CN105771925B - A kind of skeleton polymer for chondroitin sulfate extraction and preparation method thereof - Google Patents
A kind of skeleton polymer for chondroitin sulfate extraction and preparation method thereof Download PDFInfo
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- CN105771925B CN105771925B CN201410504418.6A CN201410504418A CN105771925B CN 105771925 B CN105771925 B CN 105771925B CN 201410504418 A CN201410504418 A CN 201410504418A CN 105771925 B CN105771925 B CN 105771925B
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Abstract
The present invention is on a kind of three-dimensional framework polymer and its preparation method, utilize the distinctive three dimensional skeletal structure of melamine sponge, chitosan coat is coated on skeleton, reacted again by ethylene glycol diglycidylether and chitosan coat, it is crosslinked it and carries substantial amounts of epoxide group on surface, then epoxide group and diethanol amine reaction generation tertiary amine group are utilized, recycle tertiary amine group that redox reaction occurs at normal temperatures with potassium peroxydisulfate, free base is produced on skeleton surface, further trigger the graft polymerization reaction of dimethyl diallyl ammonium chloride, substantial amounts of cation is introduced on skeleton surface, material by cationization is easy to that electrostatic interaction occurs with negatively charged chondroitin sulfate macromolecular, the material can be used as monolithic devices absorption pillar, key effect is played in chondroitin sulfate is rapidly and efficiently extracted.It is using the advantages of this material：Adsorption capacity is strong, and operation simplifies, and material can be recycled for multiple times, and reduces cost, improves production efficiency.
Description
Technical field
It is especially a kind of to be based on melamine the present invention relates to the technical field of polymer materials extracted for bioactive substance
The chemical modification method of sponge skeleton polymer, resulting sorbing material can be used for the rapidly and efficiently extraction of chondroitin sulfate.
Background technology
Chondroitin sulfate (chondroitin sulfate, CS) is the sulphation osamine obtained from animal cartilaginous tissue
Glycan (acid mucopolysaccharide), CS are a kind of polyanionic compounds, and relative molecular mass is about 10000~35000, white powder
End, odorless, tasteless, there is hygroscopicity, it is soluble in water to form thick liquid, insoluble in most of organic solvents.CS is main as medicine
For treating antimigraine, neuralgia, arthritis, the auxiliary treatment of the dysacousis caused by streptomysin and hepatitis is prevented and treated, because of it
With reducing blood lipid, anticoagulant active, the preventing and treating of the angiocardiopathies such as hyperlipemia, coronary heart disease, atherosclerosis is also used for.Closely
Found over year, CS also has anti-inflammatory, anticancer, AntiHIV1 RT activity isoreactivity, there is protection to make nerve cell, mucomembranous cell, nephrocyte etc.
With CS has wide application and development prospect, CS has turned into China's export amount maximum with its good tolerance and security
One of biochemical drug.
In the industrial production, CS extraction common method be diluted alkaline hydrolysis binding resin exchange process, its advantage be hydrolysis with
Resins exchange technology is combined, and ensures that chondroitin sulfate molecule is non-degradable, and finished product purity is high, method is easy, high income.Ion is handed over
The method of changing is to contain the fundamental characteristics of negatively charged sulfate group based on CS molecules, by being formed with cation electrostatic interaction
Compound, then eluted again under electrolyte effect, so as to reach the purpose of extraction and purification.Ion exchange should use a kind of band
The cellular solid of positive charge, conventionally used polymeric anion exchanger resin, such as Amberlite IRA-933 type trees
Fat, this resin aperture is smaller (typically less than 20nm micropore), is typically all used for exchanging the anion of low molecule amount, and CS makees
For a kind of macromolecular anion, its diffusion rate in the liquid phase is far below common low-molecular-weight, anionic, is not easily accessible micro-
Kong Zhong, the surface of exchanger resin is mostly acted only on, its exchange rate and efficiency are all problematic in viscous liquid.The present invention carries
For a kind of high polymer material of three dimensional skeletal structure, its aperture reaches 100 μm, is very beneficial for mass transfer, and material surface band
There is abundant positive charge, so being highly suitable for exchanging the CS molecules of macromolecule, the method for using globality pillar is bright
The aobvious efficiency and speed for improving ion exchange, be advantageous to improve CS industrial production efficiency.
