技术领域Technical field
本发明涉及化工技术领域，具体涉及一种基于核苷酸侧基修饰的聚乙烯醇和铜离子自组装形成的超分子聚集体及其制备方法和应用。The invention relates to the field of chemical engineering technology, and specifically relates to a supramolecular aggregate formed by self-assembly of polyvinyl alcohol and copper ions based on nucleotide side group modification and its preparation method and application.
背景技术Background technique
贻贝是一种双壳类动物，它们大部分生活在潮湿裸露的礁石上、甲板上，通过它们坚韧的足丝黏附在各种坚固的基质表面上。而这种贻贝足丝的主要成分为一种黏附蛋白，这种蛋白具有丰富多巴(dopa)氨基酸残基，这些邻苯双酚基团会通过与金属离子螯合配位在黏附蛋白分子间形成交联点，增强足丝的机械性能。Mussels are bivalves that mostly live on moist exposed reefs and decks, adhering to various solid substrate surfaces through their tough byssal threads. The main component of this mussel byssus is an adhesion protein, which is rich in dopa amino acid residues. These catechol groups will coordinate with the adhesion protein molecules by chelating metal ions. Cross-linking points are formed between them to enhance the mechanical properties of the byssus.
而受贻贝启发的聚多巴胺(polydopamine，PDA)的沉积为制造各种材料的多功能性涂层提供了一条有效途径。The deposition of polydopamine (PDA) inspired by mussels provides an effective way to create versatile coatings on a variety of materials.
聚多巴胺的生产原料通常为多巴胺(dopamine)。多巴胺氧化聚合生成聚多巴胺的反应通常需要在碱性的Tris-HCl缓冲溶液或者氨水或者NaOH溶液中反应超过24小时。The raw material for the production of polydopamine is usually dopamine. The reaction of oxidative polymerization of dopamine to produce polydopamine usually requires reaction in an alkaline Tris-HCl buffer solution or ammonia or NaOH solution for more than 24 hours.
公开号为CN 112410098 A的专利说明书采用铜离子和过氧化氢催化多巴胺聚合得到聚多巴胺，具体包括：将盐酸多巴胺粉末加入硫酸铜的水/乙醇混合溶液中，加入的比例为：得到含有多巴胺和硫酸铜的混合液，其中，水/乙醇中，乙醇和水的体积比为1:(2～3)，硫酸铜的水/乙醇混合溶液中，硫酸铜质量与水/乙醇溶液的体积的配比为：3.5～15mg/mL，多巴胺和硫酸铜的混合液中，盐酸多巴胺与硫酸铜的质量比为1:(4～8)；室温下向混合液中滴加过氧化氢，并搅拌，过氧化氢与混合液的体积比为0.03～0.06，搅拌时间为2～3小时，进行多巴胺的氧化聚合反应，得到聚多巴胺混合液。The patent specification with publication number CN 112410098 A uses copper ions and hydrogen peroxide to catalyze the polymerization of dopamine to obtain polydopamine, which specifically includes: adding dopamine hydrochloride powder to a water/ethanol mixed solution of copper sulfate in a proportion of: to obtain a polymer containing dopamine and A mixed solution of copper sulfate, in which the volume ratio of ethanol and water in water/ethanol is 1:(2~3). In a mixed solution of copper sulfate in water/ethanol, the mass of copper sulfate is proportioned to the volume of the water/ethanol solution. The ratio is: 3.5 to 15 mg/mL. In the mixture of dopamine and copper sulfate, the mass ratio of dopamine hydrochloride to copper sulfate is 1: (4 to 8); add hydrogen peroxide dropwise to the mixture at room temperature and stir. The volume ratio of hydrogen peroxide to the mixed liquid is 0.03 to 0.06, and the stirring time is 2 to 3 hours. The oxidative polymerization reaction of dopamine is performed to obtain a polydopamine mixed liquid.
多巴胺在生物体内是多巴(即贻贝足丝的主要成分)的前体，也是酪胺的氧化产物，其也可在碱性介质中氧化聚合形成黑色物质聚多巴胺。聚多巴胺具有独立于基底材质的粘附性，这与贻贝足丝适应不同表面有相似之处。Dopamine is the precursor of dopa (the main component of mussel byssus) in the organism and is also the oxidation product of tyramine. It can also be oxidized and polymerized in alkaline media to form a black substance, polydopamine. Polydopamine has adhesive properties that are independent of the substrate material, similar to the way mussel byssal threads adapt to different surfaces.
