CN105418959B - The preparation method of protamine-silica porous hybrid micro-capsule - Google Patents
The preparation method of protamine-silica porous hybrid micro-capsule Download PDFInfo
- Publication number
- CN105418959B CN105418959B CN201510902881.0A CN201510902881A CN105418959B CN 105418959 B CN105418959 B CN 105418959B CN 201510902881 A CN201510902881 A CN 201510902881A CN 105418959 B CN105418959 B CN 105418959B
- Authority
- CN
- China
- Prior art keywords
- solution
- protamine
- calcium carbonate
- ago
- gel
- 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
Abstract
The invention discloses a kind of preparation methods of protamine silica porous hybrid micro-capsule, and using calcium carbonate microspheres as template, using the method for biomimetic mineralization, protamine silica hybridized microcapsule has been prepared in situ in Ago-Gel.Calcium carbonate microspheres are added in agarose solution, and with the reduction of temperature, agarose molecules assemble to form fiber in calcium carbonate microspheres, have obtained the Ago-Gel for being dispersed with calcium carbonate microspheres.Then, implement biomimetic mineralization on calcium carbonate microspheres surface, form protamine oxidation silicon hybridization cyst wall, while the embedded fiber of calcium carbonate surface having been arrived in protamine oxidation silicon hybridization cyst wall.Then heating removal Ago-Gel removes calcium carbonate microspheres using disodium ethylene diamine tetra-acetic acid solution, obtains protamine silica porous hybrid micro-capsule.The present invention prepares that raw material is cheap, is easy to get, and preparation condition is mild, and preparation is simple, by change biomimetic mineralization in preparation process number, it can be achieved that micro-capsule pattern and cyst wall structure regulation and control.
Description
Technical field
The present invention relates to a kind of preparation methods of protamine-silica porous hybrid micro-capsule, belong to the preparation of porous material
Technology.
Background technology
Hybridized microcapsule due to unique nucleocapsid, hydridization cyst wall, high specific surface area and shorter mass transfer distance,
It is widely used in the structure of new catalyst.Wherein hollow kernel can be used for carrying active substance, and object may be implemented in hydridization cyst wall
The exchange of matter.Currently, a series of chemically and physically chemical methodes, including it is LBL self-assembly, sol-gel, molecular self-assembling, imitative
It is prepared by the design that rawore, Pickering emulsifications, interfacial polymerization etc. have been used for hybridized microcapsule.But above method preparation is miscellaneous
The cyst wall duct for changing micro-capsule is mainly formed by particle packing, and structure is comparatively dense, produces larger resistance to mass tranfer.Currently, more
The preparation method of Porous materials mainly has hard template method and soft template method, but the removal of template is usually required by calcining or extracting
It realizes, process is complicated, condition is harsh.Therefore, a kind of simple, mild porous hybrid microcapsule preparation method of exploitation has important
Value and active demand.
Invention content
The purpose of the present invention is to provide the preparation methods of protamine-silica porous hybrid micro-capsule.The present invention prepares former
Material is cheap, is easy to get, and preparation is simple.
