CN117563570A - Resin for protein adsorption and preparation method thereof - Google Patents
Resin for protein adsorption and preparation method thereof Download PDFInfo
- Publication number
- CN117563570A CN117563570A CN202410061114.0A CN202410061114A CN117563570A CN 117563570 A CN117563570 A CN 117563570A CN 202410061114 A CN202410061114 A CN 202410061114A CN 117563570 A CN117563570 A CN 117563570A
- Authority
- CN
- China
- Prior art keywords
- resin
- thiourea
- protein adsorption
- solution
- polyethyleneimine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 82
- 239000011347 resin Substances 0.000 title claims abstract description 82
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 50
- 108090000623 proteins and genes Proteins 0.000 title claims abstract description 30
- 102000004169 proteins and genes Human genes 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 14
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 76
- QRYRORQUOLYVBU-VBKZILBWSA-N carnosic acid Chemical compound CC([C@@H]1CC2)(C)CCC[C@]1(C(O)=O)C1=C2C=C(C(C)C)C(O)=C1O QRYRORQUOLYVBU-VBKZILBWSA-N 0.000 claims abstract description 42
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000243 solution Substances 0.000 claims abstract description 36
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 22
- 108010039918 Polylysine Proteins 0.000 claims abstract description 22
- 229920000656 polylysine Polymers 0.000 claims abstract description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004005 microsphere Substances 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 claims abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 238000002791 soaking Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 230000008961 swelling Effects 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 10
- 239000003463 adsorbent Substances 0.000 abstract description 9
- 239000007787 solid Substances 0.000 abstract description 3
- 235000019441 ethanol Nutrition 0.000 description 13
- 239000011148 porous material Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 210000004369 blood Anatomy 0.000 description 4
- 239000008280 blood Substances 0.000 description 4
- 230000008081 blood perfusion Effects 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229920003002 synthetic resin Polymers 0.000 description 4
- 239000000057 synthetic resin Substances 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- 206010018910 Haemolysis Diseases 0.000 description 3
- 108090001030 Lipoproteins Proteins 0.000 description 3
- 102000004895 Lipoproteins Human genes 0.000 description 3
- 230000008588 hemolysis Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 210000002966 serum Anatomy 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 208000031226 Hyperlipidaemia Diseases 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012925 biological evaluation Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 230000001951 hemoperfusion Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000010412 perfusion Effects 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- 108700012359 toxins Proteins 0.000 description 1
- 239000002441 uremic toxin Substances 0.000 description 1
Classifications
-
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28026—Particles within, immobilised, dispersed, entrapped in or on a matrix, e.g. a resin
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to the technical field of solid adsorbents, and discloses a resin for protein adsorption and a preparation method thereof. The preparation method of the resin comprises the following steps: swelling polystyrene-divinylbenzene polymer microspheres by N, N-dimethylformamide, mixing the microspheres with thiourea solution, and carrying out hydrothermal reaction to obtain a thiourea modified resin carrier; and soaking the thiourea modified resin carrier in carnosic acid solution, and finally placing the thiourea modified resin carrier in a mixed solution of polylysine and polyethyleneimine. According to the invention, the thiourea modified resin carrier treated by carnosic acid can effectively improve the loading effect of the resin on polylysine and polyethyleneimine, so that the adsorption performance is improved and the risk of falling particles is reduced.
Description
Technical Field
The invention belongs to the technical field of solid adsorbents, and discloses a resin for protein adsorption and a preparation method thereof.
