CN104672482A - Preparation and application of cell membrane bionic polymer liquid crystal membrane material - Google Patents
Preparation and application of cell membrane bionic polymer liquid crystal membrane material Download PDFInfo
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- CN104672482A CN104672482A CN201510059787.3A CN201510059787A CN104672482A CN 104672482 A CN104672482 A CN 104672482A CN 201510059787 A CN201510059787 A CN 201510059787A CN 104672482 A CN104672482 A CN 104672482A
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Abstract
The invention belongs to the field of biomedical materials and particularly relates to preparation and application of a cell membrane bionic polymer liquid crystal membrane material. The preparation method of the cell membrane bionic polymer liquid crystal membrane material comprises the following steps: coating a polymer liquid crystal material which is in a liquid crystal state at physiological temperature by a solution method to obtain a membrane; pre-irradiating the liquid crystal membrane with <60>Co-gamma rays or an electron beam, and immersing into a phosphorylcholine-containing vinyl monomer aqueous solution; and performing a grafting reaction in an anaerobic condition to obtain the cell membrane bionic polymer liquid crystal membrane material. The method has the advantages of simple technology, low cost, short production period and good practical prospect of industrialization; energy conservation and emission reduction are realized by use of a civilian nuclear technology, and environmental pollution is reduced; and the obtained cell membrane bionic polymer liquid crystal membrane material imitates the molecular structure and aggregation structure of a cell membrane at the same time, has good surface biological performance and is widely applied to the fields such as medical dressings, intervention and implantation equipment and medical equipment contacting blood.
Description
Technical field
The invention belongs to biomedical materials field, particularly a kind of preparation and uses thereof of cellular membrane biomimetic high molecule liquid crystal mould material.
Background technology
Along with biomedical development, the application of biomaterial becomes more and more extensively with important, and the key property of biomaterial is its biocompatibility.Because bio-medical material often needs and body surface, blood, bioresorbable, what have even requires in permanent implants, in order to ensure its security used, must possess excellent biocompatibility.The key of ideal biological medical material design be to realize between life system and material interface on molecular level and cell levels interactional Effective Regulation, and biomimetic material technology has been considered to the important channel of developing high-quality biological medical material.
Phosphorylcholine is that the hydrophilic polar head of the structural unit phosphatide being extensively present in animal and plant cytolemma divides, be made up of the phosphate of a band negative charge and the choline quaternary amine base of a band positive charge, not only to maintenance Normocellular shape, size and physiological function, there is important effect, also there is significant protein-repellent characteristic, protein absorption thereon can be reduced dramatically, thus reduce immune activation and hematoblastic deposition.The Biomimetic Polymers bill of material of phosphoric acid choline reveals the excellent properties such as good blood compatibility and the absorption of arrestin matter and is subject to extensive concern.Internationally famous periodical Nano Today has delivered one section of paper: R. Matsuno, K. Ishihara, Integrated functional nanocolloids covered with artificial cell membranes for biomedical applications. (Nano Today, 2011,6,61-74).Internationally famous periodical Materials Letters has delivered one section of paper: Zehu Wang, Rong Zeng, Mei Tu, Jianhao Zhao. A novel biomimetic chitosan-based nanocarrier with suppressing non-specific protein interactions. (Materials Letters, 2012,77:38-40).Chinese patent CN 195288 B discloses a kind of manufacture method preventing the ocular lens material of protein adsorption; Chinese patent CN 101979419 B discloses a kind ofly has high intensity hydrogel of anti-adsorption function and preparation method thereof, and the application in bio-medical field of the biomaterial of above preparation is also in continuous expansion.
