CN100554327C - Big molecular engram calcium orthophosphate/calcium alginate hybridized micro-balloon and preparation method thereof - Google Patents
Big molecular engram calcium orthophosphate/calcium alginate hybridized micro-balloon and preparation method thereof Download PDFInfo
- Publication number
- CN100554327C CN100554327C CNB2007100576393A CN200710057639A CN100554327C CN 100554327 C CN100554327 C CN 100554327C CN B2007100576393 A CNB2007100576393 A CN B2007100576393A CN 200710057639 A CN200710057639 A CN 200710057639A CN 100554327 C CN100554327 C CN 100554327C
- Authority
- CN
- China
- Prior art keywords
- calcium
- alginate
- protein
- microballoon
- mass percent
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Materials For Medical Uses (AREA)
- Medicinal Preparation (AREA)
Abstract
The present invention relates to a kind of protein macromolecule trace calcium phosphate/alginate calcium hybrid microspheres and preparation method thereof.The component and the weight percentage of western blotting calcium phosphate/alginate calcium hybrid microspheres are as follows: sodium alginate 20%～40%, Secondary ammonium phosphate 1%～10%, calcium chloride 50%～65%, protein 0.5～10%.Calcium phosphate/alginate calcium hybrid microspheres that the present invention is prepared shows through the protein adsorption test result, and the adsorptive capacity of trace microballoon is non-trace microballoon, does not promptly add 1.8～5 times of microballoon adsorptive capacity of protein preparation.Specific conductivity titration and examination of infrared spectrum show, Secondary ammonium phosphate and sodium alginate can with CaCl
2Acting in conjunction produces new hydridization component.Preparation method of the present invention is simple, reaction process is easy to advantages such as control, and the physical strength and the trace efficient that have solved pure alginate calcium are low, unstable properties, and deficiencies such as protein macromolecule diffusion difficulty are with a wide range of applications.
Description
Technical field
The invention belongs to materials science field, particularly a kind of protein macromolecule trace calcium phosphate/alginate calcium hybrid microspheres and preparation method thereof.
Background technology
Molecular imprinting successfully has been used for the trace of low-molecular weight compound at present, but because some characteristics of protein molecule, also unclear etc. such as easy sex change bulky, affected by environment, chemical structure complexity, recognition mechanism, the research of macro-molecular protein trace be can not show a candle to micromolecular trace research system and deeply.Zhi Bei molecularly imprinted polymer is highly cross-linked and hard material traditionally, thereby this class material does not have enough compliance and inner aperture makes huge protein template pass in and out polymkeric substance easily; Protein is generally nonrigid biomacromolecule, and its chemical structure is also very complicated, relies on several binding sites to be difficult in and produces the identification point of determining in the imprinted polymer.
Exist interaction between calcium phosphate salt and the protein, people have carried out fruitful research at calcium phosphate salt and this field of proteins interaction in recent years.The acidic amino acid group of protein surface and alkaline amino acid residue combine with calcium ion on β-TCP crystal by ionic linkage, and proteinic basic aminoacids group is by hydrogen bond and electrostatic attraction effect and PO
4 3-On the oxygen combination.Alginates has good hydrophilicity, at polyvalent cation Ca
2+Existence under, gelation reaction can take place rapidly, its gentle gelation condition helps keeping the activity of bioprotein, the soft moisture performance of alginates gel helps bioprotein and keeps its conformation, helps in the wash-out of template molecule and the recognition process absorption again to template molecule, but the alginates gel provides the choice of broad also for the design variable of western blotting alginates gel for the responsiveness of environmental parameter such as ionic strength, pH value etc.The natural polymer sodium alginate that direct employing has functional group replaces the function monomer in traditional molecular imprinting system, has simplified the building-up process of imprinted polymer.[FengJu Zhang, GuoXiang Cheng, XiaoGuang Ying.Emulsion and macromolecules templated alginate based polymer microspheres.Reactive and Functional Polymers, 2006,66, (7): 712～719] [Cheng Guoxiang, Zhang Fengju, the English twilight, double-template method hydroxyethyl cellulose modified alginate microsphere and preparation method, Chinese invention patent, application number 200510015832.1] the simple easy swelling of alginate microsphere, physical strength is low, and matter is crisp, it is relatively poor that hydroxyapatite/alginates complex microsphere is used for the proteinic effect of trace, because a little less than the effect too between hydroxyapatite and the alginates.[Cheng Guoxiang, Liu Chao, Zhao Kongyin, Zhang Fengju. the preparation method of hydroxyapatite/alginates complex microsphere. Chinese invention patent, application number 200410019979.3]
