CN102604148A - Preparation method of high strength porous chitosan microcarrier - Google Patents
Preparation method of high strength porous chitosan microcarrier Download PDFInfo
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- CN102604148A CN102604148A CN201210092265XA CN201210092265A CN102604148A CN 102604148 A CN102604148 A CN 102604148A CN 201210092265X A CN201210092265X A CN 201210092265XA CN 201210092265 A CN201210092265 A CN 201210092265A CN 102604148 A CN102604148 A CN 102604148A
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Abstract
The invention discloses a preparation method of a high strength porous chitosan microcarrier. The preparation method of the high strength porous chitosan microcarrier comprises: step S1, a solution preparation step: preparation of a chitosan acid solution, preparation of a mixed liquor of chitosan silica gel, preparation of a sodium polyphosphate solution, and preparation of a sodium hydroxide solution; step S2, a high voltage pulse balling step; step S3, a freeze-drying step: microspheres obtained in the step S2 are freeze-dried; in primary drying, the separator temperature is 45 DEG C below zero to 15 DEG C below zero, and the time is 5h to 10h; in the secondary drying, the separator temperature is 2 DEG C to 17 DEG C, and the time is 1.5h to 2h, so that the porous chitosan microcarrier is obtained; and step S4, a microwave radiation processing step: microwave radiation is carried out on the chitosan porous microcarrier obtained from the step S3 by using a microwave oven. According to the preparation method, the silica gel is used for forming holes firstly so as to more easily overcome the interfacial tension of the chitosan microspheres, so that a plurality of holes are formed on the surfaces of the microspheres, and thereby the microcarrier with higher porosity is prepared. Meanwhile, after the silica gel forms the holes, a certain channel can be formed, so that the freeze-drying is accelerated and the energy saving effect is realized.
Description
Technical field
The invention belongs to the porous material preparing technical field, relate to a kind of chitosan microcarrier, relate in particular to a kind of preparation method of high intensity, porous chitosan microcarrier.
Background technology
Microwave belongs to " body heating " to material heating, is different from the heating of general surface, and in theory, the body heating makes the material can thermally equivalent.Microwave technology successfully is used for the crosslinked carboxymethyl chitosan film, makes it can be applied to trauma care.Adopt microwave technology oven dry chitosan film, fast 6 times of its speed than traditional convection of air type of heating.
Natural macromolecular material is the human medical material that uses the earliest, has excellent biological compatibility, and nearly all degradable and degraded product are nontoxic.In the tissue engineering bracket material, typical natural macromolecular material has collagen protein, chitosan and gelatin, sodium-alginate etc.In the suspension culture research field of adherent sexual cell, the research of chitosan stent material is very extensive in recent years.Yet its preparation method often only limits to the freeze-drying used always.The chitosan stent that traditional freeze-drying is prepared; Because hydrogel thermal conduction rate in refrigerating process is different; Cause freezing rate and freezing temp bigger to the influence of support; Thereby make that the aperture of support is wayward in the preparation process; And, make the surface of the chitosan microcarrier that freeze-drying obtains be prone to form a skim because the IT of chitosan microball is very big, make microcarrier all be difficult to satisfy the requirement of the suspension culture research field of adherent sexual cell in porosity, microtexture and mechanical property.
Therefore this area press for provide a kind of microtexture evenly, easy-formation, porosity is higher, mechanical property is high porous chitosan microcarrier.
Summary of the invention
Technical problem to be solved by this invention is: a kind of preparation method of high intensity, porous chitosan microcarrier is provided, can obtains the solid chitosan microcarrier of HS.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A kind of preparation method of high intensity, porous chitosan microcarrier, said method comprises:
The preparation steps of step S1, solution; The mixed solution, preparation polyphosphoric acid sodium solution, the preparation sodium hydroxide solution that comprise preparing chitosan acid solution, preparing chitosan silica gel;
Step S2, high-voltage pulse balling-up step;
Chitosan acid solution among the step S1 and polyphosphoric acid sodium solution are prepared microballoon with high pressure electrostatic microcapsule forming instrument; Microballoon is soaked in the polyphosphoric acid sodium solution, use the washed with de-ionized water microballoon to be neutrality, and obtain white solid microsphere until solution; Again microballoon is put into sodium hydroxide solution and soak, the silica gel in the dissolving microballoon comes drilling, uses the washed with de-ionized water microballoon then;
Step S3, lyophilize step;
Microballoon to gained among the step S2 carries out lyophilize; The baffle temperature of primary drying is-45 ℃ to-15 ℃, and the time is 5-10h; The baffle temperature of redrying is 2-17 ℃, and the time is 1.5-2h, promptly obtains the porous chitosan microcarrier;
Step S4, microwave radiation processing step;
Adopt microwave oven that the chitosan multi-porous microcarrier of step S3 gained is carried out microwave radiation.