The content of the invention
Primary technical problem to be solved by this invention be directed in CS extraction process exist ion exchange resin aperture compared with
The problem of small, provides a kind of three-dimensional framework polymer, and it has the insertion duct of three-dimensional net structure and 100 μm, its skeleton surface
By special chemical modification, thus with abundant positive charge, it is easy to adsorb negatively charged CS molecules, keeps away
Exempt from because diffusion rate problem influences adsorption efficiency and speed, and can be easy to elute adsorbent, realize material
Be recycled for multiple times, improve CS production efficiency.
Another technical problem to be solved by this invention is to provide syntheti c route and the side of above-mentioned three-dimensional framework polymer
Method, it is practical, easy to operate, is easy to largely prepare.
Another technical problem to be solved by this invention is to provide a kind of above-mentioned three-dimensional framework polymer in CS extractions
Concrete application.
1st, technical scheme is used by the present invention solves primary technical problem：A kind of three-dimensional framework polymer, its feature
Being it is obtained by the chemical modification to melamine sponge (having structure as shown in Figure 1), and chemical modification only changes skeleton
Surface nature, the three-dimensional net structure without changing material, still retain about 100 μm of the duct interconnected, this hole
Road is advantageous to liquid communication.
It is beneficial that above-mentioned three-dimensional framework polymer surfaces carry a large amount of cation groups, existing very strong parent
Electrostatic interaction occurs for water-based and easy and with a large amount of barium white ionic groups CS, strengthens adsorption capacity.
2nd, technical scheme is used by the present invention solves another technical problem：A kind of above-mentioned high-molecular bone frame material
Ioning method, chemical reaction route is as shown in Fig. 2 its characterization step is：
1) chitosan of the viscosity more than 400mpa.s is dissolved in the concentration that 1~2wt.% is made into dilute acetic acid aqueous solution, added
Enter a small amount of cationic surfactant (such as DTAC, the concentration in solution is 0.1~0.2wt.%), will
Commercially available melamine sponge (melamine and foamed material, commercialization made of formaldehyde crosslinking reaction) is soaked in the solution,
Unnecessary solution is sopped up after taking-up with vacuum, ensures that it does not have solution outflow under standing, is then done in an oven at 60 DEG C
Dry 2~3 hours, then soaked 20~30 minutes in the sodium carbonate liquor of pH=9~10, formed after chitosan deprotonation insoluble
The film of property is covered in skeleton surface；2) be soaked in again after material is washed with clear water 10~12wt.% ethylene glycol two shrink it is sweet
React 1~2 hour under normal temperature in the ethanol solution of oily ether, then washed 1~2 time with 95% ethanol, then it is soaked in 12~
In the ethanol solution of 15wt.% diethanol amine, react 2~3 hours at normal temperatures, the epoxide group of suspension changes into tertiary amine groups
Group, then washed 1~2 time with 95% ethanol；3) by sample be soaked in the dimethyl diallyl ammonium chloride containing 3~4wt.% with
And in the aqueous solution of the potassium peroxydisulfates of 1~2wt. ‰, graft reaction occurs at normal temperatures 3~4 hours, washed 2~3 times with clear water,
Remove the unnecessary moisture of material internal with centrifugal method.
