CN116328742B - A core-shell magnetic molecular imprinted polymer material, preparation method and application - Google Patents
A core-shell magnetic molecular imprinted polymer material, preparation method and application Download PDFInfo
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- CN116328742B CN116328742B CN202310468864.5A CN202310468864A CN116328742B CN 116328742 B CN116328742 B CN 116328742B CN 202310468864 A CN202310468864 A CN 202310468864A CN 116328742 B CN116328742 B CN 116328742B
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- 239000011258 core-shell material Substances 0.000 title claims abstract description 71
- 229920000344 molecularly imprinted polymer Polymers 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002861 polymer material Substances 0.000 title claims abstract description 11
- BPYKTIZUTYGOLE-IFADSCNNSA-N Bilirubin Chemical compound N1C(=O)C(C)=C(C=C)\C1=C\C1=C(C)C(CCC(O)=O)=C(CC2=C(C(C)=C(\C=C/3C(=C(C=C)C(=O)N\3)C)N2)CCC(O)=O)N1 BPYKTIZUTYGOLE-IFADSCNNSA-N 0.000 claims abstract description 127
- 229920001690 polydopamine Polymers 0.000 claims abstract description 86
- 239000002245 particle Substances 0.000 claims abstract description 76
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 16
- 239000002105 nanoparticle Substances 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 239000011259 mixed solution Substances 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 14
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 239000007983 Tris buffer Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 4
- 230000002269 spontaneous effect Effects 0.000 claims description 3
- 231100000765 toxin Toxicity 0.000 claims description 3
- 230000000975 bioactive effect Effects 0.000 claims description 2
- 239000011362 coarse particle Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 34
- 239000008280 blood Substances 0.000 abstract description 14
- 210000004369 blood Anatomy 0.000 abstract description 14
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 5
- 229960003638 dopamine Drugs 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 4
- 230000004043 responsiveness Effects 0.000 abstract 1
- 238000003980 solgel method Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 30
- 239000003463 adsorbent Substances 0.000 description 9
- 229960001484 edetic acid Drugs 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000001000 micrograph Methods 0.000 description 6
- 239000000872 buffer Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 108010088751 Albumins Proteins 0.000 description 3
- 102000009027 Albumins Human genes 0.000 description 3
- 241000283973 Oryctolagus cuniculus Species 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 208000027119 bilirubin metabolic disease Diseases 0.000 description 2
- 230000008081 blood perfusion Effects 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 208000036796 hyperbilirubinemia Diseases 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 206010056375 Bile duct obstruction Diseases 0.000 description 1
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 1
- 206010008635 Cholestasis Diseases 0.000 description 1
- 206010016654 Fibrosis Diseases 0.000 description 1
- 206010019663 Hepatic failure Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940098773 bovine serum albumin Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007882 cirrhosis Effects 0.000 description 1
- 208000019425 cirrhosis of liver Diseases 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 208000007903 liver failure Diseases 0.000 description 1
- 231100000835 liver failure Toxicity 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000010412 perfusion Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 108700012359 toxins Proteins 0.000 description 1
Classifications
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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
- B01J20/22—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
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M1/00—Suction or pumping devices for medical purposes; Devices for carrying-off, for treatment of, or for carrying-over, body-liquids; Drainage systems
- A61M1/36—Other treatment of blood in a by-pass of the natural circulatory system, e.g. temperature adaptation, irradiation ; Extra-corporeal blood circuits
- A61M1/3679—Other treatment of blood in a by-pass of the natural circulatory system, e.g. temperature adaptation, irradiation ; Extra-corporeal blood circuits by absorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Engineering & Computer Science (AREA)
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- Organic Chemistry (AREA)