Liquid crystal state is also extensively exist in life system, and all microbial films all have typical liquid crystal structure, and the many critical functions in vital process are all closely related with motion with the liquid crystal state conformation of biomembrane molecule.From the angle of Bionic Design, Biomimetic membrane surface liquid crystal state structure, be mesomorphic liquid crystal and composite membrane of polymer base biomaterial thereof under having prepared a series of physiological temp, can show good blood compatibility and cell compatibility, be a kind of desirable bionic biomedical material.The surface topology that China's Tissue Engineering Study and clinical rehabilitation disclose liquid crystal by name/polyvinyl chloride composite membrane that a section is delivered with Chen Haifeng, Zeng Rong, Tu Mei etc. regulates and controls and protein adsorption research (Chinese Tissue Engineering Study and clinical rehabilitation, 2010,14(21): 3839-3842).Simultaneously, internationally famous periodical Carbohydrate Polymers also discloses: Wanqing Han, Mei Tu, Rong Zeng, Jianhao Zhao, Changren Zhou. Preparation, characterization and cytocompatibility of polyurethane/cellulose based liquid crystal composite membranes. (Carbohydrate Polymers, 2012,90 (3): 1353-1361).But above-mentioned liquid crystal state material cannot realize the manufacture of biomimetic features under physiological temp at molecular level, and there is the shortcomings such as hydrophobicity is larger, limit its application.Therefore, preparation is a kind of can realize Bionic Design on molecular level and aggregated structure, and surface hydrophilicity and the biocompatibility of liquid crystal film can be improved, the bio-medical material that can be widely used in organizational project, medical dressing and intervention and Implantable Medical Device currently has a difficult problem to be solved.
Summary of the invention
Low in order to solve prior art bionic biomedical material biomimetics degree, the defect that hydrophobicity is large.The invention provides preparation of a kind of polymer liquid crystal film material of imitative membrane structure and uses thereof, to solve an above difficult problem.
An object of the present invention is to provide a kind of preparation method of cellular membrane biomimetic high molecule liquid crystal mould material, comprises the following steps:
(1) polymer liquid crystal material is dissolved in film forming solvent forms the homogeneous solution that concentration is 1 ~ 10 wt%, be coated on base material and form liquid crystal film;
(2) liquid crystal film that step (1) obtains is carried out pre-irradiation, irradiation total dose is 5k ~ 100kGy;
(3) it is in the vinyl monomer aqueous solution of the phosphorylcholine of 3 ~ 30 wt% that the liquid crystal film after pre-irradiation process step (2) obtained immerses containing concentration, carry out graft reaction under anaerobic, take out, deionized water washings, after vacuum-drying,, namely obtain a kind of cellular membrane biomimetic high molecule liquid crystal mould material.
In the preparation method of cellular membrane biomimetic high molecule liquid crystal mould material of the present invention, the polymer liquid crystal material of step (1) is C
3 ~ 12hydroxypropylcellulose ester in one or its composition, be preferably hydroxypropylcellulose propyl ester, hydroxypropylcellulose butyl ester, hydroxypropylcellulose monooctyl ester.Under physiological temp, present liquid crystal state, the high molecule liquid crystal matrix material with good biocompatibility can be built.
Further, the film forming solvent in step (1) is one in tetrahydrofuran (THF) and acetone or its composition.
Base material is in step (1) macromolecular material, metal or pottery, wherein in step (1) coating processes be selected from spraying, spin coating, dip-coating, showering, casting or curtain coating mode polymer liquid crystal material is applied into liquid crystal film.
In the preparation method of cellular membrane biomimetic high molecule liquid crystal mould material of the present invention, the pre-irradiation described in step (2) is
60co-gamma-rays or electron beam treatment; Pre-irradiation condition is in vacuum or rare gas element or air in described step (2).
In the preparation method of cellular membrane biomimetic high molecule liquid crystal mould material of the present invention, the vinyl monomer of step (2) phosphoric acid choline is methylacryoyloxyethyl phosphorylcholine or acrylyl oxy-ethyl phosphorylcholine.
Further, in described step (3), graft reaction condition is temperature of reaction 20 ~ 80 DEG C, reaction times 1 ~ 12h.
The preparation method of cellular membrane biomimetic high molecule liquid crystal mould material of the present invention be prepared into cellular membrane biomimetic high molecule liquid crystal mould material prepare medical dressing, intervention apparatus, implantation instrument or with the application in the medicine equipment of contacting blood.
Principle of the present invention: hypromellose acid esters is cholest type liquid crystal state polymer, can be formed the basement membrane of mimic biology film state of aggregation liquid crystal structure by solution film forming; Pre-irradiation technology is utilized to introduce avtive spot on its surface further, and then the vinyl monomer-grafted causing phosphoric acid choline group forms wetting ability phosphorylcholine polymkeric substance, thus the molecular structure of cytolemma and the biomimetic liquid crystals mould material of aggregated structure are imitated in acquisition simultaneously, there is excellent wetting ability and biocompatibility, be widely used in bio-medical field.
