CN103289020B - A kind of method of modifying of medical polyethylene terephthalate - Google Patents
A kind of method of modifying of medical polyethylene terephthalate Download PDFInfo
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- CN103289020B CN103289020B CN201310258448.9A CN201310258448A CN103289020B CN 103289020 B CN103289020 B CN 103289020B CN 201310258448 A CN201310258448 A CN 201310258448A CN 103289020 B CN103289020 B CN 103289020B
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Abstract
The method of modifying that the invention provides a kind of medical polyethylene terephthalate (PET) is: by medical polyethylene terephthalate and ozone reaction, obtains the medical polyethylene terephthalate with free radical; Under protection of inert gas, the solution and the described medical polyethylene terephthalate with free radical that contain monomer molecule are carried out closed polyreaction; Described monomer molecule is saccharide compound or the vinyl monomer containing hydrophilic radical.Described method directly can form free radical on PET material surface, simplifies the activation step of material surface, operates easier.Secondly, the present invention's graftable monomer molecule kind is more, is applicable to the multiple bioactive molecules of grafting.And, modified polyethylene terephthalate good biocompatibility.
Description
Technical field
The present invention relates to technical field of biological material, particularly the method for modifying of medical polyethylene terephthalate.
Background technology
Polyethylene terephthalate (PET) a kind ofly has excellent mechanical property and chemically inert polyester material, and be often used as preparation artificial blood vessel, the raw material of artificial ligament and heart valve prosthesis, the raw material especially as artificial ligament is the most general.
But utilize PET material to prepare artificial ligament, artificial blood vessel or the artificial heart when valve, there is uncompatibility in PET and tissue, easily makes human body produce foreign body reaction thus cause inflammation.Therefore, need to carry out surface modification to PET material, to improve the consistency of itself and tissue.Application number be 200920034762.8 Chinese utility model patent disclose a kind of fibrous texture for artificial ligament, it comprises trevira inner core, toluene diisocyanate interlayer and active group, its preparation method is first then mediate, at surface grafting bio-active group with isocyano at polyester fibre surface the street tolylene diisocyanate.Described method is surface grafting method, is applicable to rich surface containing PET material that is amino or hydroxyl.The successful key of described method depends on the quantity of material surface hydroxyl, and this grafting method is only applicable to the bioactive molecules with the functional group that can react with isocyano.Described method belongs to indirect Graft Method, is applicable to rich surface containing PET material that is amino or hydroxyl.Application number be 201010292173.7 Chinese invention patent disclose a kind of at polyester fibre surface chemical graft and the method for stable coatings biomacromolecule, first it adopt the method for hydrolysis to form a large amount of oh groups on PET material surface, then mediate with isocyano, then at surface grafting bio-active group, last at material surface coating biology macromole, the cellular binding sites of fibrous material surface is increased, there is stronger stability.Described method equally also belongs to indirect grafting, there is the problem of the bioactive molecules limitednumber of grafting.
Summary of the invention
The technical problem that the present invention solves is the method for modifying providing a kind of medical polyethylene terephthalate, simple to operate, is applicable to the multiple bioactive molecules of grafting.
The invention discloses a kind of method of modifying of medical polyethylene terephthalate, comprise the following steps:
(A) by medical polyethylene terephthalate and ozone reaction, the medical polyethylene terephthalate with free radical is obtained;
(B) under protection of inert gas, the solution and the described medical polyethylene terephthalate with free radical that contain monomer molecule are carried out closed polyreaction;
Described monomer molecule is saccharide compound or the vinyl monomer containing hydrophilic radical.
Preferably, before described closed polyreaction, also comprise and purifying is carried out to described monomer molecule and the solution be configured to containing monomer molecule.
Preferably, in described step (B), the mass percent concentration of the described solution containing monomer molecule is 10 ~ 40%.
Preferably, in described step (B), the described vinyl monomer containing hydrophilic radical is vinylformic acid, methacrylic acid, methyl methacrylate, acrylamide N-phenylbenzimidazole sulfonic acid sodium, Methacrylamide N-phenylbenzimidazole sulfonic acid sodium, one or more in Sodium styrene sulfonate and glycolmethacrylate phosphoric acid salt.
Preferably, in described step (B), described saccharide compound is glucose, fructose, sucrose or saccharan.
Preferably, in described step (A), described reaction is carried out in distilled water.
Preferably, in described step (A), the time of described reaction is 5 ~ 20 minutes.
Preferably, in described step (B), the temperature of described closed polyreaction is 60 ~ 80 DEG C.
