CN116376034B - Rosin-based ordered porous membrane and preparation and application thereof - Google Patents
Rosin-based ordered porous membrane and preparation and application thereof Download PDFInfo
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- CN116376034B CN116376034B CN202310241247.1A CN202310241247A CN116376034B CN 116376034 B CN116376034 B CN 116376034B CN 202310241247 A CN202310241247 A CN 202310241247A CN 116376034 B CN116376034 B CN 116376034B
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- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 title claims abstract description 97
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 title claims abstract description 97
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 239000012528 membrane Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
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- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 67
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 15
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 150000002148 esters Chemical class 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- -1 polytetrafluoroethylene Polymers 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000287 crude extract Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 4
- 238000000502 dialysis Methods 0.000 claims description 3
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- 230000000241 respiratory effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 238000004113 cell culture Methods 0.000 abstract description 11
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000003242 anti bacterial agent Substances 0.000 abstract description 3
- 229940088710 antibiotic agent Drugs 0.000 abstract description 3
- 239000003519 biomedical and dental material Substances 0.000 abstract description 3
- 230000004663 cell proliferation Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 210000004027 cell Anatomy 0.000 description 10
- 239000011521 glass Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 6
- 239000002609 medium Substances 0.000 description 6
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 3
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- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
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- 238000001878 scanning electron micrograph Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
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- 108091003079 Bovine Serum Albumin Proteins 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
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- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N5/00—Undifferentiated human, animal or plant cells, e.g. cell lines; Tissues; Cultivation or maintenance thereof; Culture media therefor
- C12N5/06—Animal cells or tissues; Human cells or tissues
- C12N5/0602—Vertebrate cells
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- C08J2387/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N2533/00—Supports or coatings for cell culture, characterised by material
- C12N2533/30—Synthetic polymers
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Abstract
The invention discloses a rosin-based ordered porous membrane, and preparation and application thereof, wherein the raw materials of the rosin-based ordered porous membrane comprise: maleic rosin, polyethylene glycol, p-toluenesulfonic acid and dimethylbenzene, wherein the mass ratio of the maleic rosin to the polyethylene glycol is 2.5:1; the molecular weight of the polyethylene glycol is 800. The invention solves the technical problems of poor biodegradability, biocompatibility and mechanical property of the existing cell culture support material. The preparation method disclosed by the invention is mild in reaction conditions, low in cost and environment-friendly, and the prepared rosin-based ordered porous membrane has the advantages of biodegradability, good biocompatibility, antibacterial property, good mechanical property and low cost, is used as a biomedical material in cell culture, is beneficial to cell proliferation, and can reduce the use amount of antibiotics.
Description
Technical Field
The invention relates to a cell culture support material, in particular to a rosin-based ordered porous membrane, and preparation and application thereof.
Background
The support material for cell culture is mostly polystyrene because polystyrene is easy to synthesize and cheap. However, polystyrene is a non-renewable resource, and the biocompatibility and degradation performance of polystyrene as a chemically synthesized hard segment material are poor, and polystyrene as a cell culture plate generally uses a certain amount of antibiotics to prevent microbial infection during cell culture due to microbial contamination.
At present, materials with good biocompatibility, such as polylactic acid and derivatives thereof, are used as scaffold materials for cell culture to become research hot spots, but the scaffold materials containing polylactic acid frameworks are very slow to degrade, 50% of degradation needs 1-2 years, and the mechanical properties are relatively poor, and the degradable polymer synthetic materials of polylactic acid and derivatives thereof are expensive.
Disclosure of Invention
The invention aims to provide a rosin-based ordered porous membrane and preparation and application thereof, and solves the technical problems of poor biodegradability, biocompatibility and mechanical property of the existing cell culture support material.
In order to achieve the above purpose, the invention provides a polymaleic rosin polyethylene glycol ester, which comprises the following raw materials: maleic rosin, polyethylene glycol, p-toluenesulfonic acid and a water-carrying agent. The p-toluenesulfonic acid is a catalyst, sulfuric acid is usually used as the catalyst in the existing esterification reaction, but the sulfuric acid is easy to carbonize reactants, the color of the reactants after the reaction is deepened, and the p-toluenesulfonic acid has moderate acidity, no oxidative carbonization and milder reaction. Because water is generated in the esterification reaction process, the process is a reversible reaction, and the generated water can influence the generation of polyethylene glycol ester of polymaleic rosin, so that a water-carrying agent is required to be added.