The hydridization technology of preparing of material system be adopt simultaneously can and certain material of multiple substance reaction participate in and prepare, and obtain a kind of novel material that has the Chemical bond effect at least between multiple composition and the two kinds of compositions that has.Organic/inorganic hybridization material is a frontier of matrix material, it combines numerous advantageous properties of organism and inorganics, and is lower as organism density, visco-elasticity good, toughness is high, workability is good etc. and inorganics hardness height, Young's modulus and intensity height, light transmission, high refractive index etc. preferably.[sol-gel method prepares organic/inorganic hybridization material technology and application thereof for Qiu Zehao, Ye Qiaoming, Guangzhou chemistry, 2006,31 (1): 40～45] also do not see related application and report about the material that phosphoric acid salt and alginates carry out hydridization.
Summary of the invention
The purpose of this invention is to provide a kind of hydridization method and prepare calcium phosphate/alginate calcium hybrid microspheres.Compare pure calcium alginate microsphere, the intensity and the absorption property of hybrid microspheres are greatly improved.
It is the method for the embedding molecular imprinting of template preparation with the macro-molecular protein that another object of the present invention provides a kind of.Compare with non-trace microballoon, embedding trace microballoon improves a lot to the adsorptive capacity of template protein.
It is the method for the surface molecule print of template preparation with the macro-molecular protein that another object of the present invention provides a kind of.Compare with embedding trace microballoon, surface imprinted microballoon improves a lot to the adsorptive capacity of template protein.
The invention provides the preparation and the trace method of macro-molecular protein trace calcium phosphate/alginate calcium hybrid microspheres.The component and the weight percentage of western blotting calcium phosphate/alginate calcium hybrid microspheres are as follows:
Sodium alginate 20%～40%
Secondary ammonium phosphate 1%～10%
Protein 0.5～10%.
Described protein is bovine serum albumin, Protalbinic acid or N,O-Diacetylmuramidase.
Described hybrid microspheres is protein surface trace calcium phosphate/alginate calcium hybrid microspheres.
Described hybrid microspheres is protein embedding trace calcium phosphate/alginate calcium hybrid microspheres.
Preparation method's step of protein surface trace calcium phosphate of the present invention/alginate calcium hybrid microspheres is as follows:
A) the preparation mass percent concentration is 2%～3% sodium alginate and 0.25%～2% Secondary ammonium phosphate mixed solution A;
B) solution A is joined 2～4 times of solution A volumes under stirring condition, density is in the organic phase of 0.75～0.95g/ml, and restir 10～15min makes the heavy-gravity solution A be dispersed into microballoon;
C) under agitation to above-mentioned b) add the protein of mass percent concentration 0.134%～1.34% in the mixed system and the calcium chloride mixed aqueous solution B of mass percent concentration concentration 3%～5% carries out gelation reaction, continue to stir 45～50min, obtain microballoon; Wash away protein template, obtain the surface imprinted calcium polyacrylate/calcium alginate hybrid microspheres of protein macromolecule.
Preparation method's step of protein embedding trace calcium phosphate of the present invention/alginate calcium hybrid microspheres is as follows:
A) in the protein soln of mass percent concentration 0.134%～1.34%, add sodium alginate and Secondary ammonium phosphate solid, obtain mass percent concentration and be 2%～3% sodium alginate and 0.25%～2% Secondary ammonium phosphate mixed solution A 1;
B) measure 2～4 times of solution A 1 volumes, density is the organic phase of 0.75～0.95g/ml, under agitation solution A 1 is joined in the organic phase, stirs 10～15min and makes heavy-gravity solution A 1 be dispersed into microballoon;
C) under agitation to above-mentioned b) calcium chloride water that adds mass percent concentration concentration 3%～5% in the mixed system carries out gelation reaction, continues to stir 45～50min, obtains microballoon; Wash away protein template, obtain the calcium polyacrylate/calcium alginate hybrid microspheres of protein macromolecule embedding trace.
