CN112938956A - Magnetic graphene oxide capable of adsorbing beta amyloid protein and preparation method thereof - Google Patents

Magnetic graphene oxide capable of adsorbing beta amyloid protein and preparation method thereof Download PDF

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CN112938956A
CN112938956A CN202110168539.8A CN202110168539A CN112938956A CN 112938956 A CN112938956 A CN 112938956A CN 202110168539 A CN202110168539 A CN 202110168539A CN 112938956 A CN112938956 A CN 112938956A
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graphene oxide
polyethyleneimine
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CN112938956B (en
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王志刚
毕方方
梁巧仪
邹珍友
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Xiangya Hospital of Central South University
Guilin Medical University
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Abstract

本发明公开了一种可吸附β淀粉样蛋白的磁性氧化石墨烯及其制备方法，其中包括磁性氧化石墨烯、聚乙烯亚胺基体、硅烷偶联剂和叶酸，聚乙烯亚胺基体通过硅烷偶联剂合成，氧化石墨烯复合在聚乙烯亚胺基体上，叶酸负载在氧化石墨烯上；其中氧化石墨烯具有较高的比表面积以及丰富的表面官能团，使得它具有一定的吸附能力，其中采用聚乙烯亚胺对氧化石墨烯磁性材料进行了接枝改性，同时复合安全的叶酸所得到的新型吸附材料对β淀粉样蛋白的吸附效果好，将其注入脑脊液中吸附β淀粉样蛋白之后还能通过磁性回收，可以就实现β淀粉样蛋白的清除，同时磁性氧化石墨烯的制备方法相对简单，绿色环保。

Figure 202110168539

The invention discloses a magnetic graphene oxide capable of adsorbing beta amyloid and a preparation method thereof, which comprises magnetic graphene oxide, polyethyleneimine matrix, silane coupling agent and folic acid. Combined agent synthesis, graphene oxide is compounded on polyethyleneimine matrix, and folic acid is loaded on graphene oxide; wherein graphene oxide has a high specific surface area and abundant surface functional groups, which makes it have a certain adsorption capacity. The graphene oxide magnetic material was grafted and modified by polyethyleneimine, and the new adsorption material obtained by compounding safe folic acid had good adsorption effect on beta amyloid. After injecting it into the cerebrospinal fluid to adsorb beta amyloid Through magnetic recovery, the removal of beta amyloid can be achieved, and the preparation method of magnetic graphene oxide is relatively simple and environmentally friendly.

Figure 202110168539

Description

Magnetic graphene oxide capable of adsorbing beta amyloid protein and preparation method thereof
Technical Field
The invention relates to the technical field of magnetic graphene oxide, in particular to magnetic graphene oxide capable of adsorbing beta amyloid and a preparation method thereof.
Background
The beta-amyloid protein has a molecular weight of about 4kDa, is hydrolyzed from beta amyloid precursor protein, is secreted by cells, and has a strong neurotoxic effect after the accumulation of cell matrix precipitates. Amyloid beta is produced by amyloid precursor protein in a variety of cells, circulates in blood, cerebrospinal fluid and cerebral interstitial fluid, is mostly bound to chaperone molecules, and exists in a few free states. Wherein the amyloid beta is associated with Alzheimer's disease and cerebral amyloid angiopathy. The process by which amyloid beta causes disorders is: overproduction of the neurotoxic substance amyloid beta (a β) in the brain leads to a β brain aggregation → neuronal degenerative death → brain atrophy → dementia. A β deposition is one of the important pathological features of Alzheimer's Disease (AD), and is a common pathway for the induction of AD for a variety of reasons, and is also a key factor in the formation and progression of AD. Therapeutic strategies aimed at abeta clearance are one of the currently mainstream directions of research.
The graphene oxide has a high specific surface area and abundant surface functional groups, so that the graphene oxide has a certain adsorption capacity, but the existing graphene oxide has a general adsorption effect on beta amyloid protein, and meanwhile, the graphene oxide does not have magnetism, so that the graphene oxide cannot be subjected to magnetic recovery, and the practicability is poor.
Disclosure of Invention
The invention aims to provide magnetic graphene oxide capable of adsorbing beta amyloid and a preparation method thereof, and the magnetic graphene oxide has the advantages of good beta amyloid adsorption effect and relatively simple preparation, so that the problems in the background art are solved.