- Anesthesiology (AREA)
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Abstract
本发明公开了一种核壳型磁性分子印迹聚合物材料、制备方法及应用，属于生物分离及血液净化领域。本发明采用多巴胺碱性自聚合的特点，于磁性四氧化三铁纳米颗粒表面自聚合成聚多巴胺层，同步胆红素印迹处理，形成胆红素印迹化聚多巴胺颗粒。后经溶胶‑凝胶法于印迹化聚多巴胺表面修饰二氧化钛，制得核壳型磁性分子印迹聚合物材料。本发明制备的核壳型磁性分子印迹聚合物材料具有很好的磁响应性。胆红素吸附测试表明，本发明的核壳型磁性分子印迹聚合物材料具有良好的吸附效果，且吸附后方便分离且可循环，具有良好的应用前景。
The present invention discloses a core-shell magnetic molecular imprinted polymer material, a preparation method and an application, and belongs to the field of biological separation and blood purification. The present invention adopts the characteristics of dopamine alkaline self-polymerization, self-polymerizes into a polydopamine layer on the surface of magnetic ferroferric oxide nanoparticles, and simultaneously performs bilirubin imprinting treatment to form bilirubin imprinted polydopamine particles. Titanium dioxide is then modified on the surface of the imprinted polydopamine by a sol-gel method to obtain a core-shell magnetic molecular imprinted polymer material. The core-shell magnetic molecular imprinted polymer material prepared by the present invention has good magnetic responsiveness. Bilirubin adsorption test shows that the core-shell magnetic molecular imprinted polymer material of the present invention has good adsorption effect, and is convenient to separate and recyclable after adsorption, and has good application prospects.
Description
Technical Field
The invention belongs to the technical field of molecularly imprinted polymers, in particular relates to core-shell magnetic molecularly imprinted polydopamine particles, a preparation method and application thereof, and particularly belongs to the field of biological separation and blood purification.
Background
Hyperbilirubinemia is a condition in the human body where bilirubin levels are too high, causing irreversible tissue and organ changes, such as cirrhosis, liver failure, or bile duct obstruction. The removal of high content bilirubin in blood has been one of the focus of medical attention, and the current clinical bilirubin removal method is mainly a blood perfusion technology, and is the first choice therapy for treating hyperbilirubinemia due to high selectivity, less side effects and low cost. The blood perfusion refers to the process of introducing the blood of a patient to the outside of the body, flowing through a perfusion device with an adsorbent, and removing toxins by utilizing the adsorption effect between the adsorbent and harmful toxic substances in the body so as to achieve the aim of purifying the blood. The bilirubin adsorbent for clinical application on the market comprises an activated carbon adsorbent, a synthetic resin adsorbent, an affinity adsorbent and the like, but most of the bilirubin adsorbents have the problems of poor blood compatibility, complex preparation process, low adsorption capacity, high cost and the like.
Aiming at the problems, the invention provides a core-shell type magnetic molecularly imprinted polydopamine polymer particle, which utilizes the alkaline self-polymerization characteristic of dopamine to self-polymerize into a polydopamine layer on the surface of a magnetic ferroferric oxide nanoparticle, and performs bilirubin imprinting treatment synchronously to form bilirubin imprinted polydopamine particles. And then, the titanium dioxide is modified on the surface of the imprinted polydopamine through sol-gel treatment, the adsorption specific surface area is increased, the mechanical strength is improved, the action of polydopamine amino and benzene ring is combined, the adsorption performance of the titanium dioxide is improved, the adsorption capacity and the adsorption selectivity of bilirubin are improved, and the method has good application prospect.
Disclosure of Invention
In order to improve the adsorption selectivity and the adsorption capacity of bilirubin and give consideration to the blood compatibility and the mechanical strength of the adsorbent, the invention provides a core-shell type adsorbent with polydopamine as a imprinting shell and ferroferric oxide nanoparticles as cores, and titanium dioxide is modified on the surface of a imprinting layer to construct core-shell type titanium dioxide/imprinting polydopamine magnetic composite particles for bilirubin removal and biological separation.
In order to achieve the above purpose, the invention adopts the following technical scheme:
The core-shell type magnetic molecularly imprinted polymer material has an inner core of 8.72wt% of ferroferric oxide, an outer shell of 3.66wt% of titanium dioxide modified 87.62wt% of imprinted polydopamine, and is coarse particles of 200-600 nm.
