CN1752126A - Preparation method of acid resistant alkali resistant composite biopolysaccharide micro sphere - Google Patents
Preparation method of acid resistant alkali resistant composite biopolysaccharide micro sphere Download PDFInfo
- Publication number
- CN1752126A CN1752126A CN 200510105926 CN200510105926A CN1752126A CN 1752126 A CN1752126 A CN 1752126A CN 200510105926 CN200510105926 CN 200510105926 CN 200510105926 A CN200510105926 A CN 200510105926A CN 1752126 A CN1752126 A CN 1752126A
- Authority
- CN
- China
- Prior art keywords
- chitosan
- minutes
- parts
- sherwood oil
- rev
- 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.)
- Granted
Links
Images
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
A process for preparing the acid and alkali resistant composite biologic polyose microballs includes such steps as copolymerizing reaction between the gum of tamarind or sand sage, chitosan and glutaraldehyde as cross-linking agent, using p-aminophenyl sulfonic acid to sulfonylate polyose hydroxy, and dewatering-condensating by glutaraldehyde. Its advantages are high resistance to acid and alkali, low swelling coefficient and low cost.
Description
Technical field
The present invention relates to a kind of preparation method of acid resistant alkali resistant composite biopolysaccharide micro sphere
Background technology
The compound bio polysaccharide microsphere of acid and alkali-resistance is meant that with the compound bio polysaccharide be the polymer microsphere that the surface of material preparation is connected with the acid and alkali-resistance of specific function group.
The preparation method of polymer microsphere, the investigator attaches great importance to both at home and abroad.Japanese Patent 2554835 has been applied for a kind of preparation method of oil hydrosol microballoon; The open 02-286729 of Japanese Patent has applied for a kind of preparation method of vinyl aromatic compounds magnetic microsphere; The open 01-133304 of Japanese Patent has applied for a kind of polysiloxane magnetic microsphere and application thereof; The open 62-244438 of Japanese Patent has applied for a kind of magnetic microsphere and use thereof that unsaturated fatty acids forms of adsorbing; The open 61-174229 of Japanese Patent has applied for a kind of magnetic thermoplastic resin lipoid microsphere preparation; U.S. Patent application 20040126902 has applied for containing the magnetic microsphere and uses thereof of the compound of silicon and aluminium; Chinese patent CN1485362, Chinese patent CN1328083, Chinese patent CN1290524 etc. have applied for the chitosan microball preparation method and its usage; Chinese patent CN1314430, Chinese patent CN1293952 etc. have applied for chitosan and composite method and the purposes that prepare polymer microsphere such as polyacrylic acid or fibroin; Chinese patent CN1275619, Chinese patent CN1234444 etc. have applied for the preparation and the application thereof of the fixed cell carrier that the poly-mannosans in carrageenin and Portugal or konjac polysaccharide are composite;
The prepared microballoon of above-mentioned patent is to make with poly-mannosans of chemical synthetic material such as vinyl aromatic compounds, polyacrylic acid and natural biologic material chitosan, carrageenin and Portugal or konjac polysaccharide etc. basically, yet the prepared microballoon acid resistance of above-mentioned materials is relatively poor, swelling volume is bigger, limited its application in immobilized enzyme, and cost is also higher.
Summary of the invention
The objective of the invention is to overcome above-mentioned defective and provide a kind of resistance to acids and bases good, swelling volume is little, the preparation method of acid resistant alkali resistant composite biopolysaccharide micro sphere that cost is low.
The preparation method of a kind of acid resistant alkali resistant composite biopolysaccharide micro sphere of the present invention is as follows:
1) select the raw material of following volume parts for use:
40～60 parts of compound bio polysaccharide and chitosan compound aqueous solutions;
0.5～1.5 part in Glacial acetic acid;
50～70 parts of sherwood oil and whiteruss mixing solutionss;
1.1～2.7 parts of glutaraldehyde water solutions;
40～60 parts of the Sulphanilic Acid aqueous solution;
Described compound bio polysaccharide is tamarind seed gum or artemisia glue; Tamarind seed gum and chitosan concentration are the 0.06-0.08 grams per milliliter in described tamarind seed gum and the chitosan compound aqueous solution, and wherein the weight ratio of tamarind seed gum and chitosan is 2～3: 1; Artemisia glue and chitosan concentration are 0.012～0.02 grams per milliliter in described artemisia glue and the chitosan compound aqueous solution, and wherein the weight ratio of artemisia glue and chitosan is 1: 2.5～8; Described glutaraldehyde water solution volumetric concentration is 50%; Described Sulphanilic Acid concentration of aqueous solution is 0.01～0.02 grams per milliliter.
