CN104877159B - A kind of test tube of hepari cellulose esters liquid crystal material and preparation method and application - Google Patents
A kind of test tube of hepari cellulose esters liquid crystal material and preparation method and application Download PDFInfo
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Abstract
The invention belongs to technical field of biological material, and in particular to a kind of test tube of hepari cellulose esters liquid crystal material and preparation method and application.The preparation method of the test tube of hepari cellulose esters liquid crystal material, comprises the following steps：Hydroxypropyl cellulose is dissolved in ether solvent, suberic acid is added and carries out esterification, obtained mixed solution is cleaned, dialysed, dried by reaction after terminating, and obtains hydroxypropyl cellulose suberic acid ester liquid crystal；Obtained hydroxypropyl cellulose suberic acid ester liquid crystal is dissolved in organic solvent, film forming, after drying, immerse in the citrate buffer solution containing 1 (3 dimethylamino-propyl) 3 ethyl carbodiimides and stand, finally liquid crystal film is immersed in heparin sodium aqua and reacted, cleaning, obtains test tube of hepari cellulose esters liquid crystal material.Described test tube of hepari cellulose esters liquid crystal material can be applied to biomaterial, medical device or product.
Description
Technical field
The invention belongs to technical field of biological material, and in particular to a kind of test tube of hepari cellulose esters liquid crystal material and its preparation side
Method and application.
Background technology
Application of the different kind organism medical material in human cardiovascular disease prevents and treats is more and more extensive, and blood compatibility is people
Make painstaking effort tube material and the prerequisite a kind of critical function of medicine equipment institute with contacting blood.The blood phase of biomaterial
It is (red thin to the haemolysis of blood that capacitive refers to the biomaterial surface suppression thrombosed ability of vessel inner blood and biomaterial
Born of the same parents destroy), platelet function reduction, the temporary reduction of leucocyte and the blood physiology function such as function reduction and complement activation
Influence, does not cause plasma protein to be denatured, the activity of a variety of enzymes of life entity present in blood is not influenceed in addition, also including material,
Do not change electrolyte concentration osmotic pressure in blood, the problems such as harmful immune response are not caused.In New Blood compatibility
During the designing and developing of biomaterial, the problem of above-mentioned blood compatibility is related is always extremely challenging part, is also
Artificial cardiovascular's material and the Key technique problem with the medicine equipment of contacting blood.
Liquid crystal (LC) is a kind of interphase between liquid phase and solid phase, both mobility and continuity with liquid,
There is order and optical anisotropy that crystal molecule is arranged again.Many researchs are verified：Liquid crystal state is prevalent in life
In object, cell membrane, polypeptide, nucleic acid, other biomembranes, the especially cell with blood Long Term Contact in blood vessel and body
Film surface is in the class lipid layer liquid crystal state of flowing, and due to the mobility of biofilm surface, wettability and order just have it
There is good blood compatibility.ZL2013 10185088.4 is prepared for test tube of hepari liquid crystal state hydroxypropyl cellulose ester, overcomes
The small molecule liquid crystal that CN1072021C is used is easy to the deficiency being lost in, and the surface of test tube of hepari not only increases material anticoagulation
With suppression platelet adhesion, complement activation can also be suppressed, painstaking effort tube material and the medicine equipment with contacting blood is coated in
Surface can significantly improve the blood compatibility of material, with wide market prospects.In ZL2013 10185088.4,
The liquid crystal state structure of material is maintained by octanylated processing, heparin then can be used for by the acrylated introducing of liquid crystal state material
The functional group of change, is made after membrane material under alkaline environment and is grafted heparin using Michal additions.
The content of the invention
In order to overcome the deficiencies in the prior art and shortcoming, primary and foremost purpose of the invention is to provide a kind of heparin cellulose
The preparation method of ester liquid crystal material.
Another object of the present invention is to provide the test tube of hepari cellulose esters liquid crystal material that above-mentioned preparation method is prepared
Material, the liquid crystal state structure of the material is similar to the liquid crystal state structure of its hetero-organization in blood vessel endothelium and human body, and is fixed on surface
Heparin can assign material with the surface elecrtonegativity similar to blood vessel endothelium, further enhance the anticoagulation function of material,
And make biocompatibility between material surface and tissue interface closer to the biocompatibility between tissue.
