CN106046252A - Sugar-containing polymer with surface adsorption property and method for manufacturing sugar-containing polymer - Google Patents
Sugar-containing polymer with surface adsorption property and method for manufacturing sugar-containing polymer Download PDFInfo
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- CN106046252A CN106046252A CN201610415282.0A CN201610415282A CN106046252A CN 106046252 A CN106046252 A CN 106046252A CN 201610415282 A CN201610415282 A CN 201610415282A CN 106046252 A CN106046252 A CN 106046252A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
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Abstract
The invention discloses a method for manufacturing a sugar-containing polymer with a surface adsorption property. The sugar-containing polymer is made of methacrylamide sugar-containing monomers and dopamine monomers. The method includes adding initiators, chain transfer agents and catalysts into the methacrylamide sugar-containing monomers and the dopamine monomers; preparing the sugar-containing polymer by the aid of one-pot processes. The method has the advantages that the sugar-containing polymer prepared by the aid of the method is water-soluble and is excellent in surface adsorption property and can be used for preparing functional sugar-containing polymer materials; the dopamine monomers are provided with catechol functional groups, covalent bonds or strong non-covalent bonds can be formed by the aid of the catechol functional groups and material surfaces, and accordingly the sugar-containing polymer can be adsorbed on the material surfaces; the sugar-containing polymer can be adhered with the surface of metal oxide in a two-tooth chelate mode formed by hydroxyl in the catechol functional groups, and can be adhered with mica, glass and polymer substrates by the aid of electric charge or hydrogen bonds.
Description
Technical field
The present invention relates to a kind of sugar-containing polymer with surface adsorption and preparation method thereof.
Background technology
Sugar (carbohydrate) is the component units of many natural products in nature, is that energy common in biology comes
Source, is also critically important a kind of multivalent state part (receptor).Sugar includes cell recognition with the specific binding property of agglutinant protein,
The basis of many life processes such as pathogenic infection, cell sorption and differentiation, is very important research in contemporary scientific field
One of problem.From the beginning of twentieth century end, research worker utilizes the feature of sugar-containing polymer that it is carried out in-depth study, it is thus achieved that
Substantial amounts of achievement in research, but the surface adsorption function of sugar-containing polymer has much room for improvement.
Summary of the invention
In order to solve said one or multiple technical problem, the present invention provides a kind of sugary polymerization with surface adsorption
Thing.
Technical scheme is as follows:
Having the sugar-containing polymer of surface adsorption, its molecular structural formula is as follows:
Wherein the span of m is 30-200, and the span of a is 30-200.
There is the preparation method of the sugar-containing polymer of surface adsorption, with the sugary monomer of methacryl amine and dopamine
Class monomer is raw material, adds initiator and chain-transferring agent, and adds catalyst, is prepared by one kettle way,
Wherein the span of m is 30-200, and the span of a is 30-200.
In some embodiments, the described sugary monomer of methacryl amine, Dopaminergics monomer, initiator and chain turn
The mol ratio moving agent is 5-15:1:0.004:0.01.
In some embodiments, described initiator is azo-initiator or bromo initiator.
In some embodiments, described initiator is selected from azodiisobutyronitrile or 2-isobutyl ethyl bromide or α-bromine is different
Ethyl n-butyrate..
In some embodiments, described chain-transferring agent is monothioester class chain-transferring agent.
In some embodiments, described chain-transferring agent is selected from dithio naphthoic acid isopropyl cyanide ester or 4-cyano group-4-(phenyl
Sulfur acute pyogenic infection of nails acyl sulfenyl) valeric acid or 4-cyano group-4-(phenyl formyl sulfenyl) valeric acid N-succinimido ester.
In some embodiments, described catalyst is ferrum and the compositions of copper bromide or copper.
It has the beneficial effect that the present invention utilizes single electron transfer active free radical polymerization RAFT
(SET-RAFT) method of active free radical polymerization, prepares the sugar-containing polymer that compound with regular structure is controlled.
Sugar-containing polymer prepared by the present invention not only has water solublity and also has preferable surface adsorption property, can be used for making
Standby functional sugar-containing polymer material.Dopaminergics monomer has catechol functional group, sugar-containing polymer prepared by the present invention
Form covalent bond or strong non-covalent bond by catechol functional group with material surface and adsorb at material surface, itself and gold
Belonging to oxide is to glue by the way of the hydroxyl in catechol functional group and metal oxide surface form two tooth sequestration
Attached, and be to be adhered to by electric charge or hydrogen bond with Muscovitum, glass and polymeric substrates.
