CN103289116A - Surface-heparinized cellulose ester liquid crystal material and preparation method and application thereof - Google Patents
Surface-heparinized cellulose ester liquid crystal material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of biological materials and discloses a surface-heparinized cellulose ester liquid crystal material and a preparation method and application thereof. The preparation method of the liquid crystal material comprises the following steps of: (1) preparation of acryloyl-octanoyl-hydroxy propyl cellulose ester liquid crystal: dissolving hydroxy propyl cellulose into an acetone solution, adding acryloyl chloride and reacting; after the reaction is over, cleaning the obtained mixed solution for 3-5 times, and dialyzing and drying; dissolving the obtained product in acetone, dropwise adding octanoyl chloride and reacting; and cleaning, dialyzing and drying to obtain acryloyl-octanoyl-hydroxy propyl cellulose ester; and (2) preparation of surface-heparinized cellulose ester liquid crystal material: dissolving the acryloyl-octanoyl-hydroxy propyl cellulose ester liquid crystal in tetrahydrofuran, fetching the solution to form a film, then adding a sodium hydroxide solution of heparin sodium, reacting and cleaning to obtain the surface-heparinized cellulose ester liquid crystal material.
Description
Technical field
The invention belongs to technical field of biological material, be specifically related to a kind of cellulose esters liquid crystal material and preparation method and application of surface heparinization.
Background technology
For the medicine equipment that contacts with blood, when requiring it to contact with blood, do not cause that blood coagulation and thrombocyte stick together cohesion, do not destroy the undesirable actions such as haemolysis of formed elements in the blood, namely have blood compatibility.The quality of medicine equipment blood compatibility is directly connected to the effect of its clinical use.In decades, to the exploitation of novel no thrombus biomaterial be always in the technical field of biological material one have challenging problem, also be the core technology problem of medicine equipment.
Liquid crystal (LC) is a kind of intermediate phase between liquid phase and solid phase, has both had flowability and the continuity of liquid, has order and optical anisotropy that crystal molecule is arranged again.Liquid crystal state is prevalent in the organism.Many researchs are verified: cytolemma, polypeptide, nucleic acid, other microbial film in blood vessel and the body, especially all be in mobile lipoid layer liquid crystal state with the surface of cell membrane that blood contacts for a long time, because the flowability of biofilm surface, wettability and order just make it have good blood compatibility.The factor of any destruction blood vessel ordered arrangement all can cause the formation of thrombus, and any factor that causes that erythrocyte membrane liquid crystal order degree reduces all can cause microcirculatory having some setbacks.Early stage, the liquid crystal biocompatible materials mainly concentrated on the small molecules liquid crystal compound as disperse phase and polymer-based material, but studies show that, though this composite structure can improve the blood appearance property of material etc., but there is more serious loss in the small molecules liquid crystal, thereby causes the change of colloidal osmotic pressure to cause haemolysis.CN1072021C once prepared different types of polymer/liquid crystal composite membrane and improved the blood compatibility of material, and obtained certain effect.Yet, if this class matrix material is also had the following disadvantages during for the manufacture of the biomaterial that directly contacts with blood and medical device, goods:
1, the anticoagulation function of the anticoagulation function of matrix material and human vas does not more also reach perfect condition, the phenomenon that still exists thrombus to generate when causing material to contact with blood; 2, material surface does not also reach the performance that tunica intima possesses, and the biocompatibility between the tissue interface also has certain gap, and the regulation and control on material surface liquid crystal farmland still need improve; 3, be the small molecules liquid crystal owing to what select for use in the polymer/liquid crystal composite membrane preparation process, and the small molecules liquid crystal produce leakage in the simulated body fluid environment, cause the anticoagulation function of composite membrane and coating thereof to descend to some extent.
Although the present polymer/liquid crystal composite membrane of developing has improved the anticoagulation function of substrate material to a certain extent, also has big gap from the requirement of desirable blood compatibility biological material.Major cause is that small molecules liquid crystal farmland is stable inadequately, being subjected to external environment influence can deform (comprising size and orientation), cause material surface liquid crystal state structure to change, can't be really be according to biomaterial is carried out molecular designing with surface tissue form and the pass between the blood compatibility of material.The high molecule liquid crystal molecule is difficult for characteristics such as stripping more greatly and has caused investigator's attention with molecular weight, the researchdevelopment of liquid crystal biomaterial turns to the high molecule liquid crystal material.