A kind of preparation method of protamine proposed by the present invention-silica porous hybrid micro-capsule, includes the following steps：
Step 1: kayexalate is added into the calcium chloride solution of a concentration of 0.2~0.4M, it is made into polystyrene
The solution A of a concentration of 1~3mg/mL of sodium sulfonate；It prepares and the sodium carbonate liquor of calcium chloride solution equimolar concentration, 800~
Under 1200r/min rotating speeds, sodium carbonate liquor is poured into rapidly in isometric solution A, reacts 25~30s, stands 8~10min,
It centrifuges, is washed with deionized after removing supernatant, repeated centrifugation-washing, until supernatant under the rotating speed of 3000r/min
Without PSS, the calcium carbonate microspheres of kayexalate doping are obtained；
Step 2: the agarose of certain mass is added into water, after heating for dissolving, it is 1%~3% to be made into agarose concentration
The solution B of w/v；The calcium carbonate microspheres that kayexalate made from step 1 is adulterated are added in solution B, are uniformly mixed,
Natural cooling obtains the Ago-Gel for being dispersed with the calcium carbonate microspheres of kayexalate doping；
Step 3: compound concentration 1-3mg/mL is protamine solution；Compound concentration is that the sodium metasilicate of 0.01~0.03M is molten
Liquid, the pH for adjusting solution are 7.0~8.0；
Step 4: Ago-Gel made from step 2 is dipped into 5- in protamine solution made from step 3 first
15min is dipped into deionized water after taking-up and cleans；Then, the subsequent Ago-Gel after the cleaning is dipped into step
5-15min in sodium silicate solution made from three is dipped into water after taking-up and cleans；Operating procedure 4 1~2 times；
Step 5: dissolving by heating through step 4 treated Ago-Gel, the centrifugation point under the rotating speed of 3000r/min
From removal supernatant is washed repeatedly with deionized water, thoroughly removes agarose, retains microballoon；
Step 6: preparing the solution C of a concentration of 0.03~0.05M of disodium ethylene diamine tetraacetate, the pH for adjusting solution C is
5.0~6.0；According to mass ratio 20：1 uniformly mixes solution C with step 5 thus obtained microsphere, rocks 5~10min；In 3000r/
It is centrifuged under the rotating speed of min, removes supernatant, above-mentioned centrifugal separation processes are repeated, thoroughly to remove calcium carbonate；Later, it uses
Deionized water is washed, repeated centrifugation-water-washing process, until supernatant is free of disodium ethylene diamine tetraacetate, obtains protamine-silica
Porous hybrid micro-capsule.
Compared with prior art, the preparation method of a kind of protamine proposed by the present invention-silica porous hybrid micro-capsule, system
Standby raw material is cheap, is easy to get, and preparation condition is mild, and preparation is simple, by time for changing biomimetic mineralization in preparation process
Count the regulation and control, it can be achieved that micro-capsule pattern and cyst wall structure.
Description of the drawings
Fig. 1 is scanning electron microscope (SEM) photo of protamine-silica porous hybrid micro-capsule prepared by embodiment 1；
Fig. 2 is scanning electron microscope (SEM) photo of protamine-silica porous hybrid micro-capsule prepared by embodiment 2；
Fig. 3 is scanning electron microscope (SEM) photo of protamine-silica hybridized microcapsule prepared by comparative example 1；
Fig. 4 is scanning electron microscope (SEM) photo of protamine-silica hybridized microcapsule prepared by comparative example 2.
Specific implementation mode
Technical solution of the present invention is described in further detail in the following with reference to the drawings and specific embodiments, it is described specific
Embodiment is only explained the present invention, is not intended to limit the invention.
The invention discloses a kind of preparation methods of protamine-silica porous hybrid micro-capsule, are to be with calcium carbonate microspheres
Protamine-silica hybridized microcapsule has been prepared in situ using the method for biomimetic mineralization in template in Ago-Gel.Calcium carbonate
Microballoon is added in agarose solution, and with the reduction of temperature, agarose molecules assemble to form fiber in calcium carbonate microspheres, obtain
It is dispersed with the Ago-Gel of calcium carbonate microspheres.Then, implement biomimetic mineralization on calcium carbonate microspheres surface, form smart egg
In vain-oxidation silicon hybridization cyst wall, while the embedded fiber of calcium carbonate surface having been arrived in protamine-oxidation silicon hybridization cyst wall.Then
Heating removal Ago-Gel, removes calcium carbonate microspheres using disodium ethylene diamine tetra-acetic acid solution, it is more to obtain protamine-silica
Hole hybridized microcapsule.