Preferably, in described step (B), the time of described closed polyreaction is 0.5 ~ 4 hour.
Compared with prior art, first the present invention utilizes ozone to form free radical on medical PET material surface, then under liquid phase, oxygen free condition, unsaturated link(age) on described free radical attack monomers molecule carbon chain, make from free radical site monomer molecule that polymerization occurs to generate, complete the modification to medical PET.Aforesaid method directly can form free radical on PET material surface, simplifies the activation step of material surface, operates easier.Secondly, the present invention's graftable monomer molecule kind is more, is applicable to the multiple bioactive molecules of grafting.And monomer molecule is with-COO
-,-SO
3 -,-PO
3 2-isoreactivity group, it is after PET material surface aggregate, and PET material surface is also with above-mentioned active group, can infect by anti-bacteria after implanting, change the conformation being attached on the protein of material surface, reduce inflammation, promote sticking of cell, growth and propagation.
Accompanying drawing explanation
Fig. 1 is the x-ray photoelectron power spectrum of the medical PET of modification prepared by embodiment;
Fig. 2 is the mechanical property column diagram of the modified medical PET of embodiment 1 ~ 2;
Fig. 3 is that modified PET implants the electron microscopic picture in sheep model body after a year as artificial ligament.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The embodiment of the invention discloses a kind of method of modifying of medical polyethylene terephthalate, comprise the following steps:
(A) by medical polyethylene terephthalate and ozone reaction, the medical polyethylene terephthalate with free radical is obtained;
(B) under protection of inert gas, the solution and the described medical polyethylene terephthalate with free radical that contain monomer molecule are carried out closed polyreaction;
Described monomer molecule is saccharide compound or the vinyl monomer containing hydrophilic radical.
In the present invention, with medical polyethylene terephthalate for raw material, modification is carried out to it.Described medical polyethylene terephthalate is the medical pet material being used as artificial blood vessel, artificial ligament or heart valve prosthesis etc.
In the present invention, first by medical polyethylene terephthalate and ozone reaction, ozone activates the surface of PET material, makes its surface with abundant free radical, obtains the medical polyethylene terephthalate with free radical.Described reaction is preferably carried out in distilled water, and the time of described reaction is preferably 5 ~ 20 minutes, is more preferably 10 ~ 15 minutes.The temperature of the present invention to described reaction is not particularly limited, room temperature.
After obtaining the medical polyethylene terephthalate with free radical, the solution and the described medical polyethylene terephthalate with free radical that contain monomer molecule are carried out closed polyreaction, namely completes modification.Described monomer molecule is saccharide compound or the vinyl monomer containing hydrophilic radical, described free radical attacks the unsaturated link(age) in described monomer molecule carbochain, described monomer molecule is polymerized on the site of free radical, thus completes the closed polyreaction caused at the free free radical in pet sheet face.Described monomer molecule is with-COO
-,-SO
3 -,-PO
3 2-isoreactivity group, it is after the polymerization of pet sheet face, pet sheet face is also with above-mentioned active group, can infect by anti-bacteria after implanting, change the conformation being attached on the protein of material surface, reduce inflammation, promote sticking of cell, growth, propagation, effectively improves the biocompatibility of PET.Described monomer molecule can be that single type occurs to close polyreaction, also can be that closed polyreaction occurs polytype monomer molecule together.The described vinyl monomer containing hydrophilic radical is preferably vinylformic acid, methacrylic acid, methyl methacrylate, acrylamide N-phenylbenzimidazole sulfonic acid sodium, Methacrylamide N-phenylbenzimidazole sulfonic acid sodium, one or more in Sodium styrene sulfonate and glycolmethacrylate phosphoric acid salt.Described saccharide compound is preferably glucose, fructose, sucrose or saccharan.
Before carrying out closed polyreaction, preferably also comprise and purifying is carried out to described monomer molecule.The method of the present invention to described purifying is not particularly limited, and those skilled in the art can select different ordinary methods according to different monomer molecules.Described closed polyreaction carrying out containing in the solution of monomer molecule under protection of inert gas, the mass percent concentration of the described solution containing monomer molecule is preferably 10 ~ 40%, is more preferably 15 ~ 30%.Described rare gas element is preferably argon gas.The temperature of described closed polyreaction is preferably 60 ~ 80 DEG C, is more preferably 65 ~ 75 DEG C.The time of described closed polyreaction is preferably 0.5 ~ 2 hour, is more preferably 1 ~ 1.5 hour.