Summary of the invention
In order to overcome the deficiencies in the prior art, primary and foremost purpose of the present invention is to provide a kind of preparation method of cellulose esters liquid crystal material of surface heparinization.
Another object of the present invention is to provide a kind of cellulose esters liquid crystal material of the surface heparinization that is prepared from by above-mentioned preparation method.This material liquid crystal state can constitute phase separation structure, be similar to the fluid mosaic model of cytolemma, make the anticoagulation function of material reach the requirement of human vas anticoagulation function, and make biocompatibility between material surface and the tissue interface near the biocompatibility between the tissue.
A further object of the present invention is to provide the application of the cellulose esters liquid crystal material of above-mentioned surface heparinization.
The present invention realizes by following technical proposals:
A kind of preparation method of cellulose esters liquid crystal material of surface heparinization may further comprise the steps:
(1) preparation of propylene acidylate-decoylization-hydroxypropylcellulose ester liquid crystal: 1～20g hydroxypropylcellulose is dissolved in the acetone soln, add 0.5～10mL acrylate chloride, reaction is cleaned the mixing solutions that obtains 3-5 time after reaction finishes, dialysis, drying; Then the product that obtains is dissolved in the acetone, drips the capryl(yl)chloride of 0.7～14mL, reaction is cleaned the solution that obtains 3-5 time, dialysis, and drying namely obtains propylene acidylate-decoylization-hydroxypropylcellulose ester liquid crystal;
(2) preparation of the cellulose esters liquid crystal material of surface heparinization: propylene acidylate-decoylization-hydroxypropylcellulose ester liquid crystal that 2～25g is obtained is dissolved in the 50mL tetrahydrofuran (THF); get this solution film forming of 16mL; add the sodium hydroxide solution that 5～50mL mass concentration is the heparin sodium of 2～16mg/mL then; reaction; clean, obtain the cellulose esters liquid crystal material of surface heparinization.
The molecular weight of the hydroxypropylcellulose described in the step (1) is 80,000～200,000.
Reaction described in the step (1) is to react 3～6h under 45～65 ℃ of conditions;
The step of described cleaning is: add deionized water to mixing solutions and separate out throw out, after the stirring, leave standstill, remove the aqueous solution, throw out is dissolved in the acetone; Wherein, the churning time in the described cleaning step is 5h, and time of repose is 15 minutes;
Described dialysis is to dialyse in water, ethanol or tetrahydrofuran (THF);
Described drying is lyophilize, and the time is 24h.
The time of described dialysis is 8～48h;
Described sublimation drying is 24h.
The temperature of the film forming described in the step (2) is 10～35 ℃;
The sodium hydroxide solution of described heparin sodium is dissolved in the aqueous sodium hydroxide solution heparin sodium formulated; Wherein, the mass ratio of heparin sodium and sodium hydroxide is 1:1～1:5 in the sodium hydroxide solution of heparin sodium.
Described reaction is to react 2～10h under 20～30 ℃ of conditions;
Described cleaning is to use washed with de-ionized water 10 times.
The cellulose esters liquid crystal material of the surface heparinization that a kind of preparation method described above is prepared from: the heparin grafting content of the unit surface of the cellulose esters liquid crystal material of this surface heparinization is 9.2-17.1 μ g/cm
2
The application of cellulose esters liquid crystal material in the preparation of biomaterial, medical device or goods of surface heparinization described above.
The principle of the invention is: the present invention is based on the Bionic Design theory, by connecting spacerarm, the covalent linkage grafting heparin that utilizes spacerarm to have can guarantee that like this stability of heparinization can bring into play the activity of heparin again at the high molecule liquid crystal substrate material.The product that the present invention synthesizes, both made up the liquid crystal state structure of similar tunica intima, be combined with the heparin compositions of efficient blood coagulation resisting function again, this kind heparinization liquid crystal state biomimetic material is with after blood contacts, the material surface heparin plays a role at first rapidly, afterwards by the synergistic effect of heparin and high molecule liquid crystal, effectively stop or delay the material surface thrombosis, promote the material anticoagulation function.
