CN104874362B - Method for activating chitosan microspheres - Google Patents
Method for activating chitosan microspheres Download PDFInfo
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- CN104874362B CN104874362B CN201510153869.4A CN201510153869A CN104874362B CN 104874362 B CN104874362 B CN 104874362B CN 201510153869 A CN201510153869 A CN 201510153869A CN 104874362 B CN104874362 B CN 104874362B
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- chitosan microball
- pbs solution
- chitosan
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000003213 activating effect Effects 0.000 title claims abstract description 9
- 239000004005 microsphere Substances 0.000 title abstract 4
- 230000004913 activation Effects 0.000 claims abstract description 17
- 239000011806 microball Substances 0.000 claims description 47
- 238000006243 chemical reaction Methods 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000012279 sodium borohydride Substances 0.000 claims description 15
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 15
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 11
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 11
- 239000006228 supernatant Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 7
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000004132 cross linking Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 241000165940 Houjia Species 0.000 claims 1
- 239000000047 product Substances 0.000 claims 1
- 102000004169 proteins and genes Human genes 0.000 abstract description 7
- 108090000623 proteins and genes Proteins 0.000 abstract description 7
- 125000003342 alkenyl group Chemical group 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 125000003277 amino group Chemical group 0.000 abstract 2
- 150000001413 amino acids Chemical class 0.000 abstract 1
- 229920000620 organic polymer Polymers 0.000 abstract 1
- 239000002861 polymer material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000008236 heating water Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012460 protein solution Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000010414 supernatant solution Substances 0.000 description 2
- HSDVRWZKEDRBAG-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COC(CCCCC)OCC1CO1 HSDVRWZKEDRBAG-UHFFFAOYSA-N 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 108010001515 Galectin 4 Proteins 0.000 description 1
- 102100039556 Galectin-4 Human genes 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010219 correlation analysis Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Cosmetics (AREA)
Abstract
The invention belongs to the technical field of modification of organic polymer materials, and particularly discloses a method for activating chitosan microspheres. The activation method of the invention is mainly characterized in that the alkenyl directly reacts with the amino group of the protein to fix the protein, so the activation mode is different from the prior art, the active group of the chitosan microsphere obtained by activation of the invention can be well combined with the amino group in the protein amino acid, and each gram of chitosan microsphere (wet weight) can be combined with 2-5 mg of protein.
Description
Technical field
The present invention relates to high-molecular organic material technical field of modification, and in particular to a kind of side of activation chitosan microball
Method.
Background technology
Chitosan is that the chitin being widely present by nature is hydrolyzed and sloughed raw after the acetyl group of part in the basic conditions
Into derivative, structure is poly- (1 → 4) -2-amino-2-deoxy-D-Glucose, and abundance is nontoxic.From 1859, France
People Rouget is obtained after chitosan first, the biological functionality and compatibility of this natural polymer, blood compatibility, safety
The premium properties such as property, microbic resolvability are by all trades and professions extensive concern, in medicine, food, chemical industry, cosmetics, water process, gold
Category extract and reclaim,It is biochemicalApplication study with the numerous areas such as biomedical engineering achieves major progress.
The chitosan of native state is largely powdered, as absorption carrier, makes carrier and adsorbate all be difficult to reclaim,
So as to limit its application.Under given conditions, chitosan can hydrolyze, be alkylated, being acylated, carboxy methylation, sulfonation, nitre
The chemical reactions such as change, halogenation, oxidation, reduction, condensation and complexing, can generate the various chitosan derivatives with different performance,
So as to expand the application of chitosan.
Chitosan can be all applied in terms of protein-interacting, antigen-antibody reaction, the diagnosis of relevant disease, specifically
In proteopexy to microballoon, then to carry out correlation analysis or detection.At present, epoxy or-CN groups are used in the market more
It is used as activated group.Because the purposes of different activation methods is different, developing a variety of different activation methods could meet
The actual demand of scientific research.
The content of the invention
It is an object of the invention to provide a kind of method of new activation chitosan microball.
To achieve these goals, the present invention is achieved by following scheme.