After described closed polyreaction terminates, namely complete the modification of medical polyethylene terephthalate.Described method of modifying is not particularly limited for the polymkeric substance chain length on PET material surface, obtains the PET material being grafted with polymkeric substance.
Method of modifying of the present invention directly can form free radical in medical pet sheet face, simplifies the activation step of material surface, operates easier.Secondly, the present invention's graftable monomer molecule kind is more, is applicable to the multiple bioactive molecules of grafting.And monomer molecule is with-COO
-,-SO
3 -,-PO
3 2-isoreactivity group, it is after the polymerization of pet sheet face, and pet sheet face, also with above-mentioned active group, can be infected by anti-bacteria after implanting, changed the conformation being attached on the protein of material surface, reduce inflammation, promote sticking of cell, growth, propagation.
In order to understand the present invention further, be described below in conjunction with the method for modifying of embodiment to medical pet material provided by the invention, protection scope of the present invention is not limited by the following examples.
Embodiment 1
20 grams of Sodium styrene sulfonate are added the water of 100 milliliters and the mixing solutions of ethanol, and the volume ratio of water and ethanol is 1:9,70 DEG C of heating, after Sodium styrene sulfonate is dissolved, solution is filtered, filtrate places 4 degree of refrigerator overnight, and after crystal is separated out, filtering drying is stand-by.
200 ml distilled waters need be put into by medical PET to be processed, open oxygen cylinder (0.6L/ per minute), by ozone generator, by ozone (O
3) import in distilled water, coreaction 10 minutes.
Styrene sulfonic acid sodium crystal after recrystallization is made into the solution that mass percent concentration is 15%, passes into argon gas and drive oxygen in solution out of, add the medical PET after ozonize and directly close polyreactions 1 hour in 70 DEG C.
Colorimetry is utilized to measure modified medical PET, modified medical PET and concentration are 0.5mM, the toluidine blue of pH=10 was 30 DEG C of Dual culture 6 hours, after washing in a large number with the sodium hydroxide solution of 1mM, be placed in the acetic acid solution incubated overnight of 50%, acetic acid solution reads absorption value under 633 nano wave lengths, becomes the concentration of polymerizable molecular at average 4.7 micromole every gram of PET according to formula scales.
X-ray photoelectron spectroscopic analysis (XPS) is carried out to modified medical PET, result is see Fig. 1, Fig. 1 is the x-ray photoelectron power spectrum of the medical PET of modification prepared by embodiment, in Fig. 1, (A) be the C1s collection of illustrative plates in unmodified pet sheet face, (B) is the C1s collection of illustrative plates in modified pet sheet face.As shown in Figure 1, the increase of C-C ratio, the minimizing of C-O, O=C-O ratio, illustrates the derivative of C chain.
Utilize differential scanning calorimetry (DSC) to analyze modified PET, result shows, the heat deflection of modified medical PET does not change.
Carry out Mechanics Performance Testing to modified medical PET, result is the mechanical property column diagram of the modified medical PET of embodiment 1 ~ 2 see Fig. 2, Fig. 2.
Prepared by artificial ligament to the medical PET through modification and carries out extracorporeal biology assessment, the assessment display of extracorporeal biology, first the active macromolecules on these surfaces, there is no cytotoxicity, after people's ligament fibroblasts original cuiture, be evenly distributed, growth fast, the synthesis of collagen protein significantly improves, and the expression of target gene is also remarkable to improve than comparative group.Described artificial ligament is implanted into after in sheep body, the tracking result display in 1 year, and contrast control group, new ligament controls inflammation, and ligament tissue infiltrates evenly, and Biomechanical evaluation is good.Transplant after 1 year in sheep body, artificial ligament is removed, from electron micrograph, and each artificial ligament fiber of the well-proportioned infiltration parcel of ligament tissue.Concrete outcome is that modified PET implants the electron microscopic picture in sheep model body after a year as artificial ligament see Fig. 3, Fig. 3.As shown in Figure 3, modified PET has good biocompatibility.
Embodiment 2
20 grams of Sodium styrene sulfonate are added the water of 100 milliliters and the mixing solutions of ethanol, and the volume ratio of water and ethanol is 1:9,70 DEG C of heating, after Sodium styrene sulfonate is dissolved, solution is filtered, filtrate places 4 degree of refrigerator overnight, and after crystal is separated out, filtering drying is stand-by.
200 ml distilled waters need be put into by medical PET to be processed, open oxygen cylinder (0.6L/ per minute), by ozone generator, by ozone (O
3) import in distilled water, coreaction 10 minutes.