The present invention compared with prior art has following advantage and beneficial effect: reaction conditions of the present invention is gentle and significantly, production energy consumption is low, saves production cost, and the simple and technology maturation of used plant and instrument has the favorable industrial application prospect; The product that the present invention makes belongs to high molecule liquid crystal, can avoid the stripping of small molecules liquid crystal in application process; And, realize heparinization by spacerarm covalency keyed jointing, can guarantee stability and the heparin activity of heparinization.From blood compatibility macromolecular material design angle, the product that the present invention synthesizes, both presented the liquid crystal state constitutional features that tunica intima is orderly, flow, the heparin component that comprises efficient anticoagulation function again, heparin and high molecule liquid crystal produce synergy, can effectively reduce the interfacial tension between material surface and the blood, significantly improve the blood compatibility of material.The product that the present invention synthesizes also can with medical polymer commonly used, as urethane, polyvinyl chloride, compound preparation polymkeric substance such as polysiloxane/LC matrix material makes the liquid crystal state matrix material of excellent biological compatibility activity.
Description of drawings
The POM image (25 ℃) of the propylene acidylate-decoylization-hydroxypropylcellulose ester liquid crystal of Fig. 1: embodiment 1 preparation.
Fig. 2: x-ray diffractometer test result; Wherein, a is hydroxypropylcellulose among the embodiment 1; B is the propylene acidylate-decoylization-hydroxypropylcellulose ester liquid crystal of embodiment 1 preparation.
Fig. 3: cellulose esters liquid crystal material fourier transformation attenuated total reflectance attenuated total refraction infrared spectra; Wherein, the hydroxypropylcellulose among a: the embodiment 1; Propylene acidylate-decoylization among b: the embodiment 1-hydroxypropylcellulose ester liquid crystal; Heparinization propylene acidylate-decoylization-hydroxypropylcellulose ester liquid crystal among c: the embodiment 1.
Fig. 4: the static contact angle test pattern of propylene acidylate ?decoyl ?hydroxypropylcellulose ester liquid crystal material.
Fig. 5: platelet adhesion reaction figure; Propylene acidylate-decoylization of a: embodiment 1-hydroxypropylcellulose ester liquid crystal; Heparinization propylene acidylate-decoylization-hydroxypropylcellulose ester liquid crystal of b: embodiment 1; Propylene acidylate-decoylization of c: embodiment 1-hydroxypropylcellulose ester liquid crystal platelet adhesion reaction; Heparinization propylene acidylate-decoylization of d: embodiment 1-hydroxypropylcellulose ester liquid crystal platelet adhesion reaction.
Embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) preparation of propylene acidylate-decoylization-hydroxypropylcellulose ester liquid crystal: with 2g hydroxypropylcellulose (M
W=100,000, buy the company in Aldrich) be dissolved in the acetone soln; After the dissolving, to wherein dripping the 1mL acrylate chloride, under 55 ℃ of conditions, react 4h fully, reaction finishes the back and adds 200mL deionized water precipitated product to mixing solutions, behind the stirring 5h, leaves standstill 15 minutes, remove the aqueous solution, precipitated product is dissolved in the acetone, adds the 200mL deionized water again and separate out precipitated product, behind the stirring 5h, left standstill 15 minutes, remove the aqueous solution, throw out is dissolved in the acetone, repeat above-mentioned adding deionized water, stir, leave standstill, dewater, throw out is dissolved in the process 5 times of acetone after, under 25 ℃, the 48h that dialyses in deionized water removes remaining acrylate chloride, drying; Then the product that obtains is dissolved in the acetone; drip the capryl(yl)chloride of 1.4mL; under 55 ℃ of conditions; reaction 4h is to the mixing solutions adding 200mL deionized water of reaction, behind the stirring 5h; remove the aqueous solution; throw out is dissolved in the acetone, adds the 200mL deionized water again and separate out product, repeat above-mentioned adding deionized water; stir; leave standstill, dewater, throw out is dissolved in the process 5 times of acetone after; under 25 ℃; the 48h that dialyses in deionized water, lyophilize 24h namely obtains propylene acidylate-decoylization-hydroxypropylcellulose ester liquid crystal.
