技术领域Technical field
本发明涉及可植入传感技术领域，更具体地说，涉及一种颅内一氧化氮电化学传感器及其制备方法。The present invention relates to the field of implantable sensing technology, and more specifically, to an intracranial nitric oxide electrochemical sensor and a preparation method thereof.
背景技术Background technique
一氧化氮是一种由大脑中的神经元、胶质细胞和内皮细胞等合成和释放的自由基，参与大脑中的多种生理功能，如血管舒张、突触可塑性、神经调节和炎症等，例如，一氧化氮在海马体中的长期增强已被证明参与调节学习和记忆过程。异常的一氧化氮水平与免疫反应、神经毒性和脑血管疾病等异常生理活动相关，例如，一氧化氮浓度过高时，多余的一氧化氮可以与超氧阴离子反应生成一种高度活性的氧化剂分子——过氧亚硝酸，对细胞具有毒性；而一氧化氮浓度过低则会诱导一些神经疾病的发生。为了充分了解这些生理过程中一氧化氮的生化效应，开发能够定量监测一氧化氮浓度的传感技术，并对活体大脑中的一氧化氮浓度变化进行实时监测是至关重要的。Nitric oxide is a free radical synthesized and released by neurons, glial cells, and endothelial cells in the brain. It participates in various physiological functions in the brain, such as vasodilation, synaptic plasticity, neuromodulation, and inflammation. For example, long-term potentiation of nitric oxide in the hippocampus has been shown to be involved in regulating learning and memory processes. Abnormal nitric oxide levels are associated with abnormal physiological activities such as immune responses, neurotoxicity, and cerebrovascular diseases. For example, when nitric oxide concentrations are too high, excess nitric oxide can react with superoxide anions to generate a highly reactive oxidant. The molecule, peroxynitrite, is toxic to cells; and low nitric oxide concentrations can induce the occurrence of some neurological diseases. In order to fully understand the biochemical effects of nitric oxide during these physiological processes, it is crucial to develop sensing technologies that can quantitatively monitor nitric oxide concentrations and perform real-time monitoring of nitric oxide concentration changes in the living brain.
近几十年来，已经发展出多种用于检测大脑中一氧化氮浓度的技术，如Griess法、荧光探针、电子自旋共振光谱和化学发光等。然而，这些方法的局限性在于不能实时监测组织中一氧化氮浓度变化。相比之下，电化学传感技术可以将电化学传感器直接植入到大脑中，实时检测目标脑区的一氧化氮浓度变化，具有高的时间和空间分辨率，这引起了广泛的关注。目前，基于碳纤维和铂丝的各种一氧化氮电化学传感器已经被开发出来，在监测脑组织中的一氧化氮浓度已经取得了一定的效果。然而，电化学传感技术实际应用于体内仍面临重大挑战。一方面，颅内一氧化氮的浓度变化通常在几到十几纳摩尔的范围，而目前的电化学传感器的检测灵敏度(0.1-100pA·nM-1)和检测限(不低于5nM)无法满足该要求；另一方面，电化学传感器主要由碳纤维和铂丝作为导电基底材料，这些材料均为刚性探针结构，这类传感器在植入后与脑组织之间的力学不匹配会导致严重的神经炎症反应，并伴随诱导型一氧化氮合酶(iNOS)的过度表达，iNOS诱导会导致产生额外过度的一氧化氮，进而影响传感监测结果的准确性。这些问题严重限制了一氧化氮传感器在颅内实时监测中的实际应用。In recent decades, a variety of techniques for detecting nitric oxide concentration in the brain have been developed, such as the Griess method, fluorescent probes, electron spin resonance spectroscopy, and chemiluminescence. However, a limitation of these methods is that they cannot monitor changes in nitric oxide concentration in tissues in real time. In contrast, electrochemical sensing technology can directly implant electrochemical sensors into the brain to detect changes in nitric oxide concentration in target brain areas in real time with high temporal and spatial resolution, which has attracted widespread attention. Currently, various nitric oxide electrochemical sensors based on carbon fibers and platinum wires have been developed and have achieved certain results in monitoring nitric oxide concentration in brain tissue. However, the practical application of electrochemical sensing technology in vivo still faces significant challenges. On the one hand, the concentration of intracranial nitric oxide usually changes in the range of several to tens of nanomoles, but the detection sensitivity (0.1-100pA·nM-1 ) and detection limit (not less than 5nM) of current electrochemical sensors cannot To meet this requirement; on the other hand, electrochemical sensors are mainly made of carbon fiber and platinum wire as conductive base materials. These materials are rigid probe structures. The mechanical mismatch between this type of sensor and brain tissue after implantation can lead to serious The neuroinflammatory response is accompanied by the overexpression of inducible nitric oxide synthase (iNOS). iNOS induction will lead to the production of additional excessive nitric oxide, thereby affecting the accuracy of sensing monitoring results. These problems severely limit the practical application of nitric oxide sensors in real-time intracranial monitoring.