The preparation method of the core-shell type magnetic molecularly imprinted polymer material comprises the following steps:
1) Respectively adding bilirubin solution and magnetic ferroferric oxide nano particles into Tris buffer solution with pH of 7-9, and stirring and dispersing for 15-45 min at room temperature by ultrasonic; adding dopamine hydrochloride and ammonium persulfate to obtain a dispersed magnetic ferroferric oxide and dopamine hydrochloride mixed solution; wherein the concentration of bilirubin solution is 100-300 mg/L; the mass ratio of the magnetic ferroferric oxide nano particles to dopamine hydrochloride to the initiator ammonium persulfate is 10:10:1 to 15:10:1; the volume ratio of bilirubin solution to Tris buffer solution is 1:1-2: 1, a step of;
2) After ultrasonic treatment of the obtained magnetic ferroferric oxide and dopamine hydrochloride mixed solution, stirring for 0.5-6 h for spontaneous polymerization at 20-30 ℃ to obtain core-shell magnetic molecularly imprinted polydopamine particles; washing the core-shell magnetic molecularly imprinted polydopamine particles with deionized water, washing the core-shell magnetic molecularly imprinted polydopamine particles with methanol solution again for 8-12 h in the dark, soaking the core-shell magnetic molecularly imprinted polydopamine particles with template removing liquid, washing and drying the core-shell magnetic molecularly imprinted polydopamine particles to obtain the magnetic molecularly imprinted polydopamine particles; wherein the volume ratio of water to methanol of the methanol solution is 1.5:1-2:1; the template removing liquid is a mixed solution of sodium hydroxide, sodium carbonate and ethylenediamine tetraacetic acid, wherein the mass ratio of the sodium hydroxide to the sodium carbonate to the ethylenediamine tetraacetic acid is 4:4:1-2:2:1;
3) Adding magnetic molecularly imprinted polydopamine particles into isopropanol, adding titanium isopropoxide, and stirring for 0.5-3 hours, wherein the solid-liquid ratio of the magnetic molecularly imprinted polydopamine particles to the isopropanol is 1:1-1:2 g/L, and the volume ratio of the isopropanol to the titanium isopropoxide is 5:1-5:10; and adding glacial acetic acid to regulate the pH to 4-6, stirring for 1-3 hours, separating solid particles by using a magnet, washing by using ethanol, and then collecting the solid particles, and drying the solid particles in a 60 ℃ oven for 12 hours to obtain the titanium dioxide modified core-shell magnetic molecularly imprinted polymer particles.
The core-shell magnetic molecularly imprinted polymer material is used for removing biotoxin and separating bioactive molecules.
The invention has the beneficial effects that:
(1) The polydopamine with high biocompatibility contains catechol and amino, and can be combined with bilirubin efficiently through electrostatic action, hydrogen bond action and pi-pi action given by benzene ring. The imprinted polydopamine particles have the performance of selectively adsorbing bilirubin, can effectively identify bilirubin in blood, and further improve bilirubin separation effect. The monomer dopamine is easy to oxidize and self-polymerize under alkaline conditions, the process is mild and controllable, the environment is protected, and the thickness of the imprinted polydopamine layer can be controlled by adjusting the addition amount and the reaction time of the matrix material and the dopamine.
(2) The titanium dioxide has the advantages of strong oxidizing property, chemical stability, antibacterial property, greenness, no toxicity and the like, and is widely applied in the fields of biomedicine and bioengineering. The introduction of titanium dioxide can increase the adsorption specific surface area, improve the adsorption capacity of bilirubin, and improve the mechanical strength of the material.
(3) The core-shell magnetic molecular imprinting polymer particles are easier to separate and recycle, and have high application stability. The surface molecular imprinting polydopamine can selectively identify bilirubin, is favorable for improving bilirubin adsorption selectivity, and has good application prospect in the fields of blood purification and biological separation.