2) in 40～60 parts of compound bio polysaccharide and chitosan compound aqueous solutions, add 0.5～1.5 part in Glacial acetic acid, stir, polysaccharide is fully dissolved;
3) under 500～700 rev/mins rotating speed, dropwise above-mentioned polysaccharide composite solution is joined in 10～15 minutes in 50～70 parts of sherwood oil and the whiteruss mixing solutionss; Described sherwood oil and whiteruss volume ratio are 7～9: 5～3; After 15～25 minutes, add weight concentration and be 0.5～1.5 part of 50% glutaraldehyde water solution, under 500～700 rev/mins rotating speed, reacted 1～2 hour;
4) behind the removal supernatant liquid, respectively soak 5～10 minutes, suction filtration with sherwood oil, acetone, three kinds of solvents of dehydrated alcohol successively, make compound bio polysaccharide complex microsphere;
5) adding weight concentration in the above-mentioned compound bio polysaccharide complex microsphere that makes is 40～60 parts of 1～2% the Sulphanilic Acid aqueous solution, under 100～200 rev/mins rotating speed, stirred 15～25 minutes, add 0.6～1.2 part of 50% glutaraldehyde water solution, under 100～200 rev/mins rotating speed, stirred 15～25 minutes, respectively soaked 5～10 minutes with sherwood oil, acetone, three kinds of solvents of dehydrated alcohol successively, vacuum-drying under 40～60 ℃ of conditions, until draining, promptly get surface functional group and be-OSO
2(C
6H
4) N=C (CH
2)
3CHO compound bio polysaccharide complex microsphere.
The present invention has the following advantages:
1, acid resistant alkali resistant composite biopolysaccharide micro sphere of the present invention, the microsphere surface functional group is-OSO
2(C
6H
4) N=C (CH
2)
3CHO, the microballoon resistance to acids and bases is strong, and stable under the pH1-11 environment, use range is wide, and swelling coefficient is little, nontoxic, good biocompatibility, has good processing property, production performance and response characteristic; Can be used as the carrier of enzyme or other bioactive molecules.
2, tamarind seed gum of the present invention and artemisia glue are the plant seed polysaccharide, and aboundresources has reduced cost.
Description of drawings
Fig. 1 is an artemisia glue compound bio polysaccharide microsphere pattern of the present invention.
Embodiment
Embodiment 1
In 40 parts of tamarind seed gum and chitosan compound aqueous solutions, add 0.5 part in Glacial acetic acid, stir, tamarind seed gum and chitosan are fully dissolved; Tamarind seed gum and chitosan concentration are 0.06 grams per milliliter in described tamarind seed gum and the chitosan compound aqueous solution, and wherein the weight ratio of tamarind seed gum and chitosan is 2: 1; Under 500 rev/mins rotating speed, dropwise above-mentioned tamarind seed gum and chitosan compound aqueous solution are joined in 10 minutes in 50 parts of sherwood oil and the whiteruss mixing solutionss, described sherwood oil and whiteruss volume ratio are 7: 5; Add volumetric concentration after 15 minutes and be 0.5 part of 50% glutaraldehyde water solution, reaction is 1 hour under 500 rev/mins rotating speed; Remove supernatant liquid, respectively soak 5 minutes, suction filtration with sherwood oil, acetone, three kinds of solvents of dehydrated alcohol successively, make the tamarind seed gum complex microsphere; In the above-mentioned tamarind seed gum complex microsphere that makes, add concentration and be 40 parts of the Sulphanilic Acid aqueous solution of 0.01 grams per milliliter, after stirring 15 minutes under 100 rev/mins the rotating speed, add volumetric concentration and be 0.6 part of 50% glutaraldehyde water solution, under 100 rev/mins rotating speed, stirred 15 minutes, respectively soak 5 minutes, suction filtration with sherwood oil, acetone, three kinds of solvents of dehydrated alcohol successively, vacuum-drying under 40 ℃ of conditions until draining, makes surface functional group and is-OSO
2(C
6H
4) N=C (CH
2)
3CHO tamarind seed gum complex microsphere.