在相关技术中，如中国专利文献CN101430302A公开了一种一氧化氮传感器的制备方法，该方法先将石墨粉与石蜡油混合调成糊状，然后挤入到聚四乙烯管或玻璃管中，并引出铜线制作成碳糊电极，将制备的碳糊电极打磨光滑，于十六烷基三甲基澳化胺溶液中浸泡充分，然后取出在水中荡洗，自然晾干即为十六烷基三甲基澳化胺膜电极，最后取Nafion溶液滴到十六烷基三甲基澳化胺膜电极表面，制得十六烷基三甲基澳化胺和Nafion修饰碳糊电极的一氧化氮传感器，但该方法没有对现有技术中存在的一氧化氮电化学传感器植入大脑后会导致严重的神经炎症反应并产生过度的一氧化氮的问题提供任何启示。In related technologies, for example, Chinese patent document CN101430302A discloses a method for preparing a nitric oxide sensor. In this method, graphite powder and paraffin oil are first mixed into a paste, and then squeezed into a polytetraethylene tube or a glass tube. And lead out the copper wire to make a carbon paste electrode. Polish the prepared carbon paste electrode smoothly, soak it fully in the cetyltrimethylammonium solution, then take it out, wash it in water, and dry it naturally to obtain hexadecane. cetyl trimethyl amine membrane electrode, and finally drop the Nafion solution onto the surface of cetyl trimethyl amine membrane electrode to prepare a combination of cetyl trimethyl amine and Nafion modified carbon paste electrode. Nitric oxide sensor, but this method does not provide any enlightenment on the problem in the existing technology that electrochemical nitric oxide sensors can cause severe neuroinflammatory reactions and excessive production of nitric oxide after being implanted in the brain.
发明内容Contents of the invention
1.要解决的技术问题1. Technical problems to be solved
针对现有技术中存在的一氧化氮电化学传感器植入大脑后会导致严重的神经炎症反应并产生过度的一氧化氮的问题，本发明提供了一种基于酸处理碳纳米管纤维的高灵敏度和高精度的颅内一氧化氮传感器，它可以实现对脑部一氧化氮信号变化的实时监测，检测下限低，灵敏度高，信号准确没有干扰，应用范围广泛。In order to solve the problem in the prior art that nitric oxide electrochemical sensors will cause severe neuroinflammatory reactions and excessive nitric oxide production after being implanted into the brain, the present invention provides a highly sensitive sensor based on acid-treated carbon nanotube fibers. And a high-precision intracranial nitric oxide sensor, which can realize real-time monitoring of brain nitric oxide signal changes, has a low detection limit, high sensitivity, accurate signals without interference, and a wide range of applications.
2.技术方案2.Technical solutions
本发明的目的通过以下技术方案实现。The object of the present invention is achieved through the following technical solutions.