Drawings
FIG. 1 is a schematic diagram of hysteresis regression curves of core-shell magnetic molecularly imprinted polydopamine particles obtained by the method.
FIG. 2 is an SEM image and a TEM image of core-shell magnetic molecularly imprinted polydopamine particles prepared by comparative example 1, comparative example 2 and the method of the present invention; (a) scanning electron microscope image (500 nm) of the outer surface of comparative example 1, (b) transmission electron microscope image (1 μm) of comparative example 1, (c) scanning electron microscope image (1 μm) of the outer surface of comparative example 2, (d) transmission electron microscope image (1 μm) of comparative example 2, (e) core-shell magnetic molecularly imprinted polydopamine particle scanning electron microscope image (1 μm), (f) core-shell magnetic molecularly imprinted polydopamine particle transmission electron microscope image (1 μm);
FIG. 3 is an EDS spectrum analysis chart of the core-shell magnetic molecularly imprinted polydopamine particles obtained by the invention;
FIG. 4 is a graph showing the comparison of bilirubin adsorption amounts of core-shell magnetic molecularly imprinted polydopamine particles obtained in comparative example 1, comparative example 2 and the present invention;
FIG. 5 is a graph showing the comparison of bilirubin adsorption amounts of core-shell magnetic molecularly imprinted polydopamine particles obtained in comparative example 1, comparative example 2 and the present invention in bilirubin/albumin solution;
FIG. 6 is a graph showing the cycle performance of the core-shell magnetic molecularly imprinted polydopamine particles obtained by the invention for separating bilirubin;
FIG. 7 is a graph showing comparison of bilirubin adsorption amounts of core-shell magnetic molecularly imprinted polydopamine particles obtained in comparative example 1, comparative example 2 and the present invention in a rabbit whole blood/bilirubin solution.
Detailed Description
The following describes the embodiments of the present invention further with reference to the drawings and technical schemes.
Example 1
The preparation method of the core-shell magnetic molecularly imprinted polymer comprises the following steps:
(1) 20mL of bilirubin solution is added into a brown conical flask, then 15mLTris buffer (pH 8.0) is added, 100mg of ferroferric oxide is weighed, stirring is carried out for 15min at room temperature, and then the mixed solution is subjected to ultrasonic treatment for 20min; the concentration of the bilirubin solution is 200mg/L;
(2) Adding 100mg of dopamine hydrochloride and 8mg of ammonium persulfate into the mixed solution after ultrasonic treatment to obtain a well-dispersed magnetic mixed solution of ferroferric oxide and dopamine hydrochloride; transferring the mixed dispersion liquid into a distillation flask, and mechanically stirring for 3 hours at the temperature of 25 ℃ to obtain magnetic molecularly imprinted polydopamine;
(3) Washing magnetic molecularly imprinted polydopamine with deionized water, washing with methanol solution with water-alcohol volume ratio of 3:2 in darkness at room temperature for 12h, soaking with mixed solution of sodium hydroxide with concentration of 2mol/L, sodium carbonate with concentration of 2mol/L and ethylene diamine tetraacetic acid with concentration of 0.5mol/L for 24h after washing, and transferring to a 60 ℃ oven for drying;
(4) The resulting magnetic molecularly imprinted polydopamine particles were added to 50mL of isopropanol, and 10mL of titanium isopropoxide was added and stirred for 1 hour. Glacial acetic acid is added to adjust the pH to about 5, 0.3g of ammonium persulfate is added as an initiator, and the mixture is stirred and reacted for 3 hours. And (3) separating the titanium dioxide modified magnetic molecularly imprinted polydopamine particles by a magnet, washing by ethanol, and collecting, and drying in an oven at 60 ℃ for 12 hours to obtain the core-shell magnetic molecularly imprinted polydopamine particles.
