CN107286355A - Cationically ampholytic ionic copolymer and polycaprolactone blend film and its preparation method and application - Google Patents
Cationically ampholytic ionic copolymer and polycaprolactone blend film and its preparation method and application Download PDFInfo
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Abstract
The present invention discloses cationically ampholytic ionic copolymer and polycaprolactone blend film and its preparation method and application, cationically ampholytic ionic copolymer/polycaprolactone blend film is to use Invertible ideal method synthetic segmented copolymer by dimethylaminoethyl methacrylate and methacrylic sulfonic acids glycine betaine, then with polycaprolactone using solution blended process preparation blend film.The present invention is used as polymer backbone using the preferable methyl acrylic ester of biocompatibility first, cation and amphion are side base, obtain cationically ampholytic ionic copolymer, film is blended with biodegradable polycaprolactone again, the blend film with good antibacterial activity and Adhesion Resistance is prepared, while smaller to organismal toxicity.Preparation process of the present invention is simply controllable, and prepared blend film has good antibacterial activity and anti-albumen adhesion property concurrently, it is adaptable to which biomedical material surface is modified.
Description
Technical field
The invention belongs to field of biomedical polymer materials, be related to a kind of cation-amphoteric ion copolymer/gather oneself in
The preparation of ester blend film and its antibacterial/anti-adhesive application.
Background technology
Bacterium is in the adhesion on medicine equipment and implants in vivo surface, propagation and forms biomembrane (biofilm), causes to suffer from
Person infects and triggers a series of complication or even jeopardize patient vitals.The method of traditional imparting antibacterial surface property is to apply antibacterial
Agent, such as antibacterials, silver, copper and antibacterial peptide, have the disadvantage that antimicrobial component is easy to run off, and discharge to environmentally hazardous substance.Quaternary ammonium salt resists
Microbial inoculum sterilization speed is fast, safety, small toxicity, can assign other materials anti-microbial property as additive.Due to small molecule quaternary ammonium salt
There is limitation in volatile, poor chemical stability, practical application.High molecular quaternary antiseptic as cationic polymer,
Similar with imitative antibacterial peptide polymer architecture, chemical stability is always one of focus of anti-biotic material research preferably.Its antibacterial machine
Reason is similar with small molecule quaternary ammonium salt, i.e., acted on electronegative phosphatide on bacteria cell wall, hydrophobic alkyl chain and bacterial cell membrane
Middle hydrophobic lipid molecular layer is combined, and causes bacterial cell membrane to destroy and bacterial death, is used as contact-type antibacterial biological material more.Cause
This, quaternary ammonium salt antibacterial polymer has long acting antibiotic mechanism, is a kind of extremely promising green material.
Inspired by this, (Palermo E F, the Kuroda K.Chemical structure of cationic such as Kuroda
groups in amphiphilic polymethacrylates modulates the antimicrobial and
Hemolytic activities.Biomacromolecules, 2009,10,1416-1428.) utilize the cation of primary amino radical
The hydrophobicity of property and alkyl side chain, has synthesized polymethacrylate antibacterial polymer, research shows, cation property copolymer
There is outstanding antibacterial activity to Escherichia coli, and the antibacterial activity of primary amino radical is better than quaternary ammonium salt.(the Zhao such as Zhao Jie
J,Ma L,Millians W,Wu T,Ming W H.Dual-Functional Antifogging/Antimicrobial
Polymer Coating.Acs Applied Materials＆Interfaces, 2016,8,8737-8742.) utilize synthesis
The copolymer polymethylacrylic acid dimethylaminoethyl-b- poly-methyl methacrylates of the quaternary ammoniated methyl methacrylate in part
Ester, semi-interpenetrating network polymer coating is prepared for ethylene glycol dimethacrylate, difunctional with antifog/antibacterial.Both sexes
Ionomer has hydrophilic anions and canons group, can form hydration layer, so that with unique stable against biological contamination