Preferably, the mass ratio of the maleated rosin to the polyethylene glycol is 2.5:1. The molecular weight of the poly (maleic rosin-polyethylene glycol) ester has a great influence on the preparation of the porous membrane, when the mass ratio of the substances of the maleic rosin to the polyethylene glycol is smaller, the prepared poly (maleic rosin-polyethylene glycol) ester has smaller molecular weight and cannot form the porous membrane, and when the mass ratio of the substances reaches 2.5:1, the poly (maleic rosin-polyethylene glycol) ester porous membrane can be formed.
Preferably, the polyethylene glycol has a molecular weight of 800; the mass of the p-toluenesulfonic acid is 1% of the total mass of the maleated rosin and the polyethylene glycol, and the volume mass ratio of the water-carrying agent to the maleated rosin is 10ml to 12g; the water-carrying agent can be benzene, toluene or xylene, but according to the reaction temperature and toxicity problems, a water-carrying agent with a proper boiling point and low toxicity is selected, so that the xylene is preferably used as the water-carrying agent.
The invention also provides a preparation method of the polymaleic rosin polyethylene glycol ester, which comprises the following steps:
(1) Mixing and heating water-carrying agent, maleic rosin and polyethylene glycol with the mass ratio of 2.5:1, adding p-toluenesulfonic acid when the temperature reaches 60 ℃, and continuously heating for 30min at 60 ℃; the mass ratio of the maleated rosin to the polyethylene glycol is 2.5:1. The addition of p-toluenesulfonic acid at 60 ℃ (low temperature) can prevent carbonization failure at high temperature.
(2) And (3) raising the temperature to 180-220 ℃ and refluxing to obtain a product. The reflux temperature has a great influence on the reaction time, and the reflux temperature is high and the reaction time is short, so that 180-220 ℃ reflux is adopted, but the temperature cannot be too high, and carbonization and crosslinking can occur.
(3) And (3) carrying out post-treatment on the obtained product to obtain the polymaleic rosin polyethylene glycol ester.
Preferably, in the step (2), the reflux time is 10 to 18 hours.
Preferably, in step (3), the post-treatment comprises: pouring the product into a dialysis bag, filtering to obtain a crude extract, washing the crude extract by a Soxhlet extractor to obtain an extracting solution, and washing the obtained extracting solution by water, ethanol and chloroform in sequence to finally obtain the polymaleic rosin polyethylene glycol ester.
The invention also provides a rosin-based ordered porous membrane, the raw materials of which comprise the polymaleic rosin polyethylene glycol ester.
The invention also provides a preparation method of the rosin-based ordered porous membrane, which comprises the following steps:
(1) And carrying out ultrasonic dissolution on the polymaleic rosin polyethylene glycol ester and dichloromethane to obtain a polymaleic rosin polyethylene glycol ester solution. The dichloromethane has stronger polarity, is easy to dissolve polyethylene glycol ester of maleated rosin, has lower boiling point and is easy to volatilize, the lower the volatilization efficiency is, the easier the temperature difference is formed, and the porous membrane can be effectively prepared; if the boiling point of the solvent is higher, the volatilization time is long, and a sufficient temperature difference is difficult to form, so that a porous membrane is not easy to prepare; if the boiling point of the solvent is too low, the porous film formed has random integrity.