In a word, cellular membrane biomimetic high molecule liquid crystal mould material of the present invention, has following advantage and effect relative to prior art:
Compared with prior art, preparation method's technique of the present invention is simple, cost is low, with short production cycle, there is good industrialization practical prospect, and utilize civilian nuclear technique to accomplish energy-saving and emission-reduction, reduce environmental pollution; The polymer liquid crystal film material of the imitative membrane structure obtained has imitated molecular structure and the aggregated structure of cytolemma simultaneously, there is good surface biological performance, at medical dressing, get involved implantation instrument, be widely used with the field such as the medicine equipment of contacting blood.
accompanying drawing illustrates:
Fig. 1 is the x-ray photoelectron energy spectrogram before and after cellular membrane biomimetic Polymer Liquid Crystals Composites Membrane material irradiation of the present invention grafting;
Wherein: 1 is the x-ray photoelectron energy spectrogram before the grafting of cellular membrane biomimetic Polymer Liquid Crystals Composites Membrane material irradiation,
2 is the x-ray photoelectron energy spectrogram after the grafting of cellular membrane biomimetic Polymer Liquid Crystals Composites Membrane material irradiation.
embodiment:
Below by way of the description of embodiment, the invention will be further described, but this is not limitation of the present invention, those skilled in the art are according to basic thought of the present invention, various amendment or improvement can be made, but only otherwise depart from basic thought of the present invention, all within the scope of the present invention.
embodiment 1,the preparation of cellular membrane biomimetic high molecule liquid crystal mould material of the present invention
(1) form being dissolved in acetone in mesomorphic hydroxypropylcellulose monooctyl ester (OPC) under physiological temp the homogeneous solution that mass concentration is 1%, its dip-coating is formed OPC liquid crystal film on polyurethane tube;
(2) under room temperature by OPC liquid crystal film in atmosphere, adopt high-power electron beam pre-irradiation, irradiation total dose is 40kGy;
(3) be 20cm by area
2pre-irradiation after OPC liquid crystal film to immerse the concentration of 40mL be in the methylacryoyloxyethyl phosphorylcholine solution of 10wt%, pass into nitrogen deoxygenation, raised temperature to 50 DEG C, reaction 6h, take out, washed with de-ionized water, 50 DEG C of vacuum-dryings, obtain cellular membrane biomimetic high molecule liquid crystal mould material: the hydroxypropylcellulose monooctyl ester (PMPC-g-OPC) of surface grafting polymethyl acyloxyethyl phosphorylcholine.
embodiment 2,the preparation of cellular membrane biomimetic high molecule liquid crystal mould material of the present invention
(1) forming being dissolved in tetrahydrofuran (THF) in mesomorphic hydroxypropylcellulose propyl ester (PPC) under physiological temp the homogeneous solution that mass concentration is 5%, being sprayed on polypropylene counterdie and forming PPC liquid crystal film;
(2) under room temperature by PPC liquid crystal film in atmosphere, adopt
60co-gamma-rays pre-irradiation, irradiation total dose is 30kGy;
(3) be 10cm by area
2pre-irradiation after PPC liquid crystal film to immerse the concentration of 10mL be in the methylacryoyloxyethyl phosphorylcholine solution of 5wt%, pass into nitrogen deoxygenation, raised temperature to 40 DEG C, reaction 3h, take out, washed with de-ionized water, normal-temperature vacuum is dry, obtains cellular membrane biomimetic high molecule liquid crystal mould material: the hydroxypropylcellulose propyl ester (PMPC-g-PPC) of surface grafting polymethyl acyloxyethyl phosphorylcholine.
