CN102617880B - End-point fixing preparation method for multi-aldehyde alginic acid coating - Google Patents
End-point fixing preparation method for multi-aldehyde alginic acid coating Download PDFInfo
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- CN102617880B CN102617880B CN 201210109627 CN201210109627A CN102617880B CN 102617880 B CN102617880 B CN 102617880B CN 201210109627 CN201210109627 CN 201210109627 CN 201210109627 A CN201210109627 A CN 201210109627A CN 102617880 B CN102617880 B CN 102617880B
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Abstract
The invention discloses an end-point fixing preparation method for a multi-aldehyde alginic acid coating. The method comprises the following steps: firstly, polymer material is soaked into sulfuric acid solution of potassium permanganate for acidizing treatment; then the material subjected to acidizing treatment is placed into polyethylene imine solution so as to obtain an amination decorated surface after reaction; periodic acid or sodium periodate is used for oxidation treatment to sodium alginate, aldehyde group is exposed at the tail end of the segment of alginic acid, and multi-aldehyde sodium alginate is obtained; the liquid reactant of the multi-aldehyde sodium alginate is prepared, the material on the amination decorated surface is placed into the liquid reactant, and the multi-aldehyde alginic acid coating is obtained through an end-point fixing method. The preparation method provided by the invention overcomes the defects of bad biocompatibility, poor anticoagulant activity,potential toxicity and the like in common polymer material.
Description
Technical field
The present invention relates to polymer surface coating technology field, more particularly, relate to a kind of preparation method who utilizes the polysaccharide molecule fragment polymer surface coating to be carried out modification.
Background technology
Biomedical material is used and is faced biocompatibility and blood compatibility two large problems.Coating technology is passed through the pre-modification to material surface, thereby has improved biomedical material surfaces for biocompatibility and anticoagulating active.Heparin belongs to mucopolysaccharide, molecular weight 5000-40000, it is the mixture that is constituted by electronegative linear polysaccharide, the most important character of heparin is its anticoagulation characteristic, the anticoagulating active of heparin come from it can with organism in multiple coagulation inhibitor interact, reach anticoagulant purpose by the anticoagulating active that accelerates or improve these supressors, but be stained with defective for arrestin.Wherein heparin is most important to the effect of Antithrombin III (AT-III).Biomedical material surface heparin fixation principle can be summarized as physics method and chemical method at present.The physics method is namely by the winding between mechanical embedding, the molecular chain and infiltration, be fixed to biomaterial surface by modes such as porose material absorption with heparin, thereby reaches the immobilized purpose of heparin.Chemical method is namely by reactive functional group abundant on the heparin molecule chain, but reacts as corresponding reactive group on sulfonic group, amino, carboxyl etc. and the target material surface, with ionic linkage or in the mode of covalent linkage it is fixed to biomaterial surface.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, shortcomings such as the common high molecular materials biocompatibility is poor, anticoagulating active is poor in order to overcome, genotoxic potential, utilize periodate oxidation and terminal point technique for fixing, a kind of preparation method of many aldehyde radicals sodium alginate coating is provided.
Purpose of the present invention is achieved by following technical proposals:
A kind of preparation method of many aldehyde radicals sodium alginate coating, carry out according to following step:
At first, namely step (1) is immersed in macromolecular material in the sulphuric acid soln of potassium permanganate, carries out acidification, wherein:
Described macromolecular material can be selected polyethylene, polyvinyl chloride, polypropylene, polyester, silicon rubber, nylon, polycarbonate or the tetrafluoroethylene of medical grade, these materials can be used for the structure of extracorporeal circulation of blood pipeline, need carry out modification to improve the consistency of itself and blood to its surface.
The sulphuric acid soln of described potassium permanganate is adopted and utilized following mode to be prepared: elder generation is dissolved in potassium permanganate in the deionized water and mixes, slowly be reached for 10%-70% to the mass percent of sulfuric acid and get final product to wherein adding the vitriol oil (mass percent is the vitriol oil of 95-98%), mixing then.
Macromolecular material being immersed in the sulphuric acid soln of potassium permanganate, carrying out acidification, mainly is for material modified surface properties, and can select the acid treatment time is 1min-10min, and normal temperature is handled, and temperature is 20-25 ℃; The intensity that can adopt the mode of machinery or ultrasonic agitation to strengthen reacting in the acidification process can use deionized water that material is cleaned after acidification.