In order to achieve the purpose, the invention provides the following technical scheme:
the magnetic graphene oxide capable of adsorbing the beta amyloid protein comprises magnetic graphene oxide, a polyethyleneimine matrix, a silane coupling agent and folic acid, wherein the polyethyleneimine matrix is synthesized by the silane coupling agent, the graphene oxide is compounded on the polyethyleneimine matrix, and the folic acid is loaded on the graphene oxide.
Another technical problem to be solved by the present invention is to provide a method for preparing magnetic graphene oxide capable of adsorbing amyloid beta, comprising the following steps:
s1: preparing magnetic graphene oxide; weighing 15-30mg of graphene oxide, dissolving the graphene oxide in 15-30ml of diethylene glycol solution, uniformly stirring, putting the mixed solution into ultrasonic equipment for ultrasonic mixing, controlling the ultrasonic mixing time to be 26-30min, then sequentially adding 250mg of sodium acetate and 200mg of ferric chloride hexahydrate under the action of magnetic stirring to form uniform yellow suspension, putting the suspension into a reaction kettle, adjusting the temperature level in the reaction kettle to 200 ℃, enabling the suspension to react in the reaction kettle for 8-10h at 200 ℃, then putting the suspension into a centrifuge, centrifuging the suspension for 5min at the revolution of 3000r/min, then pouring out the supernatant above the precipitate to obtain the precipitate, centrifuging and washing the precipitate for 10-20 times by sequentially using 400ml of anhydrous ethanol and 350ml of distilled water, obtaining high-quality magnetic graphene oxide precipitate, and then carrying out vacuum drying on the high-quality magnetic graphene oxide precipitate to obtain magnetic graphene oxide;
s2: preparing a polyethyleneimine matrix:
a, preparing a polyethyleneimine emulsion: mixing 8-10 mL of 20% polyethyleneimine water solution, 10-12 mL of liquid paraffin and 2mL of polyvinyl alcohol pore-forming agent in percentage by mass, adding a surfactant into the mixed solution to form a mixed solution, wherein the final concentration of the surfactant is 0.04-0.06 g/mL, putting the mixed solution into ultrasonic equipment for ultrasonic mixing, and controlling the ultrasonic mixing time to be 2-3min to form polyethyleneimine emulsion;
b pre-crosslinking polymerization reaction: taking 15-20 mL of the polyethyleneimine emulsion, slowly dropwise adding 15-20 mL of a cross-linking agent under the action of magnetic stirring, and pre-crosslinking for 2-3 hours;
c, crosslinking polymerization reaction: under the condition of magnetic stirring, slowly dropwise adding 5-10 mL of sodium hydroxide solution into 20mL of pre-crosslinked mixture prepared by the pre-crosslinking polymerization reaction, controlling the concentration of the sodium hydroxide solution to be 1.0-2.0 mol/L, after the reaction is finished, performing centrifugal treatment on the mixture, and centrifuging to remove supernatant to obtain a polyethyleneimine matrix;
s3: preparing polyethyleneimine modified magnetic graphene oxide: weighing 20-40mg of magnetic graphene oxide, dissolving the magnetic graphene oxide in 20-40ml of phosphate buffer solution with the pH value of 7.4, then putting the mixed solution into ultrasonic equipment for ultrasonic mixing, and controlling the ultrasonic mixing time to be 5-10min to ensure that the mixed solution is uniformly dispersed; then sequentially adding 200mg of carbodiimide hydrochloride, 50-117mg of N-hydroxysuccinimide and 400mg of polyethyleneimine matrix into the mixed solution, uniformly stirring, filtering to obtain a filter cake, repeatedly washing the filter cake for 10 times by using 1000ml of ultrapure water to obtain a polyethyleneimine modified magnetic graphene oxide precipitate, and then carrying out vacuum drying on the polyethyleneimine modified magnetic graphene oxide precipitate at the temperature of 40-60 ℃ for 1-2 days to finally obtain the polyethyleneimine modified magnetic graphene oxide;
s4: preparing magnetic graphene oxide modified by polyethyleneimine loaded with folic acid: weighing 5-20mg of polyethyleneimine modified magnetic graphene oxide, dissolving in 5-20ml of ultrapure water, adding 1-4mg of silane coupling agent and 5-20mg of folic acid powder, placing the mixed solution into ultrasonic equipment for ultrasonic mixing, and controlling the ultrasonic mixing time to be 1-2 hours to obtain the polyethyleneimine modified magnetic graphene oxide loaded with folic acid.