embodiment 3,the preparation of cellular membrane biomimetic high molecule liquid crystal mould material of the present invention
(1) form being dissolved in acetone in mesomorphic hydroxypropylcellulose butyl ester (BPC) under physiological temp the homogeneous solution that mass concentration is 6%, its dip-coating is formed BPC liquid crystal film on a pet film;
(2) under room temperature by BPC liquid crystal film in atmosphere, adopt high-power electron beam pre-irradiation, irradiation total dose is 10kGy;
(3) be 20cm by area
2pre-irradiation after BPC liquid crystal film to immerse the concentration of 40mL be in the methylacryoyloxyethyl phosphorylcholine solution of 10wt%, pass into nitrogen deoxygenation, raised temperature to 60 DEG C, reaction 8h, take out, washed with de-ionized water, 50 DEG C of vacuum-dryings, obtain cellular membrane biomimetic high molecule liquid crystal mould material: the hydroxypropylcellulose butyl ester (PMPC-g-BPC) of surface grafting polymethyl acyloxyethyl phosphorylcholine.
embodiment 4,the preparation of cellular membrane biomimetic high molecule liquid crystal mould material of the present invention
(1) form being dissolved in acetone in mesomorphic hydroxypropylcellulose butyl ester (BPC) under physiological temp the homogeneous solution that mass concentration is 10%, its dip-coating is formed BPC liquid crystal film on medical stainless steel sheet;
(2) under room temperature by BPC liquid crystal film in atmosphere, adopt high-power electron beam pre-irradiation, irradiation total dose is 10kGy;
(3) be 10cm by area
2pre-irradiation after BPC liquid crystal film to immerse the concentration of 20mL be in the methylacryoyloxyethyl phosphorylcholine solution of 30wt%, pass into nitrogen deoxygenation, raised temperature to 60 DEG C, reaction 8h, take out, washed with de-ionized water, 50 DEG C of vacuum-dryings, obtain cellular membrane biomimetic high molecule liquid crystal mould material: the hydroxypropylcellulose butyl ester (PMPC-g-BPC) of surface grafting polymethyl acyloxyethyl phosphorylcholine.
embodiment 5,the present invention imitates the Performance Detection test of the polymer liquid crystal film material of membrane structure
The Surface Texture of the polymer liquid crystal film material of the imitative membrane structure adopting polarized light microscope observing to prepare according to embodiment 1,2,3,4 respectively; Adopt the grafting situation on the polymer liquid crystal film material surface of the imitative membrane structure of x-ray photoelectron power spectrum test, if the newly-increased proof of picture display has N, P element, namely prove grafting success; According to standard GB/T/T16886.4 and the biocompatibility in vitro of polymer liquid crystal film material of 16886.5 test cell membrane structures and the cytotoxicity to L929; Result is as shown in table 1:
The detection experiment result of the polymer liquid crystal film material of the imitative membrane structure that table 1 the present invention prepares according to embodiment 1,2,3,4 respectively
From above-mentioned table 1, the polymer liquid crystal film material of the imitative membrane structure that the present invention prepares according to embodiment 1,2,3,4 is respectively in its surface colored oily texture in typical cholesteryl liquid crystal of polarized light microscope observing; The test of x-ray photoelectron power spectrum is newly-increased N, P element after showing surface grafting, proves that PMPC success is at surface grafting; According to the biocompatibility in vitro of standard GB/T/T16886.4 and 16886.5 test PMPC-g-BPC cellular membrane biomimetic liquid crystal film, result shows that its hemolysis rate is lower than 5%, it is 0 grade to the cytotoxicity of L929, show good blood compatibility and cell compatibility, meet the security requirement of medical material and apparatus, the polymer liquid crystal film material of imitative membrane structure that wherein embodiment 2 prepares is the polymer liquid crystal film material that the best of the present invention imitates membrane structure.
embodiment 6,the present invention imitates the wetting ability detection experiment of the polymer liquid crystal film material of membrane structure
The polymer liquid crystal film material of the imitative membrane structure polymer liquid crystal film material of the imitative membrane structure before irradiation grafting and the present invention prepared according to embodiment 1,2,3,4 respectively carries out water contact angle test, and result is as shown in table 2:
The wetting ability detection experiment of the polymer liquid crystal film material of the imitative membrane structure that table 2 the present invention prepares according to embodiment 1,2,3,4 respectively
From table 2, the water contact angle of the polymer liquid crystal film material of the imitative membrane structure after irradiation grafting obviously reduces, greatly improve the wetting ability of the polymer liquid crystal film material of imitative membrane structure, wherein the reduction amplitude of the water contact angle of embodiment 2 is maximum, wetting ability is improved comparatively large, for the best of the present invention imitates the polymer liquid crystal film material of membrane structure.