A kind of method for activating chitosan microball, comprises the following steps：
S1. PBS solution and sodium borohydride are added into the good chitosan microball of glutaraldehyde cross-linking, stirring at normal temperature reaction 12 ~
24h；
S2. reaction cleans chitosan microball after terminating, and the PBS that 5 times of volumes are added into the chitosan microball after cleaning is molten
Liquid, regulation pH is 14, then adds BDDE, and it accounts for total volume percent for 0.5 ~ 3%, 30 ~ 80 DEG C
48 ~ 72h is heated, after reaction terminates, supernatant is abandoned；
S3. S2 step 2 ~ 4 time are repeated, chitosan microball is reclaimed, the PBS solution of 2 ~ 15 times of volumes are added into microballoon, so
After add allyl glycidyl ether, its percentage of the total volume be 2 ~ 5%, 30 ~ 80 DEG C heating 48 ~ 72h, reaction terminate after,
Abandon supernatant；
S4. S3 step 2 ~ 4 time are repeated, is cleaned again with PBS solution after chitosan microball is cleaned with ethanol, produces activation
Chitosan microball.
The amino that the activation method of the present invention is mainly by alkenyl directly with protein reacts and fixing protein,
Therefore the difference of its activation method and prior art.
The effect of sodium borohydride used by the present invention is reduction aldehyde radical, it is impossible to substituted with other allied substances, because other
The effect of allied substances is bad；The effect of BDDE is that hydroxyl is crosslinked, it is impossible to other same
Class material is substituted, because the effect of other allied substances is bad；The effect of allyl glycidyl ether is same with hydroxyl reaction
When retain alkenyl, it is impossible to other allied substances substitute because the effect of other allied substances is bad.
Preferably, it is 1 ~ 1.5% that the addition of the BDDE, which accounts for total volume percent,.
Preferably, the heating-up temperature described in S2 and S3 is 45 ~ 80 DEG C.
Preferably, PBS solution described in S1 is added by the addition of 10 times of chitosan microball volumes, what the sodium borohydride was accounted for
Mass percent is 0.1 ~ 4%.It is highly preferred that the mass percent that the sodium borohydride is accounted for is 0.5 ~ 1.5%.
Preferably, the speed stirred described in S1 is 100 ~ 500rpm.
Compared with prior art, the invention has the advantages that：
The obtained active group of chitosan microball of present invention activation wishes base, can be good at in gal4 amino acid
Amino be combined, and every gram of chitosan microball（Weight in wet base）2 ~ 5mg protein can be combined.
Embodiment
The present invention is further elaborated on reference to specific embodiment.But embodiment does not do any shape to the present invention
The restriction of formula.Unless stated otherwise, the present invention use reagent, method and apparatus for the art conventional reagent, method and
Equipment.
Embodiment 1
A kind of method for activating chitosan microball, comprises the following steps：
S1. to the good chitosan microball of glutaraldehyde cross-linking（25 ~ 45 microns of diameter）Adding the PBS solution of 10 times of volumes must mix
Liquid is closed, sodium borohydride is added into mixed liquor, the mass percent that sodium borohydride accounts for mixed liquor is 1%, normal-temperature reaction 12h, reaction
During be stirred, the speed of stirring is 300rpm；
S2. after reaction terminates, in the stainless steel mesh for pouring into 500 mesh, 30min is cleaned with pure water；Then it is chitosan is micro-
Ball is put into beaker, adds the PBS solution of 5 times of volumes, the use of 0.5M NaOH solutions regulation pH is 14, is then added Isosorbide-5-Nitrae-fourth
Hexanediol diglycidyl ether, its percentage of the total volume is 1%, 50 DEG C of heating in water bath for reaction 72h；After reaction terminates, abandon
Clearly；
S3. S2 step 2 ~ 4 time are repeated, chitosan microball is reclaimed using the stainless steel mesh of 500 mesh, and are put into beaker,
The PBS solution and allyl glycidyl ether of 5 times of volumes are added simultaneously, and allyl glycidyl ether percentage of the total volume is
1%, 60 DEG C of heating in water bath for reaction 48h, after reaction terminates, abandon supernatant；
S4. S3 steps 3 time are repeated；Chitosan microball is washed using 50% ethanol 3 times, is cleaned, gone using PBS solution afterwards
Except ethanol produces the chitosan microball of activation.