It is still another object of the present invention to provide the application of above-mentioned test tube of hepari cellulose esters liquid crystal material.
The present invention is achieved through the following technical solutions：
A kind of preparation method of test tube of hepari cellulose esters liquid crystal material, comprises the following steps：
(1) preparation of hydroxypropyl cellulose suberic acid ester liquid crystal
Hydroxypropyl cellulose is dissolved in ethers reagent, suberic acid is added and carries out esterification, reaction is incited somebody to action after terminating
The mixed solution arrived is cleaned, dialyses, dried, and obtains hydroxypropyl cellulose suberic acid ester liquid crystal；
(2) preparation of test tube of hepari cellulose esters liquid crystal material
The hydroxypropyl cellulose suberic acid ester liquid crystal that step (1) is prepared is dissolved in organic reagent, then film forming
And dry；Dried liquid crystal film is immersed into the citric acid containing 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides (EDC)
In salt buffer solution, stand；Finally liquid crystal film is immersed and reacted in heparin sodium aqua, cleans, obtains heparin cellulose
Ester liquid crystal material；
The molecular weight of hydroxypropyl cellulose described in step (1) is 80000~200000；
Ethers reagent described in step (1) is at least one in tetrahydrofuran, ether, dipropyl ether and 2- methylfurans
Kind；More preferably tetrahydrofuran；
Hydroxypropyl cellulose and suberic acid mass ratio described in step (1) are (1:0.4)~(1:15)；
Hydroxypropyl cellulose and suberic acid mass ratio described in step (1) are preferably (1:0.5)~(1:10)；
The condition of esterification described in step (1) is：3~6h is reacted at 45~55 DEG C；
The step of cleaning described in step (1) is：Deionized water, which is added, to mixed solution separates out sediment, after stirring,
Stand, remove the aqueous solution, sediment is dissolved in ether solvent；Wherein, the time of described stirring is 3~6h, time of repose
For 10~30min；Described ether solvent is at least one of tetrahydrofuran, ether, dipropyl ether and 2- methylfurans；It is preferred that
For tetrahydrofuran；
Dialysis described in step (1) is at least one of tetrahydrofuran, ether, dipropyl ether and 2- methylfurans
Dialysis, the time of described dialysis is 8~48h；
Drying described in step (1) is vacuum drying；Described vacuum drying condition is：Pressure is -0.05MPa,
Temperature is 45~55 DEG C, and the time is 8~48h；
The quality of hydroxypropyl cellulose suberic acid ester liquid crystal described in step (2) is preferably 2~25g；
Organic solvent described in step (2) is at least one of tetrahydrofuran, ethanol and acetone；
The volume of organic reagent described in step (2) is preferably 50mL；
The temperature of film forming described in step (2) is 10~35 DEG C；
Drying described in step (2) is vacuum drying；Described vacuum drying condition is：Temperature is 10~35 DEG C,
Time is 8~48h；
Final concentration of 0.01 of 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides (EDC) described in step (2)~
100g/mL, described citrate buffer pH=3.7~6.8；
The time of standing described in step (2) is 2~8h, and temperature is 4~40 DEG C；
Heparin sodium aqua described in step (2) is the aqueous solution of standard heparin, Calciparine/sodium salt or low molecular weight heparin；
The concentration of heparin sodium aqua described in step (2) is 0.2~100mg/mL；
The concentration of heparin sodium aqua described in step (2) is preferably 2~16mg/mL；
The volume of heparin sodium aqua described in step (2) is preferably 5~50mL；
The condition of reaction described in step (2) is：2~48h is reacted at 4~25 DEG C；
Cleaning is to be cleaned with deionized water 3~10 times described in step (2)；
A kind of test tube of hepari cellulose esters liquid crystal material, is prepared by above-mentioned preparation method；
Described test tube of hepari cellulose esters liquid crystal material can be applied to biomaterial, medical device or product；
The principle of the invention：Based on Bionic Design theory, by bonded spacerarm on high molecule liquid crystal host material, utilize
The functional group grafting heparin that spacerarm is carried, so not only can guarantee that the stability of test tube of hepari but also can play the activity of heparin.This hair
The product of bright synthesis, had both constructed the liquid crystal state structure of similar endangium, be combined with again the heparin of efficient blood coagulation resisting function into
Point, after this kind of test tube of hepari liquid crystal state biomimetic material and contacting blood, material surface heparin plays a role rapidly first, passes through afterwards
The cooperative effect of heparin and high molecule liquid crystal, effectively prevents or significantly delays material surface thrombosis, promote material anti-freezing
Courageous and upright energy.
