CN110449130B - Method for improving epoxy rate of blood adsorbent carrier - Google Patents
Method for improving epoxy rate of blood adsorbent carrier Download PDFInfo
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- CN110449130B CN110449130B CN201910707246.5A CN201910707246A CN110449130B CN 110449130 B CN110449130 B CN 110449130B CN 201910707246 A CN201910707246 A CN 201910707246A CN 110449130 B CN110449130 B CN 110449130B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
Abstract
The invention relates to the field of blood adsorbents, and particularly discloses a method for improving the epoxy rate of a blood adsorbent carrier, which comprises the following steps: s1, mixing a carrier and an alkaline solvent in a certain proportion, wherein the alkaline solvent comprises an alkaline solution and an alcohol solvent, and the alcohol solvent is alcohol with carbon atom number lower than four; s2, adding an epoxy reagent to perform an epoxy activation reaction; s3, washing to obtain the epoxidized carrier. The method improves the epoxy rate of the carrier through the pre-reaction of the carrier and the mixed solution formed by the alkali liquor and the alcohol solvent, further improves the adsorption performance of the blood adsorbent, and has good application prospect.
Description
Technical Field
The invention relates to the field of blood adsorbent preparation, in particular to a method for improving the carrier epoxy rate of a blood adsorbent.
Background
Blood adsorption, also known as hemoperfusion, refers to a treatment method in which blood is introduced into a container filled with a fixed adsorbent by means of extracorporeal circulation equipment, and some exogenous and endogenous harmful substances are adsorbed and removed, so as to purify the blood. The preparation of the adsorbent is a core technology of blood adsorption, generally, the preparation of the adsorbent is divided into two steps of carrier activation and ligand coupling, the carrier activation is the first step, and the high epoxy rate is the basis for realizing the high ligand coupling rate, so that the improvement of the carrier activation efficiency is the first step for improving the performance of the adsorbent.
The epichlorohydrin activation method is the most widely applied activation method at present, on one hand, the epichlorohydrin reagent is easy to obtain, the coupling ligand is firmer, and the price is cheaper, on the other hand, the method is simple and easy to operate, and the danger is relatively smaller. However, the method has low activation degree, small carrier loading and easy ring-opening reaction during coupling. The main reason is 3 points, firstly, the activation reaction is required to be carried out under the alkaline condition, the alkali liquor plays a catalytic role, but the epichlorohydrin is easy to hydrolyze under the alkaline condition, and secondly, the solubility of the epichlorohydrin is low, and the epichlorohydrin is slightly soluble in water, so the gel epoxidation reaction degree in the aqueous solution is low; finally, the epoxy groups may be exposed to alkali solution at high temperature for a long time to generate glycol, and the product of the activation reaction may continue to react with the hydroxyl groups on the medium to generate a cross-linked product due to the epoxy groups.
Therefore, when the epichlorohydrin activation method is adopted, the key for improving the performance of the adsorbent is to improve the activation efficiency of the epichlorohydrin activation method.
Disclosure of Invention
In view of the problems in the prior art, the present invention aims to provide a method for increasing the carrier epoxy ratio of blood adsorbent. The method effectively improves the epoxy activation reaction efficiency of the carrier by mixing and heating the carrier and the alkaline solvent in advance and adding the epichlorohydrin for reaction.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for improving the epoxy rate of a blood adsorbent carrier specifically comprises the following steps:
s1, mixing a carrier and an alkaline solvent in a certain proportion, wherein the alkaline solvent is a mixed solution of an alkali liquor and an alcohol solvent, and the alcohol solvent is alcohol with carbon atom number lower than four;
s2, adding an epoxy reagent to carry out epoxy activation reaction;
s3, washing to obtain the epoxidized carrier.
Further, in the technical scheme, the alkali liquor is a sodium hydroxide solution or a potassium hydroxide solution, the concentration of the alkali liquor is 0.5-2.5 mol/L, the alcohol solvent is glycerol, and the volume ratio of the alkali liquor to the alcohol solvent in the alkaline solvent is 1: 1-1: 0.1.