Embodiment 1
Step 1: kayexalate (PSS) is added into the calcium chloride solution of a concentration of 0.3M, it is made into PSS concentration
For the solution A of 3mg/mL；The sodium carbonate liquor with calcium chloride solution equimolar concentration is prepared, under 800r/min rotating speeds, by carbon
Acid sodium solution pours into rapidly in isometric solution A, reacts 30s, stands 10min, the centrifugation point under the rotating speed of 3000r/min
From, remove supernatant after be washed with deionized, repeated centrifugation-washing, until supernatant be free of PSS, obtain polystyrolsulfon acid
Calcium carbonate microspheres (the PSS-doped CaCO of natrium doping3Microballoon)；
Step 2: the agarose of certain mass is added into water, after heating for dissolving, it is 1%w/v's to be made into agarose concentration
Solution B；By PSS-doped CaCO3Microballoon is added in solution B, is uniformly mixed, natural cooling obtains being dispersed with PSS-doped
CaCO3The Ago-Gel of microballoon；
Step 3: compound concentration 3mg/mL is protamine solution；Compound concentration is the sodium silicate solution of 0.03M, is adjusted molten
The pH of liquid is 7.0；
Step 4: Ago-Gel is dipped into 15min in protamine solution, then by Ago-Gel be dipped into from
It is cleaned in sub- water；By 15min in soak to sodium silicate solution, then Ago-Gel is dipped into water and is cleaned；
Step 5: dissolving by heating Ago-Gel, centrifuged under the rotating speed of 3000r/min, removes supernatant, spend
Ionized water washes repeatedly, thoroughly to remove agarose；
Step 6: preparing the solution C of disodium ethylene diamine tetraacetate (EDTA) a concentration of 0.05M, the pH for adjusting solution C is
6.0；According to mass ratio 20：1 uniformly mixes solution C with step 5 thus obtained microsphere, rocks 10min；In the rotating speed of 3000r/min
Lower centrifugation removes supernatant, above-mentioned step with centrifugal separation is repeated, thoroughly to remove calcium carbonate；It is washed with deionized, weight
Multiple centrifugation-washing obtains protamine-silica porous hybrid micro-capsule until supernatant is free of EDTA.Obtain grain size be 4-6 microns,
Surface is rich in porous hybridized microcapsule, and micro-capsule collapses after freeze-drying.Fig. 1 is embodiment1Protamine~silica of preparation is porous miscellaneous
Change scanning electron microscope (SEM) photo of micro-capsule.
Embodiment 2
The present embodiment 2 and 1 step of embodiment are essentially identical, and what is be different from is：2 times is operated to the process of step 4, most
Grain size is obtained eventually and is rich in porous protamine-silica hybridized microcapsule for 4-6 microns, surface, and micro-capsule keeps spherical after freeze-drying.Figure
Scanning electron microscope (SEM) photo of the 2 protamine-silica porous hybrid micro-capsules prepared for embodiment 2.
Comparative example 1
Step 1: kayexalate (PSS) is added into the calcium chloride solution of a concentration of 0.3M, it is made into PSS concentration
For the solution A of 3mg/mL；The sodium carbonate liquor with calcium chloride solution equimolar concentration is prepared, under 800r/min rotating speeds, by carbon
Acid sodium solution pours into rapidly in isometric solution A, reacts 30s, stands 10min, the centrifugation point under the rotating speed of 3000r/min
From, remove supernatant after be washed with deionized, repeated centrifugation-washing, until supernatant be free of PSS, obtain polystyrolsulfon acid
Calcium carbonate microspheres (the PSS-doped CaCO of natrium doping3Microballoon)；
Step 2: compound concentration 3mg/mL is protamine solution；Compound concentration is the sodium silicate solution of 0.03M, is adjusted molten
The pH of liquid is 7.0；
Step 3: according to mass ratio 20：1 by protamine solution and PSS-doped CaCO3Microballoon mixes, and rocks 10min；
It is centrifuged under the rotating speed of 3000r/min, removes supernatant, washing-centrifugation 2~3 times；By obtained microballoon and sodium metasilicate
Solution mixes, and rocks 10min；It is centrifuged under the rotating speed of 3000r/min, removes supernatant, washing-centrifugation 2~3 times；
Step 4: preparing the solution C of disodium ethylene diamine tetraacetate (EDTA) a concentration of 0.05M, the pH for adjusting solution C is
6.0；According to mass ratio 20：1 uniformly mixes solution C with step 3 thus obtained microsphere, rocks 10min；In the rotating speed of 3000r/min
Lower centrifugation removes supernatant, repeats the above steps, thoroughly to remove calcium carbonate；It is washed with deionized, repeated centrifugation-
Washing obtains protamine-silica porous hybrid micro-capsule until supernatant is free of EDTA.Grain size is obtained for 4-6 microns, surface not have
There is the hybridized microcapsule in apparent duct, micro-capsule collapses after freeze-drying.Fig. 3 is protamine-silica hybridized microcapsule prepared by comparative example 1
Scanning electron microscope (SEM) photo.