Preferably, in S2, the addition mass of the cross-linking agent is the same as the addition mass of the polyethyleneimine emulsion.
Preferably, in S2, the polyethyleneimine matrix is obtained by washing with isopropanol, dehydrated ether and distilled water for 5 to 10 times.
Preferably, in S4, the silane coupling agent is 3-aminopropyltriethoxysilane.
Compared with the prior art, the invention has the beneficial effects that: the invention provides magnetic graphene oxide capable of adsorbing beta amyloid and a preparation method thereof, wherein the magnetic graphene oxide comprises magnetic graphene oxide, a polyethyleneimine matrix, a silane coupling agent and folic acid, the polyethyleneimine matrix is synthesized by the silane coupling agent, the graphene oxide is compounded on the polyethyleneimine matrix, and the folic acid is loaded on the graphene oxide; the graphene oxide has a high specific surface area and rich surface functional groups, so that the graphene oxide has certain adsorption capacity, the graphene oxide magnetic material is subjected to graft modification by using polyethyleneimine, and a novel adsorption material obtained by compounding safe folic acid has a good adsorption effect on beta amyloid protein.
Drawings
FIG. 1 is a block diagram of the overall process flow of the present invention;
FIG. 2 is a block diagram of a process for preparing a polyethyleneimine matrix according to the present invention;
FIG. 3 is a path of a mouse water maze experiment without the invention of the present invention;
FIG. 4 is a path of the mouse water maze experiment using the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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.
The magnetic graphene oxide capable of adsorbing the amyloid beta comprises magnetic graphene oxide, a polyethyleneimine matrix, a silane coupling agent and folic acid, wherein the polyethyleneimine matrix is synthesized through the silane coupling agent, the graphene oxide is compounded on the polyethyleneimine matrix, and the folic acid is loaded on the graphene oxide.
Example one
Referring to fig. 1, a method for preparing magnetic graphene oxide capable of adsorbing amyloid beta includes the following steps:
the first step is as follows: preparing magnetic graphene oxide; weighing 25mg of graphene oxide, dissolving the graphene oxide in 25ml of diethylene glycol solution, uniformly stirring, putting the mixed solution into ultrasonic equipment for ultrasonic mixing, controlling the ultrasonic mixing time to be 30min, then sequentially adding 150mg of sodium acetate and 100mg of ferric chloride hexahydrate under the action of magnetic stirring to form uniform yellow suspension, putting the suspension into a reaction kettle, adjusting the temperature of the reaction kettle to be 200 ℃, enabling the suspension to react in the reaction kettle for 8h at 200 ℃, putting the suspension into a centrifugal machine, centrifuging the suspension for 5min at the speed of 3000r/min, pouring out supernatant above the precipitate to obtain precipitate, sequentially centrifuging and washing the precipitate for 15 times by 400ml of absolute ethyl alcohol and 250ml of distilled water to obtain high-quality magnetic graphene oxide precipitate, and then carrying out vacuum drying on the high-quality magnetic graphene oxide precipitate, obtaining magnetic graphene oxide;
the second step is that: preparing a polyethyleneimine emulsion: mixing 10mL of 20% polyethyleneimine water solution, 10mL of liquid paraffin and 2mL of polyvinyl alcohol pore-forming agent in percentage by mass, adding a surfactant into the mixed solution to form a mixed solution, wherein the final concentration of the surfactant is 0.04g/mL, putting the mixed solution into ultrasonic equipment for ultrasonic mixing, and controlling the ultrasonic mixing time to be 3min to form polyethyleneimine emulsion;
the third step: preparing polyethyleneimine modified magnetic graphene oxide: weighing 40mg of magnetic graphene oxide, dissolving the magnetic graphene oxide in 40ml of phosphate buffer solution with the pH value of 7.4, then putting the mixed solution into ultrasonic equipment for ultrasonic mixing, and controlling the ultrasonic mixing time to be 5min so as to uniformly disperse the mixed solution; then sequentially adding 100mg of carbodiimide hydrochloride, 50mg of N-hydroxysuccinimide and 200mg of polyethyleneimine emulsion into the mixed solution, uniformly stirring, filtering to obtain a filter cake, repeatedly washing the filter cake for 10 times by using 1000ml of ultrapure water to obtain a polyethyleneimine modified magnetic graphene oxide precipitate, and then carrying out vacuum drying on the polyethyleneimine modified magnetic graphene oxide precipitate, wherein the temperature of the vacuum drying is controlled to be 40-60 ℃, and the drying time is 1 day, so as to finally obtain the polyethyleneimine modified magnetic graphene oxide;
the fourth step: preparing magnetic graphene oxide modified by polyethyleneimine loaded with folic acid: weighing 20mg of polyethyleneimine modified magnetic graphene oxide, dissolving in 20ml of ultrapure water, adding 4mg of silane coupling agent and 20mg of folic acid powder, wherein the silane coupling agent is 3-aminopropyltriethoxysilane, placing the mixed solution into ultrasonic equipment for ultrasonic mixing, and controlling the ultrasonic mixing time to be 2 hours to obtain the folic acid loaded polyethyleneimine modified magnetic graphene oxide.