Example 2
The preparation method of the core-shell magnetic molecularly imprinted polymer comprises the following steps:
(1) 20mL of bilirubin solution is added into a brown conical flask, then 15mLTris buffer (pH 8.0) is added, 100mg of ferroferric oxide is weighed, stirring is carried out for 15min at room temperature, and then the mixed solution is subjected to ultrasonic treatment for 20min; the concentration of the bilirubin solution is 200mg/L;
(2) Adding 100mg of dopamine hydrochloride and 8mg of ammonium persulfate into the mixed solution after ultrasonic treatment to obtain a well-dispersed magnetic mixed solution of ferroferric oxide and dopamine hydrochloride; transferring the mixed dispersion liquid into a distillation flask, and mechanically stirring for 3 hours at the temperature of 25 ℃ to obtain magnetic molecularly imprinted polydopamine;
(3) Washing magnetic molecularly imprinted polydopamine with deionized water, washing with methanol solution with water-alcohol volume ratio of 3:2 in darkness at room temperature for 12h, soaking with mixed solution of sodium hydroxide with concentration of 2mol/L, sodium carbonate with concentration of 2mol/L and ethylene diamine tetraacetic acid with concentration of 0.5mol/L for 24h after washing, and transferring to a 60 ℃ oven for drying;
(4) The resulting magnetic molecularly imprinted polydopamine particles were added to 50mL of isopropanol, and 50mL of titanium isopropoxide was added and stirred for 1 hour. Glacial acetic acid is added to adjust the pH to about 5, 0.3g of ammonium persulfate is added as an initiator, and the mixture is stirred and reacted for 3 hours. And (3) separating the titanium dioxide modified magnetic molecularly imprinted polydopamine particles by a magnet, washing by ethanol, and collecting, and drying in an oven at 60 ℃ for 12 hours to obtain the core-shell magnetic molecularly imprinted polydopamine particles.
Example 3
The preparation method of the core-shell type magnetic molecularly imprinted polydopamine particle comprises the following steps:
(1) 20mL of bilirubin solution is added into a brown conical flask, then 15mLTris buffer (pH 8.0) is added, 100mg of ferroferric oxide is weighed, stirring is carried out for 15min at room temperature, and then the mixed solution is subjected to ultrasonic treatment for 20min; the concentration of the bilirubin solution is 200mg/L;
(2) Adding 100mg of dopamine hydrochloride and 8mg of ammonium persulfate into the mixed solution after ultrasonic treatment to obtain a well-dispersed magnetic mixed solution of ferroferric oxide and dopamine hydrochloride; transferring the mixed dispersion liquid into a distillation flask, and mechanically stirring for 3 hours at the temperature of 25 ℃ to obtain magnetic molecularly imprinted polydopamine;
(3) Washing magnetic molecularly imprinted polydopamine with deionized water, washing with methanol solution with water-alcohol volume ratio of 3:2 in darkness at room temperature for 12h, soaking with mixed solution of sodium hydroxide with concentration of 2mol/L, sodium carbonate with concentration of 2mol/L and ethylene diamine tetraacetic acid with concentration of 0.5mol/L for 24h after washing, and transferring to a 60 ℃ oven for drying;
(4) The resulting magnetic molecularly imprinted polydopamine particles were added to 50mL of isopropanol, and 100mL of titanium isopropoxide was added and stirred for 1 hour. Glacial acetic acid is added to adjust the pH to about 5, 0.3g of ammonium persulfate is added as an initiator, and the mixture is stirred and reacted for 3 hours. And (3) separating the titanium dioxide modified magnetic molecularly imprinted polydopamine particles by a magnet, washing by ethanol, and collecting, and drying in an oven at 60 ℃ for 12 hours to obtain the core-shell magnetic molecularly imprinted polydopamine particles.