Can, that is, it is capable of the absorption of impedance nonspecific protein, antibacterium sticks the formation with biomembrane, and this characteristic makes it in biology
The association areas such as medical science are more and more applied.Jiang Shaoyi et al. (Chang Y, Chen S F, Zhang Z, Jiang S
Y.Highly Protein-Resistant Coatings from Well-Defined Diblock Copolymers
Containing Sulfobetaines.Langmuir, 2006,22,2222-2226.) synthesize poly-sulphonic acid betaine methyl-prop
Olefin(e) acid ester-polypropylene oxide copolymers, and during by the absorption of this copolymer on spr sensor, it is found that small protein exists
The adsorbance on surface is just very low, and adsorbance of the macro-molecular protein on surface is then higher.Jiang Shaoyi et al. (Yang W, Chen
S F,Cheng G,VaisocherováH,Xue H,Li W,Zhang J L,Jiang S Y.Film Thickness
Dependence of Protein Adsorption from Blood Serum and Plasma onto Poly
(sulfobetaine)-Grafted Surfaces.Langmuir, 2008,24,9211-9214.) and be grafted not in gold surface
Stack pile polymethylacrylic acid sulphonic acid betaine, adsorbs situations, as a result table to study their protein in protein solution
There are fairly good antifouling properties on bright surface in 100% serum and blood plasma.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide cation-amphoteric ion copolymer with gathering in oneself
Ester blend film and its preparation method and application, its application in terms of antibacterial and anti-nonspecific protein adhesion is existing to overcome
There is anti-biotic material antibacterial activity weaker, the shortcomings of easily causing protein adherence.
The technical purpose of the present invention is achieved by following technical proposals：
Cation-amphoteric ion copolymer and the preparation method of polycaprolactone blend film, are carried out as steps described below：
Step 1, polymethylacrylic acid dimethylaminoethyl homopolymer is prepared
Monomer methacrylic acid dimethylaminoethyl homopolymerization is formed, turned by chain of dithiobenzoic acid -4- cyanopentanoic acids
Agent is moved, azodiisobutyronitrile is that initiator carries out RAFT polymerizations, monomer methacrylic acid dimethylaminoethyl, chain-transferring agent and is drawn
The molar ratio for sending out agent is (150-200)：1：(0.1-0.5), preferably (160-180)：1：0.2；
In step 1, carry out inert protective gas (nitrogen, helium or argon gas) protection is lower, reaction temperature for 60-
80 degrees Celsius, at least 1 hour reaction time, preferable reaction temperature is 70-80 degrees Celsius, and the reaction time is 3-5 hours, solvent
Tetrahydrofuran provides reaction atmosphere and environment.
In step 1, monomer, chain-transferring agent and initiator are dispersed in tetrahydrofuran freeze-take out by three times-it is molten
Circulation, is placed in oil bath pan to heat up to stir under inertia protection protection and is reacted, poly- methyl-prop is obtained through multiple deposition and purification
Olefin(e) acid dimethylaminoethyl homopolymer.
Step 2, cation-amphoteric ion copolymer is prepared
Polymethylacrylic acid dimethylaminoethyl homopolymer prepared by step 1 is used as Macromolecular chain transfer agent, azo two
Isobutyronitrile is initiator, adds second comonomer methacrylic sulfonic acids glycine betaine and carries out RAFT polymerizations to obtain cation-both sexes
Ionic copolymer, the molar ratio of second comonomer methacrylic sulfonic acids glycine betaine, Macromolecular chain transfer agent and initiator is
(40—120)：1：(0.1-0.5), preferably (60-100)：1：0.2；
In step 2, carry out inert protective gas (nitrogen, helium or argon gas) protection is lower, reaction temperature for 60-
80 degrees Celsius, at least 1 hour reaction time, preferable reaction temperature is 70-80 degrees Celsius, and the reaction time is 6-10 hours, molten
Agent tetrahydrofuran provides reaction atmosphere and environment.
In step 2, Macromolecular chain transfer agent, second comonomer methacrylic sulfonic acids glycine betaine, initiator are uniformly divided
Be dispersed in tetrahydrofuran and freeze-take out-molten circulation by three times, be placed in oil bath pan the stirring under inertia protection protection that heats up carry out it is anti-
Should, obtain cation-amphoteric ion copolymer through multiple deposition and purification.