Among the preparation method of big molecular engram calcium orthophosphate/calcium alginate hybridized micro-balloon of the present invention, described organic phase is the organic phase that adopts usually, requiring organic density is 0.75～0.95g/ml, wherein dissolves mass percent and be 0.05～4% tensio-active agent or dispersion agent.But the needs for environmental protection etc. also can adopt following organic phase:
Organic phase 1: trichloromethane mixes according to 3: 1～1: 1 volume ratio with normal hexane, and tensio-active agent sorbitan mono-oleic acid ester mass percent is 2～4%.
Organic phase 2: N-BUTYL ACETATE mixes according to 1: 3～1: 1 volume ratio with Viscotrol C, and dispersion agent ethyl cellulose mass percent is 0.05～0.1%.
Calcium phosphate/alginate calcium hybrid microspheres that the present invention is prepared shows through the protein adsorption test result, and the adsorptive capacity of trace microballoon is non-trace microballoon, does not promptly add 1.8～5 times of microballoon adsorptive capacity of protein preparation.Specific conductivity titration and examination of infrared spectrum show, phosphoric acid salt and sodium alginate can with CaCl
2Acting in conjunction produces new hydridization component, and phosphoric acid salt not only plays the effect that strengthens microballoon, also is beneficial to the effect that forms proteinic imprinted sites and play pore.The present invention adopts the western blotting calcium phosphate/alginate calcium hybrid microspheres of calcium ion crosslinking preparation to have that the preparation method is simple, reaction process is easy to advantages such as control, the physical strength and the trace efficient that have solved pure alginate calcium are low, unstable properties, deficiencies such as protein macromolecule diffusion difficulty are with a wide range of applications.
Description of drawings
Fig. 1: the surface imprinted calcium phosphate of bovine serum albumin/alginate calcium hybrid microspheres photo;
Fig. 2: surface imprinted calcium phosphate/alginate calcium hybrid microspheres is to the adsorption curve of bovine serum albumin;
Fig. 3: bovine serum albumin embedding trace calcium phosphate/alginate calcium hybrid microspheres photo;
Fig. 4: embedding trace calcium phosphate/alginate calcium hybrid microspheres is to the adsorption curve of bovine serum albumin.
Fig. 5: Protalbinic acid embedding and surface imprinted calcium phosphate/alginate calcium hybrid microspheres are to the adsorption curve of Protalbinic acid.
Embodiment
The surface imprinted calcium phosphate of embodiment 1. preparation bovine serum albumins/alginate calcium hybrid microspheres may further comprise the steps:
1) sodium alginate and the 0.15g Secondary ammonium phosphate solid of adding 0.5128g in the 20ml deionized water, stirring is fully dissolved it, obtains solution A;
2) measure organic phase toluene 40ml, pour in the beaker,, stir 5min it is fully dissolved to wherein adding the 0.8g sorbitan mono-oleic acid ester; Under agitation solution A slowly is poured in the beaker of containing organic phase, stirs 10min and make the heavy-gravity solution A be dispersed into microballoon;
3) under agitation adding the bovine serum albumin of mass percent concentration 0.134%～1.34% and mass percent concentration concentration in above-mentioned mixed system is that 5% calcium chloride mixed aqueous solution B carries out gelation reaction, continues to stir 45min, obtains microballoon; Adopt the method for patent 200510015832.1 to wash away protein template, obtain the surface imprinted calcium phosphate of bovine serum albumin/alginate calcium hybrid microspheres;
The optical microscope photograph of surface imprinted calcium phosphate/alginate calcium hybrid microspheres is seen Fig. 1, and the absorption result of bovine serum albumin is seen Fig. 2.The microballoon form is better as can see from Figure 1, and microsphere surface is coarse.As seen from Figure 2, obviously greater than the loading capacity of non-trace microballoon to bovine serum albumin, its loading capacity is 3.348 times of non-trace microballoon loading capacity to surface imprinted microballoon during balance to the loading capacity of bovine serum albumin.The size of the hybrid microspheres that obtains is 50～300 μ m.