As a kind of preferred version of the present invention, said method specifically comprises the steps:
The preparation steps of step S1, solution;
Preparation W/V is 2.5% chitosan acid solution: measure 1ml acetic acid earlier and add constant volume in the volumetric flask of 100ml, make V/V and be 1% acetum, take by weighing the 2.5g chitosan again, add V/V and be in 1% the acetum and get final product; The mixed solution of preparing chitosan silica gel: according to the mass ratio M of silica gel and chitosan
s: M
CsBe 3: 1, take by weighing 7.5g silica gel, add W/V and be to stir in 2.5% the chitosan acid solution and get final product; Preparation W/V is 4.5% polyphosphoric acid sodium solution: take by weighing the 4.5g sodium polyphosphate and be dissolved in the deionized water of 100ml and get final product; Preparation W/V is 5.0% sodium hydroxide solution: take by weighing 5.0g sodium hydroxide and be dissolved in the deionized water of 100ml and get final product; Silica gel is m (SiO
2) n (H
2O);
Step S2, high-voltage pulse balling-up step;
With the W/V among the step S1 is that 2.5% chitosan acid solution and W/V are that 4.5% polyphosphoric acid sodium solution prepares microballoon with high pressure electrostatic microcapsule forming instrument; The parameter setting of high-voltage pulse microcapsule forming instrument is voltage 39-48kv; Fltting speed is 90mm/h; Pulsewidth is 5ms, and frequency is 90Hz, and the liquid level distance is 22mm; Microballoon after W/V is to soak 5h in 4.5% the polyphosphoric acid sodium solution, is used the washed with de-ionized water microballoon to be neutrality until solution, and obtains white solid microsphere; Again microballoon being put into 80 ℃ W/V is that 5.0% sodium hydroxide solution soaks 1.8h, and the silica gel in the dissolving microballoon comes drilling, uses the washed with de-ionized water microballoon then 3 times;
Step S3, lyophilize step;
Microballoon to gained among the step S2 carries out lyophilize, and concrete parameter setting is-45 ℃ for the pre-freeze temperature, and the pre-freeze time is 50min; The baffle temperature of primary drying is-25 ℃, and the time is 9h; The baffle temperature of redrying is 7 ℃, and the time is 1.5-2h, promptly obtains the porous chitosan microcarrier;
Step S4, microwave radiation processing step;
Adopting microwave oven that the chitosan multi-porous microcarrier of step S3 gained is carried out microwave radiation 1.5min gets final product.
As a kind of preferred version of the present invention, used deacetylating degree of chitosan is 80-91%.
As a kind of preferred version of the present invention, the microcarrier particle diameter that said method obtains is 400-700 μ m, and the aperture is 20-60 μ m, and porosity is 93%.
As a kind of preferred version of the present invention, among the said step S3, form certain passage with silica gel drilling meeting earlier, when carrying out lyophilize, to quicken freeze-drying.
As a kind of preferred version of the present invention, the porous chitosan microcarrier that said method makes is used for the suspension culture of adherent sexual cell.
Beneficial effect of the present invention is: the preparation method of the high intensity, porous chitosan microcarrier that the present invention proposes; Adopt static self-assembling technique and silica gel pore-creating agent to combine and prepare porous microsphere; Through the parameter setting to high-voltage pulse microcapsule forming instrument is voltage 39-48kv, and fltting speed is 90mm/h, and pulsewidth is 5ms; Frequency is 90Hz, and the liquid level distance is 22mm; Obtain the roundness height, particle diameter is 400-700 μ m, the microballoon of better performances, and the preparation method is simple, easy handling.Be employed in the silica gel system macropore in the dissolving microballoon in 80 ℃ the sodium hydroxide solution again, can increase the porosity of microballoon, then this porous microsphere is carried out lyophilize, ice crystal is distilled prepare aperture, thereby strengthen the connectedness of microballoon; Can overcome like this when only adopting freeze-drying that microballoon is carried out drilling, porosity is low, the shortcoming that connectedness is looked into.Through microwave oven microballoon is carried out the body heating more at last, make chitosan microball generation crosslinking reaction, form the build network-like structure, thereby obtain the solid chitosan microcarrier of HS, adopt this method to come enhance mechanical strength, simple to operation, cost is low.