Step (2) places polymine (PEI) solution with the material of acidified processing, and reaction is to obtain the surface that amination is modified, wherein:
The mass percentage concentration of described polymine (PEI) solution is 0.005%-0.5%, and the reaction times is 10min-60min, and normal temperature is handled, and temperature is 20-25 ℃.
Step (3) uses Periodic acid or sodium periodate oxidation to handle sodium alginate, makes to obtain many aldehyde radicals sodium alginate by Lalgine fragment ends exposed aldehyde radical, wherein:
The mol ratio of the repeating unit of Periodic acid or sodium periodate and sodium alginate is (1-3): 10, and oxidizing reaction stirring reaction at least 24 hours under the lucifuge condition, preferred 24-40 hour; Adopt the ethylene glycol termination reaction, the aqueous solution of 96wt% ethanol precipitates, post precipitation suction filtration, dialysis, and-80 ℃ of lyophilizes obtain many aldehyde radicals sodium alginate.
Step (4) disposes the reaction solution (aqueous solution) of many aldehyde radicals sodium alginate, and the material of amination modification of surfaces is placed reaction solution, obtains the coating of many aldehyde radicals sodium alginate by the terminal point fixation method, wherein:
The reaction solution of described many aldehyde radicals sodium alginate is the aqueous solution, many aldehyde radicals sodium alginate 0.05-2mg/mL wherein, NaCl0.15-0.55mol/L, sodium cyanoborohydride 0.01-0.1mg/mL; Temperature of reaction is 30 ℃-60 ℃, preferred 40-50 ℃; At least 2 hours reaction times, preferred 2-6 hour.
Technical scheme provided by the present invention adopts the fixing many aldehyde radicals Lalgine coating of terminal point, formed by polymine, many aldehyde radicals sodium alginate, it is low that native toxicity is low, cost is enriched in the source, but standing storage at room temperature, and sodium alginate group is fixed on the surface of material in the coating, increase the area contact with blood with or chance, effectively bring into play the character of sodium alginate.Periodic acid oxidation gentleness, good reproducibility; The terminal point fixation method is implemented convenient, and many aldehyde radicals sodium alginate that terminal point is fixed is in conjunction with firm, and space conformation is good, can effectively increase biocompatibility and the anticoagulating active of polymer surface.In field of biomedical materials, have broad application prospects and higher utility as extracorporeal circulation pipeline, artery filter, venous incubation etc., can effectively reduce medical treatment cost, alleviate patient's economical load.
Description of drawings
The preparation principle synoptic diagram of many aldehyde radicals of Fig. 1 sodium alginate.
Fig. 2 preparation method's of the present invention synoptic diagram, wherein OSA represents sodium alginate.
The infrared spectrogram of the PVC of Fig. 3 polyvinyl chloride (PVC) and band PEI coating, wherein a is undressed PVC, b is the PVC of band PEI coating.
Fig. 4 polyvinyl chloride (PVC) and have the infrared spectrogram of the PVC of many aldehyde radicals sodium alginate coating, wherein a is undressed PVC, b is the PVC that has many aldehyde radicals sodium alginate coating.
Embodiment
Further specify technical scheme of the present invention below in conjunction with specific embodiment.The extracorporeal circulation pipeline that the macromolecular material that uses provides as Dongguan Kewei Medical Instrument Co., Ltd, material are polyvinyl chloride.
Embodiment 1
The first step is dissolved in 0.344 gram potassium permanganate in 162 ml deionized water, slowly adds 95wt% vitriol oil 10ml, and the vitriol oil and potassium permanganate are mixed very much.
In second step, the middle macromolecular material PVC that adds in step 1 gained solution stirs fully reaction 10min.
In the 3rd step, pressed sodium periodate and sodium alginate unit mol ratio 1: 10, the oxide treatment Lalgine, make Lalgine fragment ends exposed aldehyde radical, ethylene glycol termination reaction, 96wt% aqueous ethanolic solution precipitation, post precipitation suction filtration, dialysis ,-80 ℃ of lyophilizes obtain many aldehyde radicals sodium alginate.Oxidizing reaction stirring reaction 24 hours under the lucifuge condition.
The 4th step, immerse in the 0.01wt% polyethyleneimine: amine aqueous solution through the pretreated macromolecular material of step 2,20 ℃ of reactions of normal temperature 60min obtains the surface that amination is modified.
The 5th step, many aldehyde radicals of step 3 gained sodium alginate preparation reaction solution (aqueous solution), many aldehyde radicals Lalgine concentration 0.1mg/ml wherein, NaCl 0.15mol/L, sodium cyanoborohydride 0.1mg/ml, the macromolecular material that the amination of step 4 gained is modified places many aldehyde radicals Lalgine reaction solution, 40 ℃ of temperature of reaction, 2 hours reaction times.