Example two
Referring to fig. 1-2, a method for preparing magnetic graphene oxide capable of adsorbing amyloid beta includes the following steps:
the first step is as follows: preparing magnetic graphene oxide; weighing 30mg of graphene oxide, dissolving the graphene oxide in 30ml of diethylene glycol solution, uniformly stirring, putting the mixed solution into ultrasonic equipment for ultrasonic mixing, controlling the ultrasonic mixing time to be 30min, then sequentially adding 250mg of sodium acetate and 200mg of ferric chloride hexahydrate under the action of magnetic stirring to form uniform yellow suspension, putting the suspension into a reaction kettle, adjusting the temperature of the reaction kettle to be 200 ℃, enabling the suspension to react in the reaction kettle at 200 ℃ for 10h, putting the suspension into a centrifugal machine, centrifuging the suspension for 5min at the speed of 3000r/min, pouring out supernatant above the precipitate to obtain precipitate, sequentially centrifuging and washing the precipitate for 20 times by 300ml of absolute ethyl alcohol and 350ml of distilled water to obtain high-quality magnetic graphene oxide precipitate, and then carrying out vacuum drying on the high-quality magnetic graphene oxide precipitate, obtaining magnetic graphene oxide;
the second step is that: preparing a polyethyleneimine matrix:
a, preparing a polyethyleneimine emulsion: mixing 10mL of 20% polyethyleneimine water solution, 10mL of liquid paraffin and 2mL of polyvinyl alcohol pore-forming agent in percentage by mass, adding a surfactant into the mixed solution to form a mixed solution, wherein the final concentration of the surfactant is 0.06g/mL, putting the mixed solution into ultrasonic equipment for ultrasonic mixing, and controlling the ultrasonic mixing time to be 3min to form polyethyleneimine emulsion;
b pre-crosslinking polymerization reaction: taking 20mL of the polyethyleneimine emulsion, slowly dropwise adding 20mL of a cross-linking agent under the action of magnetic stirring, and pre-crosslinking for 2 hours, wherein the adding mass of the cross-linking agent is the same as that of the polyethyleneimine emulsion;
c, crosslinking polymerization reaction: under the condition of magnetic stirring, taking 20mL of a pre-crosslinking mixture prepared by the pre-crosslinking polymerization reaction, slowly and dropwise adding 10mL of a sodium hydroxide solution, controlling the concentration of the sodium hydroxide solution to be 2.0mol/L, centrifuging the mixture after the reaction is finished, centrifuging to remove a supernatant to obtain a polyethyleneimine matrix, and washing the polyethyleneimine matrix for 10 times by using isopropanol, anhydrous ether and distilled water respectively.