The present invention has following outstanding advantage compared with prior art:
(1) comes drilling with silica gel earlier, overcome the IT of chitosan microball more easily, make microsphere surface form many holes, thereby prepare the higher microcarrier of porosity.Simultaneously, can also form certain passage after the silica gel drilling, can quicken freeze-drying and reach energy-conservation effect.
(2) the employing microwave radiation strengthens the mechanical property of chitosan microcarrier, and is simple to operation, and effect is remarkable.
Description of drawings
Fig. 1 is the preparing method's of the high intensity, porous chitosan microcarrier of the present invention schema.
Embodiment
Specify the preferred embodiments of the present invention below in conjunction with accompanying drawing.
Embodiment one
See also Fig. 1, the present invention has disclosed a kind of preparation method of high intensity, porous chitosan microcarrier, comprises the steps:
(1), the preparation of solution
1., preparation 2.5% (W/V, mass volume ratio) chitosan acid solution measures 1ml acetic acid earlier and adds constant volume in the volumetric flask of 100ml, makes 1% (V/V, volume ratio) acetum, takes by weighing the 2.5g chitosan again, add in 1% (V/V) acetum to get final product;
2., the mixed solution of preparing chitosan silica gel
Mass ratio M according to silica gel and chitosan
s: M
CsBe 3: 1, take by weighing 7.5g silica gel, adding stirs in 2.5% (W/V) chitosan acid solution gets final product;
3., preparation 4.5% (W/V) polyphosphoric acid sodium solution
Taking by weighing the 4.5g sodium polyphosphate is dissolved in the deionized water of 100ml and gets final product;
4., preparation 5.0% (W/V) sodium hydroxide solution
Taking by weighing 5.0g sodium hydroxide is dissolved in the deionized water of 100ml and gets final product;
(2), high-voltage pulse balling-up
2.5% (W/V) chitosan acid solution in the step (1) and 4.5% (W/V) polyphosphoric acid sodium solution are prepared microballoon with high pressure electrostatic microcapsule forming instrument;
The parameter setting of high-voltage pulse microcapsule forming instrument is voltage 39-48kv, and fltting speed is 90mm/h, and pulsewidth is 5ms, and frequency is 90Hz, and the liquid level distance is 22mm;
Microballoon soaked 5h in 4.5% (W/V) polyphosphoric acid sodium solution after, use the washed with de-ionized water microballoon to be neutrality, and obtain white solid microsphere until solution;
Again microballoon is put into 5.0% (W/V) sodium hydroxide solution of 80 ℃ and soak 1.8h, the silica gel in the dissolving microballoon comes drilling, uses the washed with de-ionized water microballoon then 3 times;
(3), lyophilize
To in the step (2) after washed with de-ionized water the microballoon of gained carry out lyophilize and obtain the porous chitosan microcarrier;
Above-mentioned freezing dry process control: the pre-freeze temperature is-45 ℃, and the pre-freeze time is 50min;
Above-mentioned lyophilize step comprises drying twice: the baffle temperature of primary drying is-25 ℃, and the time is 9h; The baffle temperature of redrying is 7 ℃, and the time is 1.5-2h;
(4), microwave radiation processing
Adopt microwave oven that the chitosan multi-porous microcarrier of step (3) gained is carried out microwave radiation 1.5min and promptly get high intensity, porous chitosan microcarrier; The power of above-mentioned microwave radiation process microwave oven is 160W.
Utilize the high intensity, porous chitosan microcarrier of aforesaid method gained to scan through ESEM; The aperture that can find out microsphere surface is that 20-60 μ m, particle diameter are 400-700 μ m; And the aperture of microsphere surface can improve the connectedness of microballoon; Porosity is 93%, can be used for the suspension culture of adherent sexual cell.
The silica gel that the present invention is used, m (SiO
2) n (H
2O), 200-300 order, chemical reagent ltd of Chinese Medicine group; It is pure all from Shanghai traditional Chinese medicines group that all the other all reagent are medicine.The model of the ESEM that the present invention is used is a Quanta x50 series sem (U.S. FEI Co.); Used microwave oven model is the Galanz microwave oven of WG800CTL23_K6; The high pressure electrostatic microcapsule forming instrument that the present invention is used, fltting speed is 1-99mm/h.
Embodiment two
In the present embodiment, the preparation method of said high intensity, porous chitosan microcarrier comprises the steps:
The preparation steps of [step S1] solution;
The preparing chitosan acid solution; W/V can be 1%-5%.