(2) preparation of the cellulose esters liquid crystal material of surface heparinization: 2.5g propylene acidylate-decoylization-hydroxypropylcellulose ester liquid crystal is dissolved in the 50mL tetrahydrofuran (THF); mixing solutions, getting this mixing solutions of 16mL is film forming under 25 ℃ the condition in the culture dish of 6cm at diameter.With heparin sodium (〉=150U/mg, buy the Co. in Shanghai CpG Biotech, Ltd) be dissolved in that compound concentration is the aqueous sodium hydroxide solution (mass ratio of heparin sodium and sodium hydroxide is 1:1) of the heparin sodium of 4mg/mL in the aqueous sodium hydroxide solution that concentration is 4mg/mL, the aqueous sodium hydroxide solution that in culture dish, adds this heparin heparin sodium of 10mL, 25 ℃ of reactions were washed 10 times repeatedly with deionized water after 7 hours, obtained the cellulose esters liquid crystal material of surface heparinization.(JINGHUA754PC UV/VS Spectrophotometer, the test wavelength: 630nm), the heparin grafting content of the unit surface of the cellulose esters liquid crystal material of this surface heparinization is 9.42 μ g/cm through the spectrophotometer test
2
The POM image of propylene acidylate-decoylization-hydroxypropylcellulose ester liquid crystal is seen Fig. 1 (used instrument: polarizing microscope: Axioskop40, Carl Zeiss, Germany).Propylene acidylate-decoylization-hydroxypropylcellulose ester liquid crystal shows the color texture texture of typical cholesteryl liquid crystal under polarisation as can be seen from the POM image.
Fig. 2 is the x-ray diffractometer test result; Wherein, a is hydroxypropylcellulose among the embodiment 1; B is the propylene acidylate-decoylization-hydroxypropylcellulose ester liquid crystal (used instrument: X-ray diffractometer: Dmax-1200, Japan is of science) of embodiment 1 preparation.Fig. 2 is as can be seen: the raw material hydroxypropylcellulose ° locates to present more sharp-pointed diffraction peak (corresponding to (101) crystal face) in 2 θ=20, illustrates that there is crystallization to a certain degree in hydroxypropylcellulose.The diffraction peak of propylene acidylate-decoylization-hydroxypropylcellulose ester liquid crystal obviously weakens, and this is because by behind the acyl chloride reaction introducing alkyl, soft alkyl group side chain has destroyed the intermolecular and intramolecular hydrogen bond of hydroxypropylcellulose, presents non-crystalline state.
Fig. 3 is cellulose esters liquid crystal material fourier transformation attenuated total reflectance attenuated total refraction infrared spectra; Wherein, the hydroxypropylcellulose among a: the embodiment 1; Propylene acidylate-decoylization among b: the embodiment 1-hydroxypropylcellulose ester liquid crystal; Heparinization propylene acidylate-decoylization-hydroxypropylcellulose ester liquid crystal among c: the embodiment 1 (used instrument Fourier infrared spectrograph: EQUINOX-70, Bruker, Germany).As can be drawn from Figure 3: on the hydroxypropylcellulose spectrogram at 3461cm
-1There is wide and strong hydroxyl stretching vibration absorption peak in the place; This absorption peak obviously weakens on the spectrogram of product propylene acidylate-decoylization-hydroxypropylcellulose ester liquid crystal, and at 1725cm
-1The strong stretching vibration absorption peak of the carbonyl of unsaturated link(age), 2800-3000cm appear containing in the place
-1The stretching vibration absorption peak of place's methyl and methylene radical obviously strengthens, and illustrates that acryl and capryloyl successfully are grafted on the molecular chain, have replaced the part of hydroxyl on the molecular chain by acyl chloride reaction.And on the spectrogram of heparinization propylene acidylate-decoylization-hydroxypropylcellulose ester liquid crystal, 1000cm has appearred
-1, 1191cm
-1, 1650cm
-1Vibration absorption peak, consistent with the constitutional features of heparin, and 3461cm
-1Wide and strong hydroxyl stretching vibration absorption peak further strengthens phenomenons such as (having hydroxyl on the heparin molecule) and has illustrated that heparin has been grafted on propylene acidylate-decoylization-hydroxypropylcellulose ester liquid crystal.
Table 1. contact angle test experiments result (unit/°)
The data of surveying average for 10 times for test, the wetting ability on propylene acidylate-decoylization behind the grafting heparin-hydroxypropylcellulose ester liquid crystal surface obviously improves as shown in Table 1.
The static contact angle test pattern of propylene acidylate-decoylization-hydroxypropylcellulose ester liquid crystal material is (contact angle measurement: DSA100, Kruss, Germany) as shown in Figure 4.