Claims (10)
1. a preparation method for cellular membrane biomimetic high molecule liquid crystal mould material, is characterized in that, comprises the following steps:
(1) polymer liquid crystal material is dissolved in film forming solvent forms the homogeneous solution that concentration is 1 ~ 10 wt%, be coated on base material and form liquid crystal film;
(2) liquid crystal film that step (1) obtains is carried out pre-irradiation, irradiation total dose is 5k ~ 100kGy;
(3) it is in the vinyl monomer aqueous solution of the phosphorylcholine of 3 ~ 30 wt% that the liquid crystal film after pre-irradiation process step (2) obtained immerses containing concentration, carry out graft reaction under anaerobic, take out after reaction, with deionized water washings, after vacuum-drying, obtain cellular membrane biomimetic high molecule liquid crystal mould material.
2. the preparation method of cellular membrane biomimetic high molecule liquid crystal mould material as claimed in claim 1, it is characterized in that, the polymer liquid crystal material in described step (1) is C
3 ~ 12hydroxypropylcellulose ester in one or its composition, be preferably hydroxypropylcellulose propyl ester, hydroxypropylcellulose butyl ester or hydroxypropylcellulose monooctyl ester.
3. the preparation method of cellular membrane biomimetic high molecule liquid crystal mould material as claimed in claim 1, is characterized in that, the film forming solvent in described step (1) is one in tetrahydrofuran (THF) and acetone or its composition.
4. the preparation method of cellular membrane biomimetic high molecule liquid crystal mould material as claimed in claim 1, it is characterized in that, the base material in described step (1) is macromolecular material, metal or pottery.
5. the preparation method of cellular membrane biomimetic high molecule liquid crystal mould material as claimed in claim 1, it is characterized in that, the described pre-irradiation described in step (2) is
60co-gamma-rays or electron beam treatment.
6. the preparation method of cellular membrane biomimetic high molecule liquid crystal mould material as claimed in claim 1, is characterized in that, in described step (2), pre-irradiation condition is in vacuum or rare gas element or air.
7. the preparation method of cellular membrane biomimetic high molecule liquid crystal mould material as claimed in claim 1, is characterized in that, in described step (2), the vinyl monomer of phosphoric acid choline is methylacryoyloxyethyl phosphorylcholine or acrylyl oxy-ethyl phosphorylcholine.
8. the preparation method of cellular membrane biomimetic high molecule liquid crystal mould material as claimed in claim 1, is characterized in that, in described step (3), graft reaction condition is temperature of reaction 20 ~ 80 DEG C, reaction times 1 ~ 12h.
9. the cellular membrane biomimetic high molecule liquid crystal mould material prepared by the preparation method described in any one of claim 1-8.
10. cellular membrane biomimetic high molecule liquid crystal mould material as claimed in claim 9 prepare medical dressing, intervention apparatus, implantation instrument or with the application in the medicine equipment of contacting blood.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921368A (en) * | 2009-06-12 | 2010-12-22 | 中国科学院化学研究所 | Hydroxy propyl cellulose graft copolymer, preparation method and application thereof |
| CN102887976A (en) * | 2011-07-21 | 2013-01-23 | 西北大学 | Imitation mussel attachment protein and cell membrane structure copolymer and preparation method and application thereof |
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2015
- 2015-02-05 CN CN201510059787.3A patent/CN104672482A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921368A (en) * | 2009-06-12 | 2010-12-22 | 中国科学院化学研究所 | Hydroxy propyl cellulose graft copolymer, preparation method and application thereof |
| CN102887976A (en) * | 2011-07-21 | 2013-01-23 | 西北大学 | Imitation mussel attachment protein and cell membrane structure copolymer and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| JIE CHEN等: ""Grafting copolymerization of 2-methacryloyloxyethyl phosphorylcholine (MPC) onto pre-irradiated cellulose films"", 《J. BIOMATER. SCI. POLYMER EDN》 * |
| 龚磊: ""羟丙基纤维素酯类液晶的合成及聚合物复合膜的细胞相容性研究"", 《中国优秀硕士学位论文全文数据库 医药卫生科技辑》 * |
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Application publication date: 20150603 |