Background
Blood perfusion is a blood purification technique in which the blood of a patient is introduced into a perfusion apparatus containing a solid adsorbent, and exogenous or endogenous toxins, drugs or metabolic wastes which cannot be removed by dialysis in the blood are removed by adsorption. The core technology is mainly internal adsorption resin, and the adsorption resin used in the market at present mainly comprises active carbon, polysaccharide and synthetic resin, wherein the synthetic resin has advantages in mechanical strength, chemical stability and controllability of pore structure and functional groups. In the existing synthetic resin products on the market, macroporous adsorption resin is commonly used for whole blood perfusion, and the adsorption process is realized through physical adsorption of Van der Waals force, hydrogen bonding and the like. The styrene neutral macroporous adsorption resin in the synthetic resin has wider adsorption spectrum, is suitable for adsorbing various pathogenic substances in various diseases, and achieves the purpose of quick effect. Because the molecular weight of the protein is large, the adsorption effect of the broad-spectrum adsorbent is not ideal, and the selectivity is poor. The general method is to modify and modify the framework of the adsorbent to achieve the aim of improving the adsorption effect or specific adsorption. CN112791712a discloses an adsorbent for removing protein-bound uremic toxins by blood perfusion and a preparation method thereof, which adopts a method of imprinting molecules to achieve the purpose of specific adsorption, but has poor adsorption effect. CN111957304a discloses a macroporous adsorption resin for blood perfusion, which achieves the aim of improving the adsorption effect by grafting polyvinylpyrrolidone on the surface of white spheres, but has the risk of falling off particles.
Disclosure of Invention
The object of the present invention is to improve the adsorption properties of resins and reduce the risk of their particles falling off.
In order to solve the technical problems, the present invention provides a resin for protein adsorption and a preparation method thereof to meet the needs in the art.
In one aspect, the present invention relates to a method for preparing a resin for protein adsorption, comprising: swelling polystyrene-divinylbenzene polymer microspheres by N, N-dimethylformamide, mixing the microspheres with thiourea solution, and carrying out hydrothermal reaction to obtain a thiourea modified resin carrier;
and soaking the thiourea modified resin carrier in carnosic acid solution, and finally placing the thiourea modified resin carrier in a mixed solution of polylysine and polyethyleneimine.
Further, in the preparation method of the resin for protein adsorption, the concentration of the thiourea solution is 10-20wt%, and the solvent of the thiourea solution is water;
and the ratio of the swelled polystyrene-divinylbenzene polymer microspheres to the thiourea solution is 1:20-30 in terms of g/mL.
Further, in the preparation method of the resin for protein adsorption, the temperature of the hydrothermal reaction is 150-200 ℃ and the time is 12-48 h.
Further, in the preparation method of the resin for protein adsorption, the concentration of the carnosic acid solution is 20-30wt%, and the solvent of the carnosic acid solution is ethanol;
and the ratio of the thiourea modified resin carrier to the carnosic acid solution is 1:10-20 in terms of g/mL.
Further, in the preparation method of the resin for protein adsorption, the infiltration temperature is 50-60 ℃, and the infiltration time is 8-16 h.
In the preparation method of the resin for protein adsorption, the concentration of the polylysine in the mixed solution of the polylysine and the polyethyleneimine is 3-10wt%, and the concentration of the polyethyleneimine is 3-10wt%.
Further, in the preparation method of the resin for protein adsorption, the reaction temperature in the mixed solution of polylysine and polyethyleneimine is room temperature, and the reaction time is 12-24 hours.
In another aspect, the present invention relates to a resin for protein adsorption, which is prepared by the above-mentioned method for preparing a resin for protein adsorption.
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects or advantages: (1) According to the invention, a thiourea modification mode is adopted, so that a resin skeleton is grafted with reduced thiocarbonyl and amino functional groups; (2) The invention is used for improving the adsorption effect and the specific adsorption capacity of the resin by grafting polylysine and polyethyleneimine; (3) Experiments show that compared with polystyrene-divinylbenzene polymer microspheres, the thiourea modified resin carrier treated by carnosic acid shows a better effect of combining with polylysine or polyethyleneimine, can effectively improve the adsorption performance of the resin and reduce the falling risk of particles; (4) The invention does not adopt coupling reagents with toxicity risks such as epichlorohydrin, carbonyl diimidazole and the like to deactivate the carrier coupling functional unit, and has better biocompatibility.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing the results of the test of the adsorption performance of a resin to a protein.
FIG. 2 is a graph showing the results of the particle shedding test of the resin.
Detailed Description
The following describes the technical aspects of the present invention with reference to examples, but the present invention is not limited to the following examples.
The experimental methods and the detection methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available unless otherwise specified.
Example 1
This example provides a process for preparing a resin for protein adsorption.