酪胺相较于多巴胺，是一种更为廉价的原料，酪胺直接多步氧化得到聚多巴胺具有更高的经济价值。Compared with dopamine, tyramine is a cheaper raw material. The direct multi-step oxidation of tyramine to obtain polydopamine has higher economic value.
聚乙烯醇(PVOH或PVA)是一种水溶性合成聚合物，常用作增稠剂和乳化剂。Polyvinyl alcohol (PVOH or PVA) is a water-soluble synthetic polymer commonly used as a thickener and emulsifier.
而且，PVA溶液可通过反复冻融凝胶化，产生高强度、超纯、生物相容性的水凝胶，方便回收重复利用。Moreover, the PVA solution can be gelled through repeated freezing and thawing to produce a high-strength, ultra-pure, biocompatible hydrogel that is easy to recycle and reuse.
本发明研究发现，聚乙烯醇侧链含有大量羟基，可通过磷酸酯键修饰上核苷酸分子，核苷酸分子可与铜离子螯合，实现酪胺分子的氧化，且不同核苷酸分子会表现出不同的氧化效果。The research of the present invention has found that the side chain of polyvinyl alcohol contains a large number of hydroxyl groups, which can be modified with nucleotide molecules through phosphate bonds. The nucleotide molecules can chelate with copper ions to achieve the oxidation of tyramine molecules, and different nucleotide molecules Will show different oxidation effects.
发明内容Contents of the invention
本发明涉及两个方面的技术问题的解决，其一为核苷酸修饰的聚乙烯醇的合成，二为核苷酸修饰聚乙烯醇与铜离子螯合的超分子聚集体实现了对于酪胺分子的催化氧化得到聚多巴胺产物。The present invention involves the solution of two aspects of technical problems. One is the synthesis of nucleotide-modified polyvinyl alcohol, and the other is the supramolecular aggregate of nucleotide-modified polyvinyl alcohol and copper ion chelation to realize the response to tyramine. Catalytic oxidation of the molecule yields the polydopamine product.
首先，本发明基于前期平台辅助计算的结果，提供了一种基于核苷酸侧基修饰的聚乙烯醇和铜离子自组装形成的超分子聚集体，可实现酪胺氧化制备聚多巴胺，具体的，通过过氧化氢的加入，能够产生类贻贝胶的聚多巴胺涂层。First of all, this invention is based on the previous The results of platform-assisted calculations provide a supramolecular aggregate based on the self-assembly of polyvinyl alcohol and copper ions modified with nucleotide side groups, which can realize the oxidation of tyramine to prepare polydopamine, specifically, through the addition of hydrogen peroxide. , capable of producing mussel glue-like polydopamine coatings.
具体技术方案如下：The specific technical solutions are as follows:
一种基于核苷酸侧基修饰的聚乙烯醇和铜离子自组装形成的超分子聚集体，所述核苷酸为单磷酸腺苷(AMP，A)、单磷酸尿苷(UMP，U)、单磷酸鸟苷(GMP，G)、单磷酸胸苷(CMP，C)中的至少一种；A supramolecular aggregate formed by the self-assembly of polyvinyl alcohol and copper ions based on the modification of nucleotide side groups. The nucleotides are adenosine monophosphate (AMP, A), uridine monophosphate (UMP, U), At least one of guanosine monophosphate (GMP, G) and thymidine monophosphate (CMP, C);
所述核苷酸侧基修饰的聚乙烯醇为所述核苷酸与聚乙烯醇通过磷酸酯化反应生成；The polyvinyl alcohol modified with the side group of the nucleotide is generated by a phosphoric acid esterification reaction between the nucleotide and polyvinyl alcohol;
所述超分子聚集体中，核苷酸分子与铜离子螯合。In the supramolecular aggregate, the nucleotide molecules are chelated with copper ions.
本发明所采用的四种核苷酸分子的结构分别如下式所示：The structures of the four nucleotide molecules used in the present invention are as follows:
本发明合成一种核苷酸修饰的聚乙烯醇，通过与铜离子螯合组装，得到的催化剂在过氧化氢的存在下能够催化酪胺分子的多步氧化得到聚多巴胺。催化剂的合成简单，使用的原料相较以往的工艺有更高的经济价值。The invention synthesizes a nucleotide-modified polyvinyl alcohol, chelates and assembles it with copper ions, and the resulting catalyst can catalyze the multi-step oxidation of tyramine molecules to obtain polydopamine in the presence of hydrogen peroxide. The synthesis of the catalyst is simple, and the raw materials used have higher economic value than previous processes.