It is polymerize in the present invention using reversible addion-fragmentation chain transfer and is carried out, RAFT polymerizations is a kind of activity/controllable free
Base polymerize, and is applicable the monomer containing double bond functional group.In RAFT polymerizations, conventional initiator is thermally decomposed into primary group of free radicals I.,
And trigger monomer to aggregate into Propagating Radical Pn ., during Propagating Radical is formed with the reversible addition of C=S keys progress in chain-transferring agent
S-R keys are broken in mesosome dormancy kind, dormancy kind, form new spike free radical Rn ., then triggering monomer to polymerize, reaction mechanism is such as
Shown in lower Fig. 1.Different from conventional free radical polymerization, RAFT polymerization chain tra nsfers are reversible process, intermediate dormancy kind and growing chain
The balanced reaction of reversible addition and reversible fracture is carried out between free radical, so that it is guaranteed that all chains are grown with equal probability, shape
Into the polymer of narrow ditribution, number of free radical is maintained in the reduced levels of a relative constancy, inhibition system freely in system
The biradical terminating reaction of base so that polymerization activity is controllable.Trigger the first monomer using initiator in the present invention, single with first
Body and chain-transferring agent carry out living polymerization, when adding second comonomer, and supplement initiator is to trigger second comonomer, with living polymerization
The first obtained monomer homopolymers are the living polymerization that Macromolecular chain transfer agent carries out second comonomer, that is, obtain cation-both sexes
Ionic block copolymers (cation-amphoteric ion copolymer), form the copolymer structure shown in following chemical formula, chemical formula two
End group group is the molecular structure of chain-transferring agent dithiobenzoic acid -4- cyanopentanoic acids, and centre is the repeat unit of high polymer, in view of
It is polymerize using RAFT, the first monomer methacrylic acid dimethylaminoethyl and second comonomer methacrylic sulfonic acids glycine betaine are formed
Block copolymer；Polymer number-average molecular weight is 20-45kDa, and molecular weight distribution index is 1.10-1.30, preferred polymers number
Average molecular weight is 25-40kDa, and molecular weight distribution index is 1.10-1.20；Letter m, q are respectively the first monomer methyl-prop in formula
The degree of polymerization of olefin(e) acid dimethylaminoethyl, second comonomer methacrylic sulfonic acids glycine betaine, m：Q=10：(3-7), preferably m：q
=10：(4—6).In step 1 and step 2 preparation process, polymerization conversion is up to more than 80% -90%.
Step 3, cation-amphoteric ion copolymer/polycaprolactone blend film is prepared
Polycaprolactone and obtained cation-amphion block copolymer are dispersed in trifluoroethanol (instant
In trifluoroethanol) form coating liquid and dried coating film after obtain blend film, in polycaprolactone and cation-amphion block
In the composition of copolymer, the mass percent of polycaprolactone is 10%-30%, preferably 20-25%.
In step 3, coating liquid is persistently stirred 6-12 hours under 20-25 degrees Celsius, to realize two kinds of materials
Uniform mixing.
In step 3, take after coating liquid film on the polyfluortetraethylene plate of tiling, 20-24h of surface drying, then be placed in vacuum
40-48h is dried in baking oven under 20-25 degrees Celsius of room temperature, obtained thickness is 20-100 μm, preferably 20-50 μm.
Cation-amphoteric ion copolymer and polycaprolactone blend film, by cation-amphoteric ion copolymer and gather in oneself
Ester, which is dispersed in trifluoroethanol to be formed, obtains blend film after coating liquid and film, cation-amphoteric ion copolymer according to
It is prepared by following step：Dimethylaminoethyl methacrylate is cationic monomer, with dithiobenzoic acid -4- cyano group penta
Acid is chain-transferring agent, and azodiisobutyronitrile is that initiator carries out reversible addion-fragmentation chain transfer polymerization, obtains corresponding homopolymerization
Thing；Then, methacrylic sulfonic acids glycine betaine is zwitterionic monomer (second comonomer), purified polymethylacrylic acid two
Methylamino ethyl ester homopolymer is Macromolecular chain transfer agent, and azodiisobutyronitrile is initiator, continues synthesizing cationic-amphion
Block copolymer.
The thickness of above-mentioned blend film is 20-100 μm, preferably 20-50 μm.
In the above-mentioned technical solutions, polycaprolactone number-average molecular weight is 2000-8000, preferably 6000-8000.