It is beneficial that above-mentioned ethylene glycol diglycidylether can play two effects：When with chitosan surface
Amino reaction, draw the epoxide group of suspension；Second, being reacted with the amino inside chitosan, chitosan is set to crosslink instead
Answer, be advantageous to the stabilisation of the clad；
It is beneficial that using tertiary amine with potassium peroxydisulfate redox reaction occurs at normal temperatures for above-mentioned graft reaction,
Free radical is produced on tertiary amine group, further initiation grafting polymerization, by the concentration of suitable control grafted monomers, both makes skeleton
Cation chain segments on surface grafting, make chitosan coat firm attachment again, will not come off easily.
3rd, technical scheme is used by the present invention solves another technical problem：Above-mentioned skeleton polymer is in CS extractions
Application process, it is characterised in that some block of material are superimposed, are placed in a glass columns, form globality absorption
Pillar, material solution is infiltrated and flows through the material, extract is adsorbed on the skeleton of polymer, is passing through clear water and buffering
Solution washs, and removes other impurity, is then collected extract by eluting, to reach the purpose of Separation ＆ Purification.
It is beneficial that above-mentioned processing method wants efficient quick than in general resin filling pillar, it is substantial amounts of on skeleton
Cation may all have an effect with the sulfate anion group on CS, the problem of in the absence of diffusion hindered, be found through overtesting,
Each gram of material can adsorb 79~90mg CS, and its adsorption capacity is higher than existing anion exchange resin.
The advantage of the invention is that：1) new sorbing material aperture is big, is advantageous to solid tumor, mass transfer；2) it is three-dimensional
Network structure is advantageous to the circulation of liquid, reduces flow resistance；3) polycation segment is than relatively-stationary cation group
With bigger free property, it is easier to electrostatic attraction effect occurs with CS.
Embodiment
The present invention is described in further detail with reference to embodiments.
It is prepared by material：
The 1st, chitosan of the viscosity more than 400mpa.s is dissolved in the concentration that 1~2wt.% is made into dilute acetic acid aqueous solution, added
Enter a small amount of cationic surfactant (DTAC, the concentration in solution is 0.1~0.2wt.%), by circle
Column melamine sponge (diameter 10cm, thickness 20cm) is soaked in the solution, sops up unnecessary solution after taking-up with vacuum, ensures
It does not have solution outflow under standing, is then dried 2~3 hours at 60 DEG C in baking oven again, then the sodium carbonate in pH=9~10
Soaked 20~30 minutes in solution, insoluble film is formed after chitosan deprotonation and is covered in skeleton surface；
2nd, it is soaked in again after material is washed with clear water in the ethanol solution of 10~12wt.% ethylene glycol diglycidylether
React 1~2 hour, then washed 1~2 time with 95% ethanol, then be soaked in the second of 12~15wt.% diethanol amine under normal temperature
In alcoholic solution, react 2~3 hours at normal temperatures, the epoxide group of suspension changes into tertiary amine group, then washs 1 with 95% ethanol
~2 times；
3 and then sample is soaked in the dimethyl diallyl ammonium chloride containing 3~4wt.% and the mistakes of 1~2wt. ‰
In the aqueous solution of potassium sulfate, graft reaction occurs at normal temperatures 3~4 hours, finally washed 2~3 times with clear water, with centrifugation side
Method gets rid of the unnecessary liquid of material internal.