本发明还提供了所述的基于核苷酸侧基修饰的聚乙烯醇和铜离子自组装形成的超分子聚集体的制备方法，包括步骤：The invention also provides a method for preparing supramolecular aggregates formed by self-assembly of polyvinyl alcohol modified by nucleotide side groups and copper ions, including the steps:
(1)将所述核苷酸的钠盐溶于水中，得到溶液A；(1) Dissolve the sodium salt of the nucleotide in water to obtain solution A;
将聚乙烯醇溶解于pH＝8.5的Tris缓冲液中，得到溶液B；Dissolve polyvinyl alcohol in Tris buffer with pH=8.5 to obtain solution B;
将溶液A、溶液B混合加热反应得到核苷酸侧基修饰的聚乙烯醇溶液，记为溶液C；Mix solution A and solution B and heat to react to obtain a polyvinyl alcohol solution modified with nucleotide side groups, which is marked as solution C;
(2)将硫酸铜溶于水中，得到溶液D；(2) Dissolve copper sulfate in water to obtain solution D;
将溶液C与溶液D混合，振荡反应得到溶液E，即所述基于核苷酸侧基修饰的聚乙烯醇和铜离子自组装形成的超分子聚集体。Solution C and solution D are mixed and reacted with shaking to obtain solution E, which is a supramolecular aggregate formed by self-assembly of polyvinyl alcohol modified based on nucleotide side groups and copper ions.
上述制备方法中，聚乙烯醇的用量可相对核苷酸足量或过量。In the above preparation method, the amount of polyvinyl alcohol may be sufficient or excessive relative to the nucleotide.
在一优选例中，所述的制备方法，步骤(1)中，Tris缓冲液的浓度为50mM。In a preferred embodiment, in step (1) of the preparation method, the concentration of Tris buffer is 50mM.
在一优选例中，所述的制备方法，步骤(1)中，所述加热反应的温度为50～75℃，时间为3小时。In a preferred embodiment, in step (1) of the preparation method, the temperature of the heating reaction is 50-75°C and the time is 3 hours.
在一优选例中，所述的制备方法，步骤(1)核苷酸和步骤(2)硫酸铜的摩尔用量比为2:1。In a preferred embodiment, in the preparation method, the molar ratio of nucleotides in step (1) and copper sulfate in step (2) is 2:1.
在一优选例中，所述的制备方法，步骤(1)中，所述聚乙二醇为17-99型。In a preferred embodiment, in step (1) of the preparation method, the polyethylene glycol is type 17-99.
在一优选例中，所述的制备方法，步骤(2)中，所述溶液E中铜离子的浓度不大于1mM。In a preferred embodiment, in step (2) of the preparation method, the concentration of copper ions in the solution E is not greater than 1mM.
本发明还提供了所述的基于核苷酸侧基修饰的聚乙烯醇和铜离子自组装形成的超分子聚集体或所述的制备方法制备得到的溶液E在催化酪胺氧化制备聚多巴胺中的应用。The invention also provides the use of the supramolecular aggregate formed by the self-assembly of polyvinyl alcohol and copper ions based on the modification of nucleotide side groups or the solution E prepared by the preparation method in the catalytic oxidation of tyramine to prepare polydopamine. application.
作为一个总的发明构思，本发明还提供了一种催化酪胺氧化制备聚多巴胺的方法，包括：As a general inventive concept, the present invention also provides a method for preparing polydopamine by catalyzing the oxidation of tyramine, including:
在pH＝8.5的Tris-HCl缓冲液环境中，将过氧化氢、酪胺盐酸盐和权利要求1所述的基于核苷酸侧基修饰的聚乙烯醇和铜离子自组装形成的超分子聚集体混合，进行酪胺的催化氧化得到聚多巴胺；或者，In a Tris-HCl buffer environment with pH=8.5, hydrogen peroxide, tyramine hydrochloride and the polyvinyl alcohol modified based on nucleotide side groups according to claim 1 and the supramolecular aggregate formed by the self-assembly of copper ions The mixture is mixed and catalytic oxidation of tyramine is performed to obtain polydopamine; or,
将过氧化氢、酪胺盐酸盐加入到所述的制备方法制备得到的溶液E中混合，进行酪胺的催化氧化得到聚多巴胺。Hydrogen peroxide and tyramine hydrochloride are added to the solution E prepared by the preparation method and mixed, and catalytic oxidation of tyramine is performed to obtain polydopamine.