Comparative example 2
This comparative example 2 and 1 step of comparative example are essentially identical, and what is be different from is：The process for repeating step 3 description is primary,
Finally obtain grain size does not have the protamine-silica hybridized microcapsule in apparent duct for 4-6 microns, surface, and micro-capsule is kept after freeze-drying
It is spherical.Fig. 4 is scanning electron microscope (SEM) photo of protamine-silica hybridized microcapsule prepared by comparative example 2.
To sum up, it by above-described embodiment and comparative example, finds to be successfully prepared the smart egg with hierarchical porous structure in gel
In vain-silica hybridized microcapsule；In addition, can be realized by the number that step 3 in step 4 in regulation and control embodiment and comparative example carries out
The regulation and control of hybridized microcapsule structure；And the number that step 3 carries out in step 4 and comparative example in embodiment is further increased, to micro-
Capsule pore passage structure influences smaller.
Claims (1)
1. a kind of preparation method of protamine-silica porous hybrid micro-capsule, which is characterized in that include the following steps：
Step 1: kayexalate is added into the calcium chloride solution of a concentration of 0.2~0.4M, it is made into polystyrolsulfon acid
Na concn is the solution A of 1~3mg/mL；The sodium carbonate liquor with calcium chloride solution equimolar concentration is prepared, in 800~1200r/
Under min rotating speeds, sodium carbonate liquor is poured into rapidly in isometric solution A, reacts 25~30s, stands 8~10min,
It centrifuges, is washed with deionized after removing supernatant, repeated centrifugation-washing, until supernatant is not under the rotating speed of 3000r/min
Containing kayexalate, the calcium carbonate microspheres of kayexalate doping are obtained；
Step 2: the agarose of certain mass is added into water, after heating for dissolving, it is 1%~3%w/v to be made into agarose concentration
Solution B；The calcium carbonate microspheres that kayexalate made from step 1 is adulterated are added in solution B, are uniformly mixed, natural
It is cooling, obtain the Ago-Gel for being dispersed with the calcium carbonate microspheres of kayexalate doping；
Step 3: compound concentration 1-3mg/mL is protamine solution；Compound concentration is the sodium silicate solution of 0.01~0.03M, is adjusted
The pH for saving solution is 7.0~8.0；
Step 4: Ago-Gel made from step 2 is dipped into 5-15min in protamine solution made from step 3 first,
It is dipped into deionized water and cleans after taking-up；Then, the subsequent Ago-Gel after the cleaning step 3 is dipped into be made
Sodium silicate solution in 5-15min, be dipped into water and clean after taking-up；Operating procedure 4 1~2 times；
Step 5: dissolving by heating through step 4 treated Ago-Gel, centrifuges, go under the rotating speed of 3000r/min
It except supernatant, is washed repeatedly with deionized water, thoroughly removes agarose, retain microballoon；
Step 6: prepare the solution C of disodium ethylene diamine tetraacetate a concentration of 0.03~0.05M, the pH for adjusting solution C is 5.0~
6.0；According to mass ratio 20：1 uniformly mixes solution C with step 5 thus obtained microsphere, rocks 5~10min；3000r/min's
It is centrifuged under rotating speed, removes supernatant, above-mentioned centrifugal separation processes are repeated, thoroughly to remove calcium carbonate；Later, deionization is used
Water washing repeats above-mentioned centrifugation-water-washing process, until supernatant is free of disodium ethylene diamine tetraacetate, it is more to obtain protamine-silica
Hole hybridized microcapsule.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510902881.0A CN105418959B (en) | 2015-12-09 | 2015-12-09 | The preparation method of protamine-silica porous hybrid micro-capsule |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510902881.0A CN105418959B (en) | 2015-12-09 | 2015-12-09 | The preparation method of protamine-silica porous hybrid micro-capsule |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105418959A CN105418959A (en) | 2016-03-23 |