CS extraction is carried out by following operating procedure：
A. extract, fresh clean cartilage is crushed with pulverizer, the cartilage of rubbing is placed in stainless steel reaction tank, added
1mol/L sodium hydroxide solutions soak, and are heated to 40 DEG C under agitation, insulation hydrolysis 2~3 hours, then add hydrochloric acid to be neutralized to again
Neutrality, filter and collect filtrate；
B. purify, above filtrate adjustment sodium chloride concentration is reached into 0.5mol/L, by solution by being polymerize by three-dimensional framework
Integral post made of thing (10cm × 100cm, is formed by stacking) by 5 pieces of cylindric samples, the volume of filtrate and the volume of pillar with
The ratio between should be 1: 2~1: 2.5, flow control is in 50~80mL/min, then with the 0.5mol/L sodium chloride of 1 times of amount of pillar volume
The aqueous solution washs, and elutes pillar with the 1.8mol/L sodium chloride of 1 times of amount of pillar volume, flow control is in 70~90mL/min, receipts
Collect eluent；
C. desalination, by eluent through ultrafilter desalination, ultrafiltrate is collected；
D. precipitate, above-mentioned ultrafiltrate is poured into Enamel jar, then add 95% ethanol, reach the volume fraction of ethanol
50~60%, deposit to clear, siphon removing supernatant liquor, collection precipitation；
E. dry, precipitation is filtered dry or hung with calico it is dry, with being dried in vacuo at 95% ethanol dehydration 2~3 times, 70 DEG C, i.e.,
Obtain chondroitin sulfate finished product.
Quality testing：
1) aminohexose assay, with HCl/water solution chondroitin sulfate produce aminohexose, in the basic conditions with acetyl
Acetone reacts, then is condensed with paradime thylaminobenzaldehyde, red compound is generated, using aminoglucose hydrochloride as standard control
Product, with spectrophotometry, the average content for obtaining aminohexose in sample is 31.3%；
2) sulfur determination, with HCl and H2O2Processing, chondroitin sulfate hydrolysis is discharged sulfate radical, then add barium salt to make it
Generate BaSO4Precipitation, then by BaSO4Molecular forms, using gravimetric detemination its average sulfur content as 7.2%；
Material adsorption capacity is assessed：The dry state density of anion frame material is generally 0.04~0.05g/mL, integral post
Volume be 7.85L, its quality is 314~393g, and average value 353g, integral post is after fully absorption, by eluting, carrying
The CS amounts obtained every time after pure are 28~32g, therefore every gram of material can adsorb CS amount in 79~90mg scopes, and in general from
The adsorption capacity of sub-exchange resin only has 16~25mg/g, so, material provided by the invention has obvious excellent in adsorption capacity
Gesture, the characteristics of this is mainly attributed to its large aperture and high porosity (low-density).
Brief description of the drawings
The SEM image of Fig. 1 melamine sponges
The reaction scheme figure of Fig. 2 three-dimensional frameworks materials chemistry modification.
Claims (3)
1. a kind of preparation method of three-dimensional framework polymer, it is characterised in that three-dimensional framework polymer is the change based on melamine sponge
Modification is learned, had both remained three-dimensional continuous network structure and 100 μm of the duct interconnected, makes Skeleton Table face that there is spy again
Different absorption property；
Its preparation process is followed successively by：
(1) chitosan for taking viscosity to be more than 400mPas, melamine sponge is immersed in 1~2wt.% chitosan solutions, is taken out
Unnecessary solution is sopped up with vacuum afterwards, ensures that it does not have solution outflow under standing, then in an oven at 60 DEG C dry 2~
3 hours, then soaked 20~30 minutes in the sodium carbonate liquor of pH=9~10, formed after chitosan deprotonation insoluble
Film is covered in skeleton surface；
(2) ethanol solution of 10~12wt.% diethylene glycol (DEG) diglycidyl ether is soaked in after above-mentioned material is washed with clear water again
React 1~2 hour under middle normal temperature, then washed 1~2 time with 95% ethanol；
(3) it is soaked in the 12~15wt.% ethanol solution of diethanol amine, reacts 2~3 hours at normal temperatures again, suspension
Epoxide group changes into tertiary amine group, then is washed 1~2 time with 95% ethanol；
(4) sample is soaked in the aqueous solution containing dimethyl diallyl ammonium chloride and potassium peroxydisulfate again, at normal temperatures
Generation graft reaction 3~4 hours, finally washed 2~3 times with clear water, the unnecessary liquid of material internal is got rid of with centrifugal method.