Fig. 5: platelet adhesion reaction figure; Propylene acidylate-decoylization of a: embodiment 1-hydroxypropylcellulose ester liquid crystal; Heparinization propylene acidylate-decoylization-hydroxypropylcellulose ester liquid crystal of b: embodiment 1; Propylene acidylate-decoylization of c: embodiment 1-hydroxypropylcellulose ester liquid crystal platelet adhesion reaction; Heparinization propylene acidylate-decoylization of d: embodiment 1-hydroxypropylcellulose ester liquid crystal platelet adhesion reaction.As can be drawn from Figure 5: propylene acidylate ?decoyl ?hydroxypropylcellulose ester liquid crystal (a) surface presents staggered striped texture, heparinization propylene acidylate ?decoyl ?hydroxypropylcellulose ester liquid crystal (b) appearance fragmentarily surface has new material to appear at the surface, and the striped texture of liquid crystal surfactant still exists simultaneously; Carry out the platelet adhesion reaction experiment at propylene acidylate ?decoyl ?hydroxypropylcellulose ester liquid crystal, experimental result (c) shows that there is certain blood coagulation resisting function in propylene acidylate ?decoyl ?hydroxypropylcellulose ester liquid crystal to platelet adhesion reaction; Find than being the propylene acidylate ?decoyl ?hydroxypropylcellulose ester liquid crystal (c) of heparinization and carry out platelet adhesion reaction (d) on heparinization propylene acidylate ?decoyl ?hydroxypropylcellulose ester liquid crystal surface; the amount of platelet adhesion reaction reduces; the volume of platelets that adheres to also reduces; the surface of liquid crystal film is more smooth, illustrates that the propylene acidylate ?decoyl ?hydroxypropylcellulose ester liquid crystal of heparinization has stronger anticoagulation function than propylene acidylate ?decoyl ?hydroxypropylcellulose ester liquid crystal.
Platelet adhesion reaction experimental technique title: direct electron microscopy, reference: J.Yuan, S.C.Lin, J.Shen.Enhanced blood compatibility of polyurethane functionalized with sulfobetaine[J] .Colloids and Surfaces B:Biointerfaces, 2008,66 (1): 90-95.
Experimental procedure:
(1) extract the fresh anti-freezing rabbit of 3.8% Sodium Citrate blood with vacuum test tube, behind the centrifugal 15min of 800g, careful absorption is respectively managed supernatant liquid and is mixed, and is platelet rich plasma (PRP).
(2) spend the night with the PBS solution soaking before the specimen material test.
(3) specimen material is immersed among the PRP, hatches 60min under 37 ℃; Specimen material takes out the back is washed surface relaxation gently with PBS solution thrombocyte; Fixing 2h in 2.5% glutaraldehyde stationary liquid, fixing back is with PBS flush away glutaraldehyde; Specimen material takes out seasoning under the room temperature of back.With SEM observe that thrombocyte sticks at sample surfaces, gathering and distortion situation.
Embodiment 2
(1) preparation of propylene acidylate-decoylization-hydroxypropylcellulose ester liquid crystal: with 1g hydroxypropylcellulose (M
W=200,000, buy the company in Aldrich) be dissolved in the acetone soln; After the dissolving, to wherein dripping the 0.5mL acrylate chloride, under 65 ℃ of conditions, react 3h fully, reaction finishes the back and separates out precipitated product to mixing solutions adding 200mL deionized water, after stirring 5h, left standstill 15 minutes, remove the aqueous solution, precipitated product is dissolved in the acetone, add the 200mL deionized water again and separate out precipitated product, behind the stirring 5h, left standstill 15 minutes, remove the aqueous solution, throw out is dissolved in the acetone, repeats above-mentioned adding deionized water, stir, leave standstill, dewater, throw out is dissolved in the process 5 times of acetone after, under 25 ℃, dialysis 8h removes remaining acrylate chloride, drying in ethanol; Then the product that obtains is dissolved in the acetone; drip the capryl(yl)chloride of 0.7mL; under 65 ℃ of conditions; reaction 3h is to the mixing solutions adding 200mL deionized water of reaction, behind the stirring 5h; remove the aqueous solution; throw out is dissolved in the acetone, adds the 200mL deionized water again and separate out product, repeat above-mentioned adding deionized water; stir; leave standstill, dewater, throw out is dissolved in the process 5 times of acetone after; under 20 ℃; the 12h that dialyses in ethanol, lyophilize 24h namely obtains propylene acidylate-decoylization-hydroxypropylcellulose ester liquid crystal.