Embodiment 2. preparation bovine serum albumin embedding trace calcium phosphate/alginate calcium hybrid microspheres may further comprise the steps:
1) in the bovine serum albumin solution of 20 μ mol/L of 20ml deionized water dissolving, adds 0.5128g sodium alginate and 0.15g Secondary ammonium phosphate solid, stir it is fully dissolved, obtain solution A 1;
2) measure the organic phase 40ml that 20ml trichloromethane and 20ml normal hexane are formed, pour in the beaker,, stir 5min it is fully dissolved to wherein adding the 0.8g sorbitan mono-oleic acid ester; Under agitation solution A 1 slowly is poured in the beaker of containing organic phase, stirs 15min and make heavy-gravity solution A 1 be dispersed into microballoon;
3) under agitation adding mass percent concentration in above-mentioned mixed system is that 5% calcium chloride mixed aqueous solution B1 carries out gelation reaction, continues to stir 45min, obtains microballoon; Adopt the method for patent 200510015832.1 to wash away protein template, obtain the calcium phosphate/alginate calcium hybrid microspheres of bovine serum albumin embedding trace;
The optical microscope photograph of the calcium phosphate of embedding trace/alginate calcium hybrid microspheres is seen Fig. 3, and the absorption result of bovine serum albumin is seen Fig. 4.The microballoon form is better as can see from Figure 3, and microsphere surface is coarse.As seen from Figure 4, greater than the loading capacity of non-trace microballoon to bovine serum albumin, its loading capacity is 1.666 times of non-trace microballoon loading capacity to embedding trace microballoon during balance to the loading capacity of bovine serum albumin.The size of the hybrid microspheres that obtains is 50～300 μ m.
The surface imprinted phosphoric acid of embodiment 3. preparation Protalbinic acids/alginate calcium hybrid microspheres may further comprise the steps:
1) sodium alginate and the 0.15g Secondary ammonium phosphate solid of adding 0.6186g in the 20ml deionized water, stirring is fully dissolved it, obtains solution A; N-BUTYL ACETATE 15～30ml, Viscotrol C 25～50ml;
2) measure the organic phase 40ml that 15ml N-BUTYL ACETATE and 25ml Viscotrol C are formed, pour in the beaker,, stir 5min it is fully dissolved to wherein adding the 0.04g ethyl cellulose; Under agitation solution A slowly is poured in the beaker of containing organic phase, stirs 10～15min and make the heavy-gravity solution A be dispersed into microballoon;
3) under agitation adding the Protalbinic acid of mass percent concentration 0.134%～1.34% and mass percent concentration concentration in above-mentioned mixed system is that 5% calcium chloride mixed aqueous solution B carries out gelation reaction, continues to stir 50min, obtains microballoon; Adopt the method for patent 200510015832.1 to wash away protein template, obtain the surface imprinted calcium phosphate of Protalbinic acid/alginate calcium hybrid microspheres;
The surface imprinted calcium phosphate of Protalbinic acid/alginate calcium hybrid microspheres is seen Fig. 5 to the adsorption curve of Protalbinic acid.As seen from Figure 5, greater than the loading capacity of non-trace microballoon to Protalbinic acid, its loading capacity is 4.38 times of non-trace microballoon loading capacity to surface imprinted microballoon during balance to the loading capacity of Protalbinic acid.