一种颅内一氧化氮电化学传感器的制备方法，步骤包括，A method for preparing an intracranial nitric oxide electrochemical sensor, the steps include:
制备酸处理碳纳米管一氧化氮传感纤维：Preparation of acid-treated carbon nanotube nitric oxide sensing fibers:
将碳纳米管纤维浸泡、静置、洗涤及干燥，得到酸处理碳纳米管纤维；Soak, let stand, wash and dry the carbon nanotube fibers to obtain acid-treated carbon nanotube fibers;
将铂纳米颗粒、聚丁香酚沉积于酸处理碳纳米管纤维表面；并将稀释的全氟磺酸型聚合物溶液均匀涂覆在沉积铂纳米颗粒及聚丁香酚后的酸处理碳纳米管纤维表面，得到酸处理碳纳米管一氧化氮传感纤维；Platinum nanoparticles and polyeugenol are deposited on the surface of acid-treated carbon nanotube fibers; and the diluted perfluorosulfonic acid polymer solution is evenly coated on the acid-treated carbon nanotube fibers after depositing platinum nanoparticles and polyeugenol. On the surface, acid-treated carbon nanotube nitric oxide sensing fibers were obtained;
制备酸处理碳纳米管银-氯化银传感纤维：Preparation of acid-treated carbon nanotube silver-silver chloride sensing fiber:
将碳纳米管纤维浸泡、静置、洗涤及干燥，得到酸处理碳纳米管纤维；Soak, let stand, wash and dry the carbon nanotube fibers to obtain acid-treated carbon nanotube fibers;
将银电化学沉积到酸处理碳纳米管纤维表面，得到镀银后的碳纳米管纤维；Electrochemically deposit silver onto the surface of acid-treated carbon nanotube fibers to obtain silver-plated carbon nanotube fibers;
对镀银后的酸处理碳纳米管纤维进行氯化，得到银-氯化银酸处理碳纳米管纤维；Chloride the silver-plated acid-treated carbon nanotube fibers to obtain silver-silver chloride acid-treated carbon nanotube fibers;
制备PVB混合溶液并均匀涂覆到银-氯化银酸处理碳纳米管纤维表面，得到酸处理碳纳米管银-氯化银传感纤维；Prepare a PVB mixed solution and evenly coat it on the surface of the silver-silver chloride acid-treated carbon nanotube fiber to obtain the acid-treated carbon nanotube silver-silver chloride sensing fiber;
制备基于酸处理碳纳米管纤维的颅内一氧化氮传感器：Preparation of intracranial nitric oxide sensor based on acid-treated carbon nanotube fibers:
将酸处理碳纳米管一氧化氮传感纤维和酸处理碳纳米管银-氯化银传感纤维缠绕在一起，形成螺旋结构，得到颅内一氧化氮电化学传感器。The acid-treated carbon nanotube nitric oxide sensing fiber and the acid-treated carbon nanotube silver-silver chloride sensing fiber were wound together to form a spiral structure to obtain an intracranial nitric oxide electrochemical sensor.
更进一步的，制备酸处理碳纳米管纤维的具体步骤为：Furthermore, the specific steps for preparing acid-treated carbon nanotube fibers are:
配置20mL的浓度为98％的硝酸溶液，将碳纳米管纤维浸泡在硝酸溶液中，在25℃静置12小时，静置完毕后用去离子水洗涤，洗涤完毕后进行干燥，得到酸处理碳纳米管纤维。Prepare 20 mL of nitric acid solution with a concentration of 98%, soak the carbon nanotube fibers in the nitric acid solution, let it stand at 25°C for 12 hours, wash it with deionized water after standing, and dry it after washing to obtain acid-treated carbon Nanotube fibers.
更进一步的，制备酸处理碳纳米管一氧化氮传感纤维的具体步骤为：Furthermore, the specific steps for preparing acid-treated carbon nanotube nitric oxide sensing fibers are:
配置1×10-3mol/L氯铂酸钾-0.1mol/L氯化钾溶液，作为电解液A；Prepare 1×10-3 mol/L potassium chloroplatinate-0.1mol/L potassium chloride solution as electrolyte A;
将酸处理碳纳米管纤维作为工作电极，银-氯化银电极作为参比电极，铂电极作为对电极，将三个电极浸入电解液A中，通过恒电位极化法在工作电极上交替施加0.5V和-0.7V的电压，总共持续10秒，重复该过程50次～100次；The acid-treated carbon nanotube fiber is used as the working electrode, the silver-silver chloride electrode is used as the reference electrode, and the platinum electrode is used as the counter electrode. The three electrodes are immersed in the electrolyte A, and the working electrode is alternately applied by the constant potential polarization method. The voltage of 0.5V and -0.7V lasts for 10 seconds in total, and the process is repeated 50 to 100 times;
由氯铂酸钾中被还原的铂元素形成的铂纳米颗粒沉积于酸处理碳纳米管纤维表面，得到沉积铂纳米颗粒后的酸处理碳纳米管纤维。Platinum nanoparticles formed from the reduced platinum element in potassium chloroplatinate are deposited on the surface of acid-treated carbon nanotube fibers to obtain acid-treated carbon nanotube fibers after depositing platinum nanoparticles.