Sugar-containing polymer prepared by the present invention can preferably be adsorbed in different types of matrix surface, has good table
Universality is modified in face.
The inventive method is easy and simple to handle, is conducive to saving cost of manufacture, promotes to promote.
Accompanying drawing explanation
Fig. 1 is the gpc measurement curve chart of the sugar-containing polymer with surface adsorption of the embodiment of the present invention 1；
Fig. 2 is infrared on stainless steel substrates surface of the sugar-containing polymer with surface adsorption of the embodiment of the present invention 1
Test and comparison figure；
Fig. 3 is that the surface of the stainless steel substrates of the sugar-containing polymer process with surface adsorption of the embodiment of the present invention 1 is surveyed
The comparison diagram of examination water contact angle；
Fig. 4 is the surface institute of the stainless steel substrates of the sugar-containing polymer process with surface adsorption of the embodiment of the present invention 1
Survey the confocal fluorescent image of canavaline；
Fig. 5 is the infrared survey of the silicon chip of the sugar-containing polymer process with surface adsorption of the embodiment of the present invention 2 preparation
Examination comparison diagram；
Fig. 6 is that the surface of the silicon chip of the sugar-containing polymer process with surface adsorption of the embodiment of the present invention 2 preparation is surveyed
The comparison diagram of examination water contact angle；
Fig. 7 is the polystyrene sheet table of the sugar-containing polymer process with surface adsorption of the embodiment of the present invention 3 preparation
The infrared test comparison diagram in face；
Fig. 8 is the polystyrene sheet of the sugar-containing polymer process with surface adsorption of the embodiment of the present invention 3 preparation
The comparison diagram of surface test water contact angle.
Fig. 9 is the polystyrene sheet surface that the present invention implements that the sugar-containing polymer with surface adsorption of 3 preparations processes
The confocal fluorescent image of surveyed bovine serum albumin.
Detailed description of the invention
The invention will be further described below in conjunction with the accompanying drawings.
Embodiment 1:
Weigh 2-(methacryl amido) Glucopyranose. of 0.2g, the dopamine Methacrylamide of 36mg, 0.5mg
Copper powder and the ethyl α bromoisobutyrate of the dithio naphthoic acid isopropyl cyanide ester of 1.9mg and 0.3 μ L to be dissolved in the dimethyl of 1mL sub-
In sulfone, one pot reaction 8h under 25 DEG C of room temperature oxygen free conditions, then using methanol as precipitant, product is slowly added dropwise into
200mL precipitation agent methanol is allowed to coagulation, obtains white precipitate, centrifugal, it is dried, weighs.
The structural formula of the sugar-containing polymer PDMA-MAG possessing surface adsorption prepared is as follows:
Wherein n:b=1:5 molecular weight is 6500, and molecular weight distribution is about 1.2, as shown in Figure 1.
After the tris solution of 50mL, 0.1mol/L is mixed with 22.9mL, 0.1mol/L hydrochloric acid, add water
Being diluted to 100mL, the pH value of regulation mixed liquor is 8.2, is configured to Tris-Hcl solution.
Take 0.2g there is the sugar-containing polymer PDMA-MAG of surface adsorption to be dissolved in the Tris-Hcl solution 10mL prepared
Form mixed liquor, stainless steel substrates is placed in culture dish, mixed liquor is added drop-wise on stainless steel substrates, submergence, be placed on room temperature cloudy
Surface it is washed with deionized three times, then normal temperature drying after Liang Chu, 4h.To process after stainless steel substrates carry out infrared test and
Water contact angle is tested, as in figure 2 it is shown, above one section of curve represents the surface of the stainless steel substrates not processed through sugar-containing polymer
Absworption peak, below one section of curve represent the absworption peak on surface of the stainless steel substrates processed through sugar-containing polymer, by contrast
Showing, the stainless steel substrates processed through sugar-containing polymer has obvious absworption peak, shows sugary polymerization prepared by the present embodiment
The surface adsorption property of thing is stronger.As it is shown on figure 3, the water contact angle of stainless steel substrates is reduced to 7 ° by 12 °, the water solublity on surface obtains
Improve.