Styrene sulfonic acid sodium crystal after recrystallization is made into the solution that mass percent concentration is 15%, passes into argon gas and drive oxygen in solution out of, add the medical PET after ozonize and directly close polyreactions 3 hours in 70 DEG C.
Carry out X-ray photoelectron spectroscopic analysis (XPS) to modified medical PET, result is see table 1.
The X-ray photoelectron spectroscopic analysis table of the medical PET that table 1 embodiment 1 ~ 2 is modified
Table 1 result shows, the increase of C-C ratio, the minimizing of C-O, O=C-O ratio, and the derivative of C chain is described.
The atom compositional analysis of the medical PET that table 2 embodiment 1 ~ 2 is modified
Table 2 result shows, the elements such as S appear in modified medical pet sheet face, it can thus be appreciated that, pet sheet face grafting polymkeric substance.
Carry out Mechanics Performance Testing to modified medical PET, result is the mechanical property column diagram of the modified medical PET of embodiment 1 ~ 2 see Fig. 2, Fig. 2.In Fig. 2, A is the power resistance strength of untreated medical PET, and B is the power resistance strength of the modified medical PET of embodiment 1, and C is the power resistance strength of the modified medical PET of embodiment 2.As shown in Figure 2, the anti-disconnected power of untreated medical PET is 115 newton, is 113.766 newton after polymerization in 1 hour, is 122 newton, does not have significant difference after polymerization in 3 hours.It can thus be appreciated that modification does not affect the anti-disconnected power attribute of PET material.
Embodiment 3
By methacrylic acid (MA) by distillation, obtain the methacrylic acid after purifying, under lucifuge argon gas, be kept at 4 degree of refrigerators.
200 ml distilled waters need be put into by medical PET to be processed, open oxygen cylinder (0.6L/ per minute), by ozone generator, by ozone (O
3) import in distilled water, coreaction 10 minutes.
Methacrylic acid after purifying is made into the solution that mass percent concentration is 30%, passes into argon gas and drive oxygen in solution out of, add the medical PET after ozonize and directly close polyreactions 1 hour in 70 DEG C.
Embodiment 4
20 grams of Sodium styrene sulfonate are added the water of 100 milliliters and the mixing solutions of ethanol, and the volume ratio of water and ethanol is 1:9,70 DEG C of heating, after Sodium styrene sulfonate is dissolved, solution is filtered, filtrate places 4 degree of refrigerator overnight, and after crystal is separated out, filtering drying is stand-by.
By methacrylic acid (MA) by distillation, obtain the methacrylic acid after purifying, under lucifuge argon gas, be kept at 4 degree of refrigerators.
200 ml distilled waters need be put into by medical PET to be processed, open oxygen cylinder (0.6L/ per minute), by ozone generator, by ozone (O
3) import in distilled water, coreaction 10 minutes.
Methacrylic acid after styrene sulfonic acid sodium crystal after recrystallization and purifying is configured to mass percentage concentration than the solution being 15% according to mass ratio 80:20, pass into argon gas and drive oxygen in solution out of, add the medical PET after ozonize and directly close polyreactions 1 hour in 70 DEG C.
Embodiment 5
20 grams of Sodium styrene sulfonate are added the water of 100 milliliters and the mixing solutions of ethanol, and the volume ratio of water and ethanol is 1:9,70 DEG C of heating, after Sodium styrene sulfonate is dissolved, solution is filtered, filtrate places 4 degree of refrigerator overnight, and after crystal is separated out, filtering drying is stand-by.
By methacrylic acid (MA) by distillation, obtain the methacrylic acid after purifying, under lucifuge argon gas, be kept at 4 degree of refrigerators.
200 ml distilled waters need be put into by medical PET to be processed, open oxygen cylinder (0.6L/ per minute), by ozone generator, by ozone (O
3) import in distilled water, coreaction 10 minutes.
Methacrylic acid after styrene sulfonic acid sodium crystal after recrystallization and purifying is configured to mass percentage concentration than the solution being 15% according to mass ratio 50:50, pass into argon gas and drive oxygen in solution out of, add the medical PET after ozonize and directly close polyreactions 1 hour in 70 DEG C.
Embodiment 6
20 grams of Sodium styrene sulfonate are added the water of 100 milliliters and the mixing solutions of ethanol, and the volume ratio of water and ethanol is 1:9,70 DEG C of heating, after Sodium styrene sulfonate is dissolved, solution is filtered, filtrate places 4 degree of refrigerator overnight, and after crystal is separated out, filtering drying is stand-by.