Further, in the technical scheme, the mass-to-volume ratio of the carrier to the alkaline solvent is 1g: 0.5-2 mL.
Furthermore, in the above technical scheme, after the carrier and the alkaline solvent are uniformly mixed, the carrier and the alkaline solvent are preheated for 3-30 min at 60-100 ℃.
Further, in the above technical scheme, the epoxy reagent of S2 is epichlorohydrin, the volume ratio of the epoxy reagent to the alkaline solvent is 0.3:1, and the conditions of the epoxy activation reaction are specifically 20-45 ℃ and 1-10 hours.
Compared with the prior art, the invention has the following beneficial effects:
(1) the carrier and the alkaline solvent are mixed in advance, the alkaline solvent comprises an alkaline solution and an alcohol solvent, the alkaline solution provides alkaline conditions for epoxy activation reaction, and the addition of the alcohol solvent can increase the dissolution of epoxy reagent epichlorohydrin in water, so that the defects of low degree of gel epoxidation reaction in aqueous solution, and further low degree of activation and small carrier amount of an epichlorohydrin activation method in the prior art due to low solubility of epichlorohydrin in water are overcome.
(2) Experiments prove that the best effect is achieved when the alcohol solvent is glycerol, and the glycerol can be applied to the fields of food and medicines, has low toxic and side effects on people and is easy to operate.
(3) The epoxy rate of the carrier can be further improved by preheating at a relatively high temperature before the epoxy agent is added and reacting at a lower temperature after the epoxy agent is added.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments, and the following embodiments are provided to better illustrate the contents of the present invention.
The experimental procedures in the following examples are conventional unless otherwise specified. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
Mixing the agarose gel microspheres and an alkaline solvent according to the mass-volume ratio of 1g:1mL, fully shaking for 2min, preheating at 80 ℃ for 10min, wherein the alkaline solvent is prepared by mixing 1.5mol/L sodium hydroxide solution and glycerol according to the volume ratio of 1: 0.5. When the temperature is cooled to below 50 ℃, epichlorohydrin with the volume ratio of 0.3:1 of the alkaline solvent is added for epoxy activation reaction, and the reaction conditions are 30 ℃ and 2 hours. After the reaction, the epoxidized carrier was washed with purified water.
Example 2
Mixing the agarose gel microspheres and an alkaline solvent according to the mass-volume ratio of 1g:1mL, fully shaking for 2min, wherein the alkaline solvent is formed by mixing 1.5mol/L sodium hydroxide solution and glycerol according to the volume ratio of 1: 0.5. Adding epoxy chloropropane in the volume ratio of 0.3 to 1 to the alkaline solvent for epoxy activation reaction at 30 deg.c for 2 hr. After the reaction, the epoxidized carrier was washed with purified water.
Example 3
Mixing the agarose gel microspheres and an alkaline solvent according to the mass-volume ratio of 1g:1mL, fully shaking for 2min, preheating at 100 ℃ for 3min, wherein the alkaline solvent is prepared by mixing 1.5mol/L sodium hydroxide solution and glycerol according to the volume ratio of 1: 0.5. When the temperature is cooled to below 50 ℃, epichlorohydrin with the volume ratio of 0.3:1 of the alkaline solvent is added for epoxy activation reaction, and the reaction conditions are 30 ℃ and 2 hours. After the reaction, the epoxidized carrier was washed with purified water.
Example 4
Mixing the agarose gel microspheres and an alkaline solvent according to the mass-volume ratio of 1g:1mL, fully shaking for 2min, preheating at 60 ℃ for 30min, wherein the alkaline solvent is prepared by mixing 1.5mol/L sodium hydroxide solution and glycerol according to the volume ratio of 1: 0.5. When the temperature is cooled to below 50 ℃, epichlorohydrin with the volume ratio of 0.3:1 of the alkaline solvent is added for epoxy activation reaction, and the reaction conditions are 30 ℃ and 2 hours. After the reaction, the epoxidized carrier was washed with purified water.