The present invention compared with prior art, has the following advantages that and beneficial effect：
(1) synthetic route is shortened：Design is substituted octanylated by a step esterification of suberic acid and hydroxypropyl cellulose
Then two acrylated step courses of reaction, the product of acquisition can the liquid crystal state structure of reserved materials can simultaneously introduce and be used for again
The functional group of test tube of hepari, reduces the process route in production process, it is to avoid resource, energy waste, and energy consumption is low, reduces into
This, with good industrial applications prospect；
(2) the obtained product of first step reaction of the present invention is connected with longer spacerarm, so that heparin conformation change
Steric hindrance reduces, and can assign the more preferable stability of heparin and activity after covalent bonded heparin, can preferably play the medicine of heparin
Reason is acted on.
(3) for blood compatibility high polymer material design angle, the product that the present invention is synthesized, material surface has carboxylic
Base has positive role to improving material blood compatibility, is implemented using this method after test tube of hepari graft reaction, remaining carboxyl can
Promote the improvement of material blood compatibility.Both the liquid crystal state architectural feature that endangium is orderly, flow had been presented, and comprising efficiently anti-
The heparin component of coagulant property, and the negative electrical charge of heparin assigns material and has the elecrtonegativity of similar blood vessel endothelium, when such material
When material is with contacting blood, heparin produces synergy with high molecule liquid crystal, effectively can reduce between material surface and blood
Detrimental effect, significantly improves the blood compatibility of material.
(4) product that the present invention is synthesized also can be with conventional medical polymer, such as polyurethane, polyvinyl chloride, polysiloxanes
Polymer/LC composites are prepared etc. compound, can not only improve the blood compatibility of polymer, the viscoplasticity of liquid crystal material is also
The mechanical property of common polymer can be improved, shearing, destruction of the polymer to haemocyte is reduced.
Brief description of the drawings
Fig. 1 is hydroxypropyl cellulose suberic acid ester liquid crystal and test tube of hepari cellulose esters liquid crystal material prepared by embodiment 1
The POM figures of material, wherein, a：Hydroxypropyl cellulose suberic acid ester liquid crystal；b：Test tube of hepari cellulose esters liquid crystal material.
Fig. 2 is hydroxypropyl cellulose suberic acid ester liquid crystal and test tube of hepari cellulose esters liquid crystal material prepared by embodiment 1
The x-ray electron spectrum spectrogram of material, wherein, a：Test tube of hepari cellulose esters liquid crystal material；b：Hydroxypropyl cellulose suberate
Class liquid crystal.
Fig. 3 is hydroxypropyl cellulose suberic acid ester liquid crystal and test tube of hepari cellulose esters liquid crystal material prepared by embodiment 1
The platelet adhesion reaction figure of material, wherein, a：Hydroxypropyl cellulose suberic acid ester liquid crystal platelet adhesion reaction；b：Test tube of hepari cellulose esters
Class liquid crystal material platelet adhesion reaction.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited
In this.