Embodiment 4. preparation Protalbinic acid embedding trace phosphoric acid/alginate calcium hybrid microspheres may further comprise the steps:
1) in the Protalbinic acid solution of 20 μ mol/L of 20ml deionized water dissolving, adds 0.5128g sodium alginate and 0.15g Secondary ammonium phosphate solid, stir it is fully dissolved, obtain solution A 1;
2) measure the organic phase 40ml that 20ml N-BUTYL ACETATE and 20ml Viscotrol C are formed, pour in the beaker,, stir 5min it is fully dissolved to wherein adding the 0.02g ethyl cellulose; Under agitation solution A 1 slowly is poured in the beaker of containing organic phase, stirs 10～15min and make heavy-gravity solution A 1 be dispersed into microballoon;
3) under agitation adding mass percent concentration in above-mentioned mixed system is that 5% calcium chloride mixed aqueous solution B1 carries out gelation reaction, continues to stir 50min, obtains microballoon; Adopt the method for patent 200510015832.1 to wash away protein template, obtain the calcium phosphate/alginate calcium hybrid microspheres of Protalbinic acid embedding trace;
Protalbinic acid embedding trace calcium phosphate/alginate calcium hybrid microspheres is seen Fig. 5 to the adsorption curve of Protalbinic acid.As seen from Figure 5, greater than the loading capacity of non-trace microballoon to Protalbinic acid, its loading capacity is 1.857 times of non-trace microballoon loading capacity to embedding trace microballoon during balance to the loading capacity of Protalbinic acid.
Open and protein macromolecule trace calcium phosphate/alginate calcium hybrid microspheres of proposing of the present invention and preparation method thereof, those skilled in the art can be by using for reference this paper content, and links such as appropriate change raw material, processing parameter, structure design realize.Product of the present invention and method are described by preferred embodiment, person skilled obviously can be in not breaking away from content of the present invention, spirit and scope to method as herein described with product is changed or suitably change and combination, realize the technology of the present invention.Special needs to be pointed out is, the replacement that all are similar and change apparent to those skilled in the artly, they are regarded as being included in spirit of the present invention, scope and the content.
Claims (6)
1. big molecular engram calcium orthophosphate/calcium alginate hybridized micro-balloon is characterized in that its material component and weight percentage are as follows:
Sodium alginate 20%～40%
Secondary ammonium phosphate 1%～10%
Calcium chloride 50%～65%
Protein 0.5～10%; Described protein is bovine serum albumin or Protalbinic acid;
The preparation method is:
A) the preparation mass percent concentration is 2%～3% sodium alginate and 0.25%～2% Secondary ammonium phosphate mixed solution A;
B) solution A is joined 2～4 times of solution A volumes under stirring condition, density is in the organic phase of 0.75～0.95g/ml, and restir 10～15min makes the heavy-gravity solution A be dispersed into microballoon;
C) under agitation to above-mentioned b) add the protein of mass percent concentration 0.134%～1.34% in the mixed system and the calcium chloride mixed aqueous solution B of mass percent concentration 3%～5% carries out gelation reaction, continue to stir 45～50min, obtain microballoon; Wash away protein template, obtain the surface imprinted calcium phosphate of protein macromolecule/alginate calcium hybrid microspheres.
2. big molecular engram calcium orthophosphate/calcium alginate hybridized micro-balloon as claimed in claim 1 is characterized in that described method is:
A) in the protein soln of mass percent concentration 0.134%～1.34%, add sodium alginate and Secondary ammonium phosphate solid, obtain mass percent concentration and be 2%～3% sodium alginate and 0.25%～2% Secondary ammonium phosphate mixed solution A 1;
B) measure 2～4 times of solution A 1 volumes, density is the organic phase of 0.75～0.95g/ml, under agitation solution A 1 is joined in the organic phase, stirs 10～15min and makes heavy-gravity solution A 1 be dispersed into microballoon;
C) under agitation to above-mentioned b) calcium chloride water that adds mass percent concentration 3%～5% in the mixed system carries out gelation reaction, continues to stir 45～50min, obtains microballoon; Wash away protein template, obtain the calcium phosphate/alginate calcium hybrid microspheres of protein macromolecule embedding trace.
3. big molecular engram calcium orthophosphate/calcium alginate hybridized micro-balloon as claimed in claim 1 is characterized in that described hybrid microspheres is protein surface trace calcium phosphate/alginate calcium hybrid microspheres.