Step 1: the polystyrene-divinylbenzene polymer microspheres (with the crosslinking degree of about 10 percent, the particle size distribution of 10-50 mu m and the pore size distribution of 5-100 nm) are washed by absolute ethyl alcohol and then immersed in N, N-dimethylformamide (with the purity of more than 99.9 percent) for 12 hours.
Step 2: and (3) mixing the polystyrene-divinylbenzene polymer microspheres obtained in the step (1) with 10wt% thiourea solution (solid-liquid ratio is 1:20, g/mL), putting the mixture into a high-pressure hydrothermal reaction kettle for carrying out hydrothermal reaction at 150 ℃ for 12 hours, taking out the mixture, and washing off residual chemical reagents on the resin surface and in the pore canal by using ethanol and pure water to obtain the thiourea modified resin carrier.
Step 3: and (3) soaking the thiourea modified resin carrier in a 20wt% carnosic acid solution (solid-liquid ratio is 1:10, g/mL) at 50 ℃ for 8 hours, taking out, placing the resin carrier in a mixed solution of polylysine and polyethyleneimine (the concentration of polylysine is 3wt% and the concentration of polyethyleneimine is 3 wt%) for reaction at room temperature for 12 hours, and washing with ethanol and water after the reaction is completed, and drying to obtain the resin. The carnosic acid solution is dissolved by using ethanol as a solvent and ultrasonically. The thiourea solution is dissolved by stirring with ultrapure water as a solvent.
Example 2
This example provides a process for preparing a resin for protein adsorption.
Step 1: the polystyrene-divinylbenzene polymer microspheres (with the crosslinking degree of about 10 percent, the particle size distribution of 10-50 mu m and the pore size distribution of 5-100 nm) are washed by absolute ethyl alcohol and then immersed in N, N-dimethylformamide (with the purity of more than 99.9 percent) for 12 hours.
Step 2: and (3) mixing the polystyrene-divinylbenzene polymer microspheres obtained in the step (1) with a 15wt% thiourea solution (solid-liquid ratio is 1:25, g/mL), putting the mixture into a high-pressure hydrothermal reaction kettle for hydrothermal reaction at 180 ℃ for 24 hours, taking out the mixture, and washing off residual chemical reagents on the resin surface and in the pore canal by using ethanol and pure water to obtain the thiourea modified resin carrier.
Step 3: and (3) soaking the thiourea modified resin carrier in a 25wt% carnosic acid solution (solid-to-liquid ratio is 1:15, g/mL) at 55 ℃ for 12 hours, taking out, placing the resin carrier in a mixed solution of polylysine and polyethyleneimine (the concentration of polylysine is 5wt% and the concentration of polyethyleneimine is 5 wt%) for 18 hours at room temperature, washing with ethanol and water after the reaction is completed, and drying to obtain the resin. The carnosic acid solution is dissolved by using ethanol as a solvent and ultrasonically. The thiourea solution is dissolved by stirring with ultrapure water as a solvent.
Example 3
This example provides a process for preparing a resin for protein adsorption.
Step 1: the polystyrene-divinylbenzene polymer microspheres (with the crosslinking degree of about 10 percent, the particle size distribution of 10-50 mu m and the pore size distribution of 5-100 nm) are washed by absolute ethyl alcohol and then immersed in N, N-dimethylformamide (with the purity of more than 99.9 percent) for 12 hours.
Step 2: and (3) mixing the polystyrene-divinylbenzene polymer microspheres obtained in the step (1) with a 20wt% thiourea solution (solid-liquid ratio is 1:30, g/mL), putting the mixture into a high-pressure hydrothermal reaction kettle, performing hydrothermal reaction at 200 ℃ for 48 hours, taking out, and washing off residual chemical reagents on the resin surface and in the pore canal by using ethanol and pure water to obtain the thiourea modified resin carrier.
Step 3: and (3) soaking the thiourea modified resin carrier in a 30wt% carnosic acid solution (solid-liquid ratio is 1:20, g/mL) at 60 ℃ for 16h, taking out, placing the resin carrier in a mixed solution of polylysine and polyethyleneimine (the concentration of polylysine is 10wt% and the concentration of polyethyleneimine is 10 wt%) for reaction at room temperature for 24h, washing with ethanol and water after the reaction is completed, and drying to obtain the resin. The carnosic acid solution is dissolved by using ethanol as a solvent and ultrasonically. The thiourea solution is dissolved by stirring with ultrapure water as a solvent.