Embodiment 1
(1) preparation of hydroxypropyl cellulose suberic acid ester liquid crystal
2g hydroxypropyl celluloses (MW=100,000, buy in Aldrich) are dissolved in tetrahydrofuran；Completely
After dissolving, 6g suberic acids, the esterification 4h under the conditions of 55 DEG C are added；Reaction terminate backward mixed solution add 200mL go from
After sub- water sedimentation product, stirring 5h, 15min is stood, the aqueous solution is removed, precipitated product is dissolved in tetrahydrofuran, added
200mL deionized waters are separated out after precipitated product, stirring 5h, are stood 15min, are removed the aqueous solution, sediment is dissolved in into tetrahydrofuran
In, above-mentioned addition deionized water is repeated, is stirred, is stood, water removal, after the process 5 times that sediment is dissolved in tetrahydrofuran, 25 DEG C
Under, dialyse 48h in tetrahydrofuran, removes remaining suberic acid etc., is -0.05MPa in pressure, temperature is under conditions of 45 DEG C
Dry 24h, you can obtain hydroxypropyl cellulose suberic acid ester liquid crystal；
(2) preparation of the cellulose esters liquid crystal material of surface heparinization
2.5g hydroxypropyl cellulose suberic acid ester liquid crystals are dissolved in 50mL tetrahydrofurans, mixed solution is obtained, takes 16mL
The mixed solution in a diameter of 6cm culture dish under conditions of 25 DEG C film forming and under the conditions of 25 DEG C dry 8h；After drying
Liquid crystal film immersion 1g/mL 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides (EDC) citrate buffer (pH
=5) in, stand 2h at 4 DEG C；In the heparin sodium aqua for taking out liquid crystal film immersion 20mL 10mg/mL, 24h is reacted at 4 DEG C；Go from
After sub- water is rinsed 3 times, you can obtain the suberic acid hydroxy propyl cellulose ester liquid crystal material of surface heparinization, as heparin chemical fibre
The plain ester liquid crystal material of dimension.
(JINGHUA 754PC UV/VS Spectrophotometer, test wavelength are tested through spectrophotometer：
630nm), the heparin Grafting Content of the unit area of the cellulose esters liquid crystal material of the surface heparinization is 39.42 μ g/cm2。
The hydroxypropyl cellulose suberic acid ester liquid crystal and step (2) that the present embodiment step (1) is prepared are prepared
The POM images of test tube of hepari cellulose esters liquid crystal material see Fig. 1 (instruments：Petrographic microscope：Axioskop40,Carl
Zeiss, Germany).It can be seen that hydroxypropyl cellulose suberic acid ester liquid crystal shows typical courage under polarisation from POM images
The color texture texture for having cholesteryl liquid crystal is still maintained after the color texture texture of steroid type liquid crystal, test tube of hepari.
Fig. 2 is to determine the hydroxyl that the present embodiment step (1) is prepared using ESCA LAB250 x-ray photoelectron spectroscopies
The result for the test tube of hepari cellulose esters liquid crystal material that propyl cellulose suberic acid ester liquid crystal and step (2) are prepared.From
It is visible in Fig. 2, the XPS spectrum figure of test tube of hepari cellulose esters liquid crystal material (a) occur at 168.6eV and 400.0eV S (2p) and
N (1s) absworption peak, and the spectrogram of hydroxypropyl cellulose suberic acid esters liquid crystal film (b) is without this absworption peak.Due to S and N this
Two kinds of elements only belong to heparin, illustrate that heparin has grafted on hydroxypropyl cellulose suberic acid esters liquid crystal material surface.
Fig. 3 is that the hydroxypropyl cellulose suberic acid ester liquid crystal that this implementation steps (1) are prepared and step (2) are prepared into
The platelet adhesion reaction figure of the test tube of hepari cellulose esters liquid crystal material arrived, wherein, a：Hydroxypropyl cellulose suberic acid ester liquid crystal；
b：Test tube of hepari cellulose esters liquid crystal material.Blood platelet test experiments step：(1) 3.8% (quality point is extracted with vacuum blood collection tube
Number) the fresh anti-freezing rabbit blood of sodium citrate, after 800g centrifugations 15min, carefully draw the mixing of each pipe supernatant liquor, be rich blood
Platelet-poor plasma (PRP)；(2) PBS solution soaked overnight is used before specimen material test；(3) specimen material is immersed in PRP, 37
60min is incubated at DEG C；Specimen material gently washs the blood platelet of surface relaxation with PBS solution after taking out；In 2.5% (quality
Fraction) glutaraldehyde fixer in fix 2h, it is fixed after wash away glutaraldehyde with PBS；Specimen material is done naturally at room temperature after taking out
It is dry.Sticked with SEM observation blood platelets in sample surfaces, assembled and deformation (ESEM：XL30ESEM, Philips, lotus
It is blue) (bibliography：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.).As can be seen from Fig. 3, blood platelet is not activated, but blood platelet is in heparin
The amount of cellulose ester liquid crystal material surface adhesion is less than hydroxypropyl cellulose suberic acid esters liquid crystal surfactant, illustrates heparin work(
The blood compatibility of hydroxypropyl cellulose suberic acid ester liquid crystal can further be promoted after energyization.