Example 5
Mixing the agarose gel microspheres and an alkaline solvent according to the mass volume ratio of 1g:1mL, fully shaking for 2min, wherein the alkaline solvent is formed by mixing 1.5mol/L potassium hydroxide solution and ethanol according to the volume ratio of 1: 0.5. Adding epoxy chloropropane in the volume ratio of 0.3 to 1 to the alkaline solvent for epoxy activation reaction at 30 deg.c for 2 hr. After the reaction, the epoxidized carrier was washed with purified water.
Example 6
Mixing the agarose gel microspheres and an alkaline solvent according to the mass-volume ratio of 1g:1mL, fully shaking for 2min, wherein the alkaline solvent is formed by mixing 1.5mol/L sodium hydroxide solution and ethylene glycol according to the volume ratio of 1: 0.5. Adding epoxy chloropropane in the volume ratio of 0.3 to 1 to the alkaline solvent for epoxy activation reaction at 30 deg.c for 2 hr. After the reaction, the epoxidized carrier was washed with purified water.
Example 7
Mixing the agarose gel microspheres and an alkaline solvent according to the mass-volume ratio of 1g:1mL, fully shaking for 2min, preheating at 80 ℃ for 10min, wherein the alkaline solvent is prepared by mixing 1.5mol/L sodium hydroxide solution and ethylene glycol according to the volume ratio of 1: 0.5. When the temperature is cooled to below 50 ℃, epichlorohydrin with the volume ratio of 0.3:1 of the alkaline solvent is added for epoxy activation reaction, and the reaction conditions are 30 ℃ and 2 hours. After the reaction, the epoxidized carrier was washed with purified water.
Example 8
Mixing the agarose gel microspheres and an alkaline solvent according to the mass-volume ratio of 1g:1mL, fully shaking for 2min, wherein the alkaline solvent is formed by mixing 2.5mol/L potassium hydroxide solution and glycerol according to the volume ratio of 1: 1. Adding epoxy chloropropane in the volume ratio of 0.3 to 1 to the alkaline solvent for epoxy activation reaction at 30 deg.c for 2 hr. After the reaction, the epoxidized carrier was washed with purified water.
Example 9
Mixing the agarose gel microspheres and an alkaline solvent according to the mass-volume ratio of 1g:2mL, fully shaking for 2min, wherein the alkaline solvent is formed by mixing 0.5mol/L potassium hydroxide solution and glycerol according to the volume ratio of 1: 0.1. Adding epoxy chloropropane in the volume ratio of 0.3 to 1 to the alkaline solvent for epoxy activation reaction at 30 deg.c for 2 hr. After the reaction, the epoxidized carrier was washed with purified water.
Example 10
Mixing the agarose gel microspheres and an alkaline solvent according to the mass-volume ratio of 1g:1mL, fully shaking for 2min, preheating at 80 ℃ for 10min, wherein the alkaline solvent is prepared by mixing 1.5mol/L sodium hydroxide solution and glycerol according to the volume ratio of 1: 0.5. When the temperature is cooled to below 50 ℃, epichlorohydrin with the volume ratio of 0.3:1 of the alkaline solvent is added for epoxy activation reaction, and the reaction condition is 20 ℃ and 10 hours. After the reaction, the epoxidized carrier was washed with purified water.
Example 11
Mixing the agarose gel microspheres and an alkaline solvent according to the mass-volume ratio of 1g:1mL, fully shaking for 2min, preheating at 80 ℃ for 10min, wherein the alkaline solvent is prepared by mixing 1.5mol/L sodium hydroxide solution and glycerol according to the volume ratio of 1: 0.5. When the temperature is cooled to below 50 ℃, epichlorohydrin with the volume ratio of 0.3:1 of the alkaline solvent is added for epoxy activation reaction, and the reaction condition is 45 ℃ and 1 h. After the reaction, the epoxidized carrier was washed with purified water.