更进一步的，制备酸处理碳纳米管一氧化氮传感纤维的具体步骤为：Furthermore, the specific steps for preparing acid-treated carbon nanotube nitric oxide sensing fibers are:
配置60mL的0.1mol/L的氢氧化钠溶液，用氩气将氢氧化钠溶液的氧气除尽，加入5mmol/L～15mmol/L的丁香酚，作为电解液B；Prepare 60 mL of 0.1 mol/L sodium hydroxide solution, use argon to remove all oxygen from the sodium hydroxide solution, and add 5 mmol/L to 15 mmol/L eugenol as electrolyte B;
沉积铂纳米颗粒后的酸处理碳纳米管纤维作为工作电极，银-氯化银电极作为参比电极，铂电极作为对电极，将三个电极浸入电解液B中，用循环伏安法对工作电极进行循环次数为10次的扫描，扫描速率为20mV s-1，扫描范围为0V～0.7V；The acid-treated carbon nanotube fiber after depositing platinum nanoparticles was used as the working electrode, the silver-silver chloride electrode was used as the reference electrode, and the platinum electrode was used as the counter electrode. The three electrodes were immersed in electrolyte B, and the work was performed using cyclic voltammetry. The electrode is scanned for 10 cycles, the scan rate is 20mV s-1 , and the scan range is 0V ~ 0.7V;
在工作电极表面电化学聚合丁香酚，形成聚丁香酚薄膜，聚丁香酚沉积于沉积铂纳米颗粒后的酸处理碳纳米管纤维表面，得到沉积铂纳米颗粒以及聚丁香酚后的酸处理碳纳米管纤维。Eugenol is electrochemically polymerized on the surface of the working electrode to form a polyeugenol film. Polyeugenol is deposited on the surface of the acid-treated carbon nanotube fiber after depositing platinum nanoparticles to obtain acid-treated carbon nanotubes after depositing platinum nanoparticles and polyeugenol. tube fiber.
更进一步的，制备酸处理碳纳米管一氧化氮传感纤维的具体步骤为：Furthermore, the specific steps for preparing acid-treated carbon nanotube nitric oxide sensing fibers are:
配置被稀释为1.5wt％～5wt％的全氟磺酸型聚合物溶液，取5μL稀释后的全氟磺酸型聚合物溶液均匀涂覆在沉积铂纳米颗粒以及聚丁香酚后的酸处理碳纳米管纤维表面，全氟磺酸型聚合物溶液干燥后形成全氟磺酸薄膜，得到酸处理碳纳米管一氧化氮传感纤维。Prepare a perfluorosulfonic acid polymer solution diluted to 1.5wt% to 5wt%, take 5 μL of the diluted perfluorosulfonic acid polymer solution and evenly coat it on the acid-treated carbon after depositing platinum nanoparticles and polyeugenol. On the surface of the nanotube fiber, the perfluorosulfonic acid polymer solution is dried to form a perfluorosulfonic acid film, and an acid-treated carbon nanotube nitric oxide sensing fiber is obtained.
更进一步的，制备酸处理碳纳米管银-氯化银传感纤维的具体步骤为：Furthermore, the specific steps for preparing acid-treated carbon nanotube silver-silver chloride sensing fiber are:
配置0.1mol/L硝酸银-0.1mol/L硝酸钾溶液，作为电解液C；Prepare 0.1mol/L silver nitrate-0.1mol/L potassium nitrate solution as electrolyte C;
酸处理碳纳米管纤维作为工作电极，银-氯化银电极作为参比电极，铂电极作为对电极，将三个电极浸入电解液C中，用循环伏安法对工作电极进行循环次数为14次的扫描，扫描速率为0.1V s-1，扫描范围为-0.9V～0.9V；The acid-treated carbon nanotube fiber was used as the working electrode, the silver-silver chloride electrode was used as the reference electrode, and the platinum electrode was used as the counter electrode. The three electrodes were immersed in the electrolyte C, and the working electrode was cycled for 14 times using cyclic voltammetry. times of scanning, the scanning rate is 0.1V s-1 , and the scanning range is -0.9V~0.9V;
由硝酸银中被还原的银元素形成的银颗粒电化学沉积于酸处理碳纳米管纤维表面，得到镀银后的碳纳米管纤维。Silver particles formed from reduced silver elements in silver nitrate are electrochemically deposited on the surface of acid-treated carbon nanotube fibers to obtain silver-plated carbon nanotube fibers.