Embodiment 2
(1) preparation of hydroxypropyl cellulose suberic acid ester liquid crystal
4g hydroxypropyl celluloses (MW=80,000, buy in Aldrich) are dissolved in tetrahydrofuran；It is completely molten
Xie Hou, adds 8g suberic acids, the esterification 4h under the conditions of 45 DEG C, and reaction terminates backward mixed solution and adds 200mL deionizations
After water sedimentation product, stirring 5h, 10min is stood, the aqueous solution is removed, precipitated product is dissolved in tetrahydrofuran, 200mL is added
Deionized water is separated out after precipitated product, stirring 5h, is stood 10min, is removed the aqueous solution, sediment is dissolved in tetrahydrofuran, weight
Multiple above-mentioned addition deionized water, is stirred, and is stood, water removal, after the process 5 times that sediment is dissolved in tetrahydrofuran, at 25 DEG C, in second
Dialyse 48h in ether, removes remaining suberic acid etc., is -0.05MPa in pressure, temperature is dry 24h under conditions of 45 DEG C, i.e.,
It can obtain hydroxypropyl cellulose suberic acid ester liquid crystal；
(2) preparation of the cellulose esters liquid crystal material of surface heparinization
3g hydroxypropyl cellulose suberic acid ester liquid crystals are dissolved in 50mL tetrahydrofurans, mixed solution is obtained, take 18mL should
Mixed solution in a diameter of 6cm culture dish under conditions of 25 DEG C film forming and under the conditions of 25 DEG C dry 12h；Will be dried
Citrate buffer (the pH=of liquid crystal film immersion 1g/mL 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides (EDC)
5) in, 2h is stood at 4 DEG C；In the low molecular weight heparin solution for taking out liquid crystal film immersion 20mL 10mg/mL, reacted at 25 DEG C
48h；After deionized water rinsing 5 times, you can obtain the hydroxypropyl cellulose suberic acid esters liquid crystal material of surface heparinization, it is
Test tube of hepari cellulose esters liquid crystal material.
(JINGHUA 754PC UV/VS Spectrophotometer, test wavelength are tested through spectrophotometer：
630nm), the heparin Grafting Content of the unit area of the cellulose esters liquid crystal material of the surface heparinization is 67.12 μ g/cm2。
Embodiment 3
(1) preparation of hydroxypropyl cellulose suberic acid ester liquid crystal
2g hydroxypropyl celluloses (MW=200,000, buy in Aldrich) are dissolved in tetrahydrofuran；Completely
After dissolving, add 8g suberic acids, the esterification 4h under the conditions of 55 DEG C, reaction terminate backward mixed solution add 200mL go from
After sub- water sedimentation product, stirring 3h, 15min is stood, the aqueous solution is removed, precipitated product is dissolved in tetrahydrofuran, added
200mL deionized waters are separated out after precipitated product, stirring 3h, are stood 15min, are removed the aqueous solution, sediment is dissolved in into tetrahydrofuran
In, above-mentioned addition deionized water is repeated, is stirred, is stood, water removal, after the process 5 times that sediment is dissolved in tetrahydrofuran, 25 DEG C
Under, dialyse 48h in 2- methylfurans, removes remaining suberic acid etc., is -0.05MPa in pressure, temperature is 45 DEG C of condition
Lower dry 24h, you can obtain hydroxypropyl cellulose suberic acid ester liquid crystal；
(2) preparation of the cellulose esters liquid crystal material of surface heparinization
6g hydroxypropyl cellulose suberic acid ester liquid crystals are dissolved in 50mL tetrahydrofurans, mixed solution is obtained, take 18mL should
Mixed solution film forming under conditions of 25 DEG C in a diameter of 6cm culture dish, and dry under the conditions of 25 DEG C 24h；After drying
Liquid crystal film immersion 1g/mL 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides (EDC) citrate buffer (pH
=5) in, stand 2h at 4 DEG C；In the standard heparin solution for taking out liquid crystal film immersion 40mL 10mg/mL, 2h is reacted at 4 DEG C；Go
After ionized water is rinsed 10 times, you can obtain the hydroxypropyl cellulose suberic acid esters liquid crystal material of surface heparinization, as heparin
Cellulose ester liquid crystal material.