本发明与现有技术相比，主要优点包括：Compared with the existing technology, the main advantages of the present invention include:
1、含铜的核苷酸修饰聚乙烯醇催化剂制备方法简单，且铜离子用量较少。1. The preparation method of copper-containing nucleotide-modified polyvinyl alcohol catalyst is simple and the amount of copper ions is small.
2、实现了由酪胺到聚多巴胺的直接合成，相比传统工艺的多巴胺原料具有更高的经济价值。2. Achieve direct synthesis from tyramine to polydopamine, which has higher economic value than the dopamine raw material produced by traditional processes.
3、聚乙烯醇有着很好的凝胶特性，可通过多步冻融制成高强度的水凝胶，实现催化剂的可回收再利用。3. Polyvinyl alcohol has good gel properties and can be made into high-strength hydrogel through multi-step freezing and thawing, allowing the catalyst to be recycled and reused.
附图说明Description of the drawings
图1为本发明的基于核苷酸侧基修饰的聚乙烯醇和铜离子自组装形成的超分子聚集体(铜离子螯合的核苷酸修饰聚乙烯醇)的合成示意图(以单磷酸腺苷为例)；Figure 1 is a schematic diagram of the synthesis of supramolecular aggregates (copper ion-chelated nucleotide-modified polyvinyl alcohol) formed by self-assembly of polyvinyl alcohol modified with nucleotide side groups and copper ions according to the present invention (using adenosine monophosphate for example);
图2为本发明酪胺到聚多巴胺的氧化反应机理示意图(以单磷酸腺苷为例)；Figure 2 is a schematic diagram of the oxidation reaction mechanism of tyramine to polydopamine according to the present invention (taking adenosine monophosphate as an example);
图3为四种铜离子螯合的核苷酸修饰聚乙烯醇氧化酪胺能力差异图。Figure 3 is a diagram showing the differences in the ability of four copper ion-chelated nucleotide-modified polyvinyl alcohols to oxidize tyramine.
具体实施方式Detailed ways
下面结合附图及具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments. It should be understood that these examples are only used to illustrate the invention and are not intended to limit the scope of the invention.
下列实施例中未注明具体条件的操作方法，通常按照常规条件，或按照制造厂商所建议的条件。The operating methods without specifying specific conditions in the following examples usually follow conventional conditions or conditions recommended by the manufacturer.
实施例1Example 1
步骤一 单磷酸腺苷修饰聚乙烯醇的合成Step 1 Synthesis of adenosine monophosphate modified polyvinyl alcohol
1)将39.1mg单磷酸腺苷二钠盐溶解于1mL去离子水中，在室温条件下振荡溶解，得到浓度0.1M溶液，此为溶液A。1) Dissolve 39.1 mg of adenosine monophosphate disodium salt in 1 mL of deionized water, shake and dissolve at room temperature to obtain a solution with a concentration of 0.1M, which is solution A.
2)将210mg的聚乙烯醇(17-99型)溶解于50mL的Tris缓冲液(pH＝8.5，50mM)中，在室温条件下振荡溶解，得到浓度4.2％的聚乙烯醇溶液，折合单体浓度约10mM，此为溶液B。2) Dissolve 210 mg of polyvinyl alcohol (type 17-99) in 50 mL of Tris buffer (pH=8.5, 50mM), shake and dissolve at room temperature to obtain a polyvinyl alcohol solution with a concentration of 4.2%, converted into monomers The concentration is about 10mM. This is solution B.
3)将溶液A与溶液B混合，将混合溶液加热至60℃，并保温反应3h，得到腺苷磷酸酯化的聚乙烯醇，此为溶液D。3) Mix solution A and solution B, heat the mixed solution to 60°C, and incubate the reaction for 3 hours to obtain adenosine phosphorylated polyvinyl alcohol, which is solution D.
步骤二 核苷酸修饰聚乙烯醇与铜离子自组装体的制备Step 2: Preparation of self-assembly of nucleotide-modified polyvinyl alcohol and copper ions
1)将12.5mg的五水硫酸铜晶体溶解于1mL去离子水中，在室温条件下振荡溶解，得到浓度0.05M溶液，此为溶液C。1) Dissolve 12.5mg of copper sulfate pentahydrate crystals in 1mL of deionized water, shake and dissolve at room temperature to obtain a solution with a concentration of 0.05M, which is solution C.