Utilize the mixed solution of above-mentioned chitosan acid solution preparing chitosan silica gel; The mass ratio Ms of silica gel and chitosan: Mcs can be 2: 1 to 5: 1.
Preparation polyphosphoric acid sodium solution.
The preparation sodium hydroxide solution.
[step S2] high-voltage pulse balling-up step;
Chitosan acid solution among the step S1 and polyphosphoric acid sodium solution are prepared microballoon with high pressure electrostatic microcapsule forming instrument; Microballoon is soaked in the polyphosphoric acid sodium solution, use the washed with de-ionized water microballoon to be neutrality, and obtain white solid microsphere until solution; Again microballoon is put into sodium hydroxide solution and soak, the silica gel in the dissolving microballoon comes drilling, uses the washed with de-ionized water microballoon then;
[step S3] lyophilize step;
Microballoon to gained among the step S2 carries out lyophilize; The baffle temperature of primary drying is-45 ℃ to-15 ℃, and the time is 5-10h; The baffle temperature of redrying is 2-17 ℃, and the time is 1.5-2h, promptly obtains the porous chitosan microcarrier;
[step S4] microwave radiation processing step;
Adopt microwave oven that the chitosan multi-porous microcarrier of step S3 gained is carried out microwave radiation.
In sum; The preparation method of the high intensity, porous chitosan microcarrier that the present invention proposes adopts static self-assembling technique and silica gel pore-creating agent to combine and prepares porous microsphere, is voltage 39-48kv through the parameter setting to high-voltage pulse microcapsule forming instrument; Fltting speed is 90mm/h; Pulsewidth is 5ms, and frequency is 90Hz, and the liquid level distance is 22mm; Obtain the roundness height, particle diameter is 400-700 μ m, the microballoon of better performances, and the preparation method is simple, easy handling.Be employed in the silica gel system macropore in the dissolving microballoon in 80 ℃ the sodium hydroxide solution again, can increase the porosity of microballoon, then this porous microsphere is carried out lyophilize, ice crystal is distilled prepare aperture, thereby strengthen the connectedness of microballoon; Can overcome like this when only adopting freeze-drying that microballoon is carried out drilling, porosity is low, the shortcoming that connectedness is looked into.Through microwave oven microballoon is carried out the body heating more at last, make chitosan microball generation crosslinking reaction, form the build network-like structure, thereby obtain the solid chitosan microcarrier of HS, adopt this method to come enhance mechanical strength, simple to operation, cost is low.
Here description of the invention and application is illustrative, is not to want with scope restriction of the present invention in the above-described embodiments.Here the distortion of the embodiment that is disclosed and change are possible, and the replacement of embodiment is known with the various parts of equivalence for those those of ordinary skill in the art.Those skilled in the art are noted that under the situation that does not break away from spirit of the present invention or essential characteristic, and the present invention can be with other form, structure, layout, ratio, and realize with other assembly, material and parts.Under the situation that does not break away from the scope of the invention and spirit, can carry out other distortion and change here to the embodiment that is disclosed.
Claims (6)
1. the preparation method of a high intensity, porous chitosan microcarrier is characterized in that, said method comprises:
The preparation steps of step S1, solution;
The mixed solution, preparation polyphosphoric acid sodium solution, the preparation sodium hydroxide solution that comprise preparing chitosan acid solution, preparing chitosan silica gel;
Step S2, high-voltage pulse balling-up step;
Chitosan acid solution among the step S1 and polyphosphoric acid sodium solution are prepared microballoon with high pressure electrostatic microcapsule forming instrument; Microballoon is soaked in the polyphosphoric acid sodium solution, use the washed with de-ionized water microballoon to be neutrality, and obtain white solid microsphere until solution; Again microballoon is put into sodium hydroxide solution and soak, the silica gel in the dissolving microballoon comes drilling, uses the washed with de-ionized water microballoon then;
Step S3, lyophilize step;
Microballoon to gained among the step S2 carries out lyophilize; The baffle temperature of primary drying is-45 ℃ to-15 ℃, and the time is 5-10h; The baffle temperature of redrying is 2-17 ℃, and the time is 1.5-2h, promptly obtains the porous chitosan microcarrier;
Step S4, microwave radiation processing step;
Adopt microwave oven that the chitosan multi-porous microcarrier of step S3 gained is carried out microwave radiation.