(2) preparation of the cellulose esters liquid crystal material of surface heparinization: 2g propylene acidylate-decoylization-hydroxypropylcellulose ester liquid crystal is dissolved in the 50mL tetrahydrofuran (THF); mixing solutions, getting this mixing solutions of 16mL is film forming under 10 ℃ the condition in the culture dish of 6cm at diameter.With heparin sodium (〉=150U/mg, buy the Co. in Shanghai CpG Biotech, Ltd) be dissolved in that compound concentration is the aqueous sodium hydroxide solution (mass ratio of heparin sodium and sodium hydroxide is 1:4) of the heparin sodium of 20mg/mL in the aqueous sodium hydroxide solution that concentration is 80mg/mL, the aqueous sodium hydroxide solution that in culture dish, adds this heparin heparin sodium of 5mL, 30 ℃ of reactions were washed 10 times repeatedly with deionized water after 2 hours, obtained the cellulose esters liquid crystal material of surface heparinization.(JINGHUA754PC UV/VS Spectrophotometer, the test wavelength: 630nm), the heparin grafting content of the unit surface of the cellulose esters liquid crystal material of this surface heparinization is 14.7 μ g/cm through the spectrophotometer test
2
Embodiment 3
The preparation of propylene acidylate-decoylization-hydroxypropylcellulose ester liquid crystal: with 20g hydroxypropylcellulose (M
W=80,000, buy the company in Aldrich) be dissolved in the acetone soln; After the dissolving, to wherein dripping the 10mL acrylate chloride, under 45 ℃ of conditions, react 6h fully, reaction finishes the back and adds 200mL deionized water precipitated product to mixing solutions, behind the stirring 5h, leaves standstill 15 minutes, remove out the aqueous solution, precipitated product is dissolved in the acetone, adds the 200mL deionized water again and separate out precipitated product, behind the stirring 5h, left standstill 15 minutes, remove the aqueous solution, throw out is dissolved in the acetone, repeat above-mentioned adding deionized water, stir, leave standstill, dewater, throw out is dissolved in the process 3 times of acetone after, under 25 ℃, the 8h that dialyses in tetrahydrofuran (THF) removes remaining acrylate chloride, drying; Then the product that obtains is dissolved in the acetone; drip the capryl(yl)chloride of 14mL; under 45 ℃ of conditions; reaction 6h is to the mixing solutions adding 200mL deionized water of reaction, behind the stirring 5h; remove the aqueous solution; throw out is dissolved in the acetone, adds the 200mL deionized water again and separate out product, repeat above-mentioned adding deionized water; stir; leave standstill, dewater, throw out is dissolved in the process 3 times of acetone after; under 25 ℃; the 48h that dialyses in tetrahydrofuran (THF), lyophilize 24h namely obtains propylene acidylate-decoylization-hydroxypropylcellulose ester liquid crystal.