Comparative example 1
This comparative example provides a resin preparation process of a resin carrier that has not been modified with thiourea.
Step 1: the polystyrene-divinylbenzene polymer microspheres (with the crosslinking degree of about 10 percent, the particle size distribution of 10-50 mu m and the pore size distribution of 5-100 nm) are washed by absolute ethyl alcohol and then immersed in N, N-dimethylformamide (with the purity of more than 99.9 percent) for 12 hours.
Step 2: and (3) washing the polystyrene-divinylbenzene polymer microspheres obtained in the step (1) with ethanol and pure water to remove residual chemical reagents on the resin surface and in the pore canal, thereby obtaining the resin carrier.
Step 3: soaking a resin carrier in 30wt% carnosic acid solution (solid-liquid ratio is 1:20, g/mL) at 60 ℃ for 16h, taking out, placing the resin carrier in a mixed solution of polylysine and polyethyleneimine (the concentration of polylysine is 10wt% and the concentration of polyethyleneimine is 10 wt%) for reaction at room temperature for 24h, washing with ethanol and water after the reaction is completed, and drying to obtain the resin. The carnosic acid solution is dissolved by using ethanol as a solvent and ultrasonically. The thiourea solution is dissolved by stirring with ultrapure water as a solvent.
Comparative example 2
This comparative example is identical to example 3, except that it has not been treated with carnosic acid solution.
Example 4
The present example provides performance tests for the resins prepared in examples 1-3 and comparative examples 1-2, with CN104492402a as a control.
(1) Lipoprotein adsorption Property
In a 20mL three-necked flask with a stopper, 2mL of resin (the resin prepared in example 1-3, comparative example 1-2 and example 1 of CN 104492402A) and 4mL of plasma (the lipoprotein concentration is 130-140 mg/dL) of a patient suffering from hyperlipidemia are added according to the ratio of 1mL of resin to 2mL of serum, the flask is placed in a constant temperature water tank at 37 ℃ for shaking for 1 hour, the lipoprotein content in the serum before and after absorption is detected by sucking the serum, the absorption rate is calculated, and the test result is shown in figure 1.
As can be seen from FIG. 1, the adsorption effect of the resin on the protein can be effectively improved by grafting polylysine and polyethyleneimine compared with comparative examples 1-2 and the prior art.
(2) Particle shedding performance
The resins obtained in examples 1 to 3, comparative examples 1 to 2 and example 1 of CN104492402A were subjected to a particle shedding test (refer to the particle shedding test in YY/T0464-2019, single use hemoperfusion apparatus) and the test results are shown in FIG. 2.
As can be seen from FIG. 2, the thiourea modified resin carrier treated by carnosic acid in the invention has a better effect of combining with polylysine or polyethyleneimine compared with polystyrene-divinylbenzene polymer microspheres, and can effectively improve the adsorption performance of the resin and reduce the risk of falling particles.
(3) Biocompatibility of
Part 4 of the biological evaluation of medical devices according to GB/T16886.4-2003: the hemolysis rate of the adsorbent was selectively evaluated in the blood interaction test, and the test results are shown in table 1.
TABLE 1 adsorbent hemolysis rate
As shown in Table 1, the hemolysis rate of the adsorbent provided by the invention is lower than 2%, meets the requirement of 5%, and has better biocompatibility.
As described above, the basic principles, main features and advantages of the present invention are better described. The above examples and description are merely illustrative of preferred embodiments of the present invention, and the present invention is not limited to the above examples, and various changes and modifications to the technical solution of the present invention by those skilled in the art should fall within the scope of protection defined by the present invention without departing from the spirit and scope of the present invention.
Claims (8)
1. A method for preparing a resin for protein adsorption, comprising: swelling polystyrene-divinylbenzene polymer microspheres by N, N-dimethylformamide, mixing the microspheres with thiourea solution, and carrying out hydrothermal reaction to obtain a thiourea modified resin carrier;
and soaking the thiourea modified resin carrier in carnosic acid solution, and finally placing the thiourea modified resin carrier in a mixed solution of polylysine and polyethyleneimine.