Cation-amphion block copolymer (cation-amphoteric ion copolymer) has shown in following chemical formula
Copolymer structure, chemical formula two ends group is the molecular structure of chain-transferring agent dithiobenzoic acid -4- cyanopentanoic acids, and centre is height
The repeat unit of polymers, in view of being polymerize using RAFT, the first monomer methacrylic acid dimethylaminoethyl and second comonomer methyl
Acrylic acid sulphonic acid betaine formation block copolymer；Polymer number-average molecular weight is 20-45kDa, and molecular weight distribution index is
1.10-1.30, preferred polymers number-average molecular weight is 25-40kDa, and molecular weight distribution index is 1.10-1.20；Letter m in formula,
Q is respectively the first monomer methacrylic acid dimethylaminoethyl, the degree of polymerization of second comonomer methacrylic sulfonic acids glycine betaine, m：
Q=10：(3-7), preferably m：Q=10：(4—6).
Application of the cation-amphion block copolymer (cation-amphoteric ion copolymer) in antibacterial, in anti-egg
Application in white adhesion.Cation-amphoteric ion copolymer and application of the polycaprolactone blend film in antibacterial, it is viscous in anti-albumen
The application of attached middle school.
Compared with prior art, the present invention utilizes cationic dimethylaminoethyl methacrylate and amphion
Methacrylic sulfonic acids glycine betaine is that monomer prepares block copolymer, then uses solution blending with biodegradable polycaprolactone
Method prepares blend film, to realize excellent anti-microbial property, efficiently anti-nonspecific proteins adhesiveness and significant bio-compatible
Property, harm of the anti-biotic material to human normal tissue is reduced while reduction patient medical apparatus infection risk.
Brief description of the drawings
Fig. 1 is the mechanism of polymerization schematic diagram of reversible addion-fragmentation chain transfer polymerization (RAFT) in the present invention.
Fig. 2 is that the polymethylacrylic acid dimethylaminoethyl of reversible addion-fragmentation chain transfer polymerization preparation in the present invention is equal
Polymers in CDCl3In1H-NMR spectrum.
Fig. 3 is that cation-amphion block copolymer of reversible addion-fragmentation chain transfer polymerization preparation in the present invention exists
D2In O1H-NMR spectrum.
Fig. 4 is the SEM photograph for carrying out antibacterial experiment result in the present invention using staphylococcus aureus, wherein (A) is sky
White control；(B) it is experimental group.
Fig. 5 is the SEM photograph for carrying out antibacterial experiment result in the present invention using Escherichia coli, wherein (A) is blank control；
(B) it is experimental group.
Fig. 6 is Live/Dead Coloration experiment result schematic diagram of the polymer to Escherichia coli and staphylococcus aureus, its
Middle A and B are Escherichia coli, and C and D are staphylococcus aureus.
Fig. 7 is Bactericidal test result schematic diagram of the blend film of the present invention to staphylococcus aureus.
Fig. 8 is Bactericidal test result schematic diagram of the blend film of the present invention to Escherichia coli.
Embodiment
Technical scheme is further illustrated with reference to specific embodiment.
Embodiment 1：
(1) synthesizing cationics-amphion block copolymer：
By dimethylaminoethyl methacrylate, dithiobenzoic acid -4- cyanopentanoic acids, azodiisobutyronitrile according to mole
Than for 167:1:0.2, be dissolved in purified tetrahydrofuran, be added in Schlenk bottles, be configured to mass fraction for 50% it is molten
Liquid.Through three Frozen-thawed cycled deoxygenation inflated with nitrogen, 4h is reacted in 70 DEG C of oil baths under nitrogen protection.After reaction terminates, crude product is used
N-hexane is precipitated and separated, and obtains polymethylacrylic acid dimethylaminoethyl Macromolecular chain transfer agent.
By methacrylic sulfonic acids glycine betaine, polymethylacrylic acid dimethylaminoethyl Macromolecular chain transfer agent, azo two
Isobutyronitrile is 42 according to mol ratio:1:0.2, refined trifluoroethanol is dissolved in, is added in Schlenk bottles, quality point is configured to
Number is 50% solution.Through three Frozen-thawed cycled deoxygenation inflated with nitrogen, 10h is reacted in 70 DEG C of oil baths under nitrogen protection.Reaction knot
Shu Hou, crude product dialyses product, freezes, obtains polymethylacrylic acid dimethylaminoethyl-b- polymethylacrylic acid sulfonic acid sweet teas
Dish alkali block copolymer.