2. the preparation method of high intensity, porous chitosan microcarrier according to claim 1 is characterized in that:
Said method specifically comprises the steps:
The preparation steps of step S1, solution;
Preparation W/V is 2.5% chitosan acid solution: measure 1ml acetic acid earlier and add constant volume in the volumetric flask of 100ml, make V/V and be 1% acetum, take by weighing the 2.5g chitosan again, add V/V and be in 1% the acetum and get final product; The mixed solution of preparing chitosan silica gel: according to the mass ratio M of silica gel and chitosan
s: M
CsBe 3: 1, take by weighing 7.5g silica gel, add W/V and be to stir in 2.5% the chitosan acid solution and get final product; Preparation W/V is 4.5% polyphosphoric acid sodium solution: take by weighing the 4.5g sodium polyphosphate and be dissolved in the deionized water of 100ml and get final product; Preparation W/V is 5.0% sodium hydroxide solution: take by weighing 5.0g sodium hydroxide and be dissolved in the deionized water of 100ml and get final product; Silica gel is m (SiO
2) n (H
2O);
Step S2, high-voltage pulse balling-up step;
With the W/V among the step S1 is that 2.5% chitosan acid solution and W/V are that 4.5% polyphosphoric acid sodium solution prepares microballoon with high pressure electrostatic microcapsule forming instrument; The parameter setting of high-voltage pulse microcapsule forming instrument is voltage 39-48kv; Fltting speed is 90mm/h; Pulsewidth is 5ms, and frequency is 90Hz, and the liquid level distance is 22mm; Microballoon after W/V is to soak 5h in 4.5% the polyphosphoric acid sodium solution, is used the washed with de-ionized water microballoon to be neutrality until solution, and obtains white solid microsphere; Again microballoon being put into 80 ℃ W/V is that 5.0% sodium hydroxide solution soaks 1.8h, and the silica gel in the dissolving microballoon comes drilling, uses the washed with de-ionized water microballoon then 3 times;
Step S3, lyophilize step;
Microballoon to gained among the step S2 carries out lyophilize, and concrete parameter setting is-45 ℃ for the pre-freeze temperature, and the pre-freeze time is 50min; The baffle temperature of primary drying is-25 ℃, and the time is 9h; The baffle temperature of redrying is 7 ℃, and the time is 1.5-2h, promptly obtains the porous chitosan microcarrier;
Step S4, microwave radiation processing step;
Adopting microwave oven that the chitosan multi-porous microcarrier of step S3 gained is carried out microwave radiation 1.5min gets final product.
3. the preparation method of high intensity, porous chitosan microcarrier according to claim 2 is characterized in that:
Used deacetylating degree of chitosan is 80-91%.
4. the preparation method of high intensity, porous chitosan microcarrier according to claim 2 is characterized in that:
The microcarrier particle diameter that said method obtains is 400-700 μ m, and the aperture is 20-60 μ m, and porosity is 93%.
5. the preparation method of high intensity, porous chitosan microcarrier according to claim 2 is characterized in that:
Among the said step S3, form certain passage with silica gel drilling meeting earlier, when carrying out lyophilize, to quicken freeze-drying.
6. the preparation method of high intensity, porous chitosan microcarrier according to claim 2 is characterized in that:
The porous chitosan microcarrier that said method makes is used for the suspension culture of adherent sexual cell.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105832841A (en) * | 2016-05-25 | 2016-08-10 | 山东锐基生物科技有限公司 | Poultry medicine taking chitosan as carrier and preparation method of poultry medicine |
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|---|---|---|---|---|
| CN101066469A (en) * | 2007-05-09 | 2007-11-07 | 上海理工大学 | Prepn process of porous collagen sponge |
| CN101844059A (en) * | 2010-04-22 | 2010-09-29 | 上海理工大学 | Preparation method of chitosan/sodium polyphosphate porous microcarrier |
| CN102558601A (en) * | 2012-01-04 | 2012-07-11 | 上海理工大学 | Preparation method of high-strength porous chitosan microcarrier |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101066469A (en) * | 2007-05-09 | 2007-11-07 | 上海理工大学 | Prepn process of porous collagen sponge |
| CN101844059A (en) * | 2010-04-22 | 2010-09-29 | 上海理工大学 | Preparation method of chitosan/sodium polyphosphate porous microcarrier |
| CN102558601A (en) * | 2012-01-04 | 2012-07-11 | 上海理工大学 | Preparation method of high-strength porous chitosan microcarrier |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105832841A (en) * | 2016-05-25 | 2016-08-10 | 山东锐基生物科技有限公司 | Poultry medicine taking chitosan as carrier and preparation method of poultry medicine |
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Application publication date: 20120725 |