Example 12
Mixing agarose gel microspheres and an alkaline solvent according to the mass volume ratio of 1g:1mL, fully shaking for 2min, preheating at 80 ℃ for 10min, wherein the alkaline solvent is formed by mixing 1.5mol/L sodium hydroxide solution and glycerol according to the volume ratio of 1: 0.5. When the temperature is cooled to below 50 ℃, epichlorohydrin with the volume ratio of the epichlorohydrin to the alkaline solvent being 3:1 is added for epoxy activation reaction, and the reaction conditions are 30 ℃ and 6 hours. After the reaction, the epoxidized carrier was washed with purified water.
Example 13
Mixing the agarose gel microspheres and an alkaline solvent according to the mass-volume ratio of 1g:1mL, fully shaking for 2min, preheating at 80 ℃ for 10min, wherein the alkaline solvent is prepared by mixing 1.5mol/L sodium hydroxide solution and glycerol according to the volume ratio of 1: 0.5. When the temperature is cooled to below 50 ℃, epichlorohydrin with the volume ratio of 1:2 of the alkaline solvent is added for epoxy activation reaction, and the reaction conditions are 30 ℃ and 2 hours. After the reaction, the epoxidized carrier was washed with purified water.
Example 14
Mixing the agarose gel microspheres and an alkaline solvent according to the mass-volume ratio of 1g:1mL, fully shaking for 2min, preheating at 80 ℃ for 10min, wherein the alkaline solvent is prepared by mixing 1.5mol/L sodium hydroxide solution and glycerol according to the volume ratio of 1: 0.5. When the temperature is cooled to below 50 ℃, epichlorohydrin with the volume ratio of 1:2 of the alkaline solvent is added for epoxy activation reaction, and the reaction conditions are 55 ℃ and 2 hours. After the reaction, the epoxidized carrier was washed with purified water.
Comparative example 1
Mixing the agarose gel microspheres, 1mol/L sodium hydroxide solution and epoxy chloropropane according to the mass volume ratio of 1g:1mL:0.3mL to perform epoxy activation reaction at the temperature of 30 ℃ for 2h, and cleaning with purified water after the reaction to obtain the epoxidized carrier.
Comparative example 2
Mixing the agarose gel microspheres and an alkaline solvent according to the mass volume ratio of 1g:1mL, wherein the alkaline solvent is formed by mixing 1.5mol/L sodium hydroxide solution and ether according to the volume ratio of 1: 0.5. Adding epoxy chloropropane in the volume ratio of 0.3 to 1 to the alkaline solvent for epoxy activation reaction at 30 deg.c for 2 hr. After the reaction, the epoxidized carrier was washed with purified water.
Comparative example 3
Mixing agarose gel microspheres and 1.5mol/L sodium hydroxide solution according to the mass-volume ratio of 1g:1mL, preheating at 80 ℃ for 10min, adding glycerol with the volume ratio of 1:0.5 to the sodium hydroxide solution when the temperature is cooled to below 50 ℃, and then adding epoxy chloropropane with the volume ratio of 0.3:1 to the sodium hydroxide solution for epoxy activation reaction under the reaction conditions of 30 ℃ and 2 h. After the reaction, the epoxidized carrier was washed with purified water.
Comparative example 4
Mixing agarose gel microspheres, 1mol/L sodium hydroxide solution, glycerol and epoxy chloropropane according to the mass volume ratio of 1g:1mL:0.5mL:0.3mL, carrying out epoxy activation reaction under the reaction condition of 30 ℃ for 2h, and washing with purified water after the reaction to obtain the epoxidized carrier.
Comparative example 5
Mixing agarose gel microspheres and glycerol according to the mass-volume ratio of 1g:0.5mL, preheating at 80 ℃ for 10min, adding 1.5mol/L sodium hydroxide solution with the volume ratio of 0.5:1 to the glycerol when the temperature is cooled to below 50 ℃, and then adding epoxy chloropropane with the volume ratio of 0.3:1 to the sodium hydroxide solution to perform epoxy activation reaction under the conditions of 30 ℃ and 2 h. After the reaction, the epoxidized carrier was washed with purified water.