Weigh 0.02mg canavaline (ConA) to be dissolved in the phosphate buffer solution (PBS) of 1mL, after infiltration processes
Stainless steel substrates surface, be washed with deionized after 1h, under excitation wavelength is 488nm, then does confocal fluorescent image.As
Shown in Fig. 4, through the stainless steel substrates surface that canavaline is modified, there is confocal fluorescent phenomenon obvious, show prepared by the present embodiment
Sugar-containing polymer canavaline is had identity.
Embodiment 2
Weigh 2-(methacryl amido) galactopyranose of 0.5g, 56mg dopamine Methacrylamide, 2mg (mistake
Amount) copper wire, 4-cyano group-4-(the phenyl formyl sulfenyl) valeric acid of 0.9mg azodiisobutyronitrile and 6.25mg be dissolved in the two of 1mL
In methyl sulfoxide, one pot reaction 8h under 25 DEG C of room temperature oxygen free conditions, then coagulation in 200ml methanol, obtain white heavy
Form sediment, centrifugal, it is dried, weighs.
After 50ml, 0.1mol/L trishydroxymethylaminomethane (Tris) solution mixes with 22.9ml, 0.1mol/L hydrochloric acid, add
Water is diluted to 100mL, and the pH of regulation mixed liquor is 8.2, is made into Tris-HCl solution.
Take 0.2g there is the sugar-containing polymer PDMA-MAG of surface activity to be dissolved in the Tris-HCl solution 10mL prepared
Obtain mixed liquor, silicon chip is placed in culture dish, and above-mentioned mixed liquor is added drop-wise on silicon chip, submergence, put at room temperature cool place, 4h
After be washed with deionized surface 3 times, then normal temperature drying.Silicon chip after processing carries out infrared test and water contact angle is surveyed
Examination, as it is shown in figure 5, above one section of curve represents the absworption peak on the surface of the silicon chip not processed through sugar-containing polymer, below
One section of curve represents the absworption peak on the surface of the silicon chip processed through sugar-containing polymer, is shown by contrast, through sugary polymerization
The silicon chip that thing processes has obvious absworption peak, shows that the surface adsorption property of sugar-containing polymer prepared by the present embodiment is stronger.
The surface of silicon chip substantially has absworption peak, and as shown in Figure 6, the water contact angle of silicon chip surface is reduced to 43 ° by 57 °, the suction on surface
Attached performance is substantially improved.
Embodiment 3
Weigh 2-(methacryl amido) the Glucopyranose. mannose of 0.25g, 44.7mg dopamine methacryl
4-cyano group-4-(the benzene of amine, 1mg iron powder and the compositions of 2.2mg copper bromide powder, the 2 bromopropionic acid methyl ester of 1.2uL and 4.2mg
Base sulfur acute pyogenic infection of nails acyl sulfenyl) valeric acid N-succinimido ester is dissolved in the dimethyl sulfoxide of 1mL, under 25 DEG C of room temperature oxygen free conditions
One pot reaction 8h, then coagulation in methanol, obtains white precipitate, centrifugal, is dried, weighs.
After 50ml, 0.1mol/L trishydroxymethylaminomethane (Tris) solution mixes with 22.9ml 0.1mol/L hydrochloric acid, add
Water is diluted to 100ml, and the pH of regulation mixed liquor is 8.2, is made into Tris-HCl solution.
Take 0.2 gram of sugar-containing polymer PDMA-MAG with surface activity to be dissolved in the Tris-HCl solution prepared and must mix
Close liquid, polystyrene sheet is placed in culture dish, and above-mentioned mixed liquor is added drop-wise on polystyrene sheet, submergence, put into room temperature
At Yin Liang, it is washed with deionized surface after 4h 3 times, then normal temperature drying.Polystyrene sheet after processing carries out infrared survey
Examination and water contact angle are tested, as it is shown in fig. 7, above one section of curve represents the polystyrene sheet not processed through sugar-containing polymer
The absworption peak on surface, below one section of curve represent the absworption peak on surface of the polystyrene sheet processed through sugar-containing polymer,
Being shown by contrast, the polystyrene sheet processed through sugar-containing polymer has obvious absworption peak, shows prepared by the present embodiment
The surface adsorption property of sugar-containing polymer stronger.As shown in Figure 8, the water contact angle on polystyrene sheet surface is reduced to by 85 °
44 °, surface water solublity is substantially improved.Weigh 0.02mg bovine serum albumin (BSA) and be dissolved in the phosphate buffer solution (PBS of 1mL
Buffer) in, infiltration process after polystyrene sheet surface, be washed with deionized after 1h, be then 488nm in excitation wavelength
Under do confocal fluorescent image.