Comparative example 1
The preparation method of the core-shell magnetic molecularly imprinted polymer comprises the following steps:
(1) 20mL of bilirubin solution is added into a brown conical flask, then 15mLTris buffer (pH 8.0) is added, 100mg of ferroferric oxide is weighed, stirring is carried out for 15min at room temperature, and then the mixed solution is subjected to ultrasonic treatment for 20min; the concentration of the bilirubin solution is 200mg/L;
(2) Adding 100mg of dopamine hydrochloride and 8mg of ammonium persulfate into the mixed solution after ultrasonic treatment to obtain a well-dispersed magnetic mixed solution of ferroferric oxide and dopamine hydrochloride; transferring the mixed dispersion liquid into a distillation flask, and mechanically stirring for 1h at the temperature of 25 ℃ to obtain magnetic molecularly imprinted polydopamine;
(3) Washing magnetic molecularly imprinted polydopamine with deionized water, washing with methanol solution with the water-alcohol volume ratio of 3:2 in darkness at room temperature for 12h, soaking with mixed solution with the concentration of 2mol/L sodium hydroxide, 2mol/L sodium carbonate and 0.5mol/L ethylenediamine tetraacetic acid for 24h after washing, separating magnetic molecularly imprinted polydopamine particles with magnet, collecting after washing with ethanol, and drying in an oven at 60 ℃ for 12h to obtain the magnetic molecularly imprinted polydopamine particles.
Comparative example 2
The preparation method of the core-shell magnetic molecularly imprinted polymer comprises the following steps:
(1) 20mL of bilirubin solution is added into a brown conical flask, then 15mLTris buffer (pH 8.0) is added, 100mg of ferroferric oxide is weighed, stirring is carried out for 15min at room temperature, and then the mixed solution is subjected to ultrasonic treatment for 20min; the concentration of the bilirubin solution is 200mg/L;
(2) Adding 100mg of dopamine hydrochloride and 8mg of ammonium persulfate into the mixed solution after ultrasonic treatment to obtain a well-dispersed magnetic mixed solution of ferroferric oxide and dopamine hydrochloride; transferring the mixed dispersion liquid into a distillation flask, and mechanically stirring for 3 hours at the temperature of 25 ℃ to obtain magnetic molecularly imprinted polydopamine;
(3) Washing magnetic molecularly imprinted polydopamine with deionized water, washing with methanol solution with the water-alcohol volume ratio of 3:2 in darkness at room temperature for 12h, soaking with mixed solution with the concentration of 2mol/L sodium hydroxide, 2mol/L sodium carbonate and 0.5mol/L ethylenediamine tetraacetic acid for 24h after washing, separating magnetic molecularly imprinted polydopamine particles with magnet, collecting after washing with ethanol, and drying in an oven at 60 ℃ for 12h to obtain the magnetic molecularly imprinted polydopamine particles.
Experimental mode
(1) The hysteresis regression curve of the core-shell magnetic molecularly imprinted polydopamine particles prepared by the method is measured by a liquid helium-free comprehensive physical property measuring system.
(2) Core-shell magnetic molecularly imprinted polydopamine particles prepared in comparative example 1, comparative example 2 and the method of the invention are taken, dispersed by ethanol solution, dripped on a silicon wafer, fixed on a sample stage by conductive adhesive, sprayed with gold, and observed in morphology by a Scanning Electron Microscope (SEM). The elemental composition of the core-shell magnetic molecularly imprinted polydopamine particles was scanned with energy spectrum analysis (EDS).
(3) Core-shell magnetic molecularly imprinted polydopamine particles prepared in comparative example 1, comparative example 2 and the method of the invention were dispersed in ethanol solution, transferred to a twin-wire mesh by a syringe, and observed by a Transmission Electron Microscope (TEM).
(4) 10Mg of core-shell magnetic molecularly imprinted polydopamine particles prepared by the method of the invention, 10mg of each of comparative example 1 and 2 are respectively taken and added into 10mL of bilirubin solution with the concentration of 100mg/L, the mixture is put into a water bath constant temperature oscillator (37 ℃ C., 150 r.min -1) for oscillation, and after the adsorption equilibrium is reached, the adsorption quantity of bilirubin is calculated.