(2) prepares cation-amphoteric ion copolymer/polycaprolactone blend film：
Cation made from 90mg polycaprolactones and 10mg-amphion block copolymer is taken to be codissolved in 1mL trifluoroethanols
In, the mass fraction of polycaprolactone is 90% in the mixed solution of preparation.It is stirred overnight at room temperature, two kinds of materials are sufficiently mixed.
Then take after 500 μ L mixed solutions film on the polyfluortetraethylene plate of tiling, surface drying 24h, then be placed in room temperature in vacuum drying oven
Lower drying 48h, obtained thickness is 20 μm.
Embodiment 2：
(1) synthesizing cationics-amphion block copolymer：
By dimethylaminoethyl methacrylate, dithiobenzoic acid -4- cyanopentanoic acids, azodiisobutyronitrile according to mole
Than for 167:1:0.2, be dissolved in purified tetrahydrofuran, be added in Schlenk bottles, be configured to mass fraction for 50% it is molten
Liquid.Through three Frozen-thawed cycled deoxygenation inflated with nitrogen, 4h is reacted in 70 DEG C of oil baths under nitrogen protection.After reaction terminates, crude product is used
N-hexane is precipitated and separated, and obtains polymethylacrylic acid dimethylaminoethyl Macromolecular chain transfer agent.
By methacrylic sulfonic acids glycine betaine, polymethylacrylic acid dimethylaminoethyl Macromolecular chain transfer agent, azo two
Isobutyronitrile is 70 according to mol ratio:1:0.2, refined trifluoroethanol is dissolved in, is added in Schlenk bottles, quality point is configured to
Number is 50% solution.Through three Frozen-thawed cycled deoxygenation inflated with nitrogen, 10h is reacted in 70 DEG C of oil baths under nitrogen protection.Reaction knot
Shu Hou, crude product dialyses product, freezes, obtains polymethylacrylic acid dimethylaminoethyl-b- polymethylacrylic acid sulfonic acid sweet teas
Dish alkali block copolymer.
(2) prepares cation-amphoteric ion copolymer/polycaprolactone blend film：
Cation made from 80mg polycaprolactones and 20mg-amphion block copolymer is taken to be codissolved in 1mL trifluoroethanols
In, the mass fraction of polycaprolactone is 80% in the mixed solution of preparation.It is stirred overnight at room temperature, two kinds of materials are sufficiently mixed.
Then take after 500 μ L mixed solutions film on the polyfluortetraethylene plate of tiling, surface drying 24h, then be placed in room temperature in vacuum drying oven
Lower drying 48h, obtained thickness is 36 μm.
Embodiment 3：
(1) synthesizing cationics-amphion block copolymer：
By dimethylaminoethyl methacrylate, dithiobenzoic acid -4- cyanopentanoic acids, azodiisobutyronitrile according to mole
Than for 167:1:0.2, be dissolved in purified tetrahydrofuran, be added in Schlenk bottles, be configured to mass fraction for 50% it is molten
Liquid.Through three Frozen-thawed cycled deoxygenation inflated with nitrogen, 4h is reacted in 70 DEG C of oil baths under nitrogen protection.After reaction terminates, crude product is used
N-hexane is precipitated and separated, and obtains polymethylacrylic acid dimethylaminoethyl Macromolecular chain transfer agent.
By methacrylic sulfonic acids glycine betaine, polymethylacrylic acid dimethylaminoethyl Macromolecular chain transfer agent, azo two
Isobutyronitrile is 98 according to mol ratio:1:0.2, refined trifluoroethanol is dissolved in, is added in Schlenk bottles, quality point is configured to
Number is 50% solution.Through three Frozen-thawed cycled deoxygenation inflated with nitrogen, 10h is reacted in 70 DEG C of oil baths under nitrogen protection.Reaction knot
Shu Hou, crude product dialyses product, freezes, obtains polymethylacrylic acid dimethylaminoethyl-b- polymethylacrylic acid sulfonic acid sweet teas
Dish alkali block copolymer.