(JINGHUA 754PC UV/VS Spectrophotometer, test wavelength are tested through spectrophotometer：
630nm), the heparin Grafting Content of the unit area of the cellulose esters liquid crystal material of the surface heparinization is 9.42 μ g/cm2。
Embodiment 4
(1) preparation of hydroxypropyl cellulose suberic acid ester liquid crystal
4g hydroxypropyl celluloses (MW=200,000, buy in Aldrich) are dissolved in tetrahydrofuran；Completely
After dissolving, add 2g suberic acids, the esterification 3h under the conditions of 50 DEG C, reaction terminate backward mixed solution add 200mL go from
After sub- water sedimentation product, stirring 3h, 15min is stood, the aqueous solution is removed, precipitated product is dissolved in tetrahydrofuran, added
200mL deionized waters are separated out after precipitated product, stirring 3h, are stood 15min, are removed the aqueous solution, sediment is dissolved in into tetrahydrofuran
In, above-mentioned addition deionized water is repeated, is stirred, is stood, water removal, after the process 5 times that sediment is dissolved in tetrahydrofuran, 25 DEG C
Under, dialyse 8h in 2- methylfurans, removes remaining suberic acid etc., is -0.05MPa in pressure, temperature is 55 DEG C of condition
Lower dry 8h, you can obtain hydroxypropyl cellulose suberic acid ester liquid crystal；
(2) preparation of the cellulose esters liquid crystal material of surface heparinization；
6g hydroxypropyl cellulose suberic acid ester liquid crystals are dissolved in 50mL tetrahydrofurans, mixed solution is obtained, take 18mL should
Mixed solution in a diameter of 6cm culture dish under conditions of 10 DEG C film forming and under the conditions of 10 DEG C dry 48h；Will be dried
Citrate buffer (the pH of liquid crystal film immersion 0.01g/mL 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides (EDC)
=3.7) in, stand 8h at 10 DEG C；In the standard heparin solution for taking out liquid crystal film immersion 40mL 10mg/mL, reacted at 4 DEG C
20h；After deionized water rinsing 10 times, you can obtain the hydroxypropyl cellulose suberic acid esters liquid crystal material of surface heparinization, i.e.,
For test tube of hepari cellulose esters liquid crystal material.
(JINGHUA 754PC UV/VS Spectrophotometer, test wavelength are tested through spectrophotometer：
630nm), the heparin Grafting Content of the unit area of the cellulose esters liquid crystal material of the surface heparinization is 26.83 μ g/cm2。
Embodiment 5
(1) preparation of hydroxypropyl cellulose suberic acid ester liquid crystal
2g hydroxypropyl celluloses (MW=200,000, buy in Aldrich) are dissolved in tetrahydrofuran；Completely
After dissolving, add 20g suberic acids, the esterification 6h under the conditions of 45 DEG C, reaction terminate backward mixed solution add 200mL go from
After sub- water sedimentation product, stirring 6h, 30min is stood, the aqueous solution is removed, precipitated product is dissolved in tetrahydrofuran, added
200mL deionized waters are separated out after precipitated product, stirring 6h, are stood 30min, are removed the aqueous solution, sediment is dissolved in into tetrahydrofuran
In, above-mentioned addition deionized water is repeated, is stirred, is stood, water removal, after the process 5 times that sediment is dissolved in tetrahydrofuran, 25 DEG C
Under, dialyse 36h in 2- methylfurans, removes remaining suberic acid etc., is -0.05MPa in pressure, temperature is 55 DEG C of condition
Lower dry 20h, you can obtain hydroxypropyl cellulose suberic acid ester liquid crystal；
(2) preparation of the cellulose esters liquid crystal material of surface heparinization；
6g hydroxypropyl cellulose suberic acid ester liquid crystals are dissolved in 50mL tetrahydrofurans, mixed solution is obtained, take 18mL should
Mixed solution in a diameter of 6cm culture dish under conditions of 35 DEG C film forming and under the conditions of 35 DEG C dry 8h；Will be dried
Citrate buffer (the pH of liquid crystal film immersion 100g/mL 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides (EDC)
=6.8) in, stand 3h at 40 DEG C；In the standard heparin solution for taking out liquid crystal film immersion 40mL 10mg/mL, reacted at 10 DEG C
40h；After deionized water rinsing 10 times, you can obtain the hydroxypropyl cellulose suberic acid esters liquid crystal material of surface heparinization, i.e.,
For test tube of hepari cellulose esters liquid crystal material.