(5) 10Mg of core-shell magnetic molecularly imprinted polydopamine particles prepared by the method, 10mg of each of comparative example 1 and 2 are respectively taken and added into 10mL of bilirubin solution with the concentration of 100mg/L and bovine serum albumin mixed solution with the concentration of 40g/L, the mixture is used for simulating the plasma environment of a human body, and the mixture is put into a water bath constant temperature oscillator (37 ℃ C., 150 r.min -1) for oscillation, and after adsorption balance is achieved, the bilirubin adsorption quantity is calculated.
(6) Bilirubin is removed from core-shell magnetic molecularly imprinted polydopamine particles with saturated bilirubin adsorption in a bottle filled with 100mL of 0.2mol/LNaOH eluent, and the eluent is replaced every 20 minutes until no bilirubin is detected, so that regenerated core-shell magnetic molecularly imprinted polydopamine particles are obtained and are used for cyclic adsorption.
(7) 1ML of whole rabbit blood is taken, 6mL of bilirubin solution which is 100mg/L prepared by normal saline is added for uniform dilution, 7mg of core-shell type magnetic molecularly imprinted polydopamine particles prepared by the method, 7mg of each of comparative example 1 and comparative example 2 are respectively taken, added into a mixed solution of blood and bilirubin, placed into a water bath constant temperature oscillator (37 ℃ C., 150 r.min -1) for oscillation, the clinical bilirubin adsorption process is simulated, and the bilirubin adsorption amount is calculated after the adsorption equilibrium is reached.
Experimental results
(1) From fig. 1, the hysteresis loop is s-shaped and crosses the origin, indicating that the adsorption material has superparamagnetism and the forcing force is 0. The saturated magnetization characterization result of the core-shell magnetic molecularly imprinted polydopamine particles shows that the magnetization of the core-shell magnetic molecularly imprinted polydopamine particles is 85.2emu/g, and the magnetic composite material is easy to separate in an external magnetic field.
(2) According to fig. 2 (a) (c) (e), the core-shell magnetic molecularly imprinted polydopamine particles are agglomerated to different degrees, and compared with comparative examples 1 and 2, the core-shell magnetic molecularly imprinted polydopamine particles prepared by the method disclosed by the invention have the advantages that the surfaces are coarser, the specific surface area is high, and the bilirubin adsorption quantity is improved; from fig. 2 (b) (d) (f), the particle size of the core-shell magnetic molecularly imprinted polydopamine particles is larger than that of comparative examples 1 and 2, mainly caused by the titanium dioxide modification layer.
(3) From fig. 3, eds energy spectrum shows that core-shell magnetic molecularly imprinted polydopamine particles contain C, N, O, fe, ti elements, demonstrating the introduction of a titanium dioxide modification layer.
(4) From FIG. 4, the adsorption amounts of free bilirubin of the core-shell type magnetic molecularly imprinted polydopamine particles in comparative example 1, comparative example 2 and core-shell type magnetic molecularly imprinted polydopamine particles are 53.2mg/g, 147.3mg/g and 232.5mg/g respectively, which shows that the core-shell type magnetic molecularly imprinted polymeric system prepared by the method has a good adsorption effect on free bilirubin.
(5) From FIG. 5, the adsorption amounts of bilirubin in the mixed solution of albumin/bilirubin by the core-shell type magnetic molecularly imprinted polydopamine particles in comparative example 1, comparative example 2 and core-shell type magnetic molecularly imprinted polymer particles are respectively 22.2mg/g, 38.4mg/g and 63.2mg/g, which shows that the core-shell type magnetic molecularly imprinted polymer system prepared by the method can highly selectively adsorb bilirubin under the influence of albumin.
(6) According to FIG. 6, after four adsorption-desorption cycles, the adsorption capacity of bilirubin is reduced from 232.5mg/g to 195.1mg/g, and the adsorption performance is reduced by 16.1%, which shows that the core-shell magnetic molecularly imprinted polymer system obtained by the method has good adsorption-desorption performance, meanwhile, bilirubin imprinted holes have no obvious change, and the core-shell magnetic molecularly imprinted polydopamine particles have excellent regeneration capacity.