(2) prepares cation-amphoteric ion copolymer/polycaprolactone blend film：
Cation made from 70mg polycaprolactones and 30mg-amphion block copolymer is taken to be codissolved in 1mL trifluoroethanols
In, the mass fraction of polycaprolactone is 70% in the mixed solution of preparation.It is stirred overnight at room temperature, two kinds of materials are sufficiently mixed.
Then take after 500 μ L mixed solutions film on the polyfluortetraethylene plate of tiling, surface drying 24h, then be placed in room temperature in vacuum drying oven
Lower drying 48h, obtained thickness is 50 μm.
The homopolymer of preparation is characterized using nuclear magnetic resonance, such as polymethylacrylic acid dimethylaminoethyl homopolymer
Nuclear-magnetism figure.Peak (c) at δ=4.02ppm corresponds to the signal peak for the methylene being connected on side chain with O.From figure δ=
Peak (f) at 7.9ppm corresponds to the signal peak of main chain terminal benzene ring hydrogen.Pass through the integration of peak f integral area and peak c
Area ratio is 140 come the degree of polymerization for determining the homopolymer prepared.As shown in drawings, the block that two kinds of species activity polymerizations are obtained
Copolymer is in D2In O1H-NMR spectrum, the peak (d) at δ=2.57ppm corresponds to the signal peak for the methylene being connected with N,
Peak (d ') at δ=3.52ppm corresponds to and N+The signal peak of the methylene of connected close main chain, by contrasting peak (d)
The unit number of polymethylacrylic acid sulphonic acid betaine section in block copolymer is determined with the ratio between the integral area of (d ').
The copolymer and coating material prepared to the present invention carries out performance test：
Anti-microbial property is tested using inhibition zone method：Staphylococcus aureus is selected to be represented for gram-positive bacteria, large intestine bar
Bacterium is represented for Gram-negative bacteria, and bacterium bacterial strain incubated overnight is reached into growth medium first, 3 are diluted to phosphate buffer
×108CFU/ml.Polycarbonate polyurethane membrane sample is prepared into a diameter of 1cm circular sample using card punch, it is standby.
By 3 × 108CFU/ml bacteriums liquid dilutes 1000 times, takes 200 μ L to drip to solid agar plate surface and spread even, places into sample, 37
24h is cultivated at DEG C, colony growth situation is observed.
Anti-microbial property is tested using Live/Dead decoration methods：Using card punch by sample preparation into a diameter of 1cm circle
Sample, ultraviolet lighting 10h carries out sterilization treatment.It is then placed in 48 orifice plates.Using L13152 staining kits, prepared first
Mixed liquor is dyed into 2X.By on microbionation to beef extract-peptone agar natural medium, in 37 DEG C of shaken cultivations to logarithm
In growth period (24h), take 300 μ L bacterium solutions to centrifuge 5min at 3,000 rpm, be inoculated into 48 orifice plates, resuspension breaks up cenobium,
The concussion and cultivate 3h in 37 DEG C of incubators, makes coating fully be contacted with bacterium.After culture terminates, washing is resuspended with ultra-pure water many
It is secondary, remove traces of medium.Mixed liquor is dyed then to the 2X that 100 μ L are added in bacterium solution, the ultimate density for making dyeing liquor is：
30 μM of 6 μM of SYTO9, PI.Concussion and cultivate 15min in dark at room temperature.Then supernatant is removed and with ultra-pure water by coating
Rinse multiple, then carry out mounting.Sample is placed under 63X laser confocal microscope (LSCM) and observed, is used at 488nm
Ar/Kr laser：Ex/Em：480/500nm, SYTO9, complete cell membrane show green glow；Ex/Em：490/635nm, PI are damaged
Cell membrane show feux rouges.
Utilize the anti-albumen adhesion property of bovine serum albumin(BSA) test polymer coating：With card punch by sample preparation Cheng Zhi
Footpath is 1cm circular sample, is dipped in phosphate buffer, in balancing 12h at 37 DEG C in constant incubator.1mg/ is immersed in again
In the PBS solution of mL bovine serum albumin (BSA), in cultivating 2h at 37 DEG C in constant incubator.After sample is taken out respectively
Rinsed twice with PBS solution and deionized water concussion, to remove the unadsorbed BSA in sample surfaces, prepare 1wt% SDS water
Solution, sample is moved in 24 new orifice plates, makes BSA De contaminations with lauryl sodium sulfate (SDS) aqueous solution room temperature concussion 1h.