更进一步的，制备酸处理碳纳米管银-氯化银传感纤维的具体步骤为：Furthermore, the specific steps for preparing acid-treated carbon nanotube silver-silver chloride sensing fiber are:
配置0.1mmol/L盐酸-0.01mol/L氯化钾溶液，作为电解液D，镀银后的碳纳米管纤维作为工作电极，银-氯化银电极作为参比电极，铂电极作为对电极，将三个电极浸入电解液D中，用循环伏安法对工作电极进行循环次数为4次的扫描，扫描速率为0.05V s-1，扫描范围为-0.15V～1.05V，对镀银后的酸处理碳纳米管纤维进行氯化，得到银-氯化银酸处理碳纳米管纤维。Configure 0.1mmol/L hydrochloric acid-0.01mol/L potassium chloride solution as electrolyte D, silver-plated carbon nanotube fiber as the working electrode, silver-silver chloride electrode as the reference electrode, and platinum electrode as the counter electrode. Immerse the three electrodes in the electrolyte D, and use cyclic voltammetry to scan the working electrode for 4 cycles. The scanning rate is 0.05V s-1 and the scanning range is -0.15V ~ 1.05V. After silver plating, The acid-treated carbon nanotube fibers are chlorinated to obtain silver-silver chloride acid-treated carbon nanotube fibers.
更进一步的，制备酸处理碳纳米管银-氯化银传感纤维的具体步骤为：Furthermore, the specific steps for preparing acid-treated carbon nanotube silver-silver chloride sensing fiber are:
将1mg～200mg聚乙烯醇缩丁醛树脂、1mg～100mg氯化钠、1mg～100mg聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物和1mg～10mg的MWCNT溶解于1ml甲醇中，得到PVB混合溶液；Dissolve 1mg~200mg polyvinyl butyral resin, 1mg~100mg sodium chloride, 1mg~100mg polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and 1mg~10mg MWCNT In 1 ml of methanol, obtain a PVB mixed solution;
取1滴PVB混合溶液均匀涂覆到银-氯化银酸处理碳纳米管纤维表面，得到酸处理碳纳米管银-氯化银传感纤维。Take 1 drop of the PVB mixed solution and apply it evenly on the surface of the silver-silver chloride acid-treated carbon nanotube fiber to obtain the acid-treated carbon nanotube silver-silver chloride sensing fiber.
更进一步的，制备基于酸处理碳纳米管纤维的颅内一氧化氮传感器的具体步骤为：Furthermore, the specific steps for preparing an intracranial nitric oxide sensor based on acid-treated carbon nanotube fibers are:
将酸处理碳纳米管一氧化氮传感纤维和酸处理碳纳米管银-氯化银传感纤维的传感部位平行排列，使其具有轴向位移差，将两根纤维一端固定，另一端固定在旋转装置上，运行旋转装置，将两根纤维缠绕在一起，形成螺旋结构，得到基于酸处理碳纳米管纤维的颅内一氧化氮电化学传感器。Arrange the sensing parts of the acid-treated carbon nanotube nitric oxide sensing fiber and the acid-treated carbon nanotube silver-silver chloride sensing fiber in parallel so that they have an axial displacement difference. Fix one end of the two fibers and fix the other end. Fix it on the rotating device, run the rotating device, wind the two fibers together to form a spiral structure, and obtain an intracranial nitric oxide electrochemical sensor based on acid-treated carbon nanotube fibers.