2. The method for preparing a resin for protein adsorption according to claim 1, wherein the concentration of the thiourea solution is 10-20 wt%, and the solvent of the thiourea solution is water;
and the ratio of the swelled polystyrene-divinylbenzene polymer microspheres to the thiourea solution is 1:20-30 in terms of g/mL.
3. The method for preparing a resin for protein adsorption according to claim 2, wherein the hydrothermal reaction is carried out at a temperature of 150-200 ℃ for a time of 12-48 hours.
4. The method for preparing the resin for protein adsorption according to claim 1, wherein the concentration of the carnosic acid solution is 20-30wt%, and the solvent of the carnosic acid solution is ethanol;
and the ratio of the thiourea modified resin carrier to the carnosic acid solution is 1:10-20 in terms of g/mL.
5. The method for preparing a resin for protein adsorption according to claim 4, wherein the soaking temperature is 50-60 ℃, and the soaking time is 8-16 h.
6. The method for preparing a resin for protein adsorption according to claim 1, wherein the concentration of polylysine in the mixed solution of polylysine and polyethyleneimine is 3-10wt%, and the concentration of polyethyleneimine is 3-10wt%.
7. The method for preparing a resin for protein adsorption according to claim 6, wherein the reaction temperature in the mixed solution of polylysine and polyethyleneimine is room temperature and the reaction time is 12-24 hours.
8. A resin for protein adsorption, characterized in that it is prepared by the method for preparing a resin for protein adsorption according to any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410061114.0A CN117563570B (en) | 2024-01-16 | 2024-01-16 | Resin for protein adsorption and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410061114.0A CN117563570B (en) | 2024-01-16 | 2024-01-16 | Resin for protein adsorption and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117563570A true CN117563570A (en) | 2024-02-20 |
| CN117563570B CN117563570B (en) | 2024-03-15 |
Family
ID=89886708
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410061114.0A Active CN117563570B (en) | 2024-01-16 | 2024-01-16 | Resin for protein adsorption and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117563570B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1615156A (en) * | 2002-01-18 | 2005-05-11 | 先进菲涛尼克斯有限公司 | Preparation of resinates |
| KR20090115515A (en) * | 2008-05-02 | 2009-11-05 | 방민숙 | A manufacturing method of adsorptive composition having antimicrobial and deodorant function |
| WO2013030838A2 (en) * | 2011-08-29 | 2013-03-07 | Yissum Research Development Company Of The Hebrew University Of Jerusalem Ltd. | Dendrimer-lyotropic liquid crystal (llc) systems |
| CN104525151A (en) * | 2014-12-02 | 2015-04-22 | 佛山市博新生物科技有限公司 | Endotoxin adsorbent used in hemoperfusion, and preparation method thereof |
| CN105709703A (en) * | 2016-01-30 | 2016-06-29 | 浙江理工大学 | Reparation and application of chelating resin and mercury ion detection method |
| CN112321838A (en) * | 2020-10-22 | 2021-02-05 | 华东理工大学 | Preparation method and application of nano polyethyleneimine grafted phenolic resin and photocatalytic hydrogen peroxide detection method |
| CN114288998A (en) * | 2021-12-16 | 2022-04-08 | 健帆生物科技集团股份有限公司 | Adsorption resin and preparation method and application thereof |
| CN115505166A (en) * | 2022-09-23 | 2022-12-23 | 浙江工业大学 | Thiourea modified resin-based nano material, preparation method and method for deeply removing selenate in water by using same |
| CN117123198A (en) * | 2023-09-27 | 2023-11-28 | 佛山市博新生物科技有限公司 | Modification method of blood purification adsorption material |
-
2024
- 2024-01-16 CN CN202410061114.0A patent/CN117563570B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1615156A (en) * | 2002-01-18 | 2005-05-11 | 先进菲涛尼克斯有限公司 | Preparation of resinates |
| KR20090115515A (en) * | 2008-05-02 | 2009-11-05 | 방민숙 | A manufacturing method of adsorptive composition having antimicrobial and deodorant function |