2)将溶液C与溶液D混合，室温下振荡反应2h，得到铜离子螯合的单磷酸腺苷修饰聚乙烯醇，此为溶液E。2) Mix solution C and solution D and react with shaking at room temperature for 2 hours to obtain copper ion-chelated adenosine monophosphate modified polyvinyl alcohol, which is solution E.
上述步骤一、步骤二的合成过程如图1所示。The synthesis process of the above steps one and two is shown in Figure 1.
步骤三 酪胺氧化制备聚多巴胺Step 3: Oxidation of tyramine to prepare polydopamine
1)取30wt％的过氧化氢溶液用Tris缓冲液(pH＝8.5，50mM)稀释至0.1M，共10mL，此为溶液F。1) Dilute 30wt% hydrogen peroxide solution to 0.1M with Tris buffer (pH=8.5, 50mM), making a total of 10mL. This is solution F.
2)称取86.8mg酪胺盐酸盐固体，溶解于5mL去离子水中，得到浓度0.1M溶液，此为溶液G。2) Weigh 86.8mg of solid tyramine hydrochloride and dissolve it in 5mL of deionized water to obtain a solution with a concentration of 0.1M. This is solution G.
3)取50mL铜离子螯合的单磷酸腺苷修饰聚乙烯醇，即溶液E于烧杯中，加入35mL的Tris-HCl缓冲液(pH＝8.5，50mM)混匀稀释，取10mL溶液F，取5mL溶液G，混合，进行酪胺的催化氧化得到聚多巴胺，反应机理如图2所示。聚多巴胺的生成可用紫外可见分光光度计监测，其在420nm处有吸收峰值。3) Take 50 mL of copper ion chelated adenosine monophosphate modified polyvinyl alcohol, i.e. solution E, in a beaker, add 35 mL of Tris-HCl buffer (pH=8.5, 50mM), mix and dilute, take 10 mL of solution F, and take 5 mL of solution G, mix, and perform catalytic oxidation of tyramine to obtain polydopamine. The reaction mechanism is shown in Figure 2. The production of polydopamine can be monitored with a UV-visible spectrophotometer, which has an absorption peak at 420 nm.
实施例2Example 2
步骤一 单磷酸尿苷修饰聚乙烯醇的合成Step 1 Synthesis of uridine monophosphate modified polyvinyl alcohol
1)将36.8mg单磷酸尿苷二钠盐溶解于1mL去离子水中，在室温条件下振荡溶解，得到浓度0.1M溶液，此为溶液A。1) Dissolve 36.8 mg of uridine monophosphate disodium salt in 1 mL of deionized water, shake and dissolve at room temperature to obtain a solution with a concentration of 0.1M, which is solution A.
2)将210mg的聚乙烯醇(17-99型)溶解于50mL的Tris缓冲液(pH＝8.5，50mM)中,在室温条件下振荡溶解，得到浓度4.2％的聚乙烯醇溶液，折合单体浓度约10mM，此为溶液B。2) Dissolve 210 mg of polyvinyl alcohol (type 17-99) in 50 mL of Tris buffer (pH=8.5, 50mM), shake and dissolve at room temperature to obtain a polyvinyl alcohol solution with a concentration of 4.2%, converted into monomers The concentration is about 10mM. This is solution B.
3)将溶液A与溶液B混合，将混合溶液加热至60℃，并保温反应3h，得到尿苷磷酸酯化的聚乙烯醇。3) Mix solution A and solution B, heat the mixed solution to 60°C, and incubate the reaction for 3 hours to obtain uridine phosphate-esterified polyvinyl alcohol.
步骤二 核苷酸修饰聚乙烯醇与铜离子自组装体的制备Step 2: Preparation of self-assembly of nucleotide-modified polyvinyl alcohol and copper ions
1)将12.5mg的五水硫酸铜晶体溶解于1mL去离子水中，在室温条件下振荡溶解，得到浓度0.05M溶液，此为溶液C。1) Dissolve 12.5mg of copper sulfate pentahydrate crystals in 1mL of deionized water, shake and dissolve at room temperature to obtain a solution with a concentration of 0.05M, which is solution C.