根据上述颅内一氧化氮电化学传感器的制备方法制备的颅内一氧化氮电化学传感器，包括，The intracranial nitric oxide electrochemical sensor prepared according to the above preparation method of the intracranial nitric oxide electrochemical sensor includes,
酸处理碳纳米管一氧化氮传感纤维和酸处理碳纳米管银-氯化银传感纤维，所述酸处理碳纳米管一氧化氮传感纤维和所述酸处理碳纳米管银-氯化银传感纤维的传感部位相互缠绕，形成螺旋结构；Acid-treated carbon nanotube nitric oxide sensing fiber and acid-treated carbon nanotube silver-silver chloride sensing fiber, said acid-treated carbon nanotube nitric oxide sensing fiber and said acid-treated carbon nanotube silver-chloride The sensing parts of the silver sensing fiber are entangled with each other to form a spiral structure;
所述酸处理碳纳米管一氧化氮传感纤维包括酸处理纳米管纤维、铂纳米颗粒、聚丁香酚和全氟磺酸薄膜，所述铂纳米颗粒和所述聚丁香酚沉积在所述酸处理纳米管纤维表面，所述全氟磺酸薄均匀涂覆在沉积所述纳米颗粒以及所述聚丁香酚后的酸处理纳米管纤维表面；The acid-treated carbon nanotube nitric oxide sensing fiber includes acid-treated nanotube fiber, platinum nanoparticles, polyeugenol and perfluorosulfonic acid film, and the platinum nanoparticles and the polyeugenol are deposited on the acid Treating the surface of the nanotube fiber, the perfluorosulfonic acid is thinly and uniformly coated on the surface of the acid-treated nanotube fiber after depositing the nanoparticles and the polyeugenol;
所述酸处理碳纳米管银-氯化银传感纤维包括酸处理纳米管纤维、银颗粒和PVB混合溶液，所述银颗粒沉积在所述酸处理纳米管纤维表面，所述PVB混合溶液均匀涂覆在沉积所述银颗粒后的酸处理纳米管纤维表面。The acid-treated carbon nanotube silver-silver chloride sensing fiber includes acid-treated nanotube fiber, silver particles and PVB mixed solution, the silver particles are deposited on the surface of the acid-treated nanotube fiber, and the PVB mixed solution is uniform Coating the surface of acid-treated nanotube fibers after depositing the silver particles.
3.有益效果3. Beneficial effects
相比于现有技术，本发明的优点在于：Compared with the existing technology, the advantages of the present invention are:
本发明利用酸处理碳纳米管纤维，酸处理碳纳米管纤维具有优异的电化学比表面积和丰富的含氧官能团，促进了碳纳米管纤维对一氧化氮的吸附能力，增强了电极表面的反应速率，显著提高了传感器的灵敏度，并降低了检测下限。The invention uses acid to treat carbon nanotube fibers. The acid-treated carbon nanotube fibers have excellent electrochemical specific surface area and rich oxygen-containing functional groups, which promotes the adsorption capacity of carbon nanotube fibers to nitric oxide and enhances the reaction on the electrode surface. rate, significantly improving the sensitivity of the sensor and lowering the lower detection limit.
本发明利用酸处理碳纳米管纤维，酸处理碳纳米管纤维可以与生物组织的力学性能相匹配，在植入大脑后不会引起脑部的神经炎症反应以及额外的一氧化氮表达从而显著提高了传感的准确性。The present invention utilizes acid-treated carbon nanotube fibers. The acid-treated carbon nanotube fibers can match the mechanical properties of biological tissues. After being implanted into the brain, they will not cause neuroinflammatory reactions in the brain and additional nitric oxide expression, thereby significantly improving improve the accuracy of sensing.
附图说明Description of drawings
图1为本发明一实施例中颅内电化学一氧化氮传感器的结构示意图；Figure 1 is a schematic structural diagram of an intracranial electrochemical nitric oxide sensor in one embodiment of the present invention;
图2为本发明一实施例中酸处理碳纳米管一氧化氮传感纤维的结构示意图；Figure 2 is a schematic structural diagram of an acid-treated carbon nanotube nitric oxide sensing fiber in one embodiment of the present invention;
图3为本发明一实施例中酸处理碳纳米管一氧化氮传感纤维的一氧化氮吸附能力示意图；Figure 3 is a schematic diagram of the nitric oxide adsorption capacity of acid-treated carbon nanotube nitric oxide sensing fibers in one embodiment of the present invention;
图4为本发明一实施例中酸处理碳纳米管一氧化氮传感纤维的性能示意图；Figure 4 is a schematic diagram of the performance of acid-treated carbon nanotube nitric oxide sensing fibers in one embodiment of the present invention;
图5为本发明一实施例中酸处理碳纳米管一氧化氮传感纤维的生物相容性示意图；Figure 5 is a schematic diagram of the biocompatibility of acid-treated carbon nanotube nitric oxide sensing fibers in one embodiment of the present invention;
图6为本发明一实施例中的颅内电化学一氧化氮传感器植入大鼠脑部示意图；Figure 6 is a schematic diagram of an intracranial electrochemical nitric oxide sensor implanted into the brain of a rat in one embodiment of the present invention;
图7为本发明一实施例中酸处理碳纳米管纤维的颅内电化学一氧化氮传感器植入大鼠脑部后检测到大脑中一氧化氮浓度的变化示意图；Figure 7 is a schematic diagram of changes in the concentration of nitric oxide in the brain detected after the intracranial electrochemical nitric oxide sensor of acid-treated carbon nanotube fibers is implanted into the brain of a rat in one embodiment of the present invention;
图8为本发明一实施例中的颅内电化学一氧化氮传感器植入大鼠脑部后检测到脑卒中疾病模型中一氧化氮浓度的变化示意图；Figure 8 is a schematic diagram of changes in nitric oxide concentration detected in a stroke model after the intracranial electrochemical nitric oxide sensor is implanted into the brain of a rat in one embodiment of the present invention;
图9为本发明一实施例中的颅内电化学一氧化氮传感器植入大鼠脑部后检测到脑卒中疾病模型中的大鼠的行为学示意图。Figure 9 is a schematic diagram of the behavior of a rat in a stroke disease model detected after the intracranial electrochemical nitric oxide sensor is implanted in the brain of the rat in one embodiment of the present invention.