The epoxidized carriers obtained in the respective examples and comparative examples were measured for epoxy ratio by the following test method: weighing the carrier which is dehydrated by vacuum filtration, adding Na2S2O3Reacting at room temperature for 2H at pH7.0, and adding H2O, titration with HClThe unactivated gel was used as a blank in the experiment. The epoxy rate determination experiment was repeated 3 times for each carrier and averaged. The carrier epoxy ratios of examples 1-9, comparative example 1 and comparative example 2 were compared, and the results are shown in table 1; the results of comparing the carrier epoxy ratios of example 1 and examples 10 to 14 are shown in Table 2.
As can be seen from table 1 in comparative examples 1, 3, 4 and 5, the addition of an appropriate amount of alcohol during activation slightly increases the epoxy ratio of the carrier presumably because: the addition of the alcohol solvent can increase the dissolution of the epichlorohydrin in water; when the alcohol solvent is glycerol, the epoxy rate of the carrier is the highest probably because the epoxy reagent epichlorohydrin can be hydrolyzed to generate glycerol after contacting with the alkali liquor for a long time at high temperature, and the glycerol not only can increase the dissolution of the epichlorohydrin in water, but also can inhibit the hydrolysis reaction of the epichlorohydrin to a certain extent.
As can be seen from the comparison between the examples and comparative examples 1 to 2, the effect of adding the epoxy agent after premixing the carrier with the alkali agent composed of alkali and alcohol is much greater than the effect obtained by directly mixing the same. As can be seen from comparison between each example and comparative examples 3-5, the alcohol reagent has other positive effects besides promoting dissolution of propylene oxide and consistent hydrolysis of propylene oxide, and has a synergistic effect with alkali liquor, so that the carrier epoxy rate is improved.
TABLE 1 Effect of different pretreatment conditions on the epoxy ratio
| Carrier sample | Epoxy Rate (. mu. mol/g) |
| Example 1 | 62 |
| Example 2 | 45 |
| Example 3 | 56 |
| Example 4 | 53 |
| Example 5 | 29 |
| Example 6 | 27 |
| Example 7 | 42 |
| Example 8 | 38 |
| Example 9 | 37 |
| Comparative example 1 | 21 |
| Comparative example 2 | 16 |
| Comparative example 3 | 27 |
| Comparative example 4 | 25 |
| Comparative example 5 | 29 |
It can be seen from the comparison among examples 1 to 4, 6 and 7 that the epoxy activation efficiency can be further improved by pre-heating the carrier and the alkaline agent after pre-mixing the carrier and the alkaline agent, and the optimal temperature for pre-heating is 80 ℃, because the particle size, pore size or surface area of the carrier immersed in the alkaline solvent is slightly changed at a higher temperature, which is beneficial to the epoxy activation reaction.
The best concentrations and ratios of the substances can be derived from a comparison of example 2, example 8 and example 9. In summary, the addition of the alcohol solvent increases the epoxy ratio of the carrier, and when glycerin is mixed as the alcohol solvent with the alkali solution, the obtained carrier has a high epoxy ratio, and on this basis, the epoxy ratio of the carrier can be further increased by performing a preheating treatment on the mixed solution of the carrier and the alkaline solvent.
As can be seen from Table 2, the reaction temperature for epoxy activation has a large influence on the epoxy efficiency, because the side reactions of epoxy groups which are in contact with alkali liquor for a long time at high temperature are more, and the reaction is slower at lower temperature; the ratio of epoxy reagent to alkaline solvent also has an effect on the reaction efficiency.