By methacrylic acid (MA) by distillation, obtain the methacrylic acid after purifying, under lucifuge argon gas, be kept at 4 degree of refrigerators.
200 ml distilled waters need be put into by medical PET to be processed, open oxygen cylinder (0.6L/ per minute), by ozone generator, by ozone (O
3) import in distilled water, coreaction 10 minutes.
Styrene sulfonic acid sodium crystal after recrystallization and the methacrylic acid after purifying are configured to according to mass ratio 20:80 the solution that mass percentage concentration is 15%, pass into argon gas and drive oxygen in solution out of, add the medical PET after ozonize and directly close polyreactions 1 hour in 70 DEG C.
Embodiment 7
200 ml distilled waters need be put into by PET artificial ligament to be processed, open oxygen cylinder (0.6L/ per minute), by ozone generator, by ozone (O
3) import in distilled water, coreaction 10 minutes.
By Sodium styrene sulfonate, methacrylic acid, methyl methacrylate according to mass ratio be 30:40:30 be configured to the solution that mass percentage concentration is 15%, pass into argon gas and drive oxygen in solution out of, add the medical PET material after ozonize and directly close polyreactions 2 hours in 65 DEG C.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (7)
1. a method of modifying for medical polyethylene terephthalate, is made up of following steps:
(A) by medical polyethylene terephthalate and ozone reaction, the medical polyethylene terephthalate with free radical is obtained; The time of described reaction is 10 ~ 15 minutes;
(B) under protection of inert gas, the solution and the described medical polyethylene terephthalate with free radical that contain monomer molecule are carried out closed polyreaction;
Before described closed polyreaction, purifying is carried out to described monomer molecule and is configured to the solution containing monomer molecule;
Described monomer molecule is saccharide compound or the vinyl monomer containing hydrophilic radical.
2. method of modifying according to claim 1, is characterized in that, in described step (B), the mass percent concentration of the described solution containing monomer molecule is 10 ~ 40%.
3. method of modifying according to claim 1, it is characterized in that, in described step (B), the described vinyl monomer containing hydrophilic radical is vinylformic acid, methacrylic acid, methyl methacrylate, acrylamide N-phenylbenzimidazole sulfonic acid sodium, Methacrylamide N-phenylbenzimidazole sulfonic acid sodium, one or more in Sodium styrene sulfonate and glycolmethacrylate phosphoric acid salt.
4. method of modifying according to claim 1, is characterized in that, in described step (B), described saccharide compound is glucose, fructose, sucrose or saccharan.
5. method of modifying according to claim 2, is characterized in that, in described step (A), described reaction is carried out in distilled water.
6. method of modifying according to claim 2, is characterized in that, in described step (B), the temperature of described closed polyreaction is 60 ~ 80 DEG C.
7. method of modifying according to claim 2, is characterized in that, in described step (B), the time of described closed polyreaction is 0.5 ~ 4 hour.
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| NL2013016B1 (en) * | 2014-06-17 | 2016-07-05 | Academisch Ziekenhuis Leiden | In situ tissue engineering. |
| CN107376020B (en) * | 2017-07-13 | 2020-06-26 | 北京万洁天元医疗器械股份有限公司 | Artificial ligament surface modification method |
| CN108853593B (en) * | 2018-06-11 | 2021-03-26 | 陈俊 | Preparation method of composite amnion biological patch |
| CN108866744A (en) * | 2018-06-19 | 2018-11-23 | 嘉兴市盛翔织造有限公司 | A kind of two-sided tearable fabric and its processing method for medical adhesive tape |
| CN109078503B (en) * | 2018-08-17 | 2021-01-12 | 东华大学 | Hydrophilic treatment process for PET precision transfusion filtering nuclear pore membrane |
| CN109731146B (en) * | 2018-12-21 | 2021-07-20 | 东华大学 | Modified polybutylene terephthalate PBT patch, and preparation and application thereof |
| CN113717326A (en) * | 2021-09-24 | 2021-11-30 | 张家港市顾乐仕生活家居科技有限公司 | Bio-based polyester type hydrophilic cotton and preparation method thereof |
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| Title |
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| "Plasma-induced graft polymerization of acrylic acid onto poly(ethtylene terephthalate) films:characterization and human smooth muscle cell growth on grafted films";Bhuvanesh Gupta et al.;《Biomaterials》;20021231;第23卷;863-871 * |
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