WO2023045115A1 - High-stability self-linked mxene nanosheet, preparation method therefor, and application thereof - Google Patents

High-stability self-linked mxene nanosheet, preparation method therefor, and application thereof Download PDF

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WO2023045115A1
WO2023045115A1 PCT/CN2021/137978 CN2021137978W WO2023045115A1 WO 2023045115 A1 WO2023045115 A1 WO 2023045115A1 CN 2021137978 W CN2021137978 W CN 2021137978W WO 2023045115 A1 WO2023045115 A1 WO 2023045115A1
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mxene
nanosheets
layer
ions
sulfonic acid
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都展宏
沙葆凝
赵生卓
程宇航
顾敏铃
毕国强
王立平
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中国科学院深圳先进技术研究院
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    • C01B32/00—Carbon; Compounds thereof
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    • C01B32/921—Titanium carbide
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    • A61N1/05—Electrodes for implantation or insertion into the body, e.g. heart electrode
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
    • A61N1/00—Electrotherapy; Circuits therefor
    • A61N1/02—Details
    • A61N1/04—Electrodes
    • A61N1/05—Electrodes for implantation or insertion into the body, e.g. heart electrode
    • A61N1/0551—Spinal or peripheral nerve electrodes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • C01B32/914—Carbides of single elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • C01B32/914—Carbides of single elements
    • C01B32/949—Tungsten or molybdenum carbides

Abstract

A high-stability self-linked MXene nanosheet, a preparation method therefor, and an application thereof. Specifically provided is a surface-modified MXene nanosheet. The MXene nanosheet comprises Na ions and a sulfonic acid intercalation layer, and the surface thereof comprises a polydopamine layer and a polyethylene dioxythiophene layer, the polydopamine layer and the polyethylene dioxythiophene layer being sequentially provided; specifically, the polydopamine layer is polymerized on the surface of the MXene nanosheet comprising Na ions and a sulfonic acid intercalation layer, then the polyethylene dioxythiophene layer is polymerized in situ. Modifications to the MXene nanosheet interact with one another, and various properties, such as the physical and chemical stability, film-forming ability, and biocompatibility, of the MXene nanosheet in a biological body are enhanced. Therefore, the MXene nanosheet can be used as an electrode modification material, a peripheral nerve cell repair material, a neural electrode lead, a central nervous electrode site, and so on.

Description

一种高稳定的自连结MXene纳米片及其制备方法和应用A kind of highly stable self-linked MXene nanosheet and its preparation method and application 技术领域technical field
本发明属于生物用材料领域，具体涉及一种高稳定的自连结MXene纳米片及其制备方法和应用。The invention belongs to the field of biological materials, and in particular relates to a highly stable self-connected MXene nanosheet and its preparation method and application.
背景技术Background technique
从石墨机械剥离的石墨烯的奇异特性表明，通过将三维材料的厚度减薄到二维原子薄片，可以深刻地调整电学、光学、机械和电化学特性，这一突破性发现极大地促进了对石墨烯以外的高质量二维材料的合成和表征的研究。MXenes是一类新的二维材料，已经在许多方面引起了越来越多的研究关注，站在二维材料界的前沿。MXene材料是一类层状二维碳/氮化物，通常通过化学蚀刻法抽离其母相材料MAX相(Mn+1AXn，n=1-3，M为过渡金属，A为IIIA或IVA族元素，X为C或N)中的A层原子层得到。到目前为止，已经通过实验合成了30多个MXene材料，预计还有更多（数百个）在热力学上是稳定的。因此，与其他二维材料不同，MXenes本身是一大类材料，具有高导电性、体积电容和电磁干扰屏蔽性能等多种特性。这些出色的表现表明MXenes 在电化学储能、透明导电电极和薄膜晶体管的电触点、电磁干扰屏蔽、光电探测器、传感等许多应用中都有前景。这些应用的核心在于制造先进的基于MXene架构，包括纳米结构电极、高质量连续薄膜/触点，以及功能器件的图案。The singular properties of graphene mechanically exfoliated from graphite demonstrate that electrical, optical, mechanical, and electrochemical properties can be profoundly tuned by reducing the thickness of a three-dimensional material to a two-dimensional atomically thin sheet, a breakthrough discovery that greatly advances the understanding of Research on the synthesis and characterization of high-quality two-dimensional materials other than graphene. MXenes, a new class of two-dimensional materials, have attracted more and more research attention in many aspects, standing at the forefront of the two-dimensional materials community. MXene material is a kind of layered two-dimensional carbon/nitride, and its parent phase material MAX phase (Mn+1AXn, n=1-3, M is transition metal, A is IIIA or IVA group element) is usually extracted by chemical etching , X is obtained from the atomic layer of layer A in C or N). So far, more than 30 MXene materials have been experimentally synthesized, and many more (hundreds) are expected to be thermodynamically stable. Therefore, unlike other 2D materials, MXenes themselves are a large class of materials with various properties such as high electrical conductivity, bulk capacitance, and electromagnetic interference shielding properties. These outstanding performances suggest that MXenes are promising in many applications such as electrochemical energy storage, transparent conductive electrodes and electrical contacts of thin-film transistors, electromagnetic interference shielding, photodetectors, and sensing. Central to these applications lies the fabrication of advanced MXene-based architectures, including nanostructured electrodes, high-quality continuous films/contacts, and patterning of functional devices.
截止到目前为止，MXene材料在生物工程学领域的应用主要集中在载药，导电聚合物和电极修饰上，而在神经科学领域少有应用。其原因主要有MXene容易氧化和在组织内扩散和生物相容性低使得MXene很难应用在复杂的神经系统。So far, the application of MXene materials in the field of bioengineering is mainly focused on drug loading, conductive polymers and electrode modification, while there are few applications in the field of neuroscience. The main reasons are that MXene is easy to oxidize and diffuse in tissues and has low biocompatibility, which makes it difficult to apply MXene to the complex nervous system.
技术问题technical problem
现有技术对MXene材料的改性通常集中于导电性、分散性和稳定性等某一特性的改进，尤其是稳定性，常规的改性方式如引入败血酸钠、离子分散剂等，这些改性方式是对材料的边缘晶格缺陷进行钝化，而这种改性方式会引起其他性质的降低。The modification of MXene materials in the prior art usually focuses on the improvement of certain characteristics such as conductivity, dispersibility and stability, especially stability. Conventional modification methods such as the introduction of sodium septicate, ionic dispersants, etc., these The modification method is to passivate the edge lattice defects of the material, and this modification method will cause the reduction of other properties.
公布号为CN 111447968 A的专利公开了一种使用2D金属碳化物和氮化物（MXene）的植入型器件，具体公开了一种包含MXene的接触材料，所述MXene上还包含导电聚合物，如聚(3 ,4-乙撑二氧噻吩)或类似物。但是该专利中，并未公开如何制备导电聚合物，聚乙烯二氧噻吩通常是通过三种方法获得，化学聚合、电聚合和光聚合。其中电聚合和光聚合并不能实现纳米片表面修饰，只能用于镀层、镀膜或体积成形等。然而，在MXene上原位聚合乙烯二氧噻吩是困难的，因为常规乙烯二氧噻吩化学聚合需要利用包含三价铁离子在内的氧化性的催化剂，而由于MXene有较强的还原性，所以会破坏MXene。The patent with publication number CN 111447968 A discloses an implantable device using 2D metal carbides and nitrides (MXene), specifically discloses a contact material containing MXene, which also contains a conductive polymer, Such as poly(3,4-ethylenedioxythiophene) or similar. However, this patent does not disclose how to prepare conductive polymers. Polyethylenedioxythiophene is usually obtained by three methods, chemical polymerization, electropolymerization and photopolymerization. Among them, electropolymerization and photopolymerization cannot realize the surface modification of nanosheets, and can only be used for coating, coating or volume forming. However, in-situ polymerization of ethylenedioxythiophene on MXene is difficult, because the conventional chemical polymerization of ethylenedioxythiophene requires the use of oxidative catalysts including ferric ions, and because MXene has strong reducibility, so Will destroy MXene.
公布号为CN 109096754 A的专利公开了一种MXene-聚多巴胺复合材料，其通过将MXene和多巴胺进行反应获得原位聚合的聚多巴胺，但是该方案由于直接在MXene表面进行聚合，聚合活性弱导致聚合时间较长，需要24小时。另外聚合后的多巴胺置于MXene表面，和外界直接接触，很容易受到过于强烈的氧化环境的影响导致结构破坏，使其原本能够增加稳定性的聚多巴胺层维持稳定性的效果部分丧失。The publication number is CN Patent No. 109096754 A discloses a MXene-polydopamine composite material, which obtains in-situ polymerized polydopamine by reacting MXene and dopamine. However, due to direct polymerization on the surface of MXene, the polymerization activity is weak and the polymerization time is relatively long. , takes 24 hours. In addition, the polymerized dopamine is placed on the surface of MXene and is in direct contact with the outside world. It is easily affected by an overly strong oxidative environment and causes structural damage, which partially loses the stability-maintaining effect of the polydopamine layer that can increase stability.
技术解决方案technical solution
本发明的目的在于针对现有技术的不足和缺陷，提出一种可以适应复杂的体内环境的MXene纳米片，其同时强化了MXene纳米片在生物体内的物理化学稳定性、成膜能力、生物相容性等多种性质。The purpose of the present invention is to address the deficiencies and defects of the prior art, and propose a MXene nanosheet that can adapt to the complex in vivo environment, which simultaneously strengthens the physical and chemical stability, film-forming ability, and biological phase of the MXene nanosheet in the living body. Capacitance and other properties.
本发明一个方面提供了一种表面改性的MXene纳米片，所述MXene纳米片中具有Na离子和磺酸插层，同时表面还具有聚多巴胺层和聚乙烯二氧噻吩层。One aspect of the present invention provides a surface-modified MXene nanosheet, the MXene nanosheet has Na ions and sulfonic acid intercalation, and the surface also has a polydopamine layer and a polyethylenedioxythiophene layer.
在本发明的技术方案中，聚乙烯二氧噻吩层选自聚(3 ,4-乙烯二氧噻吩)层，或包含聚(3 ,4-乙烯二氧噻吩)的聚合物的层。In the technical scheme of the present invention, the polyethylenedioxythiophene layer is selected from poly(3 , 4-ethylenedioxythiophene) layer, or a layer comprising a polymer of poly(3,4-ethylenedioxythiophene).
在本发明的技术方案中，Na离子和磺酸插层通过以下方法获得：将二维MXene纳米片分散在含有钠离子的碱性溶液中，混合获得Na离子插层的二维MXene纳米片；将Na离子插层的二维MXene纳米片与磺胺酸重氮盐反应，得到Na离子和磺酸的插层改性的MXene纳米片。In the technical solution of the present invention, Na ion and sulfonic acid intercalation are obtained by the following method: two-dimensional MXene nanosheets are dispersed in an alkaline solution containing sodium ions, and mixed to obtain two-dimensional MXene nanosheets intercalated by Na ions; The 2D MXene nanosheets intercalated with Na ions were reacted with sulfonamide diazonium salt to obtain intercalated modified MXene nanosheets of Na ions and sulfonic acid.
在本发明的技术方案中，聚多巴胺层和聚乙烯二氧噻吩层依次设置。In the technical solution of the present invention, the polydopamine layer and the polyethylene dioxythiophene layer are arranged in sequence.