图中标号说明：10、颅内电化学一氧化氮传感器；100、酸处理碳纳米管一氧化氮传感纤维；200、酸处理碳纳米管银-氯化银传感纤维；110、酸处理纳米管纤维；120、铂纳米颗粒；130、聚丁香酚；140、全氟磺酸薄膜。Description of numbers in the figure: 10. Intracranial electrochemical nitric oxide sensor; 100. Acid-treated carbon nanotube nitric oxide sensing fiber; 200. Acid-treated carbon nanotube silver-silver chloride sensing fiber; 110. Acid-treated Nanotube fiber; 120, platinum nanoparticles; 130, polyeugenol; 140, perfluorosulfonic acid film.
具体实施方式Detailed ways
下面结合说明书附图和具体的实施例，对本发明作详细描述。The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
实施例1Example 1
如图1所示，本方案提供了一种颅内一氧化氮电化学传感器10，包括酸处理碳纳米管一氧化氮传感纤维100和酸处理碳纳米管银-氯化银传感纤维200。酸处理碳纳米管一氧化氮传感纤维100包括酸处理纳米管纤维110、铂纳米颗粒120、聚丁香酚130和全氟磺酸薄膜140，其中铂纳米颗粒120和聚丁香酚130沉积在酸处理纳米管纤维110表面，全氟磺酸薄膜140涂覆在沉积纳米颗粒120以及聚丁香酚130后的酸处理纳米管纤维110表面。酸处理碳纳米管银-氯化银传感纤维包括酸处理纳米管纤维、银颗粒和PVB混合溶液，银颗粒沉积在酸处理纳米管纤维表面，PVB混合溶液均匀涂覆在沉积银颗粒后的酸处理纳米管纤维表面。As shown in Figure 1, this solution provides an intracranial nitric oxide electrochemical sensor 10, including an acid-treated carbon nanotube nitric oxide sensing fiber 100 and an acid-treated carbon nanotube silver-silver chloride sensing fiber 200 . The acid-treated carbon nanotube nitric oxide sensing fiber 100 includes acid-treated nanotube fiber 110, platinum nanoparticles 120, polyeugenol 130 and perfluorosulfonic acid film 140, wherein the platinum nanoparticles 120 and polyeugenol 130 are deposited in the acid The surface of the nanotube fiber 110 is treated, and the perfluorosulfonic acid film 140 is coated on the acid-treated surface of the nanotube fiber 110 after depositing the nanoparticles 120 and polyeugenol 130 . The acid-treated carbon nanotube silver-silver chloride sensing fiber includes acid-treated nanotube fiber, silver particles and PVB mixed solution. The silver particles are deposited on the surface of the acid-treated nanotube fiber, and the PVB mixed solution is evenly coated on the surface after depositing the silver particles. Acid-treated nanotube fiber surface.
酸处理碳纳米管一氧化氮传感纤维作为工作电极感知颅内的一氧化氮信号分子，酸处理碳纳米管银-氯化银传感纤维作为参比电极，酸处理碳纳米管一氧化氮传感纤维和酸处理碳纳米管银-氯化银传感纤维的传感部位平行排列，形成螺旋结构。The acid-treated carbon nanotube nitric oxide sensing fiber is used as the working electrode to sense intracranial nitric oxide signal molecules. The acid-treated carbon nanotube silver-silver chloride sensing fiber is used as the reference electrode. The acid-treated carbon nanotube nitric oxide sensor fiber is used as the reference electrode. The sensing parts of the sensing fiber and the acid-treated carbon nanotube silver-silver chloride sensing fiber are arranged in parallel to form a spiral structure.