(2) Opening a sealed polytetrafluoroethylene film, casting the polymaleic rosin polyethylene glycol ester solution obtained in the step (1) on the polytetrafluoroethylene film (the polytetrafluoroethylene film is a film forming substrate) by adopting a respiratory pattern method, sealing the casted polytetrafluoroethylene film, and finally preparing the rosin-based ordered porous film after the solvent volatilizes; the sealing temperature is 25-40 ℃ and the humidity is 70-90%. The temperature is 25-40 ℃ and the humidity is 70-90% which are film forming conditions, and if the temperature and the humidity are too high or too low, an ordered porous film is not easy to form. When the temperature is too high, the solvent volatilizes too quickly, the condensation time of water drops is shortened, and the aperture is reduced; when the temperature is too low, the viscosity of the casting solution becomes large, water drops cannot penetrate into the inner part so as to continuously grow on the surface, reach a certain stage, and penetrate into the inner part under the action of gravity to form a larger aperture. When the humidity is too low, water drops are not formed; too high a humidity, the water droplets will coalesce and cause a larger pore size. In addition, the molecular weight and concentration of the poly (maleic rosin polyethylene glycol) ester can influence the viscosity of the poly (maleic rosin polyethylene glycol) ester to regulate the surface morphology of the porous membrane, and if the molecular weight and concentration of the poly (maleic rosin polyethylene glycol) ester are too high, the viscosity is high, so that no pores or few pores can be formed; if the molecular weight and concentration are lower, the viscosity is lower, and the water drops cannot be stably wrapped, so that the regularity of the porous film is reduced.
Preferably, the mass concentration of the polymaleic rosin polyethylene glycol ester solution is 30-40 mg/ml.
The invention also provides an application of the rosin-based ordered porous membrane in preparing biomedical materials.
The rosin-based ordered porous membrane, the preparation and the application thereof solve the technical problems of relatively poor biodegradability, biocompatibility and mechanical properties of the existing biomedical material for cell culture support materials, and have the following advantages:
1. According to the invention, the rosin which is a renewable resource is used as a base material, and water is used as a template to prepare the porous membrane, so that the reaction condition is mild, the cost is low, and the porous membrane is environment-friendly.
2. The ordered porous membrane prepared from the rosin PEG (polyethylene glycol) ester has the advantages of biodegradability, good biocompatibility, antibacterial property, good mechanical property and low cost.
3. The rosin-based ordered porous membrane prepared by the invention is applied to cell culture as a biomedical material, is beneficial to cell proliferation, can reduce the dosage of antibiotics, and is expected to show better application prospects in the field of cell culture plates in biomedical materials.
Drawings
FIG. 1 is a nuclear magnetic diagram of the hydrogen spectrum of the PEG ester of polymaleic rosin in the present invention.
FIG. 2 is a GPC chart of a PEG ester of polymaleic rosin obtained in example 1 of the present invention.
FIG. 3 is an SEM image of an ordered porous film produced in examples 1-3 of the present invention.
FIG. 4 is a graph of the relative survival results of rosin-based ordered porous membranes of the present invention.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A method of preparing a rosin-based ordered porous membrane, the method comprising:
(1) Placing maleic rosin (12 g) and PEG800 (9.6 g) with the mass ratio of 2.5:1 into a three-necked flask, installing a thermometer, a water separator and a reflux condenser on the three-necked flask, then adding 10ml of dimethylbenzene, heating to 60 ℃, adding a catalyst p-toluenesulfonic acid (the mass of the p-toluenesulfonic acid is 1% of the total mass of the maleic rosin and the polyethylene glycol), heating for 30min, and refluxing to 210 ℃ for 15h to generate a black-red sticky mixture; pouring the mixture into a dialysis bag with larger molecular weight cut-off, filtering to obtain a crude extract, repeatedly washing the obtained crude extract by using a siphon principle in a Soxhlet extractor to obtain an extracting solution, washing the obtained extracting solution with water, ethanol and chloroform for multiple times in sequence to obtain a polymaleic rosin PEG ester, and determining whether the molecular weight GPC and the weight average molecular weight are more than 5 ten thousand;
(2) Dissolving 30mg of the polymaleic rosin PEG ester obtained in the step (1) in 1ml of dichloromethane to prepare 30mg/ml of polymaleic rosin PEG ester solution, and carrying out ultrasonic treatment for 10min until the solution is completely dissolved for later use;
(3) Washing the glass slide with deionized water and ethanol in an ultrasonic cleaner for 10 min, drying in an oven, and paving a polytetrafluoroethylene film above the washed glass slide for later use; firstly, reversely buckling an evaporation dish in deionized water (serving as a support of a glass slide), then placing the glass slide paved with a polytetrafluoroethylene film above the evaporation dish, placing the polytetrafluoroethylene film above the glass slide, and then adding a proper amount of deionized water into a beaker, wherein the water surface is not higher than the glass slide; then placing the beaker with the evaporation pan and the glass slide in a water bath kettle at about 50 ℃ for heating, sealing the mouth of the beaker by using a multilayer preservative film, and observing the sealing condition and whether a humidity atmosphere of 80-90% is formed in the beaker by using a hygrometer; and (3) taking 150-200 mu l of the polymaleic rosin PEG ester solution obtained in the step (2) by using a micropipette after the humidity reaches 80-90%, opening a preservative film, rapidly casting on a polytetrafluoroethylene film of a glass slide, and sealing until the solvent is completely volatilized.