The amino in its albumen with De contamination is set to occur chromogenic reaction using MicroBCA kits, using ELIASA at 570nm
Determine absorption value.The calibration curve solution of BSA a series of is prepared simultaneously, is obtained the albumen that each sample adsorbed by calculating and is contained
Amount.
As shown in figs. 4 and 5, after cement-based powder material and its film are handled, staphylococcus aureus thalline is still possessed more intact
Formalness, but phage surface is coarse, and notable gauffer and rupture occurs in thalline cell wall, and observes that bacterium surface has many
Granular substance occurs, and has vesicle and bead to be formed；Most of surface of E. coli has obvious hole to occur, and also has in addition
Part bacterium occurs in that fracture and the phenomenon caved in.As shown in Figure 6, polymer and its film are to Escherichia coli (A, B) and golden yellow
The Live/Dead Coloration experiments of color staphylococcus (C, D) are dyed to red results, it can be seen that bacterium is substantially all, and illustrate thin
Bacterium cell membrane has been destroyed.As depicted in figures 7 and 8, blend film of the present invention to staphylococcus aureus, Escherichia coli it is antibacterial
Experimental result schematic diagram is enclosed, control group (P0) still has bacterial growth at blank film covering, and experimental group (P1, P2, P3) is altogether
Apparently without bacterial growth at mixed film covering, P0, P1, P2, P3 is respectively the blend film of different component, i.e. polycaprolactone content point
Wei not 100% (P0 be dissolved in trifluoroethanol using polycaprolactone and carries out film), 90% (P1), 80% (P2), 70%
(P3).From anti-albumen adhesion results：Polymer and its film can averagely resist 50%-70% bovine serum albumin adhesion
(albumen for not adhering to or adsorbing accounts for the ratio of total amount).
The adjustment of technological parameter is carried out according to present invention, the preparation of copolymer film, and performance and reality can be achieved
Apply example basically identical.Exemplary description is done to the present invention above, it should explanation, do not departed from the core of the present invention
In the case of, any simple deformation, modification or other skilled in the art can not spend being equal for creative work to replace
Change and each fall within protection scope of the present invention.
Claims (10)
1. cation-amphoteric ion copolymer and the preparation method of polycaprolactone blend film, it is characterised in that as steps described below
Carry out：
Step 1, polymethylacrylic acid dimethylaminoethyl homopolymer is prepared
Monomer methacrylic acid dimethylaminoethyl homopolymerization is formed, using dithiobenzoic acid -4- cyanopentanoic acids as chain-transferring agent,
Azodiisobutyronitrile is that initiator carries out RAFT polymerizations, monomer methacrylic acid dimethylaminoethyl, chain-transferring agent and initiator
Molar ratio be (150-200)：1：(0.1-0.5), preferably (160-180)：1：0.2；
Step 2, cation-amphoteric ion copolymer is prepared
Polymethylacrylic acid dimethylaminoethyl homopolymer prepared by step 1 is used as Macromolecular chain transfer agent, the isobutyl of azo two
Nitrile is initiator, adds second comonomer methacrylic sulfonic acids glycine betaine and carries out RAFT polymerizations to obtain cation-amphion
Copolymer, the molar ratio of second comonomer methacrylic sulfonic acids glycine betaine, Macromolecular chain transfer agent and initiator for (40-
120)：1：(0.1-0.5), preferably (60-100)：1：0.2；
Step 3, cation-amphoteric ion copolymer/polycaprolactone blend film is prepared
Polycaprolactone and obtained cation-amphion block copolymer are dispersed in trifluoroethanol and (are dissolved in three
In fluoroethanol) form coating liquid and dried coating film after obtain blend film, in polycaprolactone and cation-amphion block copolymerization
In the composition of thing, the mass percent of polycaprolactone is 10%-30%, preferably 20-25%.