| WO2013030838A2 (en) * | 2011-08-29 | 2013-03-07 | Yissum Research Development Company Of The Hebrew University Of Jerusalem Ltd. | Dendrimer-lyotropic liquid crystal (llc) systems |
| CN104525151A (en) * | 2014-12-02 | 2015-04-22 | 佛山市博新生物科技有限公司 | Endotoxin adsorbent used in hemoperfusion, and preparation method thereof |
| CN105709703A (en) * | 2016-01-30 | 2016-06-29 | 浙江理工大学 | Reparation and application of chelating resin and mercury ion detection method |
| CN112321838A (en) * | 2020-10-22 | 2021-02-05 | 华东理工大学 | Preparation method and application of nano polyethyleneimine grafted phenolic resin and photocatalytic hydrogen peroxide detection method |
| CN114288998A (en) * | 2021-12-16 | 2022-04-08 | 健帆生物科技集团股份有限公司 | Adsorption resin and preparation method and application thereof |
| CN115505166A (en) * | 2022-09-23 | 2022-12-23 | 浙江工业大学 | Thiourea modified resin-based nano material, preparation method and method for deeply removing selenate in water by using same |
| CN117123198A (en) * | 2023-09-27 | 2023-11-28 | 佛山市博新生物科技有限公司 | Modification method of blood purification adsorption material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117563570B (en) | 2024-03-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102049242B (en) | Anion resin for bilirubin absorption and preparation method thereof | |
| CN108421536B (en) | A kind of preparation method and application of halloysite nanotubes/polypyrrole compound adsorbent | |
| JP2023130402A (en) | Use of hemocompatible porous polymer bead sorbent for removal of endotoxemia-inducing molecules | |
| WO2017174016A1 (en) | Medical macromolecular microsphere adsorbent for blood perfusion apparatus and manufacturing method thereof | |
| CN104174386B (en) | A kind of for removing the adsorbent of B2M in blood | |
| CN108371945B (en) | Adsorbent for eliminating middle and large molecular toxin in body of uremia patient and preparation method thereof | |
| CN114288998B (en) | Adsorption resin and preparation method and application thereof | |
| CN112871139B (en) | Whole blood perfusion adsorbent, preparation method and application thereof | |
| CN102423687A (en) | Preparation method of resin carbon for blood purification | |
| Uzun et al. | Bilirubin removal performance of immobilized albumin in a magnetically stabilized fluidized bed | |
| CN113509919B (en) | Adsorbent for removing endotoxin and inflammatory factor in blood of sepsis patient and preparation method thereof | |
| CN109734839B (en) | High-anticoagulation polystyrene microsphere and preparation method and application thereof | |
| CN108079974A (en) | A kind of preparation method and adsorbent equipment of western blot polymeric sorbent | |
| CN117563570B (en) | Resin for protein adsorption and preparation method thereof | |
| US20040076845A1 (en) | Hemocompatible polymer systems & related methods | |
| CN107159156B (en) | Adsorbent resin, secondary crosslinking post-modification method thereof and blood perfusion device | |
| Gan et al. | MOFs-alginate/polyacrylic acid/poly (ethylene imine) heparin-mimicking beads as a novel hemoadsorbent for bilirubin removal in vitro and vivo models | |
| CN114733492A (en) | Microcrystalline cellulose gel adsorbent for adsorbing and separating tetrodotoxin and preparation method thereof | |
| US20070160848A1 (en) | Hemocompatible polymer systems and related devices | |
| CN113231040B (en) | Graphene adsorption material for removing radioactive cesium ions in water | |
| Liu et al. | Metal–organic framework (UiO-66 and UiO-66-NH 2)-based adsorbents for bilirubin removal used in hemoperfusion | |
| CN114405488B (en) | Protein-bound toxoid blood perfusion adsorbent and preparation method and application thereof | |
| Liu et al. | Sodium tripolyphosphate (TPP) crosslinked chitosan membranes and application in humic acid removal | |
| CN109046282B (en) | Adsorbent for removing endotoxin by hemoperfusion and water solution and preparation method thereof | |
| CN114540332B (en) | Preparation method and application of uricase immobilized resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |