homogeneous phase mixing, rock 5 ~ 10min; Centrifugation under the rotating speed of 3000r/min, removes supernatant liquor, repeats above-mentioned centrifugal separation processes, thoroughly to remove calcium carbonate; Afterwards, with deionized water wash, repeat above-mentioned centrifugal-water washing process, to supernatant liquor not containing disodium ethylene diamine tetraacetate, obtain protamine-silicon oxide porous hybrid micro-capsule.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108751126A (en) * | 2018-06-08 | 2018-11-06 | 陕西师范大学 | The method for preparing three-dimensional self-supporting film based on lysozyme nano thin-film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101693181A (en) * | 2009-10-15 | 2010-04-14 | 天津大学 | Silicon oxide and protamine microcapsule and preparation method thereof |
| CN103159257A (en) * | 2013-03-22 | 2013-06-19 | 中国石油天然气集团公司 | Biomimetic preparation method of hollow titanium dioxide nanospheres in sepharose gel |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101693181A (en) * | 2009-10-15 | 2010-04-14 | 天津大学 | Silicon oxide and protamine microcapsule and preparation method thereof |
| CN103159257A (en) * | 2013-03-22 | 2013-06-19 | 中国石油天然气集团公司 | Biomimetic preparation method of hollow titanium dioxide nanospheres in sepharose gel |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108751126A (en) * | 2018-06-08 | 2018-11-06 | 陕西师范大学 | The method for preparing three-dimensional self-supporting film based on lysozyme nano thin-film |
| CN108751126B (en) * | 2018-06-08 | 2019-10-25 | 陕西师范大学 | The method for preparing three-dimensional self-supporting film based on lysozyme nano thin-film |
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