The third step: preparing polyethyleneimine modified magnetic graphene oxide: weighing 20mg of magnetic graphene oxide, dissolving the magnetic graphene oxide in 20ml of phosphate buffer solution with the pH value of 7.4, then putting the mixed solution into ultrasonic equipment for ultrasonic mixing, and controlling the ultrasonic mixing time to be 5min so as to uniformly disperse the mixed solution; then sequentially adding 100mg of carbodiimide hydrochloride, 100mg of N-hydroxysuccinimide and 300mg of polyethyleneimine matrix into the mixed solution, uniformly stirring, filtering to obtain a filter cake, repeatedly washing the filter cake for 10 times by using 1000ml of ultrapure water to obtain a polyethyleneimine modified magnetic graphene oxide precipitate, and then carrying out vacuum drying on the polyethyleneimine modified magnetic graphene oxide precipitate, wherein the temperature of the vacuum drying is controlled to be 40-60 ℃, and the drying time is 1 day, so as to finally obtain polyethyleneimine modified magnetic graphene oxide;
the fourth step: preparing magnetic graphene oxide modified by polyethyleneimine loaded with folic acid: weighing 20mg of polyethyleneimine modified magnetic graphene oxide, dissolving in 20ml of ultrapure water, adding 3mg of silane coupling agent and 20mg of folic acid powder, wherein the silane coupling agent is 3-aminopropyl triethoxysilane, then placing the mixed solution into ultrasonic equipment for ultrasonic mixing, and controlling the ultrasonic mixing time to be 2 hours, so as to obtain the polyethyleneimine modified magnetic graphene oxide loaded with folic acid.
It is now known that a β deposition is one of the important pathological features of Alzheimer's Disease (AD), and is a common pathway for the induction of AD for a variety of reasons, and is also a key factor in the development and progression of AD. Therapeutic strategies aimed at abeta clearance are one of the currently mainstream directions of research. The magnetic graphene oxide capable of adsorbing the beta-amyloid has wide application prospect in research and development of medicines for diseases related to the beta-amyloid, and experiments show that the magnetic graphene oxide can realize rapid elimination of the beta-amyloid, does not participate in metabolism, and is an ideal elimination material. In the performance experiment of the mouse model with the Alzheimer's disease, namely the Morris water maze experiment, before and after the application of the invention, the comparison graphs are shown in the attached drawings 3 and 4, the attached drawing 3 is a mouse path without the application of the invention, and the attached drawing 4 is a mouse path without the application of the invention. The invention provides a brand new thought for the research and development of medicaments for beta amyloid related diseases including Alzheimer's disease, and is expected to become a medicament for preventing and treating Alzheimer's disease.
In summary, the magnetic graphene oxide capable of adsorbing amyloid beta and the preparation method thereof provided by the invention comprise magnetic graphene oxide, a polyethyleneimine matrix, a silane coupling agent and folic acid, wherein the polyethyleneimine matrix is synthesized by the silane coupling agent, the graphene oxide is compounded on the polyethyleneimine matrix, and the folic acid is loaded on the graphene oxide; the graphene oxide has a high specific surface area and rich surface functional groups, so that the graphene oxide has certain adsorption capacity, the graphene oxide magnetic material is subjected to graft modification by using polyethyleneimine, and a novel adsorption material obtained by compounding safe folic acid has a good adsorption effect on beta amyloid protein.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.