The PVC of undressed PVC, band PEI coating, the PVC that has many aldehyde radicals sodium alginate coating are carried out examination of infrared spectrum (infrared spectra manufacturer and model Thermo NICOLET 6700, detector are that DTGs KBr, beam splitter are that KBr, wavelength region are 650-4000nm), from shown in accompanying drawing 3 and 4 as can be known, 1550cm
-1The place is NH
2Charateristic avsorption band, 3400cm
-1About the charateristic avsorption band of visible sodium alginate, illustrate that many aldehyde radicals sodium alginate passes through NH
2Be fixed on the surface of material.
Embodiment 2
The first step is dissolved in 0.328 gram potassium permanganate in 144 ml deionized water, slowly adds 95% vitriol oil 20ml, and the vitriol oil and potassium permanganate are mixed very much.
Second step added macromolecular material in step 1 gained solution, stir fully reaction 1min.
In the 3rd step, pressed sodium periodate and sodium alginate unit mol ratio 3: 10, the oxide treatment Lalgine, make Lalgine fragment ends exposed aldehyde radical, ethylene glycol termination reaction, 96% ethanol sedimentation, post precipitation suction filtration, dialysis ,-80 ℃ of lyophilizes obtain many aldehyde radicals sodium alginate.Oxidizing reaction stirring reaction 40 hours under the lucifuge condition.
The 4th step, immerse in the 0.5% polyethyleneimine: amine aqueous solution through the pretreated macromolecular material of step 2,25 ℃ of reactions of normal temperature 10min obtains the surface that amination is modified.
The 5th step, many aldehyde radicals of step 3 gained sodium alginate preparation reaction solution (aqueous solution), many aldehyde radicals Lalgine concentration 2mg/ml wherein, NaCl 0.15mol/L, sodium cyanoborohydride 0.1mg/ml, the macromolecular material that the amination of step 4 gained is modified places many aldehyde radicals Lalgine reaction solution, 50 ℃ of temperature of reaction, 6 hours reaction times.
Embodiment 3
The first step is dissolved in 0.328 gram potassium permanganate in 144 ml deionized water, slowly adds 95% vitriol oil 20ml, and the vitriol oil and potassium permanganate are mixed very much.
Second step added macromolecular material in step 1 gained solution, stir fully reaction 8min.
In the 3rd step, pressed sodium periodate and sodium alginate unit mol ratio 1: 10, the oxide treatment Lalgine, make Lalgine fragment ends exposed aldehyde radical, ethylene glycol termination reaction, 96% ethanol sedimentation, post precipitation suction filtration, dialysis ,-80 ℃ of lyophilizes obtain many aldehyde radicals sodium alginate.Oxidizing reaction stirring reaction 30 hours under the lucifuge condition.
The 4th step, immerse in the 0.05% polyethyleneimine: amine aqueous solution through the pretreated macromolecular material of step 2,25 ℃ of reactions of normal temperature 30min obtains the surface that amination is modified.
The 5th step, many aldehyde radicals of step 3 gained sodium alginate preparation reaction solution (aqueous solution), many aldehyde radicals Lalgine concentration 0.05mg/ml wherein, NaCl 0.35mol/L, sodium cyanoborohydride 0.01mg/ml, the macromolecular material that the amination of step 4 gained is modified places many aldehyde radicals Lalgine reaction solution, 60 ℃ of temperature of reaction, 4 hours reaction times.
Embodiment 4
The first step is dissolved in 0.328 gram potassium permanganate in 144 ml deionized water, slowly adds 95% vitriol oil 20ml, and the vitriol oil and potassium permanganate are mixed very much.
Second step added macromolecular material in step 1 gained solution, stir fully reaction 5min.
In the 3rd step, pressed sodium periodate and sodium alginate unit mol ratio 2: 10, the oxide treatment Lalgine, make Lalgine fragment ends exposed aldehyde radical, ethylene glycol termination reaction, 96% ethanol sedimentation, post precipitation suction filtration, dialysis ,-80 ℃ of lyophilizes obtain many aldehyde radicals sodium alginate.Oxidizing reaction stirring reaction 35 hours under the lucifuge condition.
The 4th step, immerse in the 0.005% polyethyleneimine: amine aqueous solution through the pretreated macromolecular material of step 2,25 ℃ of reactions of normal temperature 50min obtains the surface that amination is modified.