(2) preparation of the cellulose esters liquid crystal material of surface heparinization: 25g propylene acidylate-decoylization-hydroxypropylcellulose ester liquid crystal is dissolved in the 50mL tetrahydrofuran (THF); mixing solutions, getting this mixing solutions of 16mL is film forming under 35 ℃ the condition in the culture dish of 6cm at diameter.With heparin sodium (〉=150U/mg, buy the Co. in Shanghai CpG Biotech, Ltd) be dissolved in that compound concentration is the aqueous sodium hydroxide solution (mass ratio of heparin sodium and sodium hydroxide is 1:2) of the heparin sodium of 30mg/mL in the aqueous sodium hydroxide solution that concentration is 60mg/mL, the aqueous sodium hydroxide solution that in culture dish, adds this heparin heparin sodium of 50mL, 20 ℃ of reactions were washed 10 times repeatedly with deionized water after 10 hours, obtained the cellulose esters liquid crystal material of surface heparinization.(JINGHUA754PC UV/VS Spectrophotometer, the test wavelength: 630nm), the heparin grafting content of the unit surface of the cellulose esters liquid crystal material of this surface heparinization is 17.1 μ g/cm through the spectrophotometer test
2
Claims (8)
1. the preparation method of the cellulose esters liquid crystal material of a surface heparinization is characterized in that: may further comprise the steps:
(1) preparation of propylene acidylate-decoylization-hydroxypropylcellulose ester liquid crystal: 1～20g hydroxypropylcellulose is dissolved in the acetone soln, add 0.5～10mL acrylate chloride, reaction is cleaned the mixing solutions that obtains 3-5 time after reaction finishes, dialysis, drying; Then the product that obtains is dissolved in the acetone, drips the capryl(yl)chloride of 0.7～14mL, reaction is cleaned the solution that obtains 3-5 time, dialysis, and drying namely obtains propylene acidylate-decoylization-hydroxypropylcellulose ester liquid crystal;
(2) preparation of the cellulose esters liquid crystal material of surface heparinization: propylene acidylate-decoylization-hydroxypropylcellulose ester liquid crystal that 2～25g is obtained is dissolved in the 50mL tetrahydrofuran (THF); get this solution film forming of 16mL; add the sodium hydroxide solution that 5～50mL mass concentration is the heparin sodium of 2～16mg/mL then; reaction; clean, obtain the cellulose esters liquid crystal material of surface heparinization.
2. preparation method according to claim 1, it is characterized in that: the molecular weight of the hydroxypropylcellulose described in the step (1) is 80,000～200,000.
3. preparation method according to claim 1, it is characterized in that: the reaction described in the step (1) is to react 3～6h under 45～65 ℃ of conditions;
The step of described cleaning is: add deionized water to mixing solutions and separate out throw out, after the stirring, leave standstill, remove the aqueous solution, throw out is dissolved in the acetone;
Described dialysis is to dialyse in water, ethanol or tetrahydrofuran (THF);
Described drying is lyophilize, and the time is 24h.
4. preparation method according to claim 3, it is characterized in that: the churning time in the described cleaning step is 5h, time of repose is 15 minutes;
The time of described dialysis is 8～48h.
5. preparation method according to claim 1, it is characterized in that: the temperature of the film forming described in the step (2) is 10～35 ℃;
The sodium hydroxide solution of described heparin sodium is dissolved in the aqueous sodium hydroxide solution heparin sodium formulated;
Described reaction is to react 2～10h under 20～30 ℃ of conditions;
Described cleaning is to use washed with de-ionized water 10 times.
6. preparation method according to claim 5, it is characterized in that: the mass ratio of heparin sodium and sodium hydroxide is 1:1～1:5 in the sodium hydroxide solution of described heparin sodium.
7. the cellulose esters liquid crystal material of a surface heparinization that is prepared from by each described preparation method of claim 1～6, it is characterized in that: the heparin grafting content of the unit surface of the cellulose esters liquid crystal material of this surface heparinization is 9.2-17.1 μ g/cm
2
8. the application of cellulose esters liquid crystal material in the preparation of biomaterial, medical device or goods of surface heparinization according to claim 7.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739866A (en) * | 2013-12-19 | 2014-04-23 | 暨南大学 | Preparation and application of bio-functional hydroxy propyl cellulose ester type liquid crystal membrane |
| CN104877159A (en) * | 2015-05-20 | 2015-09-02 | 暨南大学 | Heparinization cellulose ester liquid crystal material as well as preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1230405A (en) * | 1998-12-31 | 1999-10-06 | 暨南大学 | Composite blood compatible polymer/liquid crystal film and its preparation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1230405A (en) * | 1998-12-31 | 1999-10-06 | 暨南大学 | Composite blood compatible polymer/liquid crystal film and its preparation |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739866A (en) * | 2013-12-19 | 2014-04-23 | 暨南大学 | Preparation and application of bio-functional hydroxy propyl cellulose ester type liquid crystal membrane |
| CN103739866B (en) * | 2013-12-19 | 2015-12-09 | 暨南大学 | A kind of preparation of biological functional hydroxy propyl cellulose ester liquid crystal film and application thereof |
| CN104877159A (en) * | 2015-05-20 | 2015-09-02 | 暨南大学 | Heparinization cellulose ester liquid crystal material as well as preparation method and application thereof |
| CN104877159B (en) * | 2015-05-20 | 2017-11-07 | 暨南大学 | A kind of test tube of hepari cellulose esters liquid crystal material and preparation method and application |
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