2)将溶液C与50mL步骤一得到的单磷酸尿苷修饰聚乙烯醇溶液混合，室温下振荡反应2h，得到铜离子螯合的单磷酸尿苷修饰聚乙烯醇。2) Mix solution C with 50 mL of the uridine monophosphate-modified polyvinyl alcohol solution obtained in step 1, and react with shaking at room temperature for 2 hours to obtain copper ion-chelated uridine monophosphate-modified polyvinyl alcohol.
步骤三 酪胺氧化制备聚多巴胺Step 3: Oxidation of tyramine to prepare polydopamine
1)取30wt％的过氧化氢溶液用Tris-HCl缓冲液(pH＝8.5，50mM)稀释至0.1M，共10mL，此为溶液D。1) Take 30wt% hydrogen peroxide solution and dilute it to 0.1M with Tris-HCl buffer (pH=8.5, 50mM), making a total of 10mL. This is solution D.
2)称取86.8mg酪胺盐酸盐固体，溶解于5mL去离子水中，得到浓度0.1M溶液，此为溶液E。2) Weigh 86.8mg of solid tyramine hydrochloride and dissolve it in 5mL of deionized water to obtain a solution with a concentration of 0.1M. This is solution E.
3)取50mL步骤二得到的铜离子螯合的单磷酸尿苷修饰聚乙烯醇于烧杯中，加入35mL的Tris-HCl缓冲液(pH＝8.5，50mM)混匀稀释，反应开始前，将裁剪好的大小合适的微滤膜放置于烧杯中，作为聚多巴胺反应沉积吸附的基底，优选地，可采用聚四氟乙烯或聚丙烯腈微滤膜，然后取10mL溶液D，取5mL溶液E，加入混合，进行酪胺的催化氧化得到聚多巴胺。氧化过程中取清液于紫外可见分光光度计监测，聚多巴胺在420nm处有特征吸收。3) Take 50 mL of the copper ion chelated uridine monophosphate modified polyvinyl alcohol obtained in step 2 into a beaker, add 35 mL of Tris-HCl buffer (pH=8.5, 50mM), mix and dilute, and before starting the reaction, cut Place a good microfiltration membrane of suitable size in a beaker as the substrate for polydopamine reaction deposition and adsorption. Preferably, a polytetrafluoroethylene or polyacrylonitrile microfiltration membrane can be used. Then take 10mL of solution D and 5mL of solution E. Add and mix to perform catalytic oxidation of tyramine to obtain polydopamine. During the oxidation process, take the clear solution and monitor it with a UV-visible spectrophotometer. Polydopamine has a characteristic absorption at 420nm.
实施例3、实施例4Example 3, Example 4
与实施例1、实施例2类似，区别在于分别采用等摩尔的单磷酸鸟苷、单磷酸胸苷替代实施例1的单磷酸腺苷、实施例2的单磷酸尿苷，其余均相同。Similar to Example 1 and Example 2, the difference is that equimolar amounts of guanosine monophosphate and thymidine monophosphate are used instead of adenosine monophosphate and uridine monophosphate in Example 1 and uridine monophosphate respectively, and the rest are the same.
实施例1～4制备的四种铜离子螯合的核苷酸修饰聚乙烯醇氧化酪胺速率差异如图3所示，单磷酸腺苷(AMP，A)修饰的超分子聚集体具有最佳的催化效率。The differences in the oxidation rates of tyramine among the four types of copper ion-chelated nucleotide-modified polyvinyl alcohol prepared in Examples 1 to 4 are shown in Figure 3. The supramolecular aggregate modified with adenosine monophosphate (AMP, A) has the best performance. catalytic efficiency.
此外应理解，在阅读了本发明的上述描述内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。In addition, it should be understood that after reading the above description of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of this application.
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| CN104870022A (en)* | 2012-04-02 | 2015-08-26 | 现代治疗公司 | protein production in vivo |
| CN108341962A (en)* | 2017-01-25 | 2018-07-31 | 翁秋梅 | A kind of dynamic aggregation object and its application |
| CN112410098A (en)* | 2020-11-29 | 2021-02-26 | 清华大学 | A kind of preparation method and application of copper-doped polydopamine nanoparticles |
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104870022A (en)* | 2012-04-02 | 2015-08-26 | 现代治疗公司 | protein production in vivo |
| CN108341962A (en)* | 2017-01-25 | 2018-07-31 | 翁秋梅 | A kind of dynamic aggregation object and its application |
| CN112410098A (en)* | 2020-11-29 | 2021-02-26 | 清华大学 | A kind of preparation method and application of copper-doped polydopamine nanoparticles |
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