Claims (6)

1.可吸附β淀粉样蛋白的磁性氧化石墨烯，包括磁性氧化石墨烯、聚乙烯亚胺基体、硅烷偶联剂和叶酸，其特征在于：所述聚乙烯亚胺基体通过硅烷偶联剂合成，氧化石墨烯复合在聚乙烯亚胺基体上，叶酸负载在氧化石墨烯上。1. the magnetic graphene oxide that can adsorb beta amyloid, comprises magnetic graphene oxide, polyethyleneimine matrix, silane coupling agent and folic acid, it is characterized in that: described polyethyleneimine matrix is synthesized by silane coupling agent , graphene oxide is composited on polyethyleneimine matrix, and folic acid is loaded on graphene oxide. 2.如权利要求1所述的可吸附β淀粉样蛋白的磁性氧化石墨烯的制备方法，其特征在于，包括如下步骤：2. the preparation method of the magnetic graphene oxide that can adsorb beta amyloid protein as claimed in claim 1, is characterized in that, comprises the steps: S1：磁性氧化石墨烯的制备；称取氧化石墨烯15-30mg溶于二乙二醇溶液15-30ml中，搅拌均匀，然后将混合液放入超声设备中进行超声波混合，超声波混合的时间控制在26-30min，然后在磁力搅拌的作用下，依次加入醋酸钠150-250mg、六水合氯化铁100-200mg，形成均匀黄色的悬浮液，将悬浮液置于反应釜中，反应釜中的温度档调节到200℃，并使悬浮液在反应釜中以200℃反应8-10h，再将悬浮液置于离心机中，以3000r/min的转数将悬浮液离心5min，然后将沉淀物上方的上清液倒掉得沉淀物，沉淀物依次用无水乙醇100-400ml、蒸馏水200-350ml离心洗涤10-20次后，得到高质量磁性氧化石墨烯沉淀物，再将高质量磁性氧化石墨烯沉淀物进行真空干燥，得磁性氧化石墨烯；S1: preparation of magnetic graphene oxide; 15-30 mg of graphene oxide is weighed and dissolved in 15-30 ml of diethylene glycol solution, stirred evenly, and then the mixed solution is put into ultrasonic equipment for ultrasonic mixing, and the time of ultrasonic mixing is controlled In 26-30min, then under the action of magnetic stirring, add sodium acetate 150-250mg, ferric chloride hexahydrate 100-200mg in turn to form a uniform yellow suspension, place the suspension in the reaction kettle, the The temperature was adjusted to 200°C, and the suspension was reacted in the reactor at 200°C for 8-10h, then the suspension was placed in a centrifuge, and the suspension was centrifuged at 3000r/min for 5min, and then the sediment The upper supernatant is poured out to obtain a precipitate, and the precipitate is washed 10-20 times with 100-400ml of absolute ethanol and 200-350ml of distilled water in turn to obtain a high-quality magnetic graphene oxide precipitate, which is then subjected to high-quality magnetic oxidation. The graphene precipitate is vacuum-dried to obtain magnetic graphene oxide; S2：聚乙烯亚胺基体的制备：S2: Preparation of polyethyleneimine matrix: a聚乙烯亚胺乳液的制备：取质量百分数为20％的聚乙烯亚胺水溶液8～10mL、液体石蜡10～12mL和2mL聚乙烯醇致孔剂进行混合，再向混合液中加入表面活性剂形成混合液，表面活性剂的终浓度为0.04～0.06g/mL，然后将混合液放入超声设备中进行超声波混合，超声波混合的时间控制在2-3min，形成聚乙烯亚胺乳液；a Preparation of polyethyleneimine emulsion: take 8-10 mL of polyethyleneimine aqueous solution with a mass percentage of 20%, 10-12 mL of liquid paraffin and 2 mL of polyvinyl alcohol porogen to mix, and then add surfactant to the mixture A mixed solution is formed, and the final concentration of the surfactant is 0.04-0.06 g/mL, and then the mixed solution is put into an ultrasonic device for ultrasonic mixing, and the time of ultrasonic mixing is controlled at 2-3 min to form a polyethyleneimine emulsion; b预交联聚合反应：取上述聚乙烯亚胺乳液15～20mL，然后在磁力搅拌的作用下，缓慢滴加交联剂15～20mL，预交联2～3小时；b Pre-cross-linking polymerization reaction: take 15-20 mL of the above polyethyleneimine emulsion, then slowly add 15-20 mL of cross-linking agent dropwise under the action of magnetic stirring, and pre-cross-link for 2-3 hours; c交联聚合反应：在磁力搅拌条件下，取上述预交联聚合反应制成的预交联混合物20mL，缓慢滴加5～10mL的氢氧化钠溶液，氢氧化钠溶液的浓度控制在1.0～2.0mol/L，反应结束后对混合物进行离心处理，离心去除上清液，得到聚乙烯亚胺基体；c Cross-linking polymerization reaction: under the condition of magnetic stirring, take 20 mL of the pre-cross-linking mixture prepared by the above-mentioned pre-cross-linking polymerization reaction, slowly add 5-10 mL of sodium hydroxide solution dropwise, and control the concentration of the sodium hydroxide solution at 1.0-1. 