4. big molecular engram calcium orthophosphate/calcium alginate hybridized micro-balloon as claimed in claim 2 is characterized in that described hybrid microspheres is protein embedding trace calcium phosphate/alginate calcium hybrid microspheres.
5. big molecular engram calcium orthophosphate/calcium alginate hybridized micro-balloon as claimed in claim 1 or 2, it is characterized in that among the described preparation method, the density of organic phase is 0.75～0.95g/ml, and the dissolving mass percent is 0.05～4% tensio-active agent or dispersion agent in the organic phase.
6. big molecular engram calcium orthophosphate/calcium alginate hybridized micro-balloon as claimed in claim 5 is characterized in that described organic phase is:
Organic phase 1: trichloromethane mixes according to 3: 1～1: 1 volume ratio with normal hexane, and tensio-active agent sorbitan mono-oleic acid ester mass percent is 2～4%;
Or organic phase 2: N-BUTYL ACETATE mixes according to 1: 3～1: 1 volume ratio with Viscotrol C, and dispersion agent ethyl cellulose mass percent is 0.05～0.1%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100576393A CN100554327C (en) | 2007-06-15 | 2007-06-15 | Big molecular engram calcium orthophosphate/calcium alginate hybridized micro-balloon and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100576393A CN100554327C (en) | 2007-06-15 | 2007-06-15 | Big molecular engram calcium orthophosphate/calcium alginate hybridized micro-balloon and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101081911A CN101081911A (en) | 2007-12-05 |
| CN100554327C true CN100554327C (en) | 2009-10-28 |
Family
ID=38911709
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100576393A Expired - Fee Related CN100554327C (en) | 2007-06-15 | 2007-06-15 | Big molecular engram calcium orthophosphate/calcium alginate hybridized micro-balloon and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100554327C (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101940916B (en) * | 2009-07-03 | 2013-03-27 | 湖北工业大学 | Konjac glucomannan stroma protein molecularly imprinted membrane as well as preparation method and application thereof |
| CN102619089A (en) * | 2012-01-16 | 2012-08-01 | 天津工业大学 | Preparation method of fiber carrier-based western blotting calcium alginate hybrid gel membrane |
| CN102558599B (en) * | 2012-01-16 | 2013-07-10 | 天津工业大学 | Preparation method of calcium silicate/calcium alginate hybrid material with mesoporous silica gel on surface |
| CN103041445A (en) * | 2013-01-21 | 2013-04-17 | 天津工业大学 | Method for preparing molecular imprinting porous gel membrane for tissue engineering |
| CN104888226A (en) * | 2014-03-06 | 2015-09-09 | 中国科学院大连化学物理研究所 | Protein and/or polypeptide substance preparation |
| CN107057085B (en) * | 2017-04-06 | 2019-04-19 | 扬州大学 | A kind of preparation method of calcium alginate sub-micron gel particles |
| CN109381734A (en) * | 2017-08-04 | 2019-02-26 | 天津工业大学 | A kind of preparation method of thickness and the controllable Calcium alginate film antiseptic dressing of roughness |
| CN107789332B (en) * | 2017-08-31 | 2020-01-14 | 西南交通大学 | Calcium carbonate/calcium alginate composite microspheres capable of adjusting drug release rate and prepared based on double-aqueous-phase biomineralization technology |
| CN112858435A (en) * | 2021-01-12 | 2021-05-28 | 齐鲁工业大学 | Preparation method of long-term anti-pollution electrochemical biosensor based on human serum albumin molecularly imprinted polymer gel |
-
2007
- 2007-06-15 CN CNB2007100576393A patent/CN100554327C/en not_active Expired - Fee Related
Non-Patent Citations (7)
| Title |
|---|
| Emulsion and macromolecules templated alginatebasedpolymer microspheres. FengJu Zhang, GuoXiang Cheng, XiaoGuang Ying.Reactive & Functional Polymers,Vol.66 . 2005 |
| Emulsion and macromolecules templated alginatebasedpolymer microspheres. FengJu Zhang, GuoXiang Cheng, XiaoGuang Ying.Reactive & * |