Embodiment 2
In 60 parts of tamarind seed gum and chitosan compound aqueous solutions, add 1.5 parts in Glacial acetic acid, stir, tamarind seed gum and chitosan are fully dissolved; Tamarind seed gum and chitosan concentration are 0.08 grams per milliliter in described tamarind seed gum and the chitosan compound aqueous solution, and wherein the weight ratio of tamarind seed gum and chitosan is 3: 1; Under 700 rev/mins rotating speed, dropwise above-mentioned tamarind seed gum and chitosan compound aqueous solution are joined in 20 minutes in 70 parts of sherwood oil and the whiteruss mixing solutionss, described sherwood oil and whiteruss volume ratio are 3: 1; Add volumetric concentration after 25 minutes and be 1.5 parts of 50% glutaraldehyde water solutions, reaction is 2 hours under 700 rev/mins rotating speed; Remove supernatant liquid, respectively soak 15 minutes, suction filtration with sherwood oil, acetone, three kinds of solvents of dehydrated alcohol successively, make the tamarind seed gum complex microsphere; In the above-mentioned tamarind seed gum complex microsphere that makes, add concentration and be 60 parts of the Sulphanilic Acid aqueous solution of 0.02 grams per milliliter, after stirring 15 minutes under 100 rev/mins the rotating speed, add volumetric concentration and be 0.6 part of 50% glutaraldehyde water solution, under 200 rev/mins rotating speed, stirred 15 minutes, respectively soak 15 minutes, suction filtration with sherwood oil, acetone, three kinds of solvents of dehydrated alcohol successively, vacuum-drying under 60 ℃ of conditions until draining, makes surface functional group and is-OSO
2(C
6H
4) N=C (CH
2)
3CHO tamarind seed gum complex microsphere.
Embodiment 3
In 50 parts of tamarind seed gum and chitosan compound aqueous solutions, add 1.0 parts in Glacial acetic acid, stir, tamarind seed gum and chitosan are fully dissolved; Tamarind seed gum and chitosan concentration are 0.07 grams per milliliter in described tamarind seed gum and the chitosan compound aqueous solution, and wherein the weight ratio of tamarind seed gum and chitosan is 2.5: 1; Under 600 rev/mins rotating speed, dropwise above-mentioned tamarind seed gum and chitosan compound aqueous solution are joined in 15 minutes in 60 parts of sherwood oil and the whiteruss mixing solutionss, described sherwood oil and whiteruss volume ratio are 2: 1; Add volumetric concentration after 20 minutes and be 1 part of 50% glutaraldehyde water solution, reaction is 1.5 hours under 600 rev/mins rotating speed; Remove supernatant liquid, respectively soak 10 minutes, suction filtration with sherwood oil, acetone, three kinds of solvents of dehydrated alcohol successively, make the tamarind seed gum complex microsphere; In the above-mentioned tamarind seed gum complex microsphere that makes, add concentration and be 50 parts of the Sulphanilic Acid aqueous solution of 0.015 grams per milliliter, after stirring 20 minutes under 150 rev/mins the rotating speed, add volumetric concentration and be 0.9 part of 50% glutaraldehyde water solution, under 150 rev/mins rotating speed, stirred 20 minutes, respectively soak 10 minutes, suction filtration with sherwood oil, acetone, three kinds of solvents of dehydrated alcohol successively, vacuum-drying under 50 ℃ of conditions until draining, makes surface functional group and is-OSO
2(C
6H
4) N=C (CH
2)
3CHO tamarind seed gum complex microsphere.