在本发明的技术方案中，聚乙烯二氧噻吩层占表面改性的MXene纳米片总质量的0.01%-50%，例如，0.01%、0.02%、0.03%、0.04%、0.05%、0.06%、0.07%、0.08%、0.09%、0.1%、0.2%、0.3%、0.4%、0.5%、0.6%、0.7%、0.8%、0.9%、1%、2%、3%、4%、5%、6%、7%、8%、9%、10%、11%、12%、13%、14%、15%、16%、17%、18%、19%、20%、21%、22%、23%、24%、25%、26%、27%、28%、29%、30%、31%、32%、33%、34%、35%、36%、37%、38%、39%、40%、41%、42%、43%、44%、45%、46%、47%、48%、49%。In the technical solution of the present invention, the polyethylene dioxythiophene layer accounts for 0.01%-50% of the total mass of the surface-modified MXene nanosheets, for example, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06% , 0.07%, 0.08%, 0.09%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, 5 %, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38% , 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%.
在本发明的技术方案中，先通过Na离子对MXene进行插层，然后利用磺酸插层剥离MXene到单层或少层，然后再在MXene纳米片表面聚合多巴胺层，最终再在原位聚合乙烯二氧噻吩。In the technical solution of the present invention, Na ions are used to intercalate MXene first, then use sulfonic acid intercalation to peel off MXene to a single layer or few layers, then polymerize the dopamine layer on the surface of MXene nanosheets, and finally polymerize in situ Ethylenedioxythiophene.
在本发明的技术方案中，原位聚合聚多巴胺层为通过将多巴胺或进行预聚的多巴胺与具有Na离子和磺酸插层的MXene纳米片混合反应获得In the technical solution of the present invention, the in-situ polymerized polydopamine layer is obtained by mixing dopamine or prepolymerized dopamine with MXene nanosheets with Na ions and sulfonic acid intercalation
在本发明的技术方案中，预聚的多巴胺通过将多巴胺分散在碱性缓冲液中获得。In the technical solution of the present invention, prepolymerized dopamine is obtained by dispersing dopamine in alkaline buffer.
在本发明的技术方案中，聚乙烯二氧噻吩层通过将乙烯二氧噻吩进行原位聚合获得。优选地，乙烯二氧噻吩选自3,4-乙烯二氧噻吩。In the technical solution of the present invention, the polyethylenedioxythiophene layer is obtained by in-situ polymerization of ethylenedioxythiophene. Preferably, ethylenedioxythiophene is selected from 3,4-ethylenedioxythiophene.
在本发明的技术方案中，聚乙烯二氧噻吩层的聚合过程中不添加具有氧化性的催化剂。所述催化剂例如包含三价铁离子的催化剂。In the technical solution of the present invention, no oxidizing catalyst is added during the polymerization of the polyethylene dioxythiophene layer. The catalyst is, for example, a catalyst containing ferric ions.
在本发明的技术方案中，所述的MXene纳米片的基片选自Ti 3C 2、Ti 2C、Nb 2C、V 2C、Mo 2C。 In the technical solution of the present invention, the substrate of the MXene nanosheet is selected from Ti 3 C 2 , Ti 2 C, Nb 2 C, V 2 C and Mo 2 C.
在本发明的技术方案中，所述表面改性的MXene纳米片通过以下方法获得：In the technical scheme of the present invention, the MXene nanosheets of the surface modification are obtained by the following methods:
1）Na离子和磺酸的插层改性：将二维MXene纳米片分散在含有钠离子的碱性溶液中，混合获得Na离子插层的二维MXene纳米片；将Na离子插层的二维MXene纳米片与磺胺酸重氮盐反应，得到Na离子和磺酸的插层改性的MXene纳米片；1) Intercalation modification of Na ions and sulfonic acid: Disperse two-dimensional MXene nanosheets in an alkaline solution containing sodium ions, and mix to obtain two-dimensional MXene nanosheets intercalated with Na ions; two-dimensional MXene nanosheets intercalated with Na ions Reaction of dimensional MXene nanosheets with sulfanilic acid diazonium salts to obtain intercalation modified MXene nanosheets of Na ions and sulfonic acid;
2）利用迈克尔加成反应聚合多巴胺：将多巴胺在碱性缓冲溶液中进行预聚合，然后将预聚溶液与Na离子和磺酸的插层改性的MXene纳米片混合反应，得到具有聚合多巴胺层且Na离子和磺酸的插层改性的MXene纳米片；2) Polymerization of dopamine by Michael addition reaction: prepolymerization of dopamine in alkaline buffer solution, and then mixing the prepolymerization solution with Na ion and sulfonic acid intercalation modified MXene nanosheets to obtain a polymerized dopamine layer And Na ion and sulfonic acid intercalation modified MXene nanosheets;
3）进一步原位聚合获得非氧化性聚乙烯二氧噻吩层：将乙烯二氧噻吩原料分散在水溶性有机溶剂中，并加入步骤2）所得MXene纳米片的水溶液中，在不包含氧化剂的条件下进行获得具有聚合多巴胺层和非氧化性聚乙烯二氧噻吩层，且Na离子和磺酸的插层改性的MXene纳米片。3) Further in-situ polymerization to obtain a non-oxidative polyethylenedioxythiophene layer: disperse the ethylenedioxythiophene raw material in a water-soluble organic solvent, and add it to the aqueous solution of MXene nanosheets obtained in step 2). MXene nanosheets with a polymerized dopamine layer and a non-oxidative polyethylenedioxythiophene layer, and intercalation modification of Na ions and sulfonic acid were obtained.
本发明另一个方面提供了一种表面改性的MXene纳米片的制备方法，其包括以下步骤：Another aspect of the present invention provides a method for preparing surface-modified MXene nanosheets, comprising the following steps:
1）Na离子和磺酸的插层改性：将二维MXene纳米基片分散在含有钠离子的碱性溶液中，混合获得Na离子插层的二维MXene纳米片；将Na离子插层的二维MXene纳米片与磺胺酸重氮盐反应，得到Na离子和磺酸的插层改性的MXene纳米片；1) Intercalation modification of Na ions and sulfonic acid: Disperse the two-dimensional MXene nanosheets in an alkaline solution containing sodium ions, and mix to obtain two-dimensional MXene nanosheets intercalated with Na ions; Two-dimensional MXene nanosheets were reacted with sulfanilic acid diazonium salt to obtain intercalation modified MXene nanosheets of Na ions and sulfonic acid;
2）利用迈克尔加成反应聚合多巴胺：将多巴胺在碱性缓冲溶液中进行预聚合，然后将预聚溶液与Na离子和磺酸的插层改性的MXene纳米片混合反应，得到具有聚合多巴胺层且Na离子和磺酸的插层改性的MXene纳米片；2) Polymerization of dopamine by Michael addition reaction: prepolymerization of dopamine in alkaline buffer solution, and then mixing the prepolymerization solution with Na ion and sulfonic acid intercalation modified MXene nanosheets to obtain a polymerized dopamine layer And Na ion and sulfonic acid intercalation modified MXene nanosheets;
3）进一步原位聚合获得非氧化性聚乙烯二氧噻吩层：将乙烯二氧噻吩原料分散在水溶性有机溶剂中，并加入步骤2）所得MXene纳米片的水溶液中，在不包含氧化剂的条件下进行获得具有聚合多巴胺层和非氧化性聚乙烯二氧噻吩层，且Na离子和磺酸的插层改性的MXene纳米片。3) Further in-situ polymerization to obtain a non-oxidative polyethylenedioxythiophene layer: disperse the ethylenedioxythiophene raw material in a water-soluble organic solvent, and add it to the aqueous solution of MXene nanosheets obtained in step 2). MXene nanosheets with a polymerized dopamine layer and a non-oxidative polyethylenedioxythiophene layer, and intercalation modification of Na ions and sulfonic acid were obtained.
在本发明的技术方案中，其中步骤1）中所述二维MXene纳米基片选自Ti 3C 2、Ti 2C、Ta 4C 3、Nb 2C、V 2C或Mo 2C中的其中一种或多种的组合。 In the technical solution of the present invention, the two-dimensional MXene nano-substrate in step 1) is selected from Ti 3 C 2 , Ti 2 C, Ta 4 C 3 , Nb 2 C, V 2 C or Mo 2 C One or more combinations of them.
在本发明的技术方案中，其中步骤1）中所述二维MXene纳米基片通过将MAX相陶瓷通过HF酸进行选择性刻蚀获得。In the technical solution of the present invention, the two-dimensional MXene nano-substrate in step 1) is obtained by selectively etching the MAX phase ceramics with HF acid.
在本发明的技术方案中，其中步骤1）中所述MAX相陶瓷选自Ti 3AlC 2、Ti 2AlC、Nb 2AlC、V 2AlC、Mo 2AlC、Ta 4AlC 3中的其中一种或多种的组合。 In the technical solution of the present invention, the MAX phase ceramics in step 1) are selected from one of Ti 3 AlC 2 , Ti 2 AlC, Nb 2 AlC, V 2 AlC, Mo 2 AlC, and Ta 4 AlC 3 or a combination of several.
在本发明的技术方案中，其中步骤1）中含有钠离子的碱性溶液选自NaOH溶液、Na 2CO 3溶液、NaHCO 3溶液、KOH溶液、K 2CO 3溶液、KHCO 3溶液。 In the technical solution of the present invention, the alkaline solution containing sodium ions in step 1) is selected from NaOH solution, Na 2 CO 3 solution, NaHCO 3 solution, KOH solution, K 2 CO 3 solution, KHCO 3 solution.
在本发明的技术方案中，其中步骤1）中钠离子插层后采用水冲洗至中性，例如冲洗至pH值为7-8。In the technical solution of the present invention, after sodium ion intercalation in step 1), water is used to wash to neutrality, for example, to a pH value of 7-8.
在本发明的技术方案中，其中步骤1）中磺胺酸重氮盐通过将磺胺酸、盐酸与亚硝酸钠反应获得，优选地，上述反应在-5~10℃条件下反应。In the technical solution of the present invention, the diazonium salt of sulfanilic acid in step 1) is obtained by reacting sulfanilic acid, hydrochloric acid and sodium nitrite, preferably, the above reaction is carried out at -5~10°C.
在本发明的技术方案中，其中步骤1）中磺胺酸重氮盐与钠离子插层MXene纳米片在0-5℃下反应2-10小时，离心去除分离大的聚集体和未反应的颗粒。In the technical solution of the present invention, in step 1), sulfanilic acid diazonium salt and sodium ion intercalated MXene nanosheets are reacted at 0-5°C for 2-10 hours, and centrifuged to remove and separate large aggregates and unreacted particles .
在本发明的技术方案中，其中步骤2）中碱性缓冲溶液的pH值选自8.5-9。In the technical solution of the present invention, wherein the pH value of the alkaline buffer solution in step 2) is selected from 8.5-9.
在本发明的技术方案中，其中步骤2）中多巴胺与Na离子和磺酸的插层改性的MXene纳米片的质量比为1:5-20，例如1:6、1:7、1:8、1:9、1:10、1:11、1:12、1:13、1:14、1:15、1:16、1:17、1:18、1:19、1:20。In the technical scheme of the present invention, the mass ratio of dopamine to Na ion and sulfonic acid intercalation modified MXene nanosheets in step 2) is 1:5-20, such as 1:6, 1:7, 1: 8. 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, 1:20.
在本发明的技术方案中，其中步骤3）中乙烯二氧噻吩原料选自3,4-乙烯二氧噻吩。In the technical solution of the present invention, the raw material of ethylenedioxythiophene in step 3) is selected from 3,4-ethylenedioxythiophene.