TABLE 2 Effect of epoxy activation reaction conditions on epoxy Rate
| Carrier sample | Epoxy Rate (. mu. mol/g) |
| Example 1 | 62 |
| Example 10 | 42 |
| Example 11 | 30 |
| Example 12 | 53 |
| Example 13 | 52 |
| Example 14 | 23 |
In conclusion, the addition of the alcohol solvent improves the epoxy rate of the carrier, when glycerin is used as the alcohol solvent to be mixed with the alkali liquor, the obtained carrier has high epoxy rate, and on the basis, the epoxy rate of the carrier can be further improved through the preheating treatment of the carrier; in addition, the temperature during the epoxy activation reaction also has a large influence on the reaction.
The present invention may be better understood and appreciated by those skilled in the art with reference to the following examples. However, the protection of the invention and the scope of the claims are not limited to the examples provided. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (6)
1. A method for improving the epoxy rate of a blood adsorbent carrier is characterized by comprising the following steps:
s1, mixing a carrier and an alkaline solvent in a certain proportion, wherein the alkaline solvent is a mixed solution of an alkali liquor and an alcohol solvent, and the alcohol solvent is alcohol with carbon atom number lower than four;
s2, adding an epoxy reagent to perform an epoxy activation reaction, wherein the conditions of the epoxy activation reaction are specifically 20-45 ℃ and 2-6 hours;
s3, washing to obtain an epoxidized carrier;
the carrier is agarose gel microspheres;
s1, uniformly mixing the carrier and the alkaline solvent, and preheating at 60-100 ℃ for 3-30 min.
2. The method for improving the epoxidizing rate of a blood adsorbent carrier according to claim 1, wherein the mass-to-volume ratio of the carrier of S1 to the alkaline solvent is 1g: 0.5-2 mL.
3. The method for improving the epoxidation rate of a blood adsorbent carrier according to claim 1, wherein the volume ratio of the alkali solution to the alcohol solvent in the alkaline solvent of S1 is 1: 1-1: 0.1.
4. The method of claim 1, wherein the alcoholic solvent of S1 is glycerol.
5. The method for increasing the epoxidizing rate of a blood adsorbent carrier according to claim 1, wherein the alkali solution S1 is a sodium hydroxide solution or a potassium hydroxide solution, and the concentration of the alkali solution is 0.5-2.5 mol/L.
6. The method for improving the epoxidation rate of a blood adsorbent carrier according to claim 1, wherein S2 said epoxy reagent is epichlorohydrin, and the volume ratio of said epoxy reagent to the alkaline solvent is 0.3: 1.
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| CN103831066A (en) * | 2012-11-27 | 2014-06-04 | 山东鼎欣生物科技有限公司 | Preparation technology of CM agar-based chromatographical microspheres |
| CN104910296A (en) * | 2015-05-20 | 2015-09-16 | 集美大学 | Preparation method of high-viscosity low-melting-point agarose |
| CN105363417A (en) * | 2015-11-09 | 2016-03-02 | 山东大学 | Preparation method for cross-linked carboxymethylated agarose-base gel microsphere |
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| KR940003440Y1 (en) * | 1989-06-21 | 1994-05-25 | 대우전자 주식회사 | Control device for audio head |
| KR100470502B1 (en) * | 1996-06-21 | 2005-03-16 | 가네가후치 가가쿠고교 가부시키가이샤 | Adsorbent carrier used in direct hemoperfusion and method for reducing the particle size thereof |
| ATE274372T1 (en) * | 2001-05-09 | 2004-09-15 | Karsten Dr Thies | ADSORBENTS FOR PERFUSING BLOOD AND THEIR PRODUCTION PROCESS |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103831066A (en) * | 2012-11-27 | 2014-06-04 | 山东鼎欣生物科技有限公司 | Preparation technology of CM agar-based chromatographical microspheres |
| CN104910296A (en) * | 2015-05-20 | 2015-09-16 | 集美大学 | Preparation method of high-viscosity low-melting-point agarose |
| CN105363417A (en) * | 2015-11-09 | 2016-03-02 | 山东大学 | Preparation method for cross-linked carboxymethylated agarose-base gel microsphere |
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