Embodiment 4
In 40 parts of artemisia glue and chitosan compound aqueous solutions, add 0.5 part in Glacial acetic acid, stir, artemisia glue and chitosan are fully dissolved; Artemisia glue and chitosan concentration are 0.012 grams per milliliter in described artemisia glue and the chitosan compound aqueous solution, and wherein the weight ratio of artemisia glue and chitosan is 1: 2.5; Under 500 rev/mins rotating speed, dropwise above-mentioned artemisia glue and chitosan compound aqueous solution are joined in 10 minutes in 50 parts of sherwood oil and the whiteruss mixing solutionss, described sherwood oil and whiteruss volume ratio are 7: 5; Add volumetric concentration after 15 minutes and be 0.5 part of 50% glutaraldehyde water solution, reaction is 1 hour under 500 rev/mins rotating speed; Remove supernatant liquid, respectively soak 5 minutes, suction filtration with sherwood oil, acetone, three kinds of solvents of dehydrated alcohol successively, make the artemisia glue complex microsphere; In the above-mentioned artemisia glue complex microsphere that makes, add concentration and be 40 parts of the Sulphanilic Acid aqueous solution of 0.01 grams per milliliter, under 100 rev/mins rotating speed, stirred 15 minutes, add volumetric concentration and be 0.6 part of 50% glutaraldehyde water solution, under 100 rev/mins rotating speed, stirred 15 minutes, respectively soak 5 minutes, suction filtration with sherwood oil, acetone, three kinds of solvents of dehydrated alcohol successively, vacuum-drying under 40 ℃ of conditions until draining, makes surface functional group and is-OSO
2(C
6H
4) N=C (CH
2)
3CHO artemisia glue complex microsphere
Embodiment 5
In 60 parts of artemisia glue and chitosan compound aqueous solutions, add 1.5 parts in Glacial acetic acid, stir, artemisia glue and chitosan are fully dissolved; Artemisia glue and chitosan concentration are 0.02 grams per milliliter in described artemisia glue and the chitosan compound aqueous solution, and wherein the weight ratio of artemisia glue and chitosan is 1: 8; Under 700 rev/mins rotating speed, dropwise above-mentioned artemisia glue and chitosan compound aqueous solution are joined in 20 minutes in 70 parts of sherwood oil and the whiteruss mixing solutionss; Described sherwood oil and whiteruss volume ratio are 3: 1; Add volumetric concentration after 25 minutes and be 1.5 parts of 50% glutaraldehyde water solutions, reaction is 2 hours under 700 rev/mins rotating speed; Remove supernatant liquid, respectively soak 15 minutes, suction filtration with sherwood oil, acetone, three kinds of solvents of dehydrated alcohol successively, make the artemisia glue complex microsphere; In the above-mentioned artemisia glue complex microsphere that makes, add concentration and be 60 parts of the Sulphanilic Acid aqueous solution of 0.02 grams per milliliter, under 100 rev/mins rotating speed, stirred 15 minutes, add volumetric concentration and be 0.6 part of 50% glutaraldehyde water solution, under 200 rev/mins rotating speed, stirred 15 minutes, respectively soak 15 minutes, suction filtration with sherwood oil, acetone, three kinds of solvents of dehydrated alcohol successively, vacuum-drying under 60 ℃ of conditions until draining, makes surface functional group and is-OSO
2(C
6H
4) N=C (CH
2)
3CHO artemisia glue complex microsphere.
Embodiment 6
In 50 parts of artemisia glue and chitosan compound aqueous solutions, add 1.0 parts in Glacial acetic acid, stir, artemisia glue and chitosan are fully dissolved; Artemisia glue and chitosan concentration are 0.016 grams per milliliter in described artemisia glue and the chitosan compound aqueous solution, and wherein the weight ratio of artemisia glue and chitosan is 1: 5; Under 600 rev/mins rotating speed, dropwise above-mentioned artemisia glue and chitosan compound aqueous solution are joined in 15 minutes in 60 parts of sherwood oil and the whiteruss mixing solutionss; Described sherwood oil and whiteruss volume ratio are 2: 1; Add volumetric concentration after 20 minutes and be 1 part of 50% glutaraldehyde water solution, reaction is 1.5 hours under 600 rev/mins rotating speed; Remove supernatant liquid, respectively soak 10 minutes, suction filtration with sherwood oil, acetone, three kinds of solvents of dehydrated alcohol successively, make the artemisia glue complex microsphere; In the above-mentioned artemisia glue complex microsphere that makes, add concentration and be 50 parts of the Sulphanilic Acid aqueous solution of 0.015 grams per milliliter, under 150 rev/mins rotating speed, stirred 20 minutes, add volumetric concentration and be 0.9 part of 50% glutaraldehyde water solution, under 150 rev/mins rotating speed, stirred 20 minutes, respectively soak 10 minutes, suction filtration with sherwood oil, acetone, three kinds of solvents of dehydrated alcohol successively, vacuum-drying under 50 ℃ of conditions until draining, makes surface functional group and is-OSO
2(C
6H
4) N=C (CH
2)
3CHO artemisia glue complex microsphere.