在本发明的技术方案中，其中步骤3）中乙烯二氧噻吩原料与具有聚合多巴胺层且Na离子和磺酸的插层改性的MXene纳米片的比例为每1克具有聚合多巴胺层且Na离子和磺酸的插层改性的MXene纳米片加入0.1克-15克乙烯二氧噻吩原料，例如0.5克、1克、2克、3克、4克、5克、6克、7克、8克、9克、10克、11克、12克、13克、14克、15克。In the technical scheme of the present invention, the ratio of ethylenedioxythiophene raw material in step 3) to the MXene nanosheets having a polymerized dopamine layer and the intercalation modification of Na ions and sulfonic acid is that per 1 gram has a polymerized dopamine layer and Na MXene nanosheets modified by intercalation of ions and sulfonic acids Add 0.1 g-15 g of ethylenedioxythiophene raw materials, such as 0.5 g, 1 g, 2 g, 3 g, 4 g, 5 g, 6 g, 7 g, 8 grams, 9 grams, 10 grams, 11 grams, 12 grams, 13 grams, 14 grams, 15 grams.
在本发明的技术方案中，其中步骤3）反应中不添加氧化剂。In the technical solution of the present invention, no oxidizing agent is added in the step 3) reaction.
本发明再一个方面提供了所述表面改性的MXene纳米片作为电极修饰材料、外周神经的细胞修复材料、神经电极的导线、中枢神经电极的位点的用途。Another aspect of the present invention provides the use of the surface-modified MXene nanosheets as electrode modification materials, peripheral nerve cell repair materials, nerve electrode wires, and central nerve electrode sites.
在本发明的技术方案中，所述的电极修饰材料选自用于神经的电极的修饰材料，例如用于中枢神经以及外周神经的电极修饰。In the technical solution of the present invention, the electrode modification material is selected from materials for modifying electrodes of nerves, for example, for modifying electrodes of central nerves and peripheral nerves.
本发明再一个方面提供了一种生物用电极，所述电极表面具有上述表面改性的MXene纳米片作为电极表面修饰材料。Another aspect of the present invention provides a biological electrode, the surface of the electrode has the above-mentioned surface-modified MXene nanosheet as the electrode surface modification material.
本发明再一个方面提供了一种分散体系，所述分散体系中包含上述表面改性的MXene纳米片以及分散基质，所述分散基质选自水凝胶、弹性体、溶剂。Another aspect of the present invention provides a dispersion system, which includes the above-mentioned surface-modified MXene nanosheets and a dispersion matrix, and the dispersion matrix is selected from hydrogels, elastomers, and solvents.
在本发明的技术方案中，所述水凝胶选自聚丙烯酰胺水凝胶、聚乙烯醇水凝胶、玻尿酸、玻尿酸衍生物、胶原、明胶、纤网蛋白、纤维蛋白原、藻酸盐、几丁聚醣中的至少一种。溶剂选自水溶液、有机溶液。In the technical solution of the present invention, the hydrogel is selected from polyacrylamide hydrogel, polyvinyl alcohol hydrogel, hyaluronic acid, hyaluronic acid derivatives, collagen, gelatin, fibrin, fibrinogen, alginate , at least one of chitosan. The solvent is selected from aqueous solution and organic solution.
在本发明的技术方案中，所述分散体系中表面改性的MXene纳米片的浓度为0.1-10mg/mL。例如0.5 mg/mL、1 mg/mL、2 mg/mL、3 mg/mL、4 mg/mL、5 mg/mL、6mg/mL、7mg/mL、8 mg/mL、9 mg/mL、10 mg/mL。In the technical solution of the present invention, the concentration of the surface-modified MXene nanosheets in the dispersion system is 0.1-10 mg/mL. For example 0.5 mg/mL, 1 mg/mL, 2 mg/mL, 3 mg/mL, 4 mg/mL, 5 mg/mL, 6 mg/mL, 7 mg/mL, 8 mg/mL, 9 mg/mL, 10 mg/mL.
有益效果Beneficial effect
1、本发明的MXene材料针对需要用在生物体内，化学环境复杂容易氧化，导致电学性能变化大的缺陷，钝化了MXene边界处的晶格缺陷，并利用活跃的氧化还原活性实现抗氧化性的提高，使其更适合生物体内化学环境，能够维持电学性能稳定。具体进行了小鼠体内植入实验，经证实在6周内材料附近的组织健康，并未发生氧化应激，同时可观察到一定的新生血管。1. The MXene material of the present invention aims at the defects that need to be used in living organisms, the complex chemical environment is easy to oxidize, resulting in large changes in electrical properties, passivates the lattice defects at the boundaries of MXene, and uses active redox activity to achieve oxidation resistance The improvement makes it more suitable for the chemical environment in vivo and can maintain the stability of electrical properties. Specifically, the implantation experiment in mice was carried out, and it was confirmed that within 6 weeks, the tissue near the material was healthy, no oxidative stress occurred, and certain new blood vessels could be observed at the same time.
2、针对体积性的生物用途如电极，印刷电子等方面，需要生物材料具有低组织扩散性以及抗细胞侵蚀的能力，而本发明MXene材料细胞的具有优异的组织粘附能力，降低了组织扩散性，非常适合用于体积性的生物用途。具体进行了小鼠体内植入实验，经证实在6周内材料和组织的边界清晰并没有发生明显的组织扩散。此外我们进行了凝胶粘性测试，通过将本发明的纳米片混合在聚丙烯酰胺水凝胶内，对比测试了未添加MXene的聚丙烯酰胺水凝胶，和未聚合乙烯二氧噻吩的水凝胶的粘性。结果显示本添加了发明的纳米片的聚丙烯酰胺水凝胶具有最强的粘性和时间尺度上的粘性稳定性。2. For volumetric biological applications such as electrodes and printed electronics, biological materials are required to have low tissue diffusivity and the ability to resist cell erosion, while the cells of the MXene material of the present invention have excellent tissue adhesion ability, which reduces tissue diffusion Very suitable for bulky biological use. In vivo implantation experiments in mice were carried out, and it was confirmed that within 6 weeks, the boundary between the material and the tissue was clear and no obvious tissue diffusion occurred. In addition, we conducted a gel viscosity test. By mixing the nanosheets of the present invention in polyacrylamide hydrogel, we compared the hydrogel of polyacrylamide hydrogel without MXene and unpolymerized ethylenedioxythiophene. The stickiness of the glue. The results show that the polyacrylamide hydrogel added with the inventive nanosheet has the strongest viscosity and the viscosity stability on the time scale.
3、本发明不用引入石墨烯或更改分散体系，就可以实现在水凝胶、弹性体等分散体系内的稳定性和分散性。3. The present invention can achieve stability and dispersibility in dispersion systems such as hydrogels and elastomers without introducing graphene or changing the dispersion system.
4、本发明的MXene不同于现有技术中MXene的成膜能力，本发明MXene材料之间形成了依靠共价键连接的稳定结构，而现有技术中MXene是靠片层的重新堆叠和片层间的范德华力实现的，所以本发明的MXene具有更好的水中的成膜稳定性。4. The MXene of the present invention is different from the film-forming ability of MXene in the prior art. The MXene materials of the present invention form a stable structure that relies on covalent bonds, while the MXene in the prior art relies on the re-stacking of sheets and sheets. The van der Waals force between layers is realized, so the MXene of the present invention has better film-forming stability in water.
5、本发明的MXene进一步增加了材料的生物相容性和过氧化物酶活性，能够实现增加细胞粘附，降低细胞活性氧并促进神经细胞迁移和分化的效果。我们进行了PC12、Row264.7、S16细胞培养，经证实本发明的MXene 材料可以降低细胞的氧化应激，促进细胞的粘附、扩散、分裂分化。5. The MXene of the present invention further increases the biocompatibility and peroxidase activity of the material, and can achieve the effects of increasing cell adhesion, reducing cellular reactive oxygen species and promoting nerve cell migration and differentiation. We have carried out PC12, Row264.7, S16 cell culture, confirmed that the MXene of the present invention The material can reduce the oxidative stress of cells and promote cell adhesion, diffusion, division and differentiation.
6、本发明材料从各个方面同时强化了MXene纳米片在生物体内的物理化学稳定性，成膜能力，生物相容性等多种性质，使其可以用于中枢神经以及外周神经的电极修饰，可以用于制作中枢以及外周神经电极的导线，还可以用于外周神经的细胞修复。在工作中可以有效的抵御体内环境的氧化压力和细胞侵蚀。6. The material of the present invention simultaneously strengthens the physical and chemical stability of MXene nanosheets in vivo, film-forming ability, biocompatibility and other properties from various aspects, so that it can be used for electrode modification of central and peripheral nerves, It can be used to make wires for central and peripheral nerve electrodes, and can also be used for cell repair of peripheral nerves. At work, it can effectively resist the oxidative stress and cell erosion of the internal environment.
7、本发明的MXene具有非线性的降解速率。在材料工作的后期，材料将加速降解，具有更好的自去除能力，这在可降解电极领域有很好的前景。7. The MXene of the present invention has a non-linear degradation rate. In the later stage of material work, the material will accelerate degradation and have better self-removal ability, which has a good prospect in the field of degradable electrodes.
8、本发明的MXene各层修饰间进行协同，获得了更适合在体内复杂高稳定性、低组织内扩散以及高生物相容性的复合材料。首先，磺酸和Na离子插层提高了了纳米片表面的电子活跃，促进了随后进行的原位纳米尺度的多巴胺聚合。同时经过拉曼光谱证实在本发明中之前添加的磺酸钠离子插层以及聚多巴胺层可以在无需外加氧化剂的情况下，促进乙烯二氧噻吩在MXene纳米片表面的原位聚合。同时拉曼光谱也证实了这样合成的聚乙烯二氧噻吩相比于常规利用氧化方法合成的聚乙烯二氧噻吩具有更低的聚合度。而更令人意外的是这种低聚合度的聚合乙烯二氧噻吩MXene纳米片具有更好的氧化还原性能、粘性、溶液稳定性和随着氧化程度渐进的疏水性。而反过来，聚乙烯二氧噻吩能够有效可以隔绝聚多巴胺及内部的MXene主体与外界氧化环境反应，用于聚多巴胺层的保护。聚合后的多巴胺具有受限空间内的可逆氧化还原性能，这产生了类似贻贝的粘性，同时使MXene的稳定性得到一定的提高，但因为聚多巴胺和外界直接接触，很容易受到过于强烈的氧化环境的影响导致结构破坏，粘性也因此消失，而原位乙烯二氧噻吩聚合能够进一步对其进行保护。所有尤其是在氧化体系下，低聚乙烯二氧噻吩在接触氧化环境下或常规状态下作为聚多巴胺氧化还原可逆反应的电子供体，增加聚多巴胺的氧化还原性能，显示出不易被氧化环境影响的粘性和稳定性。8. The synergy between the modification of each layer of MXene of the present invention obtains a composite material that is more suitable for complex and high stability in vivo, low diffusion in tissues, and high biocompatibility. First, the intercalation of sulfonic acid and Na ions enhanced the electronic activity on the surface of the nanosheets, facilitating the subsequent in situ nanoscale dopamine polymerization. At the same time, it was confirmed by Raman spectroscopy that the sodium sulfonate ion intercalation and polydopamine layer added before in the present invention can promote the in-situ polymerization of ethylenedioxythiophene on the surface of MXene nanosheets without adding an oxidant. At the same time, Raman spectroscopy also confirmed that the polyethylenedioxythiophene synthesized in this way has a lower degree of polymerization than the polyethylenedioxythiophene synthesized by conventional oxidation methods. What is even more surprising is that the polymerized ethylenedioxythiophene MXene nanosheets with a low degree of polymerization have better redox performance, viscosity, solution stability, and progressive hydrophobicity with the degree of oxidation. In turn, polyethylene dioxythiophene can effectively isolate polydopamine and the internal MXene main body from reacting with the external oxidative environment, and is used for the protection of the polydopamine layer. The polymerized dopamine has reversible redox properties in a confined space, which produces a mussel-like viscosity and improves the stability of MXene. However, because polydopamine is in direct contact with the outside world, it is easily affected by too strong The influence of an oxidative environment leads to structural damage and thus loss of tack, which is further protected by in situ ethylenedioxythiophene polymerization. All especially in oxidative systems, oligoethylenedioxythiophene acts as an electron donor for the reversible redox reaction of polydopamine in contact with oxidative environments or under conventional conditions, increasing the redox properties of polydopamine, showing that it is not easily affected by oxidative environments viscosity and stability.