As shown in FIG. 1, the hydrogen spectrum nuclear magnetic patterns of the PEG esters of the maleic rosin and the polymaleic rosin in the example 1 of the present invention show that the esterification reaction of the maleic rosin and the polyethylene glycol is completed to generate the PEG ester of polymaleic rosin from FIG. 1.
As shown in FIG. 2, a GPC chart of a PEG ester of polymaleic rosin obtained in example 1 of the present invention, wherein MW refers to weight average molecular weight and dw/dlogM curve refers to molecular weight logarithmic differential weight distribution; the Curve of CumHt refers to the cumulative weight fraction. As can be seen from FIG. 2, when the weight average molecular weight of the maleic rosin and the poly (maleic rosin) PEG ester reaches 90217 (90217 is the highest point of dw/dlogM curve, the molar ratio of the maleic rosin to the PEG800 in the raw material is 2.5:1), the polydispersity index (PDI) is about 1.143, which indicates that the relative molecular weight distribution of the maleic rosin and the poly (maleic rosin) PEG ester is narrow, and the optimal film forming molecular weight is achieved.
Example 2
A rosin-based ordered porous membrane was prepared substantially the same as in example 1, except that:
In the step (2), the polymaleic rosin PEG ester obtained in the step (1) was dissolved in methylene chloride to prepare a polymaleic rosin PEG ester solution of 35 mg/ml.
Example 3
A rosin-based ordered porous membrane was prepared substantially the same as in example 1, except that:
in the step (2), the polymaleic rosin PEG ester obtained in the step (1) was dissolved in methylene chloride to prepare a 40mg/ml polymaleic rosin PEG ester solution.
Example 4
A rosin-based ordered porous membrane was prepared substantially the same as in example 1, except that:
in step (1), the amounts of the substances of the maleated rosin and PEG800 are changed to 1.8:1 or 2:1.
Experimental example 1 ordered porous Membrane Electron microscopy analysis
Electron microscopic analysis was performed on the polymaleic rosin PEG ester porous membranes prepared in examples 1 to 3.
As shown in FIG. 3, SEM pictures of the ordered porous films prepared in examples 1 to 3 of the present invention, wherein the scale of the SEM pictures is 10 μm, and a is the SEM picture of the ordered porous film prepared from 30mg/ml of the film-forming liquid in example 1; b is an SEM image of an ordered porous membrane prepared from 35mg/ml membrane-forming liquid in example 2; c is an SEM image of an ordered porous membrane prepared from 40mg/ml membrane-forming liquid in example 3. From the microstructure, it is known that when the mass concentration of the poly (maleic rosin) PEG ester solution is 30-40 mg/ml, a uniform microporous membrane can be formed, the average pore diameter is 1-3 μm, and the pore wall is thicker and thicker, because the concentration of the poly (maleic rosin) PEG ester solution affects the viscosity and density of the membrane forming liquid, and further affects the immersion depth of water drops, when the concentration of the poly (maleic rosin) PEG ester solution is increased, the viscosity of the membrane forming liquid is increased, more polymer is aggregated around water drops, and aggregation among water drops is blocked, so that the probability of aggregation growth of water drops on the surface of the membrane forming liquid is smaller.