Utilize scanning electron microscope, infrared spectra etc. to characterize the compound bio polysaccharide microsphere of acid and alkali-resistance, at room temperature measure swelling coefficient, under different pH values, measure its acid-fast alkali-proof.Scanning electron microscopic observation confirms that magnetic microsphere is the porous surface polynuclear plane, microballoon form homogeneous, and particle diameter is 1.6 * 10
2-5.1 * 10
2In the mu m range; Swelling coefficient is 2.34-2.73ml/g, and is stable under pH1-11.
Claims (1)
1, a kind of preparation method of acid resistant alkali resistant composite biopolysaccharide micro sphere, its step is as follows:
1) select the raw material of following volume parts for use:
40～60 parts of compound bio polysaccharide and chitosan compound aqueous solutions;
0.5～1.5 part in Glacial acetic acid;
50～70 parts of sherwood oil and whiteruss mixing solutionss;
1.1～2.7 parts of glutaraldehyde water solutions;
40～60 parts of the Sulphanilic Acid aqueous solution;
Described compound bio polysaccharide is tamarind seed gum or artemisia glue; Tamarind seed gum and chitosan concentration are the 0.06-0.08 grams per milliliter in described tamarind seed gum and the chitosan compound aqueous solution, and wherein the weight ratio of tamarind seed gum and chitosan is 2～3: 1; Artemisia glue and chitosan concentration are 0.012～0.02 grams per milliliter in described artemisia glue and the chitosan compound aqueous solution, and wherein the weight ratio of artemisia glue and chitosan is 1: 2.5～8; Described glutaraldehyde water solution volumetric concentration is 50%; Described Sulphanilic Acid concentration of aqueous solution is 0.01～0.02 grams per milliliter.
2) in 40～60 parts of compound bio polysaccharide and chitosan compound aqueous solutions, add 0.5～1.5 part in Glacial acetic acid, stir, polysaccharide is fully dissolved;
3) under 500～700 rev/mins rotating speed, dropwise above-mentioned polysaccharide composite solution is joined in 10～15 minutes in 50～70 parts of sherwood oil and the whiteruss mixing solutionss; Described sherwood oil and whiteruss volume ratio are 7～9: 5～3; After 15～25 minutes, add weight concentration and be 0.5～1.5 part of 50% glutaraldehyde water solution, under 500～700 rev/mins rotating speed, reacted 1～2 hour;
4) behind the removal supernatant liquid, respectively soak 5～10 minutes, suction filtration with sherwood oil, acetone, three kinds of solvents of dehydrated alcohol successively, make compound bio polysaccharide complex microsphere;
5) adding weight concentration in the above-mentioned compound bio polysaccharide complex microsphere that makes is 40～60 parts of 1～2% the Sulphanilic Acid aqueous solution, under 100～200 rev/mins rotating speed, stirred 15～25 minutes, add 0.6～1.2 part of 50% glutaraldehyde water solution, under 100～200 rev/mins rotating speed, stirred 15～25 minutes, respectively soaked 5～10 minutes with sherwood oil, acetone, three kinds of solvents of dehydrated alcohol successively, vacuum-drying under 40～60 ℃ of conditions, until draining, promptly get surface functional group and be-OSO
2(C
6h
4) N=C (CH
2)
3CHO compound bio polysaccharide complex microsphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101059268A CN100336848C (en) | 2005-09-30 | 2005-09-30 | Preparation method of acid resistant alkali resistant composite biopolysaccharide micro sphere |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101059268A CN100336848C (en) | 2005-09-30 | 2005-09-30 | Preparation method of acid resistant alkali resistant composite biopolysaccharide micro sphere |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1752126A true CN1752126A (en) | 2006-03-29 |
| CN100336848C CN100336848C (en) | 2007-09-12 |
Family
ID=36679137
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101059268A Expired - Fee Related CN100336848C (en) | 2005-09-30 | 2005-09-30 | Preparation method of acid resistant alkali resistant composite biopolysaccharide micro sphere |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100336848C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101565515B (en) * | 2008-04-25 | 2011-05-11 | 西北师范大学 | Karaya gum complex polysaccharide microsphere used as bioactive molecular vector and preparation method thereof |
| CN102443186A (en) * | 2011-09-30 | 2012-05-09 | 浙江省海洋开发研究院 | Preparation method of epoxy chloropropane cross-linked chitosan microspheres |