附图说明Description of drawings
图1为纳米片结构示意图。Figure 1 is a schematic diagram of the nanosheet structure.
图2为实施例1-4所得纳米片的SEM扫描电子显微镜形貌。Figure 2 is the SEM scanning electron microscope morphology of the nanosheets obtained in Examples 1-4.
图3为实施例1-4所得纳米片分散液的SEM扫描电子显微镜，表征自连接性能。FIG. 3 is a SEM scanning electron microscope of the nanosheet dispersion liquid obtained in Examples 1-4, characterizing the self-connection performance.
图4为纳米片抗氧化学实验结果。Figure 4 shows the results of the nanosheet antioxidant chemistry experiment.
图5为纳米片在动物体组织内稳定性结果图。Fig. 5 is a graph showing the stability results of nanosheets in animal tissues.
图6为循环伏安曲线图。Figure 6 is a graph of cyclic voltammetry.
图7为含纳米片水凝胶稳定性对比图。Figure 7 is a comparison chart of the stability of hydrogels containing nanosheets.
图8为含纳米片水凝胶抗压强度结果图。Figure 8 is a graph showing the compressive strength results of hydrogels containing nanosheets.
图9为含纳米片水凝胶粘性实验结果图。Fig. 9 is a graph showing the results of the viscosity experiment of the hydrogel containing nanosheets.
图10为含纳米片水凝胶抗压强度结果图。Fig. 10 is a graph showing the results of compressive strength of the hydrogel containing nanosheets.
图11为纳米片细胞黏附性实验结果，其中a为MXene-NS纳米片组、b为MXene-NSD-PEDOT纳米片组。Figure 11 shows the results of the nanosheet cell adhesion experiment, where a is the MXene-NS nanosheet group, and b is the MXene-NSD-PEDOT nanosheet group.
图12为实施例1所得纳米片拉曼光谱。Figure 12 is the Raman spectrum of the nanosheets obtained in Example 1.
图13为实施例9所得纳米片的SEM扫描电子显微镜形貌。FIG. 13 is the SEM scanning electron microscope morphology of the nanosheets obtained in Example 9.
本发明的实施方式Embodiments of the present invention
首先，使用HF酸选择性蚀刻MAX相陶瓷以获得手风琴状MXene，然后使用Na离子嵌入MXene并获得MXeneN。然后我们使用磺胺酸重氮继续嵌入MXene-N，得到MXene-NS。在碱性和有氧条件下，利用迈克尔加成反应聚合多巴胺在MXene-NS上得到MXene-NSD，随后在未加入氧化剂的情况下将PEDOT聚合在MXene-NSD上得到MXenen-NSD-PEDOTFirst, the MAX phase ceramics were selectively etched using HF acid to obtain accordion-shaped MXenes, and then Na ions were used to intercalate the MXenes and obtain MXeneNs. Then we continued to intercalate MXene-N using sulfadiazonium to obtain MXene-NS. Polymerization of dopamine on MXene-NS to MXene-NSD under alkaline and aerobic conditions, followed by polymerization of PEDOT on MXene-NSD without addition of oxidant to MXenen-NSD-PEDOT
为了使本发明的上述目的、特征和优点能够更加明显易懂，下面对本发明的具体实施方式做详细的说明，但不能理解为对本发明的可实施范围的限定。In order to make the above objects, features and advantages of the present invention more obvious and understandable, the specific implementation modes of the present invention will be described in detail below, but they should not be construed as limiting the scope of implementation of the present invention.
实施例1 改性MXene材料的制备Embodiment 1 Preparation of modified MXene material
1）将3g Ti 3AlC 2粉末缓慢浸入装有40mL HF水溶液的聚四氟乙烯烧杯中，并在室温下蚀刻48小时。然后将所得悬浮液转移到离心管中并离心。湿沉淀物用去离子水洗涤并离心数次。得到HF酸选择性蚀刻的手风琴状二维MXene材料Ti 3C 2。 1) Slowly immerse 3 g of Ti3AlC2 powder into a Teflon beaker filled with 40 mL of HF aqueous solution and etch at room temperature for 48 h. The resulting suspension was then transferred to a centrifuge tube and centrifuged. The wet pellet was washed with deionized water and centrifuged several times. The accordion-like two-dimensional MXene material Ti 3 C 2 selectively etched by HF acid was obtained.
2）倾析上一步液体后，向离心管中滴加少量稀NaOH溶液，将溶液转移至烧杯中，搅拌2小时。将产物离心并用大量去离子水洗涤数次，直至顶部液体的pH值为7-8，得到MXene-N（Na +插层的MXene材料）。此结构下Na离子嵌入MXene片层之间，此时MXene片层间距将会被扩大，这促进了后续磺酸改性反应的发生。 2) After decanting the liquid in the previous step, add a small amount of dilute NaOH solution dropwise to the centrifuge tube, transfer the solution to a beaker, and stir for 2 hours. The product was centrifuged and washed several times with plenty of deionized water until the pH of the top liquid was 7–8 to obtain MXene-N (Na + intercalated MXene material). Under this structure, Na ions are intercalated between MXene sheets, and the interlayer spacing of MXene will be enlarged, which promotes the subsequent sulfonic acid modification reaction.
3）将10g 磺胺酸悬浮在40 mL水中，冷却至0-5℃。将9 mL HCl 和30 mL水的溶液预冷至0-5℃，并在冰浴条件下搅拌下缓慢加入悬浮液中。15分钟后，将4g亚硝酸钠（18 mL）的冷溶液滴加到悬浮液中，反应完全，得到重氮盐溶液。将上述合成的重氮盐溶液在冰浴中边搅拌边滴加到MXene-N的水分散液中，混合物在0-5℃保持约4小时。反应结束后，将混合物离心并洗涤数次，然后离心以分离大的聚集体和未反应的颗粒。然后，将上清液冻干成 MXene-NS 粉末（Na离子和磺酸的插层改性的MXene纳米片）。此结构下磺酸基团嵌入MXene片层之间，此时MXene片层间距将会被继续扩大，并发生彻底的剥离，剥离下来的单层或多层MXene可以通过扫描电子显微镜和透射电子显微镜等方法观察到。此时MXene表面的磺酸基团具有很好的反应活性，是后续聚多巴胺和聚乙烯二氧噻吩反应发生的前提条件。3) Suspend 10g of sulfanilic acid in 40 mL of water and cool to 0-5°C. A solution of 9 mL HCl and 30 mL water was precooled to 0-5 °C and slowly added to the suspension with stirring in an ice bath. After 15 min, a cold solution of 4 g of sodium nitrite (18 mL) was added dropwise to the suspension, and the reaction was complete to obtain a diazonium salt solution. The diazonium salt solution synthesized above was added dropwise to the aqueous dispersion of MXene-N while stirring in an ice bath, and the mixture was kept at 0-5°C for about 4 hours. After the reaction, the mixture was centrifuged and washed several times, then centrifuged to separate large aggregates and unreacted particles. Then, the supernatant was lyophilized into MXene-NS powder (MXene nanosheets modified by intercalation of Na ions and sulfonic acid). Under this structure, the sulfonic acid groups are embedded between the MXene sheets. At this time, the distance between the MXene sheets will continue to expand, and a complete exfoliation will occur. The exfoliated single-layer or multi-layer MXene can be detected by scanning electron microscopy and transmission electron microscopy. observed by other methods. At this time, the sulfonic acid groups on the surface of MXene have good reactivity, which is the prerequisite for the subsequent reaction between polydopamine and polyethylenedioxythiophene.
4）将获得的MXene-NS粉末以3 mg/mL的浓度用60 mL去离子水分散，并向溶液中滴加15 mL Tris-HCl溶液（pH 8.5）。同时，将30 mg多巴胺（DA）加入15 mL Tris-HCl 溶液（pH 8.5）搅拌15分钟进行预聚合。然后将DA预聚合溶液滴加到MXene-NS溶液中并搅拌4小时，得到MXene-NSD纳米片（具有聚合多巴胺层且Na离子和磺酸的插层改性的MXene纳米片）此时纳米或亚微米尺度聚多巴胺覆盖在MXene纳米片表面。MXene-NSD 纳米片经过离心和洗涤数次。4) The obtained MXene-NS powder was dispersed with 60 mL of deionized water at a concentration of 3 mg/mL, and 15 mL of Tris-HCl solution (pH 8.5) was added dropwise to the solution. At the same time, 30 mg of dopamine (DA) was added to 15 mL of Tris-HCl solution (pH 8.5) and stirred for 15 minutes for prepolymerization. Then the DA pre-polymerization solution was added dropwise to the MXene-NS solution and stirred for 4 hours to obtain MXene-NSD nanosheets (MXene nanosheets with a polymerized dopamine layer and intercalation modification of Na ions and sulfonic acid). At this time, nano or Submicron-scale polydopamine covers the surface of MXene nanosheets. MXene-NSD nanosheets were centrifuged and washed several times.
5）用 1升去离子水将1克MXene-NSD 纳米片重新分散，将10克3,4-乙烯二氧噻吩（EDOT）溶于100毫升乙醇中；然后将EDOT溶液滴加到MXene-NSD溶液中并在室温下搅拌24小时。之后，将溶液离心，洗涤数次后冻干，获得MXene-NSD-PEDOT纳米片（具有聚合多巴胺层和非氧化性聚乙烯二氧噻吩层，且Na离子和磺酸的插层改性的MXene纳米片）此时非氧化性聚乙烯二氧噻吩层覆盖在4）中和合成的MXene-NSD表面。5) Redisperse 1 g of MXene-NSD nanosheets with 1 liter of deionized water, dissolve 10 g of 3,4-ethylenedioxythiophene (EDOT) in 100 ml of ethanol; then add the EDOT solution dropwise to MXene-NSD solution and stirred at room temperature for 24 hours. Afterwards, the solution was centrifuged, washed several times and then freeze-dried to obtain MXene-NSD-PEDOT nanosheets (with a layer of polymerized dopamine and a layer of non-oxidative polyethylenedioxythiophene, and the intercalation of Na ions and sulfonic acid modified MXene Nanosheets) At this time, the non-oxidizing polyethylene dioxythiophene layer covers the surface of the neutralized and synthesized MXene-NSD in 4).