2. cation-amphoteric ion copolymer according to claim 1 and the preparation method of polycaprolactone blend film, it is special
Levy and be, in step 1, carried out under inert protective gas (nitrogen, helium or argon gas) protection, reaction temperature is 60-80
Degree Celsius, at least 1 hour reaction time, preferable reaction temperature is 70-80 degrees Celsius, and the reaction time is 3-5 hours, solvent four
Hydrogen furans provides reaction atmosphere and environment.
3. cation-amphoteric ion copolymer according to claim 1 and the preparation method of polycaprolactone blend film, it is special
Levy and be, in step 2, carried out under inert protective gas (nitrogen, helium or argon gas) protection, reaction temperature is 60-80
Degree Celsius, at least 1 hour reaction time, preferable reaction temperature is 70-80 degrees Celsius, and the reaction time is 6-10 hours, solvent
Tetrahydrofuran provides reaction atmosphere and environment.
4. cation-amphoteric ion copolymer according to claim 1 and the preparation method of polycaprolactone blend film, it is special
Levy and be, in step 3, coating liquid is persistently stirred 6-12 hours under 20-25 degrees Celsius, to realize the equal of two kinds of materials
Even mixing；Take after coating liquid film on the polyfluortetraethylene plate of tiling, 20-24h of surface drying, then be placed in room temperature in vacuum drying oven
40-48h is dried under 20-25 degrees Celsius, obtained thickness is 20-100 μm, preferably 20-50 μm.
5. cation-amphion block copolymer, it is characterised in that the first monomer methacrylic acid diformazan is polymerize using RAFT
Amino ethyl ester, second comonomer methacrylic sulfonic acids glycine betaine formation block copolymer, form the copolymerization shown in following chemical formula
Thing structure, chemical formula two ends group is the molecular structure of chain-transferring agent dithiobenzoic acid -4- cyanopentanoic acids, and centre is high polymer
Repeat unit, letter m, q are respectively the first monomer methacrylic acid dimethylaminoethyl, second comonomer methacrylic acid in formula
The degree of polymerization of sulphonic acid betaine, m：Q=10：(3—7).
6. cation according to claim 5-amphion block copolymer, it is characterised in that the equal molecule of polymer number
Measure as 20-45kDa, molecular weight distribution index is 1.10-1.30, preferred polymers number-average molecular weight is 25-40kDa, molecular weight
Breadth coefficient is 1.10-1.20；It is preferred that m：Q=10：(4—6).
7. cation-amphoteric ion copolymer and polycaprolactone blend film, it is characterised in that by cation-amphion copolymerization
Thing and polycaprolactone are dispersed in trifluoroethanol and obtain blend film, cation-amphion after formation coating liquid and film
Copolymer is prepared as steps described below：Dimethylaminoethyl methacrylate is cationic monomer, with two thio phenyl first
Acid -4- cyanopentanoic acids are chain-transferring agent, and azodiisobutyronitrile is that initiator carries out reversible addion-fragmentation chain transfer polymerization, is obtained
Corresponding homopolymer；It is zwitterionic monomer as second comonomer using methacrylic sulfonic acids glycine betaine, purified poly- first
Base dimethylaminoethyl acrylate homopolymer be Macromolecular chain transfer agent, azodiisobutyronitrile is initiator, continue synthesize sun from
Son-amphion block copolymer.
8. cation-amphoteric ion copolymer according to claim 7 and polycaprolactone blend film, it is characterised in that altogether
The thickness of mixed film is 20-100 μm, preferably 20-50 μm；Polycaprolactone number-average molecular weight be 2000-8000, preferably 6000-
8000。
9. application of the cation-amphion block copolymer in antibacterial or the application in the adhesion of anti-albumen.
10. application in antibacterial of cation-amphoteric ion copolymer and polycaprolactone blend film or in the adhesion of anti-albumen
Application.
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| CN110681264B (en) * | 2019-11-20 | 2021-10-15 | 哈尔滨工业大学（威海） | Preparation method of amphiphilic terpolymer modified ultrafiltration membrane |
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| CN113105826B (en) * | 2020-01-13 | 2022-02-18 | 四川大学 | Biodegradable antibacterial poly (ester) -poly (weak amphiphilic acrylic acid) copolymer coating for magnesium alloy surface modification |
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