The chitosan microball after activation is weighed, its weight in wet base is 20g, is put into 100ml protein solution, concentration 2mg/
ml.Ammonium persulfate solution is added, the concentration of ammonium persulfate is 1%；Normal-temperature reaction, the reaction time is 50 min.Use trace detection
Protein content in supernatant solution, calculates protein-bonded amount on chitosan microball, the results are shown in Table 1.
Embodiment 2
A kind of method for activating chitosan microball, comprises the following steps：
S1. to the good chitosan microball of glutaraldehyde cross-linking（25 ~ 45 microns of its diameter）Add 10 times of volumes PBS solution and
Enter sodium borohydride, the mass percent that sodium borohydride is accounted for is 1%, normal-temperature reaction 12h, be stirred in course of reaction, the speed of stirring
Spend for 400rpm；
S2. after reaction terminates, in the stainless steel mesh for pouring into 500 mesh, 30min then is cleaned with pure water, then shell is gathered
Sugared microballoon is put into beaker, adds the PBS solution of 8 times of volumes, the use of 0.5M NaOH solutions regulation pH is 14, is then added 1,
4- butanediol diglycidyl ethers, it is 2% that BDDE, which accounts for total volume percent, and 50 DEG C of heating water baths are anti-
72h is answered, reacts after terminating, abandons supernatant；
S3. S2 step 2 ~ 4 time are repeated, chitosan microball is reclaimed using the stainless steel mesh of 500 mesh, and are put into beaker,
The PBS solution and allyl glycidyl ether of 5 times of volumes are added simultaneously, and allyl glycidyl ether percentage of the total volume is
2.5%, 60 DEG C of heating in water bath for reaction 48h, after reaction terminates, abandon supernatant；
S4. S3 steps 3 time are repeated, chitosan microball is washed 3 times using 50% ethanol, is cleaned, gone using PBS solution afterwards
Except ethanol produces the chitosan microball of activation.
Chitosan microball is weighed, its weight in wet base is 20g, is put into 100ml protein solution, concentration 2mg/ml.Added
Ammonium sulfate, the concentration of ammonium persulfate is 1%；Normal-temperature reaction, the reaction time is 50 min.Use trace detection supernatant solution
In protein content, calculate chitosan microball on protein-bonded amount, the results are shown in Table 2.
Embodiment 3
A kind of method for activating chitosan microball, comprises the following steps：
S1. to the good chitosan microball of glutaraldehyde cross-linking（25 ~ 45 microns of its diameter）Add 10 times of volumes PBS solution and
Enter sodium borohydride, the mass percent that sodium borohydride is accounted for is 0.5%, normal-temperature reaction 24h, be stirred in course of reaction, stirring
Speed is 250rpm；
S2. after reaction terminates, in the stainless steel mesh for pouring into 500 mesh, 30min then is cleaned with pure water, then shell is gathered
Sugared microballoon is put into beaker, adds the PBS solution of 10 times of volumes, the use of 0.5M NaOH solutions regulation pH is 14, is then added 1,
4- butanediol diglycidyl ethers, it is 3% that BDDE, which accounts for total volume percent, and 35 DEG C of heating water baths are anti-
72h is answered, reacts after terminating, abandons supernatant；
S3. S2 step 2 ~ 4 time are repeated, chitosan microball is reclaimed using the stainless steel mesh of 500 mesh, and are put into beaker,
The PBS solution and allyl glycidyl ether of 5 times of volumes are added simultaneously, and allyl glycidyl ether percentage of the total volume is
2.5%, 60 DEG C of heating in water bath for reaction 48h, after reaction terminates, abandon supernatant；
S4. S3 steps 3 time are repeated, chitosan microball is washed 3 times using 50% ethanol, is cleaned, gone using PBS solution afterwards
Except ethanol produces the chitosan microball of activation.