实施例2改性MXene材料的制备The preparation of embodiment 2 modified MXene materials
1）将4g Ti 3AlC 2粉末缓慢浸入装有40mL HF水溶液的聚四氟乙烯烧杯中，并在室温下蚀刻48小时。然后将所得悬浮液转移到离心管中并离心。湿沉淀物用去离子水洗涤并离心数次。 1) Slowly immerse 4 g of Ti3AlC2 powder into a Teflon beaker filled with 40 mL of HF aqueous solution and etch at room temperature for 48 h. The resulting suspension was then transferred to a centrifuge tube and centrifuged. The wet pellet was washed with deionized water and centrifuged several times.
2）倾析上一步液体后，向离心管中滴加少量稀NaOH溶液，将溶液转移至烧杯中，搅拌2小时。将产物离心并用大量去离子水洗涤数次，直至顶部液体的pH值为7-8，得到MXene-N（Na +插层的MXene材料）。 2) After decanting the liquid in the previous step, add a small amount of dilute NaOH solution dropwise to the centrifuge tube, transfer the solution to a beaker, and stir for 2 hours. The product was centrifuged and washed several times with plenty of deionized water until the pH of the top liquid was 7–8 to obtain MXene-N (Na + intercalated MXene material).
3）将 6.3g 磺胺酸悬浮在30 mL水中，冰浴冷却。将9 mL HCl 和30 mL水的溶液预冷，并在冰浴条件下搅拌下缓慢加入悬浮液中。15分钟后，将2.4 g亚硝酸钠（18 mL）的冷溶液滴加到悬浮液中，搅拌30分钟，得到重氮盐溶液。将上述合成的重氮盐溶液在冰浴中边搅拌边滴加到MXene-N的水分散液中，混合物在0-5℃保持约4小时。反应结束后，将混合物离心并洗涤数次，然后离心分离大的聚集体和未反应的颗粒。然后，将上清液冻干成 MXene-NS 粉末（Na离子和磺酸的插层改性的MXene纳米片）。3) Suspend 6.3g of sulfanilic acid in 30 mL of water and cool in an ice bath. A solution of 9 mL HCl and 30 mL water was precooled and slowly added to the suspension with stirring in an ice bath. After 15 min, a cold solution of 2.4 g of sodium nitrite (18 mL) was added dropwise to the suspension and stirred for 30 min to obtain a diazonium salt solution. The diazonium salt solution synthesized above was added dropwise to the aqueous dispersion of MXene-N while stirring in an ice bath, and the mixture was kept at 0-5°C for about 4 hours. After the reaction, the mixture was centrifuged and washed several times, and then centrifuged to separate large aggregates and unreacted particles. Then, the supernatant was lyophilized into MXene-NS powder (MXene nanosheets modified by intercalation of Na ions and sulfonic acid).
4）将获得的MXene-NS粉末以2.5 mg/mL的浓度用60 mL去离子水分散，并向溶液中滴加15 mL Tris-HCl溶液（pH 8.5）。同时，将 15 mg多巴胺（DA）加入15 mL Tris-HCl 溶液（pH 8.5）搅拌15分钟进行预聚合。然后将DA预聚合溶液滴加到MXene-NS溶液中并搅拌4小时，得到MXene-NSD纳米片（具有聚合多巴胺层且Na离子和磺酸的插层改性的MXene纳米片）此时纳米或亚微米尺度聚多巴胺覆盖在MXene纳米片表面。MXene-NSD 纳米片经过离心和洗涤数次。4) The obtained MXene-NS powder was dispersed with 60 mL of deionized water at a concentration of 2.5 mg/mL, and 15 mL of Tris-HCl solution (pH 8.5) was added dropwise to the solution. At the same time, 15 mg of dopamine (DA) was added to 15 mL of Tris-HCl solution (pH 8.5) and stirred for 15 minutes for prepolymerization. Then the DA pre-polymerization solution was added dropwise to the MXene-NS solution and stirred for 4 hours to obtain MXene-NSD nanosheets (MXene nanosheets with a polymerized dopamine layer and intercalation modification of Na ions and sulfonic acid). At this time, nano or Submicron-scale polydopamine covers the surface of MXene nanosheets. MXene-NSD nanosheets were centrifuged and washed several times.
5）用 1升去离子水将1克MXene-NSD 纳米片重新分散，将5克3,4-乙烯二氧噻吩（EDOT）溶于100毫升乙醇中；然后将EDOT溶液滴加到MXene-NSD溶液中并在室温下搅拌24小时。之后，将溶液离心，洗涤数次后冻干，获得MXene-NSD-PEDOT纳米片（具有聚合多巴胺层和非氧化性聚乙烯二氧噻吩层，且Na离子和磺酸的插层改性的MXene纳米片）此时非氧化性聚乙烯二氧噻吩层覆盖在4）中和合成的MXene-NSD表面。5) Redisperse 1 g of MXene-NSD nanosheets with 1 liter of deionized water, dissolve 5 g of 3,4-ethylenedioxythiophene (EDOT) in 100 ml of ethanol; then add the EDOT solution dropwise to MXene-NSD solution and stirred at room temperature for 24 hours. Afterwards, the solution was centrifuged, washed several times and then freeze-dried to obtain MXene-NSD-PEDOT nanosheets (with a layer of polymerized dopamine and a layer of non-oxidative polyethylenedioxythiophene, and the intercalation of Na ions and sulfonic acid modified MXene Nanosheets) At this time, the non-oxidizing polyethylene dioxythiophene layer covers the surface of the neutralized and synthesized MXene-NSD in 4).
实施例3改性MXene材料的制备The preparation of embodiment 3 modified MXene materials
1）将3g Ti 3AlC 2粉末缓慢浸入装有40mL HF水溶液的聚四氟乙烯烧杯中，并在室温下蚀刻48小时。然后将所得悬浮液转移到离心管中并离心。湿沉淀物用去离子水洗涤并离心数次。得到HF酸选择性蚀刻的手风琴状二维MXene材料Ti 3C 2。 1) Slowly immerse 3 g of Ti3AlC2 powder into a Teflon beaker filled with 40 mL of HF aqueous solution and etch at room temperature for 48 h. The resulting suspension was then transferred to a centrifuge tube and centrifuged. The wet pellet was washed with deionized water and centrifuged several times. The accordion-like two-dimensional MXene material Ti 3 C 2 selectively etched by HF acid was obtained.
2）倾析上一步液体后，向离心管中滴加少量稀NaOH溶液，将溶液转移至烧杯中，搅拌2小时。将产物离心并用大量去离子水洗涤数次，直至顶部液体的pH值为7-8，得到MXene-N（Na +插层的MXene材料）。此结构下Na离子嵌入MXene片层之间，此时MXene片层间距将会被扩大，这促进了后续磺酸改性反应的发生。 2) After decanting the liquid in the previous step, add a small amount of dilute NaOH solution dropwise to the centrifuge tube, transfer the solution to a beaker, and stir for 2 hours. The product was centrifuged and washed several times with plenty of deionized water until the pH of the top liquid was 7–8 to obtain MXene-N (Na + intercalated MXene material). Under this structure, Na ions are intercalated between MXene sheets, and the interlayer spacing of MXene will be enlarged, which promotes the subsequent sulfonic acid modification reaction.
3）将 6.3g 磺胺酸悬浮在30 mL水中，冷却至0-5℃。将9 mL HCl 和30 mL水的溶液预冷至0-5℃，并在冰浴条件下搅拌下缓慢加入悬浮液中。15分钟后，将2.4 g亚硝酸钠（18 mL）的冷溶液滴加到悬浮液中，搅拌30分钟，得到重氮盐溶液。将上述合成的重氮盐溶液在冰浴中边搅拌边滴加到MXene-N的水分散液中，混合物在0-5℃保持约4小时。反应结束后，将混合物离心并洗涤数次，然后以4000 rpm离心1小时以分离大的聚集体和未反应的颗粒。然后，将上清液冻干成 MXene-NS 粉末（Na离子和磺酸的插层改性的MXene纳米片）。此结构下磺酸基团嵌入MXene片层之间，此时MXene片层间距将会被继续扩大，并发生彻底的剥离，剥离下来的单层或多层MXene可以通过扫描电子显微镜和透射电子显微镜等方法观察到。此时MXene表面的磺酸基团具有很好的反应活性，是后续聚多巴胺和聚乙烯二氧噻吩反应发生的前提条件。3) Suspend 6.3g of sulfanilic acid in 30 mL of water and cool to 0-5°C. A solution of 9 mL HCl and 30 mL water was precooled to 0-5 °C and slowly added to the suspension with stirring in an ice bath. After 15 min, a cold solution of 2.4 g of sodium nitrite (18 mL) was added dropwise to the suspension and stirred for 30 min to obtain a diazonium salt solution. The diazonium salt solution synthesized above was added dropwise to the aqueous dispersion of MXene-N while stirring in an ice bath, and the mixture was kept at 0-5°C for about 4 hours. After the reaction, the mixture was centrifuged and washed several times, and then centrifuged at 4000 rpm for 1 h to separate large aggregates and unreacted particles. Then, the supernatant was lyophilized into MXene-NS powders (MXene nanosheets modified by intercalation of Na ions and sulfonic acid). Under this structure, the sulfonic acid groups are embedded between the MXene sheets. At this time, the distance between the MXene sheets will continue to expand, and a complete exfoliation will occur. The exfoliated single-layer or multi-layer MXene can be detected by scanning electron microscopy and transmission electron microscopy. observed by other methods. At this time, the sulfonic acid groups on the surface of MXene have good reactivity, which is the prerequisite for the subsequent reaction between polydopamine and polyethylenedioxythiophene.
4）将获得的MXene-NS粉末以5 mg/mL的浓度用60 mL去离子水分散，并向溶液中滴加15 mL Tris-HCl溶液（pH 8.5）。同时，将 15 mg多巴胺（DA）加入15 mL Tris-HCl 溶液（pH 8.5）搅拌15分钟进行预聚合。然后将DA预聚合溶液滴加到MXene-NS溶液中并搅拌4小时，得到MXene-NSD纳米片（具有聚合多巴胺层且Na离子和磺酸的插层改性的MXene纳米片）此时纳米或亚微米尺度聚多巴胺覆盖在MXene纳米片表面。MXene-NSD 纳米片经过离心和洗涤数次。4) The obtained MXene-NS powder was dispersed with 60 mL of deionized water at a concentration of 5 mg/mL, and 15 mL of Tris-HCl solution (pH 8.5) was added dropwise to the solution. At the same time, 15 mg of dopamine (DA) was added to 15 mL of Tris-HCl solution (pH 8.5) and stirred for 15 minutes for prepolymerization. Then the DA pre-polymerization solution was added dropwise to the MXene-NS solution and stirred for 4 hours to obtain MXene-NSD nanosheets (MXene nanosheets with a polymerized dopamine layer and intercalation modification of Na ions and sulfonic acid). At this time, nano or Submicron-scale polydopamine covers the surface of MXene nanosheets. MXene-NSD nanosheets were centrifuged and washed several times.
5）用 1升去离子水将1克MXene-NSD 纳米片重新分散，将3克3,4-乙烯二氧噻吩（EDOT）溶于100毫升乙醇中；然后将EDOT溶液滴加到MXene-NSD溶液中并在室温下搅拌24小时。之后，将溶液离心，洗涤数次后冻干，获得MXene-NSD-PEDOT纳米片（具有聚合多巴胺层和非氧化性聚乙烯二氧噻吩层，且Na离子和磺酸的插层改性的MXene纳米片）此时非氧化性聚乙烯二氧噻吩层覆盖在4）中和合成的MXene-NSD表面。5) Redisperse 1 g of MXene-NSD nanosheets with 1 liter of deionized water, dissolve 3 g of 3,4-ethylenedioxythiophene (EDOT) in 100 ml of ethanol; then add the EDOT solution dropwise to MXene-NSD solution and stirred at room temperature for 24 hours. Afterwards, the solution was centrifuged, washed several times and then freeze-dried to obtain MXene-NSD-PEDOT nanosheets (with a layer of polymerized dopamine and a layer of non-oxidative polyethylenedioxythiophene, and the intercalation of Na ions and sulfonic acid modified MXene Nanosheets) At this time, the non-oxidizing polyethylene dioxythiophene layer covers the surface of the neutralized and synthesized MXene-NSD in 4).