Electron microscopy analysis of the poly (maleic rosin) PEG ester porous membrane prepared in example 4 showed that when the amounts of the substances of maleic rosin and PEG800 were 1.8:1 and 2: the molecular weight is low in 1, and film formation is impossible.
Thus, the molecular weight of the film-forming material in which the amounts of the substances of the maleated rosin and PEG800 are 2.5:1 reaches the film-forming amount, and a porous film can be produced.
Experimental example 2 cytotoxicity test
Cytotoxicity test was performed on the polymaleic rosin PEG ester porous membranes prepared in examples 1 to 3, and the test procedure was as follows: inoculating mouse fibroblast (L929) into a culture bottle of fetal calf serum and a culture medium in a volume ratio of 9:1, culturing conventionally in an incubator under the conditions of 37 ℃ and 5% CO 2 and saturation humidity reaching 95%, taking L929 cells in logarithmic phase, counting cells, regulating cell concentration, inoculating into a 48-well plate according to 2X 10 4 cells/well, and culturing overnight in a constant temperature incubator at 37 ℃ and 5% CO 2; the cells after overnight culture were divided into four experimental groups, 500 μl/well of complete medium containing cells, designated as a blank group; the nonporous film prepared in example 4 was added to 500. Mu.L/well of the cell-containing complete medium, designated as a nonporous film stack; the porous membrane prepared in example 1 was added to 500. Mu.L/well of the cell-containing complete medium, and the resulting mixture was designated as example 1 group; the porous membrane prepared in example 2 was added to 500. Mu.L/well of cell-containing complete medium, designated as example 2 group, and 3 duplicate wells were set for each experimental group; after 48h incubation, the medium was removed from each experimental group, each well was washed three times with PBS, 500. Mu.L of medium containing 0.5mg/mL MTT was added to each well, the supernatant was discarded after 4 hours incubation in a 5% CO 2, 37℃incubator, 500. Mu.L of DMSO (dimethyl sulfoxide) was added to each well and gently shaken for 10min, absorbance at 570nm was measured, the average was measured 3 times, and the relative cell proliferation rate was calculated by the formula: relative% viability = (experimental OD)/(control OD mean) ×100, the results are detailed in fig. 4.
As shown in fig. 4, a graph of the relative survival results of the rosin-based ordered porous membranes of the present invention. It can be seen from fig. 4 that the relative proliferation rates of the non-porous membrane, example 1, example 2 cells were 71.6%, 94.9%, 95.9%, respectively, the proliferation rate of the non-porous membrane was lower, and the proliferation rate of the ordered porous membrane was higher. According to cytotoxicity grading standards, the nonporous membrane has slight cytotoxicity, and the ordered porous membranes prepared in the examples 1 and 2 are non-cytotoxic materials and have good biocompatibility.
Experimental example 3 determination of antibacterial Properties
The antibacterial activity of the nonporous film and the antibacterial activity of the ordered porous film prepared in examples 1 and 2 are detected by adopting a bacteriostasis circle method, the bacteria to be tested are staphylococcus aureus, escherichia coli bacillus subtilis and bacillus, and the specific measuring results are shown in table 1 in detail.
TABLE 1 antibacterial test results of rosin-based ordered porous membranes of the present invention
As shown by the results in Table 1, the non-porous film has no bacteriostasis, and the porous films prepared in examples 1 and 2 have obvious bacteriostasis, i.e., the porous film has bacteriostasis.
While the present invention has been described in detail through the foregoing description of the preferred embodiment, it should be understood that the foregoing description is not to be considered as limiting the invention. Many modifications and substitutions of the present invention will become apparent to those of ordinary skill in the art upon reading the foregoing. Accordingly, the scope of the invention should be limited only by the attached claims.
Claims (8)
1. The poly (maleic rosin) polyethylene glycol ester is characterized by comprising the following raw materials:
maleic rosin, polyethylene glycol, p-toluenesulfonic acid and a water-carrying agent;
The mass ratio of the maleated rosin to the polyethylene glycol is 2.5:1;
the molecular weight of the polyethylene glycol is 800; the mass of the p-toluenesulfonic acid is 1% of the total mass of the maleated rosin and the polyethylene glycol; the volume mass ratio of the water-carrying agent to the maleated rosin is 10ml to 12g; the water-carrying agent is benzene, toluene or xylene;
The weight average molecular weight of the polymaleic rosin PEG ester is 90217.