2.0mol/L, after the reaction, the mixture is centrifuged, and the supernatant is removed by centrifugation to obtain a polyethyleneimine matrix; S3：制备聚乙烯亚胺修饰的磁性氧化石墨烯：称取磁性氧化石墨烯20-40mg溶于pH7.4的磷酸盐缓冲液20-40ml中，然后将混合液放入超声设备中进行超声波混合，超声波混合的时间控制在5-10min，使之分散均匀；然后向混合液中依次加入碳化二亚胺盐酸盐100-200mg、N-羟基丁二酰亚胺50-117mg、聚乙烯亚胺基体200-400mg，搅拌均匀后用进行过滤，得滤饼，滤饼用超纯水400-1000ml反复洗涤10次，得到得聚乙烯亚胺修饰的磁性氧化石墨烯沉淀物，再将聚乙烯亚胺修饰的磁性氧化石墨烯沉淀物进行真空干燥，最后得聚乙烯亚胺修饰的磁性氧化石墨烯；S3: Preparation of polyethyleneimine-modified magnetic graphene oxide: Weigh 20-40 mg of magnetic graphene oxide and dissolve it in 20-40 ml of pH 7.4 phosphate buffer, and then put the mixture into ultrasonic equipment for ultrasonic mixing , the ultrasonic mixing time is controlled at 5-10min to make it disperse uniformly; then add carbodiimide hydrochloride 100-200mg, N-hydroxysuccinimide 50-117mg, polyethyleneimine to the mixed solution in turn The matrix is 200-400 mg, and it is filtered after stirring to obtain a filter cake. The filter cake is repeatedly washed 10 times with 400-1000 ml of ultrapure water to obtain a polyethyleneimine-modified magnetic graphene oxide precipitate. The amine-modified magnetic graphene oxide precipitate is vacuum-dried, and finally polyethyleneimine-modified magnetic graphene oxide is obtained; S4：制备负载叶酸的聚乙烯亚胺修饰的磁性氧化石墨烯：称取聚乙烯亚胺修饰的磁性氧化石墨烯5-20mg溶于超纯水5-20ml中，再加入硅烷偶联剂1-4mg和叶酸粉末5-20mg，然后将混合液放入超声设备中进行超声波混合，超声波混合的时间控制在1-2小时，即得负载叶酸的聚乙烯亚胺修饰的磁性氧化石墨烯。S4: Preparation of polyethyleneimine-modified magnetic graphene oxide loaded with folic acid: 5-20 mg of polyethyleneimine-modified magnetic graphene oxide was weighed and dissolved in 5-20 ml of ultrapure water, and then silane coupling agent 1- 4 mg of folic acid powder and 5-20 mg of folic acid powder, and then put the mixed solution into ultrasonic equipment for ultrasonic mixing, and the time of ultrasonic mixing is controlled within 1-2 hours to obtain the polyethyleneimine-modified magnetic graphene oxide loaded with folic acid. 3.如权利要求2所述的可吸附β淀粉样蛋白的磁性氧化石墨烯的制备方法，其特征在于，所述S2中，交联剂的加入质量与聚乙烯亚胺乳液的加入质量相同。3. The preparation method of the magnetic graphene oxide capable of adsorbing beta amyloid as claimed in claim 2, wherein in the S2, the added quality of the crosslinking agent is the same as the added quality of the polyethyleneimine emulsion. 4.如权利要求2所述的可吸附β淀粉样蛋白的磁性氧化石墨烯的制备方法，其特征在于，所述S2中，得到聚乙烯亚胺基体需要分别用异丙醇、无水乙醚、蒸馏水洗涤5-10次。4. the preparation method of the magnetic graphene oxide that can adsorb beta amyloid as claimed in claim 2, is characterized in that, in described S2, obtains polyethyleneimine matrix and needs to use respectively isopropanol, anhydrous ether, Wash with distilled water 5-10 times. 5.如权利要求2所述的可吸附β淀粉样蛋白的磁性氧化石墨烯的制备方法，其特征在于，S3的真空干燥的温度控制在40-60℃，干燥时间1-2天。5 . The preparation method of magnetic graphene oxide capable of adsorbing beta amyloid as claimed in claim 2 , wherein the vacuum drying temperature of S3 is controlled at 40-60° C., and the drying time is 1-2 days. 6 . 6.如权利要求2所述的可吸附β淀粉样蛋白的磁性氧化石墨烯的制备方法，其特征在于，所述S4中，硅烷偶联剂为3-氨基丙基三乙氧基硅烷。6 . The preparation method of magnetic graphene oxide capable of adsorbing beta amyloid according to claim 2 , wherein, in S4 , the silane coupling agent is 3-aminopropyltriethoxysilane. 7 .
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