(7) From FIG. 7, the adsorption amounts of bilirubin in the mixed solution of rabbit whole blood and bilirubin by the core-shell type magnetic molecularly imprinted polydopamine particles in comparative example 1, comparative example 2 and core-shell type magnetic molecularly imprinted polymer particles are 72.4mg/g, 77.3mg/g and 166.7mg/g respectively, which shows that the core-shell type magnetic molecularly imprinted polymer system prepared by the method can efficiently adsorb bilirubin in the clinical blood purification process.
Although embodiments of the present invention have been disclosed in the foregoing description and illustrated in the drawings, it is not intended to be limited to the details and illustrations of specific embodiments, but rather to be fully applicable to the various fields of adaptation of the present invention as those skilled in the art will readily appreciate additional modifications, equivalent substitutions or changes in the technical solution of the present invention and its inventive concepts, and the present invention is not limited to the specific details and illustrations shown and described herein.
Claims (5)
1. The core-shell magnetic molecularly imprinted polymer material has a core of ferroferric oxide and a shell of titanium dioxide modified imprinted polydopamine, and is a coarse particle of 200-600 nm; the method is characterized by comprising the following steps of:
1) Respectively adding bilirubin solution and magnetic ferroferric oxide nano particles into Tris buffer solution with pH of 7-9, and stirring and dispersing for 15-45 min at room temperature by ultrasonic; adding dopamine hydrochloride and ammonium persulfate to obtain a dispersed magnetic ferroferric oxide and dopamine hydrochloride mixed solution; wherein the concentration of bilirubin solution is 100-300 mg/L; the mass ratio of the magnetic ferroferric oxide nano particles to dopamine hydrochloride to the initiator ammonium persulfate is 10:10:1 to 15:10:1; the volume ratio of bilirubin solution to Tris buffer solution is 1:1-2: 1, a step of;
2) After ultrasonic treatment of the obtained magnetic ferroferric oxide and dopamine hydrochloride mixed solution, stirring and spontaneous polymerization are carried out at 20-30 ℃ to obtain core-shell magnetic molecularly imprinted polydopamine particles; washing the core-shell magnetic molecularly imprinted polydopamine particles with deionized water, washing the core-shell magnetic molecularly imprinted polydopamine particles with methanol solution again for 8-12 h in the dark, soaking the core-shell magnetic molecularly imprinted polydopamine particles with template removing liquid, washing and drying the core-shell magnetic molecularly imprinted polydopamine particles to obtain the magnetic molecularly imprinted polydopamine particles;
3) Adding magnetic molecularly imprinted polydopamine particles into isopropanol, adding titanium isopropoxide, and stirring for 0.5-3 hours, wherein the solid-liquid ratio of the magnetic molecularly imprinted polydopamine particles to the isopropanol is 1:1-1:2 g/L, and the volume ratio of the isopropanol to the titanium isopropoxide is 5:1-5:10; and adding glacial acetic acid to regulate the pH to 4-6, stirring for 1-3 hours, separating solid particles by using a magnet, washing by using ethanol, and then collecting the solid particles, and drying the solid particles in a 60 ℃ oven for 12 hours to obtain the titanium dioxide modified core-shell magnetic molecularly imprinted polymer particles.
2. The process according to claim 1, wherein in step 2), the reaction time for the spontaneous polymerization is 0.5 to 6 hours.
3. The method according to claim 1, wherein in step 2), the water/methanol volume ratio of the methanol solution is 1.5:1 to 2:1.
4. The method according to claim 1, wherein in the step 2), the template removing liquid is a mixed solution of sodium hydroxide, sodium carbonate and ethylenediamine tetraacetic acid, wherein the mass ratio of sodium hydroxide, sodium carbonate and ethylenediamine tetraacetic acid is 4:4:1-2:2:1.
5. The core-shell magnetic molecularly imprinted polymer material obtained by the preparation method of claim 1 is used for removing biotoxin and separating bioactive molecules.
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