The 5th step, many aldehyde radicals of step 3 gained sodium alginate preparation reaction solution (aqueous solution), many aldehyde radicals Lalgine concentration 0.5mg/ml wherein, NaCl 0.25mol/L, sodium cyanoborohydride 0.05mg/ml, the macromolecular material that the amination of step 4 gained is modified places many aldehyde radicals Lalgine reaction solution, 30 ℃ of temperature of reaction, 4 hours reaction times.
Embodiment 5
The first step is dissolved in 0.328 gram potassium permanganate in 144 ml deionized water, slowly adds 95% vitriol oil 20ml, and the vitriol oil and potassium permanganate are mixed very much.
Second step added macromolecular material in step 1 gained solution, stir fully reaction 5min.
In the 3rd step, pressed sodium periodate and sodium alginate unit mol ratio 2: 10, the oxide treatment Lalgine, make Lalgine fragment ends exposed aldehyde radical, ethylene glycol termination reaction, 96% ethanol sedimentation, post precipitation suction filtration, dialysis ,-80 ℃ of lyophilizes obtain many aldehyde radicals sodium alginate.Oxidizing reaction stirring reaction 35 hours under the lucifuge condition.
The 4th step, immerse in the 0.005% polyethyleneimine: amine aqueous solution through the pretreated macromolecular material of step 2,25 ℃ of reactions of normal temperature 50min obtains the surface that amination is modified.
The 5th step, many aldehyde radicals of step 3 gained sodium alginate preparation reaction solution (aqueous solution), many aldehyde radicals Lalgine concentration 1mg/ml wherein, NaCl 0.25mol/L, sodium cyanoborohydride 0.05mg/ml, the macromolecular material that the amination of step 4 gained is modified places many aldehyde radicals Lalgine reaction solution, 30 ℃ of temperature of reaction, 4 hours reaction times.
Utilize the phenolsulfuric acid method, change by sodium alginate (OSA) reaction solution absorbance before and after calculating reaction, obtain the fixed amount of OSA indirectly, prove fixing (the Dubois M really of OSA simultaneously, Gilles K A, Hamilton JK, et al.Colorimetric method for determination of sugars and related substances[J] .AnalyticalChemistry, 1956,28 (3): 350-356).
| Abs before the reaction | Reaction back Abs | Fixed amount ug/cm 2 | |
| Embodiment 1 | 0.394 | 0.338 | 0.79 |
| Embodiment 2b | 0.235 | 0.224 | 7.78 |
| Embodiment 3 | 0.153 | 0.127 | 0.49 |
| Embodiment 4a | 0.292 | 0.266 | 3.62 |
| Embodiment 5b | 0.126 | 0.109 | 5.03 |
50 times of 10 times of b:OSA test fluid dilutions of a:OSA test fluid dilution
There is the macromolecular material PVC of sodium alginate to experimentize to coating, after the sample of embodiment 1-5 being carried out the test of four of coagulation functions and arrestin absorption respectively, take the mean, adopt 5 groups of identical PVC to carry out identical test in contrast after, take the mean; Wherein the STA-R of Diagnostica Stago is adopted in the test of four of coagulation functions
Automatic blood coagulation analyzer; Protein adsorption adopts BCA method (Ishihara K, Fukumoto K, Iwasaki Y, Nakabayashi N.Modification of polysulfone with phospholipid polymer for improvement of the blood compatibility.Part 1.Surface characterization.Biomaterials 1999,20 (17): 1545-1551)
Arrestin absorption (having improved biocompatibility)
| Types of coatings | HAS adsorbs (ug/cm 2) | HPF adsorbs (ug/cm 2) |
| Control group | 270.7 | 544.3 |
| The OSA single coating | 145.6 | 221.8 |
* adhesion protein adopts the BCA standard measure
* HAS: human serum albumin HPF: human fibrinogen
As can be seen, the macromolecular material of process sodium alginate OSA single coating is compared with control group in four of coagulation functions of test, protein adsorption performance from above-mentioned experiment, and obviously anticoagulant and protein adsorption are effectively improved biocompatibility and coagulation function.
More than the present invention has been done exemplary description; should be noted that; under the situation that does not break away from core of the present invention, the replacement that is equal to that any simple distortion, modification or other those skilled in the art can not spend creative work all falls into protection scope of the present invention.