As it is shown in figure 9, through the polystyrene sheet surface of bovine serum albumin modification without obvious confocal fluorescent phenomenon, show
Sugar-containing polymer prepared by the present embodiment is to bovine serum albumin indistinction.
Shown in Fig. 4 of embodiment 1 and Fig. 9 of embodiment 3, the sugary polymerization with surface adsorption of the present invention
Thing has specific recognition to albumen.
Above-described is only some embodiments of the present invention, for those of ordinary skill in the art, is not paying
On the premise of going out creative work, it is also possible to make some deformation and improvement, these broadly fall into protection scope of the present invention.
Claims (8)
1. there is the sugar-containing polymer of surface adsorption, it is characterised in that its molecular structural formula is as follows:
Wherein the span of m is 30-200, and the span of a is 30-200.
The preparation method of the sugar-containing polymer with surface adsorption the most according to claim 1, it is characterised in that with first
Base acrylic amide is raw material containing sugar monomer and Dopaminergics monomer, adds initiator and chain-transferring agent, and adds catalyst, logical
Cross one kettle way to be prepared,
Wherein the span of n is 30-200, and the span of b is 30-200.
The preparation method of the sugar-containing polymer with surface adsorption the most according to claim 2, it is characterised in that described
The mol ratio of the sugary monomer of methacryl amine, Dopaminergics monomer, initiator and chain-transferring agent is 5-15:1:0.004:
0.01。
The preparation method of the sugar-containing polymer with surface adsorption the most according to claim 2, it is characterised in that described
Initiator is azo-initiator or bromo initiator.
The preparation method of the sugar-containing polymer with surface adsorption the most according to claim 4, it is characterised in that described
Initiator is selected from azodiisobutyronitrile or 2-isobutyl ethyl bromide or ethyl α bromoisobutyrate.
The preparation method of the sugar-containing polymer with surface adsorption the most according to claim 2, it is characterised in that described
Chain-transferring agent is monothioester class chain-transferring agent.
The preparation method of the sugar-containing polymer with surface adsorption the most according to claim 6, it is characterised in that described
Chain-transferring agent is selected from dithio naphthoic acid isopropyl cyanide ester or 4-cyano group-4-(phenyl formyl sulfenyl) valeric acid or 4-cyano group-4-
(phenyl formyl sulfenyl) valeric acid N-succinimido ester.
The preparation method of the sugar-containing polymer with surface adsorption the most according to claim 2, it is characterised in that described
Catalyst is ferrum and the compositions of copper bromide or copper.
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Cited By (4)
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| CN107652393A (en) * | 2017-10-20 | 2018-02-02 | 苏州大学 | Adsorption antibacterial sugar-containing polymer and preparation method thereof |
| CN109343309A (en) * | 2018-12-03 | 2019-02-15 | 深圳市华星光电技术有限公司 | Negative photoresist and its application |
| CN109350739A (en) * | 2018-11-12 | 2019-02-19 | 苏州大学 | A kind of new type anticancer immunologic adjuvant and preparation method thereof |
| CN110204755A (en) * | 2019-06-12 | 2019-09-06 | 苏州大学 | Purposes of the dopamine containing sugar copolymer |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107652393A (en) * | 2017-10-20 | 2018-02-02 | 苏州大学 | Adsorption antibacterial sugar-containing polymer and preparation method thereof |
| CN109350739A (en) * | 2018-11-12 | 2019-02-19 | 苏州大学 | A kind of new type anticancer immunologic adjuvant and preparation method thereof |
| CN109350739B (en) * | 2018-11-12 | 2021-11-05 | 苏州大学 | Novel anti-cancer immunologic adjuvant and preparation method thereof |
| CN109343309A (en) * | 2018-12-03 | 2019-02-15 | 深圳市华星光电技术有限公司 | Negative photoresist and its application |
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| CN110204755A (en) * | 2019-06-12 | 2019-09-06 | 苏州大学 | Purposes of the dopamine containing sugar copolymer |
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