| Functional Polymers,Vol.66 . 2005 * |
| pH/temperature-sensitiveimprintedionicpoly(N-tert-butylacrylamide-co-acrylamide/maleicacid)hydrogels for bovine serum albumin. G*khan Demirel, et. al.Macromolecular Bioscience,Vol.5 . 2005 |
| pH/temperature-sensitiveimprintedionicpoly(N-tert-butylacrylamide-co-acrylamide/maleicacid)hydrogels for bovine serum albumin. G*khan Demirel, et. al.Macromolecular Bioscience,Vol.5 . 2005 * |
| 蛋白质模板印迹法制备纳米"孔穴"结构特异性生物材料. 陆书来，成国祥，蔡志江，庞兴收.中国医学科学院学报，第25卷第5期. 2003 |
| 蛋白质模板印迹法制备纳米"孔穴"结构特异性生物材料. 陆书来，成国祥，蔡志江，庞兴收.中国医学科学院学报，第25卷第5期. 2003 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101081911A (en) | 2007-12-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100554327C (en) | Big molecular engram calcium orthophosphate/calcium alginate hybridized micro-balloon and preparation method thereof | |
| CN101092494A (en) | Hybridized microballons of calcium polyacrylate / calcium alginate of macro molecule engram | |
| Quong et al. | External versus internal source of calcium during the gelation of alginate beads for DNA encapsulation | |
| CN102558599B (en) | Preparation method of calcium silicate/calcium alginate hybrid material with mesoporous silica gel on surface | |
| CN103254539A (en) | High-strength high-tenacity protein molecule imprinting hybrid gel film and preparation method thereof | |
| CN103806123A (en) | Silk fibroin/sodium alginate composite fiber and preparation method thereof | |
| AU2020101565A4 (en) | Hollow porous cellulose microsphere and preparation method and use thereof | |
| CN109134890A (en) | A kind of preparation method and application of cellulose microsphere carrier | |
| Niu et al. | Design and performance of a poly (vinyl alcohol)/silk fibroin enzymatically crosslinked semi-interpenetrating hydrogel for a potential hydrophobic drug delivery | |
| CN101186721B (en) | Macromolecule engram phosphoric acid/polyacrylic acid/calcium alginate multi-hybrid polymer micro-sphere and preparation method thereof | |
| Zheng et al. | pH‐sensitive alginate/soy protein microspheres as drug transporter | |
| CN106496608B (en) | Collagen-based compounds the preparation method of non-ionic polysaccharide building composite hydrogel | |
| CN103102512B (en) | Chitosan-fullerene compound and preparation method | |
| CN103304735A (en) | Method for preparing polymeric microsphere in alcohol-water mixed solvent | |
| CN109876780A (en) | A kind of dephosphorization adsorbent and preparation method thereof | |
| KR100962007B1 (en) | Interpenetrating polymer network hydrogel bead comprising polyethylene glycol and polyacrylamide, and method for immobilizing enzymes by using the same | |
| Xiao et al. | Fabrication of protease XIV-loaded microspheres for cell spreading in silk fibroin hydrogels | |
| CN112625158A (en) | Enzyme catalysis mineralization polyacryl glycinamide hydrogel and preparation method thereof | |
| Ren et al. | Nontoxic fluorescent wood with reconstructed porous structure and increased sorption sites towards selective detection and efficient removal of Hg (II) | |
| CN109943558A (en) | A method of based on double-aqueous phase system biomimetic mineralization process immobilised enzymes | |
| CN110437491A (en) | Nattokinase molecular imprinted polymer on surface and its preparation method and application | |
| CN101265332A (en) | Macro molecule engram polyvinylpyrrolidone/calcium alginate polymer micro-sphere and preparation method thereof | |
| CN108421366A (en) | Gelatin hydrolysate removes aldehyde composite material and preparation method with diatomite covalent bonding | |
| CN101548714B (en) | Dihydropyridine gel microsphere and preparation method thereof | |
| CN101081882A (en) | Large molecular engram cross-linking polyethylene pyrrolidone micro-balloon and low-temperature suspension polymerization preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20091028 Termination date: 20100615 |