实施例4改性MXene材料的制备The preparation of embodiment 4 modified MXene materials
1）将3g Ti 3AlC 2粉末缓慢浸入装有40mL HF水溶液的聚四氟乙烯烧杯中，并在室温下蚀刻48小时。然后将所得悬浮液转移到离心管中并离心。湿沉淀物用去离子水洗涤并离心数次。得到HF酸选择性蚀刻的手风琴状二维MXene材料Ti 3C 2。 1) Slowly immerse 3 g of Ti3AlC2 powder into a Teflon beaker filled with 40 mL of HF aqueous solution and etch at room temperature for 48 h. The resulting suspension was then transferred to a centrifuge tube and centrifuged. The wet pellet was washed with deionized water and centrifuged several times. The accordion-like two-dimensional MXene material Ti 3 C 2 selectively etched by HF acid was obtained.
2）倾析上一步液体后，向离心管中滴加少量稀NaOH溶液，将溶液转移至烧杯中，搅拌2小时。将产物离心并用大量去离子水洗涤数次，直至顶部液体的pH值为7-8，得到MXene-N（Na +插层的MXene材料）。此结构下Na离子嵌入MXene片层之间，此时MXene片层间距将会被扩大，这促进了后续磺酸改性反应的发生。 2) After decanting the liquid in the previous step, add a small amount of dilute NaOH solution dropwise to the centrifuge tube, transfer the solution to a beaker, and stir for 2 hours. The product was centrifuged and washed several times with plenty of deionized water until the pH of the top liquid was 7–8 to obtain MXene-N (Na + intercalated MXene material). Under this structure, Na ions are intercalated between MXene sheets, and the interlayer spacing of MXene will be enlarged, which promotes the subsequent sulfonic acid modification reaction.
3）将 6.3g 磺胺酸悬浮在30 mL水中，冷却至0-5℃。将9 mL HCl 和30 mL水的溶液预冷至0-5℃，并在冰浴条件下搅拌下缓慢加入悬浮液中。15分钟后，将2.4 g亚硝酸钠（18 mL）的冷溶液滴加到悬浮液中，搅拌30分钟，得到重氮盐溶液。将上述合成的重氮盐溶液在冰浴中边搅拌边滴加到MXene-N的水分散液中，混合物在0-5℃保持约4小时。反应结束后，将混合物离心并洗涤数次，然后以4000 rpm离心1小时以分离大的聚集体和未反应的颗粒。然后，将上清液冻干成 MXene-NS 粉末（Na离子和磺酸的插层改性的MXene纳米片）。此结构下磺酸基团嵌入MXene片层之间，此时MXene片层间距将会被继续扩大，并发生彻底的剥离，剥离下来的单层或多层MXene可以通过扫描电子显微镜和透射电子显微镜等方法观察到。此时MXene表面的磺酸基团具有很好的反应活性，是后续聚多巴胺和聚乙烯二氧噻吩反应发生的前提条件。3) Suspend 6.3g of sulfanilic acid in 30 mL of water and cool to 0-5°C. A solution of 9 mL HCl and 30 mL water was precooled to 0-5 °C and slowly added to the suspension with stirring in an ice bath. After 15 min, a cold solution of 2.4 g of sodium nitrite (18 mL) was added dropwise to the suspension and stirred for 30 min to obtain a diazonium salt solution. The diazonium salt solution synthesized above was added dropwise to the aqueous dispersion of MXene-N while stirring in an ice bath, and the mixture was kept at 0-5°C for about 4 hours. After the reaction, the mixture was centrifuged and washed several times, and then centrifuged at 4000 rpm for 1 h to separate large aggregates and unreacted particles. Then, the supernatant was lyophilized into MXene-NS powders (MXene nanosheets modified by intercalation of Na ions and sulfonic acid). Under this structure, the sulfonic acid groups are embedded between the MXene sheets. At this time, the distance between the MXene sheets will continue to expand, and a complete exfoliation will occur. The exfoliated single-layer or multi-layer MXene can be detected by scanning electron microscopy and transmission electron microscopy. observed by other methods. At this time, the sulfonic acid groups on the surface of MXene have good reactivity, which is the prerequisite for the subsequent reaction between polydopamine and polyethylenedioxythiophene.
4）将获得的MXene-NS粉末以3.75 mg/mL的浓度用60 mL去离子水分散，并向溶液中滴加15 mL Tris-HCl溶液（pH 9）。同时，将 15 mg多巴胺（DA）加入15 mL Tris-HCl 溶液（pH 8.5）搅拌15分钟进行预聚合。然后将DA预聚合溶液滴加到MXene-NS溶液中并搅拌4小时，得到MXene-NSD纳米片（具有聚合多巴胺层且Na离子和磺酸的插层改性的MXene纳米片）此时纳米或亚微米尺度聚多巴胺覆盖在MXene纳米片表面。MXene-NSD 纳米片经过离心和洗涤数次。4) The obtained MXene-NS powder was dispersed with 60 mL of deionized water at a concentration of 3.75 mg/mL, and 15 mL of Tris-HCl solution (pH 9) was added dropwise to the solution. At the same time, 15 mg of dopamine (DA) was added to 15 mL of Tris-HCl solution (pH 8.5) and stirred for 15 minutes for prepolymerization. Then the DA pre-polymerization solution was added dropwise to the MXene-NS solution and stirred for 4 hours to obtain MXene-NSD nanosheets (MXene nanosheets with a polymerized dopamine layer and intercalation modification of Na ions and sulfonic acid). At this time, nano or Submicron-scale polydopamine covers the surface of MXene nanosheets. MXene-NSD nanosheets were centrifuged and washed several times.
5）用 1升去离子水将1克MXene-NSD 纳米片重新分散，将15克3,4-乙烯二氧噻吩（EDOT）溶于100毫升乙醇中；然后将EDOT溶液滴加到MXene-NSD溶液中并在室温下搅拌24小时。之后，将溶液离心，洗涤数次后冻干，获得MXene-NSD-PEDOT纳米片（具有聚合多巴胺层和非氧化性聚乙烯二氧噻吩层，且Na离子和磺酸的插层改性的MXene纳米片）此时非氧化性聚乙烯二氧噻吩层覆盖在4）中和合成的MXene-NSD表面。5) Redisperse 1 g of MXene-NSD nanosheets with 1 liter of deionized water, dissolve 15 g of 3,4-ethylenedioxythiophene (EDOT) in 100 ml of ethanol; then add the EDOT solution dropwise to MXene-NSD solution and stirred at room temperature for 24 hours. Afterwards, the solution was centrifuged, washed several times and then freeze-dried to obtain MXene-NSD-PEDOT nanosheets (with a layer of polymerized dopamine and a layer of non-oxidative polyethylenedioxythiophene, and the intercalation of Na ions and sulfonic acid modified MXene Nanosheets) At this time, the non-oxidizing polyethylene dioxythiophene layer covers the surface of the neutralized and synthesized MXene-NSD in 4).
实施例5扫描电镜检测Embodiment 5 Scanning electron microscope detection
对实施例1-4制备获得的MXene-NSD-PEDOT纳米片进行扫描电镜检测，实验结果见图2-3。Scanning electron microscopy was performed on the MXene-NSD-PEDOT nanosheets prepared in Examples 1-4, and the experimental results are shown in Figures 2-3.
图2显示的是最终合成的MXene-NSD-PEDOT纳米片，从其中的断面可以看出纳米片具有比较明显的三层结构，其中外层为非氧化性聚乙烯二氧噻吩层，内层为MXene-NSD。可以看出合成的聚合多巴胺层是相对薄的，这是因为纳米或亚微米尺度的可逆氧化还原可以增加材料的粘性，同时较厚的非氧化性聚乙烯二氧噻吩层可以提供充足的电子，保护内部结构。Figure 2 shows the final synthesized MXene-NSD-PEDOT nanosheets. It can be seen from the cross-section that the nanosheets have a relatively obvious three-layer structure, in which the outer layer is a non-oxidizing polyethylene dioxythiophene layer, and the inner layer is MXene-NSD. It can be seen that the synthesized polydopamine layer is relatively thin, because the reversible redox at the nanometer or submicrometer scale can increase the viscosity of the material, while the thicker non-oxidizing polyethylenedioxythiophene layer can provide sufficient electrons, Protect internal structures.
图3显示的是含有最终合成的MXene-NSD-PEDOT纳米片的水溶液在室温自然状态下干燥时的表面形貌，通过氧化聚合，MXene-NSD-PEDOT纳米之间片形成了大面积的共价连接。同时在表面可以看到细微的褶皱凸起，这促进了细胞的粘附和扩散。Figure 3 shows the surface morphology of the aqueous solution containing the final synthesized MXene-NSD-PEDOT nanosheets when dried in the natural state at room temperature. Through oxidative polymerization, the MXene-NSD-PEDOT nanosheets form a large area of covalent connect. At the same time, subtle folds and bumps can be seen on the surface, which promote cell adhesion and spreading.
实施例6不同聚合程度聚乙烯二氧噻吩的制备以及拉曼光谱检测Example 6 Preparation of Polyethylenedioxythiophene with Different Degrees of Polymerization and Raman Spectroscopy Detection
利用氧化性催化剂化学合成法合成聚合乙烯二氧噻吩，具体而言将160 µL3,4-乙烯二氧噻吩（EDOT）溶于 10 mL 乙醇中并加入FeCl 3催化剂洗涤干燥后，获得对比PEDOT纳米颗粒。通过拉曼光谱检测实施例1所得纳米片拉曼光谱和对比例。拉曼光谱结果见图12。 Polymerized ethylenedioxythiophene was synthesized by oxidative catalyst chemical synthesis, specifically, 160 µL of 3,4-ethylenedioxythiophene (EDOT) was dissolved in 10 mL of ethanol and added with FeCl catalyst to wash and dry to obtain comparative PEDOT nanoparticles . The Raman spectrum of the nanosheets obtained in Example 1 and the comparative example were detected by Raman spectroscopy. The results of Raman spectroscopy are shown in Figure 12.
拉曼光谱结果显示本发明实施例1-4合成的聚合乙烯二氧噻吩相比于常规利用氧化方法合成的聚合乙烯二氧噻吩具有更低的聚合度。The results of Raman spectroscopy show that the polymerized ethylenedioxythiophene synthesized in Examples 1-4 of the present invention has a lower degree of polymerization than the polymerized ethylenedioxythiophene synthesized by conventional oxidation methods.
通过拉曼光谱观察不同氧化阶段下的纳米片的特征官能团峰的变化，结果显示本发明的MXene不同于现有技术中MXene的成膜能力，本发明MXene材料之间形成了依靠共价键连接的稳定结构，而现有技术中MXene是靠片层的重新堆叠和片层间的范德华力实现的，所以本发明的MXene具有更好的水中的成膜稳定性。Observing the changes of the characteristic functional group peaks of nanosheets under different oxidation stages by Raman spectroscopy, the results show that the MXene of the present invention is different from the film-forming ability of MXene in the prior art, and the MXene materials of the present invention are formed by covalent bonds. The stable structure of the MXene in the prior art is realized by the re-stacking of the sheets and the van der Waals force between the sheets, so the MXene of the present invention has better film-forming stability in water.