| CN114106363A (en) * | 2021-11-12 | 2022-03-01 | 陕西科技大学 | Method for preparing zein/artemisia glue nano-microspheres by electrostatic spraying |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1207326C (en) * | 2003-07-18 | 2005-06-22 | 清华大学 | Preparation method of natural high-molecular microsphere whose surface has loaded functional group |
| CN1281746C (en) * | 2004-08-30 | 2006-10-25 | 西北师范大学 | Biological polysaccharide high molecular micro ball fixnig beta-galactosidase and its prearing method |
-
2005
- 2005-09-30 CN CNB2005101059268A patent/CN100336848C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101565515B (en) * | 2008-04-25 | 2011-05-11 | 西北师范大学 | Karaya gum complex polysaccharide microsphere used as bioactive molecular vector and preparation method thereof |
| CN102443186A (en) * | 2011-09-30 | 2012-05-09 | 浙江省海洋开发研究院 | Preparation method of epoxy chloropropane cross-linked chitosan microspheres |
| CN114106363A (en) * | 2021-11-12 | 2022-03-01 | 陕西科技大学 | Method for preparing zein/artemisia glue nano-microspheres by electrostatic spraying |
| CN114106363B (en) * | 2021-11-12 | 2023-05-12 | 陕西科技大学 | Method for preparing zein/artemisia glue nano-microspheres by electrostatic spraying |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100336848C (en) | 2007-09-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107753949B (en) | Black phosphorus nanosheet, composite hydrogel, and preparation method and application thereof | |
| CN101274985B (en) | Magnetic cellulose microsphere, preparation thereof and use thereof | |
| CN1861639A (en) | Process of preparing chitosan/carbon nano tube composite material by covalence graft | |
| CN113004543B (en) | Nano lignin/polyvinyl alcohol composite medical hydrogel and preparation method thereof | |
| Barhoum et al. | Nanocelluloses as new generation materials: Natural resources, structure-related properties, engineering nanostructures, and technical challenges | |
| Kono et al. | Nanofibrillated bacterial cellulose surface modified with methyltrimethoxysilane for fiber-reinforced composites | |
| CN105749876B (en) | A kind of preparation method of chitosan-modified graphene oxide quantum dot sorbing material | |
| CN100336848C (en) | Preparation method of acid resistant alkali resistant composite biopolysaccharide micro sphere | |
| CN104624130A (en) | Method for preparing regenerated chitin microspheres | |
| CN109908876A (en) | A kind of preparation method and application of the chitosan-based bionical attractive gel of polysaccharide nano microcrystalline doping | |
| CN111944066A (en) | Cellulose-containing biomass material with nano-crystallized surface and preparation method and application thereof | |
| CN113292762B (en) | Dialdehyde nano-cellulose three-dimensional flexible material and preparation method and application thereof | |
| CN113402724B (en) | Preparation method of nano composite pour point depressant | |
| CN111187531B (en) | Bionic antifouling paint and preparation method and application thereof | |
| CN1271135C (en) | Biological polysaccharide macromolecule magnetic microsphere and preparation method | |
| CN111303491A (en) | Preparation method of bacterial cellulose/polymeric dopamine composite nano material | |
| CN112980002A (en) | Preparation method of furfural residue-based lignin-nanocellulose gel composite material | |
| CN1807464A (en) | Double-template method hydroxyethyl cellulose modified alginate microsphere and its preparation method | |
| CN1793269A (en) | Liquid biological adhesvie using soybean separated protein as base material and production process thereof | |
| CN100351007C (en) | Method for preparing molecular engram CS/TEOS hybridized film by separation of phenylalanine isomer | |
| JP5787338B2 (en) | Porous membrane | |
| CN112111217A (en) | Modified graphene oxide bio-based polyurethane anticorrosive paint and preparation method thereof | |
| CN105039299B (en) | A kind of immobilized HRP carrier and its preparation, application process | |
| CN1281746C (en) | Biological polysaccharide high molecular micro ball fixnig beta-galactosidase and its prearing method | |
| CN1772365A (en) | Layer-by-layer microcapsule assembling process based on mutual covalent action |
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: 20070912 Termination date: 20110930 |