2. three-dimensional framework method for producing polymer according to claim 1, it is characterised in that two in graft polymerization reaction
The concentration of methyl diallyl ammonium chloride and potassium peroxydisulfate is respectively 3~4wt.% and 1~2wt. ‰.
3. three-dimensional framework method for producing polymer according to claim 1, it is characterised in that three-dimensional framework polymer can be with
The mode of globality pillar adsorbs negatively charged chondroitin sulfate macromolecular by ion exchange principle, make its adsorption capacity with
Speed significantly improves.
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| CN105619968A (en) * | 2016-03-03 | 2016-06-01 | 惠州赛力珑新材料有限公司 | Environment-friendly weather-resistant and stain-resistant wallpaper and making method |
| CN107459778B (en) * | 2017-08-30 | 2019-10-15 | 复旦大学 | A kind of epoxy matrix composite and preparation method thereof with high heat conductance |
| WO2020052679A1 (en) * | 2018-09-14 | 2020-03-19 | Versitech Limited | Gravity-driven chitosan-enhanced melamine sponge for stable ultrafast filtration |
| CN112756016A (en) * | 2020-12-11 | 2021-05-07 | 安徽皖仪科技股份有限公司 | Grafting type anion exchange resin chromatographic packing and preparation method thereof |
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| US6723539B1 (en) * | 1998-10-06 | 2004-04-20 | Bioprocessing, Ltd. | Absorbent medium containing particles of chopped cellulose or agarose sponge material having functional groups |
| CN101445636A (en) * | 2009-01-04 | 2009-06-03 | 武汉理工大学 | A sodium alginate and polyvinyl alcohol compound sponges material and preparation method thereof |
| CN102068714A (en) * | 2011-01-19 | 2011-05-25 | 北京大学 | Collagen sponge and preparation method thereof |
| CN104998622A (en) * | 2014-04-17 | 2015-10-28 | 宁波大学 | Cationic skeleton polymer capable of removing bacteria in air, and preparation method thereof |
| CN105013453A (en) * | 2014-04-17 | 2015-11-04 | 宁波大学 | Anionic framework polymer for extracting muramidase, preparation method of anionic framework polymer |
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Patent Citations (5)
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|---|---|---|---|---|
| US6723539B1 (en) * | 1998-10-06 | 2004-04-20 | Bioprocessing, Ltd. | Absorbent medium containing particles of chopped cellulose or agarose sponge material having functional groups |
| CN101445636A (en) * | 2009-01-04 | 2009-06-03 | 武汉理工大学 | A sodium alginate and polyvinyl alcohol compound sponges material and preparation method thereof |
| CN102068714A (en) * | 2011-01-19 | 2011-05-25 | 北京大学 | Collagen sponge and preparation method thereof |
| CN104998622A (en) * | 2014-04-17 | 2015-10-28 | 宁波大学 | Cationic skeleton polymer capable of removing bacteria in air, and preparation method thereof |
| CN105013453A (en) * | 2014-04-17 | 2015-11-04 | 宁波大学 | Anionic framework polymer for extracting muramidase, preparation method of anionic framework polymer |
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Effective date of registration: 20210528 Address after: 210000 Lishui Economic Development Zone, Nanjing, Jiangsu Province Patentee after: NANJING FENCHEM BIOLOGICAL TECHNOLOGY Co.,Ltd. Address before: No. 412, 4th floor, building 4, No. 588 Shuhui Road, Qingyang District, Chengdu, Sichuan 610000 Patentee before: Chengdu Feiyou Trading Co.,Ltd. Effective date of registration: 20210528 Address after: No. 412, 4th floor, building 4, No. 588 Shuhui Road, Qingyang District, Chengdu, Sichuan 610000 Patentee after: Chengdu Feiyou Trading Co.,Ltd. Address before: 315211 School of Material Chemistry, Ningbo University, 818 Fenghua Road, Jiangbei District, Ningbo City, Zhejiang Province Patentee before: Ningbo University |
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