实施例7MXene纳米片抗氧化性能测试Example 7 MXene nanosheet antioxidant performance test
实验方法：分别将MXene、MXene-NS、MXene-NSD-PEDOT分散去离子水中，并敞口放置在25摄氏度空气中观察状态。结果见图4，实验结果显示MXene-NSD-PEDOT相比于MXene、MXene-NS具有更好的抗氧化性能。在放置4周后依然保持原状，而MXene、MXene-NS分别在一周和三天左右显示出氧化。由于本发明的MXene纳米片MXene-NSD-PEDOT中的聚多巴胺层和聚乙烯二氧噻吩层，即PDA/PEDOT的动态平衡系统将 Ti 3C 2晶体与外部环境分离，并通过邻苯二酚到醌的转化诱导氧化还原活性：0.34 单位电子从 PEDOT 流向 Ti 3C 2并减少 PDA 中邻苯二酚基团的氧化，因此，本发明显示出比较高的抗氧化活性。 Experimental method: disperse MXene, MXene-NS, and MXene-NSD-PEDOT in deionized water, and place them in air at 25 degrees Celsius to observe the state. The results are shown in Figure 4. The experimental results show that MXene-NSD-PEDOT has better antioxidant properties than MXene and MXene-NS. It remained intact after 4 weeks of storage, while MXene and MXene-NS showed oxidation around one week and three days, respectively. Due to the polydopamine layer and polyethylenedioxythiophene layer in the MXene nanosheet MXene-NSD-PEDOT of the present invention, that is, the dynamic equilibrium system of PDA/PEDOT separates the Ti 3 C 2 crystal from the external environment, and through catechol Conversion to quinones induces redox activity: 0.34 unit electrons flow from PEDOT to Ti 3 C 2 and reduce the oxidation of catechol groups in PDA, therefore, the present invention shows relatively high antioxidant activity.
实施例8小鼠体内植入实验Example 8 Implantation experiment in mice
实验方法：将小鼠麻醉，将MXene-NSD-PEDOT纳米片以1mg/mL的浓度分散在生理盐水内，利用注射器，将0.15mlMXene-NSD-PEDOT纳米片分散液注射在小鼠大腿外侧，6周后对小鼠大腿进行固定切片，并用苏木精-伊红染色法染色观察。Experimental method: mice were anesthetized, MXene-NSD-PEDOT nanosheets were dispersed in normal saline at a concentration of 1 mg/mL, and 0.15ml MXene-NSD-PEDOT nanosheet dispersion was injected into the outer thigh of mice with a syringe, 6 One week later, the mouse thighs were fixed and sectioned, and stained with hematoxylin-eosin staining for observation.
实验结果见图5，经证实在6周内材料和组织的边界清晰并没有发生明显的组织扩散、材料附近的组织健康，并未发生氧化应激，同时可观察到一定的新生血管。说明本发明提供的材料具有较好的稳定性。The experimental results are shown in Figure 5. It was confirmed that within 6 weeks, the boundary between the material and the tissue was clear and no obvious tissue diffusion occurred. The tissue near the material was healthy, and no oxidative stress occurred. At the same time, certain new blood vessels could be observed. It shows that the material provided by the present invention has better stability.
实施例7循环伏安法曲线与降解实验Embodiment 7 Cyclic voltammetry curve and degradation experiment
采用循环伏安法（图 6）研究 MXene-NSD-PEDOT 纳米片的氧化还原行为。分别检测本发明不添加FeCl3制备获得的MXene-NSD-PEDOT 纳米片（即低PEDOT聚合度的纳米片），位于0.13 V的氧化峰对应于邻苯二酚向醌的转变；位于 -0.41 V 的还原峰对应于醌到儿茶酚的转变。进行加速实验，即提供氧化环境。随着在提供氧化环境，低PEDOT聚合度的纳米片表面PEDOT不断进一步聚合，得到的高度聚合的纳米片在 0.41 V 处显示一个额外的峰值，这对应于 Ti 3C 2晶格的氧化。通过加速实验证明了：随着在体内时间延长PEDOT聚合度可以增加，可以观察到 CV 曲线的失真和阻抗的急剧上升。这表明随着 MXene-NSD-PEDOT 纳米片在体内时间跨度的增加，PEDOT 层将继续聚合直至完全状态——纳米片的电子转移能力将达到其峰值。从那时起，Ti 3C 2晶体将参与氧化过程：ROS 将不断消耗 Ti 3C 2电子积累并逐渐降解纳米片结构。这种特性可以实现纳米片的非线性降解——通过加速氧化分解——以及在功能后期更好的自我去除能力。 The redox behavior of MXene-NSD-PEDOT nanosheets was investigated by cyclic voltammetry (Fig. 6). The MXene-NSD-PEDOT nanosheets (that is, nanosheets with low PEDOT polymerization degree) prepared by the present invention without adding FeCl3 were detected, and the oxidation peak at 0.13 V corresponds to the transformation of catechol to quinone; the oxidation peak at -0.41 V The reduction peak corresponds to the conversion of quinone to catechol. Accelerated experiments were performed, ie an oxidizing environment was provided. With the continuous further polymerization of PEDOT on the surface of nanosheets with low PEDOT polymerization degree under the provision of an oxidizing environment, the resulting highly polymerized nanosheets showed an additional peak at 0.41 V, which corresponded to the oxidation of the Ti3C2 lattice. It is proved by accelerated experiments that the degree of polymerization of PEDOT can increase with the prolongation of time in vivo, and the distortion of CV curve and the sharp rise of impedance can be observed. This suggests that as the in vivo time span of MXene-NSD-PEDOT nanosheets increases, the PEDOT layer will continue to aggregate to a complete state—the electron transfer capability of the nanosheets will reach its peak. From then on, the Ti3C2 crystal will participate in the oxidation process: ROS will continuously consume the Ti3C2 electron accumulation and gradually degrade the nanosheet structure. This property enables nonlinear degradation of nanosheets—via accelerated oxidative decomposition—as well as better self-removal capabilities at later stages of function.
实施例10含MXene纳米片水凝胶的制备性能检测Example 10 Preparation performance detection of MXene nanosheet hydrogel
通过将本发明的实施例1所得MXene纳米片MXene-NSD-PEDOT或中间体MXene-NS混合在聚丙烯酰胺水凝胶内，比例为1 mg MXene纳米片加入1mL水凝胶中，制得MXene-NS凝胶、MXene-NSD-PEDOT凝胶以及未添加MXene纳米片的空白水凝胶（PAM）。By mixing the MXene nanosheets MXene-NSD-PEDOT obtained in Example 1 of the present invention or the intermediate MXene-NS in polyacrylamide hydrogel, the ratio is 1 mg MXene nanosheets are added to 1 mL hydrogel to prepare MXene -NS gel, MXene-NSD-PEDOT gel, and blank hydrogel (PAM) without MXene nanosheets added.
凝胶稳定性实验结果见图7，从左到右依次为PAM、MXene-NS凝胶、MXene-NSD-PEDOT凝胶，可以看出MXene-NSD-PEDOT凝胶没有发生团聚现象，而其他两个水凝胶发生了明显的团聚现象。The results of the gel stability experiment are shown in Figure 7. From left to right, they are PAM, MXene-NS gel, and MXene-NSD-PEDOT gel. It can be seen that the MXene-NSD-PEDOT gel did not aggregate, while the other two Agglomeration of the hydrogels was evident.
分别检测PAM、MXene-NS凝胶、MXene-NSD-PEDOT凝胶的抗拉强度，实验结果见图8，结果显示MXene-NSD-PEDOT凝胶具有最高的抗拉强度，相比于MXene-NS，MXene-NSD-PEDOT为水凝胶抗拉强度带来了显著的提升。The tensile strength of PAM, MXene-NS gel, and MXene-NSD-PEDOT gel were tested respectively. The experimental results are shown in Figure 8. The results show that MXene-NSD-PEDOT gel has the highest tensile strength, compared to MXene-NSD , MXene-NSD-PEDOT brought a significant increase in the tensile strength of hydrogels.
分别检测PAM、MXene-NS凝胶、MXene-NSD-PEDOT凝胶与聚乙烯（Polytheylene）和不锈钢（Stainless steel）之间粘度，用于评估粘性。实验结果见图9，结果显示在聚乙烯和不锈钢表面，MXene-NSD-PEDOT凝胶均显示了最高的粘性。相比于MXene-NS，MXene-NSD-PEDOT为水凝胶的粘性带来了显著的提升。Respectively detect PAM, MXene-NS gel, MXene-NSD-PEDOT gel and polyethylene (Polytheylene) and stainless steel (Stainless steel steel) for the evaluation of viscosity. The experimental results are shown in Figure 9. The results show that the MXene-NSD-PEDOT gel shows the highest viscosity on both polyethylene and stainless steel surfaces. Compared with MXene-NS, MXene-NSD-PEDOT brought a significant improvement to the viscosity of the hydrogel.
分别检测PAM、MXene-NS凝胶、MXene-NSD-PEDOT凝胶与聚乙烯（Polytheylene）在不同频率下的阻抗值，实验结果见图10，结果显示，在不同频率下MXene-NSD-PEDOT凝胶都显示了更高的导电性能。The impedance values of PAM, MXene-NS gel, MXene-NSD-PEDOT gel and polyethylene (Polytheylene) were detected at different frequencies. The experimental results are shown in Figure 10. The results show that at different frequencies MXene-NSD-PEDOT Both glues showed higher conductivity properties.
实施例11细胞黏附性实验Example 11 Cell Adhesion Experiment
将纳米片MXene-NS和MXene-NSD-PEDOT分别以栅格状态成型在盖玻片上，并在上面接种大鼠施旺细胞，进行两天的培养，观察细胞状态。The nanosheets MXene-NS and MXene-NSD-PEDOT were formed on the cover glass in a grid state, and rat Schwann cells were inoculated on it, and cultured for two days to observe the state of the cells.
实验结果见图11，与MXene-NS组比，培养在MXene-NSD-PEDOT上的细胞具有更好的区分度，说明细胞对MXene-NSD-PEDOT纳米片的结合和相关生理反应优于MXene-NS纳米片如图11。施旺细胞主要分布在周围神经系统中神经元的突起周围，是周围神经纤维的鞘细胞，在周围神经再生中起重要作用。实验结果显示可以本发明的纳米片可以进一步增加神经细胞的粘附。The experimental results are shown in Figure 11. Compared with the MXene-NS group, the cells cultured on MXene-NSD-PEDOT have better discrimination, indicating that the binding and related physiological responses of cells to MXene-NSD-PEDOT nanosheets are better than those of MXene-NSD-PEDOT. NS nanosheets are shown in Figure 11. Schwann cells are mainly distributed around the processes of neurons in the peripheral nervous system. They are the sheath cells of peripheral nerve fibers and play an important role in the regeneration of peripheral nerves. Experimental results show that the nanosheets of the present invention can further increase the adhesion of nerve cells.
实施例12改性MXene材料的制备The preparation of embodiment 12 modified MXene materials
采用实施例1相同的方法，区别仅在于将Ti 3AlC 2替换为 Ti 2AlC。 The same method as in Example 1 was adopted, the only difference being that Ti 3 AlC 2 was replaced by Ti 2 AlC.