(JINGHUA 754PC UV/VS Spectrophotometer, test wavelength are tested through spectrophotometer：
630nm), the heparin Grafting Content of the unit area of the cellulose esters liquid crystal material of the surface heparinization is 38.53 μ g/cm2。
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by above-described embodiment of the invention
Limitation, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of test tube of hepari cellulose esters liquid crystal material, it is characterised in that comprise the following steps：
(1) preparation of hydroxypropyl cellulose suberic acid ester liquid crystal
Hydroxypropyl cellulose is dissolved in ethers reagent, suberic acid is added and carries out esterification, reaction will be obtained after terminating
Mixed solution is cleaned, dialyses, dried, and obtains hydroxypropyl cellulose suberic acid ester liquid crystal；
(2) preparation of test tube of hepari cellulose esters liquid crystal material
The hydroxypropyl cellulose suberic acid ester liquid crystal that step (1) is prepared is dissolved in organic reagent, then film forming and is done
It is dry；Dried liquid crystal film is immersed into the Citrate buffer containing 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides molten
In liquid, stand；Finally liquid crystal film is immersed and reacted in heparin sodium aqua, cleans, obtains test tube of hepari cellulose esters liquid crystal
Material.
2. the preparation method of test tube of hepari cellulose esters liquid crystal material according to claim 1, it is characterised in that：
The molecular weight of hydroxypropyl cellulose described in step (1) is 80000~200000.
3. the preparation method of test tube of hepari cellulose esters liquid crystal material according to claim 1, it is characterised in that：
Hydroxypropyl cellulose and suberic acid mass ratio described in step (1) are (1:0.4)~(1:15).
4. the preparation method of test tube of hepari cellulose esters liquid crystal material according to claim 1, it is characterised in that：
The condition of esterification described in step (1) is：3~6h is reacted at 45~55 DEG C.
5. the preparation method of test tube of hepari cellulose esters liquid crystal material according to claim 1, it is characterised in that：
Final concentration of 0.01~the 100g/mL of 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides described in step (2),
Described citrate buffer pH=3.7~6.8.
6. the preparation method of test tube of hepari cellulose esters liquid crystal material according to claim 1, it is characterised in that：
The time of standing described in step (2) is 2~8h, and temperature is 4~40 DEG C.
7. the preparation method of test tube of hepari cellulose esters liquid crystal material according to claim 1, it is characterised in that：
The condition of reaction described in step (2) is：2~48h is reacted at 4~25 DEG C.
8. the preparation method of test tube of hepari cellulose esters liquid crystal material according to claim 1, it is characterised in that：
Heparin sodium aqua described in step (2) is the aqueous solution of standard heparin, Calciparine/sodium salt or low molecular weight heparin；
The concentration of heparin sodium aqua described in step (2) is 0.2~100mg/mL.
9. a kind of test tube of hepari cellulose esters liquid crystal material, it is characterised in that：Pass through the system described in any one of claim 1~8
Preparation Method is prepared.
10. application of the test tube of hepari cellulose esters liquid crystal material in biomaterial or medical article described in claim 9.
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| CN101024150A (en) * | 2007-01-12 | 2007-08-29 | 中国科学院上海有机化学研究所 | Porous film material fixed with heparin on surface, its preparing method and use |
| CN103289116A (en) * | 2013-05-17 | 2013-09-11 | 暨南大学 | Surface-heparinized cellulose ester liquid crystal material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101024150A (en) * | 2007-01-12 | 2007-08-29 | 中国科学院上海有机化学研究所 | Porous film material fixed with heparin on surface, its preparing method and use |
| CN103289116A (en) * | 2013-05-17 | 2013-09-11 | 暨南大学 | Surface-heparinized cellulose ester liquid crystal material and preparation method and application thereof |
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