Embodiment 4
A kind of method for activating chitosan microball, comprises the following steps：
S1. to the good chitosan microball of glutaraldehyde cross-linking（25 ~ 45 microns of its diameter）Add 10 times of volumes PBS solution and
Enter sodium borohydride, the mass percent that sodium borohydride is accounted for is 3.5%, normal-temperature reaction 18h, be stirred in course of reaction, stirring
Speed is 500rpm；
S2. after reaction terminates, in the stainless steel mesh for pouring into 500 mesh, 30min then is cleaned with pure water, then shell is gathered
Sugared microballoon is put into beaker, adds the PBS solution of 6 times of volumes, the use of 0.5M NaOH solutions regulation pH is 14, is then added 1,
4- butanediol diglycidyl ethers, it is 0.5%, 50 DEG C of heating water baths that BDDE, which accounts for total volume percent,
72h is reacted, after reaction terminates, supernatant is abandoned；
S3. S2 step 2 ~ 4 time are repeated, chitosan microball is reclaimed using the stainless steel mesh of 500 mesh, and are put into beaker,
The PBS solution and allyl glycidyl ether of 5 times of volumes are added simultaneously, and allyl glycidyl ether percentage of the total volume is
2.5%, 60 DEG C of heating in water bath for reaction 48h, after reaction terminates, abandon supernatant；
S4. S3 steps 3 time are repeated, chitosan microball is washed 3 times using 50% ethanol, is cleaned, gone using PBS solution afterwards
Except ethanol produces the chitosan microball of activation.
Claims (6)
1. a kind of method for activating chitosan microball, it is characterised in that comprise the following steps：
S1. PBS solution and sodium borohydride are added into the good chitosan microball of glutaraldehyde cross-linking, stirring at normal temperature reacts 12 ~ 24h；
S2. reaction cleans chitosan microball after terminating, and the PBS that 5 ~ 10 times of volumes are added into the chitosan microball after cleaning is molten
Liquid, regulation pH is 14, then adds BDDE, and it accounts for total volume percent for 0.5 ~ 3%, 30 ~ 80 DEG C
48 ~ 72h is heated, after reaction terminates, supernatant is abandoned；
S3. S2 step 2 ~ 4 time are repeated, chitosan microball is reclaimed, the PBS solution of 2 ~ 15 times of volumes, Ran Houjia are added into microballoon
Enter allyl glycidyl ether, its percentage of the total volume is 2 ~ 5%, 30 ~ 80 DEG C of 48 ~ 72h of heating, after reaction terminates, is abandoned
Clearly；
S4. S3 step 2 ~ 4 time are repeated, are cleaned again with PBS solution after chitosan microball is cleaned with ethanol, the shell for producing activation gathers
Sugared microballoon.
2. according to the method described in claim 1, it is characterised in that the addition of BDDE accounts for totality
Product percentage is 1 ~ 1.5%.
3. according to the method described in claim 1, it is characterised in that the heating-up temperature described in S2 and S3 is 45 ~ 80 DEG C.
4. according to the method described in claim 1, it is characterised in that PBS solution described in S1 is by 10 times of chitosan microball volumes
Addition is added, the sodium borohydride account for the mass percent of chitosan microball and PBS solution mixing gained mixed liquor for 0.1 ~
4%。
5. method according to claim 4, it is characterised in that the sodium borohydride accounts for chitosan microball and PBS solution is mixed
The mass percent for closing gained mixed liquor is 0.5 ~ 1.5%.
6. according to the method described in claim 1, it is characterised in that the speed stirred described in S1 is 100 ~ 500rpm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510153869.4A CN104874362B (en) | 2015-04-02 | 2015-04-02 | Method for activating chitosan microspheres |
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|---|---|---|---|
| CN201510153869.4A CN104874362B (en) | 2015-04-02 | 2015-04-02 | Method for activating chitosan microspheres |
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| CN104874362B true CN104874362B (en) | 2017-07-11 |
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| US4089746A (en) * | 1976-07-19 | 1978-05-16 | The United States Of America As Represented By The Secretary Of Agriculture | Method for insolubilizing enzymes on chitosan |
| CN100487000C (en) * | 2005-09-02 | 2009-05-13 | 中国科学院海洋研究所 | Carboxymethyl chitosan quaternary ammonium salt and its preparation method |
| CN102526811B (en) * | 2010-12-16 | 2013-10-09 | 上海其胜生物制剂有限公司 | Preparation method and application of degradable carboxymethyl chitosan composite nerve conduit |
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