通过扫描电镜观察实施例9所得纳米材料以及上述纳米材料的分散液，能够观察到与实施例1所述纳米材料类似的自连接性质和三层结构如图13。Observing the nanomaterials obtained in Example 9 and the dispersion liquid of the above nanomaterials through a scanning electron microscope, it can be observed that the nanomaterials described in Example 1 have similar self-connecting properties and a three-layer structure as shown in Figure 13 .
实施例13改性MXene材料的制备The preparation of embodiment 13 modified MXene materials
采用实施例1相同的方法，区别仅在于将Ti 3AlC 2替换为Ta4AlC3。 The same method as in Example 1 is adopted, the only difference is that Ti 3 AlC 2 is replaced by Ta4AlC3.
实施例14改性MXene材料的制备The preparation of embodiment 14 modified MXene materials
采用实施例1相同的方法，区别仅在于将Ti 3AlC 2替换为 V 2AlC。 The same method as in Example 1 is adopted, the only difference is that Ti 3 AlC 2 is replaced by V 2 AlC.
实施例15改性MXene材料的制备The preparation of embodiment 15 modified MXene materials
采用实施例1相同的方法，区别仅在于将Ti 3AlC 2替换为 Mo 2AlC。 The same method as in Example 1 is adopted, the only difference is that Ti 3 AlC 2 is replaced by Mo 2 AlC.

Claims (10)

  1. 一种表面改性的MXene纳米片，其特征在于，所述MXene纳米片中具有Na离子和磺酸插层，同时表面还具有聚多巴胺层和聚乙烯二氧噻吩层；A surface-modified MXene nanosheet, characterized in that, the MXene nanosheet has Na ion and sulfonic acid intercalation, and the surface also has a polydopamine layer and a polyethylene dioxythiophene layer;
    优选地，聚多巴胺层和聚乙烯二氧噻吩层依次设置；Preferably, the polydopamine layer and the polyethylenedioxythiophene layer are arranged in sequence;
    更优选地，先在具有Na离子和磺酸插层的MXene纳米片表面聚合聚多巴胺层，然后再原位聚合聚乙烯二氧噻吩层。More preferably, the polydopamine layer is first polymerized on the surface of the MXene nanosheets with Na ions and sulfonic acid intercalation, and then the polyethylenedioxythiophene layer is polymerized in situ.
  2. 根据权利要求1所述的表面改性的MXene纳米片，其特征在于，聚乙烯二氧噻吩层通过将乙烯二氧噻吩进行原位聚合获得；The surface-modified MXene nanosheet according to claim 1, wherein the polyethylenedioxythiophene layer is obtained by in-situ polymerization of ethylenedioxythiophene;
    优选地，所述聚乙烯二氧噻吩层的聚合过程中不添加具有氧化性的催化剂；Preferably, no oxidizing catalyst is added during the polymerization of the polyethylenedioxythiophene layer;
    更优选地，所述催化剂三价铁离子的催化剂。More preferably, the catalyst is a catalyst for ferric ions.
  3. 根据权利要求1所述的表面改性的MXene纳米片，其特征在于，所述的MXene纳米片的基片选自Ti 3C 2、Ti 2C、Ta 4C 3、Nb 2C、V 2C、Mo 2C。 The surface-modified MXene nanosheet according to claim 1, wherein the substrate of the MXene nanosheet is selected from Ti 3 C 2 , Ti 2 C, Ta 4 C 3 , Nb 2 C, V 2 C, Mo2C .
  4. 根据权利要求1-3任一项所述的表面改性的MXene纳米片的制备方法，其特征在于，其包括以下步骤：The preparation method of the surface-modified MXene nanosheet according to any one of claims 1-3, is characterized in that, it comprises the following steps:
    1）Na离子和磺酸的插层改性：将二维MXene纳米片分散在含有钠离子的碱性溶液中，混合获得Na离子插层的二维MXene纳米片；将Na离子插层的二维MXene纳米片与磺胺酸重氮盐反应，得到Na离子和磺酸的插层改性的MXene纳米片；1) Intercalation modification of Na ions and sulfonic acid: Disperse two-dimensional MXene nanosheets in an alkaline solution containing sodium ions, and mix to obtain two-dimensional MXene nanosheets intercalated with Na ions; two-dimensional MXene nanosheets intercalated with Na ions Reaction of dimensional MXene nanosheets with sulfanilic acid diazonium salts to obtain intercalation modified MXene nanosheets of Na ions and sulfonic acid;
    2）利用迈克尔加成反应聚合多巴胺：将多巴胺在碱性缓冲溶液中进行预聚合，然后将预聚溶液与Na离子和磺酸的插层改性的MXene纳米片混合反应，得到具有聚合多巴胺层且Na离子和磺酸的插层改性的MXene纳米片；2) Polymerization of dopamine by Michael addition reaction: prepolymerization of dopamine in alkaline buffer solution, and then mixing the prepolymerization solution with Na ion and sulfonic acid intercalation modified MXene nanosheets to obtain a polymerized dopamine layer And Na ion and sulfonic acid intercalation modified MXene nanosheets;
    3）进一步原位聚合获得非氧化性聚乙烯二氧噻吩层：将乙烯二氧噻吩原料分散在水溶性有机溶剂中，并加入步骤2）所得MXene纳米片的水溶液中，在不包含氧化剂的条件下进行获得具有聚合多巴胺层和非氧化性聚乙烯二氧噻吩层，且Na离子和磺酸的插层改性的MXene纳米片。3) Further in-situ polymerization to obtain a non-oxidative polyethylenedioxythiophene layer: disperse the ethylenedioxythiophene raw material in a water-soluble organic solvent, and add it to the aqueous solution of MXene nanosheets obtained in step 2). MXene nanosheets with a polymerized dopamine layer and a non-oxidative polyethylenedioxythiophene layer, and intercalation modification of Na ions and sulfonic acid were obtained.
  5. 根据权利要求4所述的制备方法，其特征在于，其中步骤1）中所述二维MXene纳米基片选自Ti 3C 2、Ti 2C、Ta 4C 3、Nb 2C、V 2C或Mo 2C中的其中一种或多种的组合； The preparation method according to claim 4, wherein the two-dimensional MXene nano-substrate in step 1) is selected from Ti 3 C 2 , Ti 2 C, Ta 4 C 3 , Nb 2 C, V 2 C or a combination of one or more of Mo 2 C;
    优选地，其中步骤1）中所述二维MXene纳米基片通过将MAX相陶瓷通过HF酸进行选择性刻蚀获得；Preferably, the two-dimensional MXene nano-substrate described in step 1) is obtained by selectively etching the MAX phase ceramics with HF acid;
    优选地，步骤1）中磺胺酸重氮盐通过将磺胺酸、盐酸与亚硝酸钠反应获得；Preferably, the diazonium salt of sulfanilic acid in step 1) is obtained by reacting sulfanilic acid, hydrochloric acid and sodium nitrite;
    更优选地，所述MAX相陶瓷选自Ti 3AlC 2、Ti 2AlC、Nb 2AlC、V 2AlC、Mo 2AlC中的其中一种或多种的组合。 More preferably, the MAX phase ceramic is selected from one or more of Ti 3 AlC 2 , Ti 2 AlC, Nb 2 AlC, V 2 AlC, and Mo 2 AlC.
  6. 根据权利要求4所述的制备方法，其特征在于，其中步骤2）中其中步骤2）中多巴胺与Na离子和磺酸的插层改性的MXene纳米片的质量比为1:5-20。The preparation method according to claim 4, wherein in step 2), the mass ratio of dopamine to intercalation modified MXene nanosheets of Na ions and sulfonic acid in step 2) is 1:5-20.
  7. 根据权利要求4所述的制备方法，其特征在于，其中步骤3）中乙烯二氧噻吩原料选自3,4-乙烯二氧噻吩；The preparation method according to claim 4, wherein the raw material of ethylenedioxythiophene in step 3) is selected from 3,4-ethylenedioxythiophene;
    优选地，其中步骤3）中乙烯二氧噻吩原料与具有聚合多巴胺层且Na离子和磺酸的插层改性的MXene纳米片的比例为每1 g具有聚合多巴胺层且Na离子和磺酸的插层改性的MXene纳米片加入0.1克-15克乙烯二氧噻吩原料；Preferably, the ratio of the ethylenedioxythiophene raw material in step 3) to the intercalation-modified MXene nanosheets having a polymerized dopamine layer and Na ions and sulfonic acid per 1 g has a polymerized dopamine layer and Na ions and sulfonic acid Add 0.1 g-15 g of ethylenedioxythiophene raw materials to the intercalated modified MXene nanosheets;
    优选地，其中步骤3）反应中不添加氧化剂。Preferably, no oxidizing agent is added in the step 3) reaction.
  8. 根据权利要求1-3任一项所述表面改性的MXene纳米片，或者权利要求4-7任一项所述的制备方法获得的MXene纳米片作为电极修饰材料、外周神经的细胞修复材料、神经电极的导线、中枢神经电极的位点的用途；According to the surface-modified MXene nanosheets described in any one of claims 1-3, or the MXene nanosheets obtained by the preparation method described in any one of claims 4-7 as electrode modification materials, peripheral nerve cell repair materials, The use of wires for nerve electrodes and sites for central nerve electrodes;
    优选地，所述的电极修饰材料选自用于神经的电极的修饰材料，更优选地，用于中枢神经以及外周神经的电极修饰。Preferably, the electrode modification material is selected from materials used for modifying electrodes of nerves, more preferably, for modifying electrodes of central nerves and peripheral nerves.
  9. 一种生物用电极，所述生物用电极表面具有权利要求1-3任一项所述表面改性的MXene纳米片或者权利要求4-7任一项所述的制备方法获得的MXene纳米片作为电极表面修饰材料；A biological electrode, the surface of the biological electrode has the surface-modified MXene nanosheets described in any one of claims 1-3 or the MXene nanosheets obtained by the preparation method described in any one of claims 4-7 as Electrode surface modification materials;
    优选地，所述的电极修饰材料选自用于神经的电极的修饰材料，更优选地，用于中枢神经以及外周神经的电极修饰。Preferably, the electrode modification material is selected from materials used for modifying electrodes of nerves, more preferably, for modifying electrodes of central nerves and peripheral nerves.
  10. 一种分散体系，所述分散体系中包含权利要求1-3任一项所述表面改性的MXene纳米片或者权利要求4-7任一项所述的制备方法获得的MXene纳米片，以及分散基质，A dispersion system comprising the surface-modified MXene nanosheets of any one of claims 1-3 or the MXene nanosheets obtained by the preparation method of any one of claims 4-7, and dispersion matrix,
    优选地，所述分散基质选自水凝胶、弹性体、溶剂；Preferably, the dispersion matrix is selected from hydrogels, elastomers, solvents;
    更优选地，所述水凝胶选自聚丙烯酰胺水凝胶、聚乙烯醇水凝胶、玻尿酸、玻尿酸衍生物、胶原、明胶、纤网蛋白、纤维蛋白原、藻酸盐、几丁聚醣中的至少一种；溶剂选自水溶液或有机溶剂；More preferably, the hydrogel is selected from polyacrylamide hydrogel, polyvinyl alcohol hydrogel, hyaluronic acid, hyaluronic acid derivatives, collagen, gelatin, fibrin, fibrinogen, alginate, chitin At least one of sugar; solvent is selected from aqueous solution or organic solvent;
    优选地，所述分散体系中表面改性的MXene纳米片的浓度为0.1-10mg/mL。Preferably, the concentration of the surface-modified MXene nanosheets in the dispersion system is 0.1-10 mg/mL.
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