| CN105418959B true CN105418959B (en) | 2018-08-10 |
Family
ID=55497530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510902881.0A Active CN105418959B (en) | 2015-12-09 | 2015-12-09 | The preparation method of protamine-silica porous hybrid micro-capsule |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105418959B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (2)
| 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 |
-
2015
- 2015-12-09 CN CN201510902881.0A patent/CN105418959B/en active Active
Patent Citations (2)
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105418959A (en) | 2016-03-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105858634B (en) | A kind of emulsion gel base polyacrylonitrile/carbon porous material and preparation method thereof | |
| CN112723303B (en) | Microbead chip and spin coating preparation method thereof | |
| CN100484618C (en) | Method for preparing microcapsule by using doping porous calcium carbonate mould plates | |
| CN109796019A (en) | A kind of hollow silicon dioxide nanosphere and its preparation method and application | |
| CN108330686A (en) | The preparation method of the chitin modified basalt fibre carrier of hydrophily | |
| CN102745698A (en) | Preparation method of carrier silica gel | |
| CN101347720A (en) | Method for preparing chitosan porous microsphere sorbent by metal ion imprinting and crosslinking methods as well as use | |
| CN109012638B (en) | Preparation method of carboxylated hierarchical porous cellulose adsorption balls | |
| EP3250672B1 (en) | Silicone nanoemulsion comprising c3-c6 alkylene glycol alkyl ether | |
| CN105418959B (en) | The preparation method of protamine-silica porous hybrid micro-capsule | |
| CN107556521A (en) | The three-dimensional porous sponge composite of supported nano zinc oxide | |
| CN106943885A (en) | A kind of membrane modifying method of control fouling membrane | |
| CN102617874A (en) | Two-dimensional colloid crystal thin film and preparation method thereof | |
| CN108889328A (en) | A kind of quantum-dot modified counter opal g-C3N4 catalyst of carbonitride | |
| CN104628006A (en) | Method for preparing half-strawberry type Janus particle | |
| Nagai et al. | Fabrication of boehmite films with cage-like pores and their properties as enzyme immobilization supports | |
| CN107311188B (en) | The modified method for preparing nano carrier material of attapulgite depth | |
| CN110004198B (en) | Preparation method of functional nucleic acid hydrogel for rapid self-assembly of soft brush | |
| CN110655676A (en) | Preparation method of super-hydrophobic sponge with emulsion separation function | |
| CN100431686C (en) | Method for preparing nano hollow inorganic microsphere | |
| CN101343629A (en) | Improved process for polyvinyl alcohol aluminum salt immobilization microorganism | |
| CN104707653B (en) | A kind of novel polystyrene sulfonate-oxidation silicon hybridization solid acid catalyst and preparation method | |
| CN105396522B (en) | A kind of wall thickness is the preparation method of nano level PAH silica hybridized microcapsule | |
| CN108676615A (en) | A kind of preparation method of nano controlled-release essence | |
| CN105734036B (en) | A kind of tannic acid is the preparation method of the mesoporous silicon immobilizing trypsinase of template |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP02 | Change in the address of a patent holder | ||
| CP02 | Change in the address of a patent holder |
Address after: 300350 Haijing garden, Haihe Education Park, Jinnan, Tianjin, 135, Tianjin University. Patentee after: Tianjin University Address before: 300072 Tianjin City, Nankai District Wei Jin Road No. 92 Patentee before: Tianjin University |