Claims (6)
1. the preparation method of the coating of aldehyde radical sodium alginate more than a kind is characterized in that, carries out according to following step:
Step (1) is immersed in macromolecular material in the sulphuric acid soln of potassium permanganate, carries out acidification;
Step (2) places the polyethyleneimine: amine aqueous solution with the material of acidified processing, and reaction is to obtain the surface that amination is modified;
Step (3) uses Periodic acid or sodium periodate oxidation to handle sodium alginate, makes to obtain many aldehyde radicals sodium alginate by Lalgine fragment ends exposed aldehyde radical;
Step (4) disposes the reaction solution of many aldehyde radicals sodium alginate, and the material of amination modification of surfaces is placed reaction solution, obtains the coating of many aldehyde radicals sodium alginate by the terminal point fixation method; In described step (4), in the reaction solution of described many aldehyde radicals sodium alginate, many aldehyde radicals sodium alginate 0.05-2mg/mL, NaCl0.15-0.55mol/L, sodium cyanoborohydride 0.01-0.1mg/mL; Temperature of reaction is 30 ℃-60 ℃; At least 2 hours reaction times.
2. the preparation method of a kind of many aldehyde radicals sodium alginate coating according to claim 1, it is characterized in that, in the described step (1), described macromolecular material is selected polyethylene, polyvinyl chloride, polypropylene, polyester, silicon rubber, nylon, polycarbonate or the tetrafluoroethylene of medical grade; The sulphuric acid soln of described potassium permanganate is adopted and utilized following mode to be prepared: elder generation is dissolved in potassium permanganate in the deionized water and mixes, be 95-98% the vitriol oil to wherein adding mass percent slowly then, mix and be reached for 10%-70% to the mass percent of sulfuric acid and get final product; The time of carrying out acidification is 1min-10min, and temperature is 20-25 ℃, the intensity that the mode of employing machinery or ultrasonic agitation is strengthened reacting in the acidification process.
3. the preparation method of a kind of many aldehyde radicals sodium alginate coating according to claim 1, it is characterized in that in the described step (2), the mass percentage concentration of described polyethyleneimine: amine aqueous solution is 0.005%-0.5%, reaction times is 10min-60min, and temperature is 20-25 ℃.
4. the preparation method of a kind of many aldehyde radicals sodium alginate coating according to claim 1, it is characterized in that, in the described step (3), the mol ratio of the repeating unit of Periodic acid or sodium periodate and sodium alginate is (1-3): 10, and oxidizing reaction stirring reaction at least 24 hours under the lucifuge condition; Adopt the ethylene glycol termination reaction, the aqueous solution of 96wt% ethanol precipitates, post precipitation suction filtration, dialysis, and-80 ℃ of lyophilizes obtain many aldehyde radicals sodium alginate.
5. the preparation method of a kind of many aldehyde radicals sodium alginate coating according to claim 4 is characterized in that, in the described step (3), and oxidizing reaction preferred 24-40 hours of stirring reaction under the lucifuge condition.
6. the preparation method of a kind of many aldehyde radicals sodium alginate coating according to claim 1 is characterized in that, in the described step (4), and preferred 40-50 ℃ of temperature of reaction; Preferred 2-6 hours of reaction times.
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| CN102872484A (en) * | 2012-10-16 | 2013-01-16 | 天津市第三中心医院 | Preparation method of dexamethasone sodium phosphate composite sustained-release coating and application thereof |
| CN102861364A (en) * | 2012-10-16 | 2013-01-09 | 天津市第三中心医院 | Preparation method and application of dexamethasone sodium phosphate-sodium alga acid composite slow-release coating |
| TWI622647B (en) * | 2017-05-19 | 2018-05-01 | 臺灣塑膠工業股份有限公司 | Support, method of making the same, and method of immobilizing microorganism |
| CN108503721A (en) * | 2018-03-28 | 2018-09-07 | 美瑞多生物科技（天津）有限公司 | With anticoagulant functions active polysaccharide and its preparation and application |
| CN108384246A (en) * | 2018-04-09 | 2018-08-10 | 王景硕 | A kind of preparation method of addition thermal conductive Silica hydrogel |
| CN111203115B (en) * | 2020-01-07 | 2022-02-11 | 天津市第三中心医院 | Oxidized polysaccharide anticoagulant coating hemodialysis membrane material and preparation method thereof |
| CN113244442B (en) * | 2021-06-01 | 2022-11-15 | 北京化工大学 | Application of polyamino cationic compound in preparation of surface procoagulant enhanced hemostatic material |
| CN113975463A (en) * | 2021-11-22 | 2022-01-28 | 湖南普林特医疗器械有限公司 | Porous tantalum implant with bioactive coating and preparation method thereof |
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