2. A process for the preparation of a polymaleic rosin polyethylene glycol ester according to claim 1 comprising:
(1) Mixing and heating the water-carrying agent, the maleated rosin and the polyethylene glycol, adding the p-toluenesulfonic acid when the temperature reaches 60 ℃, and continuously heating for 30min at 60 ℃; the mass ratio of the maleated rosin to the polyethylene glycol is 2.5:1;
(2) Raising the temperature to 210-220 ℃ and refluxing to obtain a product;
(3) And (3) carrying out post-treatment on the obtained product to obtain the polymaleic rosin polyethylene glycol ester.
3. The preparation method according to claim 2, wherein in the step (2), the time of refluxing is 10 to 18 hours.
4. The method of claim 2, wherein in step (3), the post-treatment comprises: pouring the product into a dialysis bag, filtering to obtain a crude extract, washing the crude extract by a Soxhlet extractor to obtain an extracting solution, and washing the obtained extracting solution by water, ethanol and chloroform in sequence to finally obtain the polymaleic rosin polyethylene glycol ester.
5. A rosin-based ordered porous membrane, wherein the raw material comprises the polymaleic rosin polyethylene glycol ester according to claim 1.
6. The ordered porous rosin-based membrane of claim 5, wherein the mass concentration of the polyethylene glycol ester solution of polymaleic rosin is 30-40 mg/ml.
7. A method of making a rosin-based ordered porous membrane of claim 5, comprising:
(1) Placing the poly (maleic rosin) polyethylene glycol ester in dichloromethane for ultrasonic dissolution to obtain a poly (maleic rosin) polyethylene glycol ester solution;
(2) Opening a sealed polytetrafluoroethylene film, casting the polymaleic rosin polyethylene glycol ester solution obtained in the step (1) on the polytetrafluoroethylene film by adopting a respiratory pattern method, sealing the casted polytetrafluoroethylene film, and finally preparing the rosin-based ordered porous film after the solvent volatilizes; the sealing temperature is 25-40 ℃ and the humidity is 70-90%.
8. Use of the rosin-based ordered porous membrane of claim 5 in the preparation of biomedical materials.
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| US4260550A (en) * | 1979-09-25 | 1981-04-07 | Johnson & Johnson Baby Products Company | Modified rosin esters |
| SE9203499L (en) * | 1992-11-20 | 1994-05-21 | Eka Nobel Ab | Rosin derivative as surfactant |
| US20080109922A1 (en) * | 2006-11-03 | 2008-05-08 | Watack Chemical Company | Coated seeds and materials for seed coating |
| CN101961620B (en) * | 2010-08-20 | 2013-05-08 | 中国林业科学研究院林产化学工业研究所 | Rosin-based chelating gemini surfactant and preparation method thereof |
| US8604128B2 (en) * | 2011-02-15 | 2013-12-10 | University Of South Carolina | Rosin-derived cationic compounds and polymers along with their methods of preparation |
| CN103894109B (en) * | 2014-03-10 | 2015-01-14 | 深圳诺普信农化股份有限公司 | Rosin-based emulsifier, preparation method and application of emulsifier |
| CN104558095A (en) * | 2015-01-06 | 2015-04-29 | 上海华谊（集团）公司 | Preparation method of N-substituted maleopimarimide |
| JP2019073615A (en) * | 2017-10-16 | 2019-05-16 | 三井化学株式会社 | Microporous film formed from resin composition containing 4-methyl-1-pentene-based polymer, separator for battery, and lithium ion battery |
| WO2021048879A1 (en) * | 2019-09-14 | 2021-03-18 | Asian Paints Ltd. | Polyester based wood coating composition |
| CN111528277A (en) * | 2020-06-02 | 2020-08-14 | 中国林业科学研究院林产化学工业研究所 | Water-soluble rosin resin and preparation method and application thereof |
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