本发明在酸处理碳纳米管纤维上电化学沉积活性物质来开发颅内新型电化学一氧化氮传感器。该传感器利用碳纳米管纤维优异的比表面积和丰富的含氧官能团，比表面积是指单位质量物料所具有的总面积，提高了电极对溶液中一氧化氮的吸附能力，实现了达到3245pA·nM-1的灵敏度，且检测下限达到了0.1nmol/L。The present invention develops a new intracranial electrochemical nitric oxide sensor by electrochemically depositing active substances on acid-treated carbon nanotube fibers. This sensor utilizes the excellent specific surface area and abundant oxygen-containing functional groups of carbon nanotube fibers. The specific surface area refers to the total area per unit mass of material to improve the electrode's adsorption capacity of nitric oxide in the solution, achieving a detection rate of 3245pA·nM.-1 sensitivity, and the lower detection limit reaches 0.1nmol/L.
本发明开发的颅内电化学一氧化氮传感器具有高柔性，与脑组织力学性能相匹配，不会引起炎症反应以及额外的一氧化氮表达。另外，该传感还具有高度的选择性和稳定性，可以植入到目标脑区实时监测不同生理状态下一氧化氮的浓度变化，在可植入传感领域具有广阔的应用前景。The intracranial electrochemical nitric oxide sensor developed by the present invention is highly flexible, matches the mechanical properties of brain tissue, and will not cause inflammatory reactions or additional nitric oxide expression. In addition, the sensor is highly selective and stable and can be implanted into the target brain area to monitor changes in nitric oxide concentration in different physiological states in real time. It has broad application prospects in the field of implantable sensing.
本实施例公开一种颅内一氧化氮电化学传感的制备方法，包括以下步骤，This embodiment discloses a preparation method for intracranial nitric oxide electrochemical sensing, which includes the following steps:
制备酸处理碳纳米管一氧化氮传感纤维：Preparation of acid-treated carbon nanotube nitric oxide sensing fibers:
将碳纳米管纤维浸泡在20mL的浓度为98％的硝酸溶液中，并在25℃静置12小时后，静置完毕后用去离子水进行洗涤，洗涤完毕后进行干燥，得到酸处理碳纳米管纤维；Soak the carbon nanotube fiber in 20 mL of nitric acid solution with a concentration of 98%, and let it stand at 25°C for 12 hours. After the rest is completed, it is washed with deionized water and dried after the washing is completed to obtain the acid-treated carbon nanotube fiber. tube fiber;
通过配置1×10-3mol/L氯铂酸钾-0.1mol/L氯化钾溶液，得到电解液A。将得到的酸处理碳纳米管纤维作为工作电极，银-氯化银电极作为参比电极，铂电极作为对电极，将三个电极浸入电解液A中，通过恒电位极化法在工作电极上交替施加0.5V和-0.7V的电压，总共持续10秒，并重复该过程50次。Electrolyte solution A is obtained by preparing a 1×10-3 mol/L potassium chloroplatinate-0.1 mol/L potassium chloride solution. The obtained acid-treated carbon nanotube fiber was used as the working electrode, the silver-silver chloride electrode was used as the reference electrode, and the platinum electrode was used as the counter electrode. The three electrodes were immersed in the electrolyte A, and the electrodes were polarized on the working electrode through the constant potential polarization method. Apply voltages of 0.5V and -0.7V alternately for a total of 10 seconds, and repeat the process 50 times.
在此步骤中，氯铂酸钾中的铂元素被还原，形成铂纳米颗粒，从而实现铂纳米颗粒在酸处理碳纳米管纤维表面的沉积，得到沉积铂纳米颗粒后的酸处理碳纳米管纤维。In this step, the platinum element in potassium chloroplatinate is reduced to form platinum nanoparticles, thereby realizing the deposition of platinum nanoparticles on the surface of the acid-treated carbon nanotube fiber, and obtaining the acid-treated carbon nanotube fiber after depositing the platinum nanoparticles. .
配置60mL的0.1mol/L的氢氧化钠溶液，用氩气将氢氧化钠溶液的氧气除尽，加入10mmol/L的丁香酚得到电解液B，沉积铂纳米颗粒后的酸处理碳纳米管纤维作为工作电极，银-氯化银电极作为参比电极，铂电极作为对电极，将三个电极浸入电解液B中，用循环伏安法对工作电极进行循环次数为10次的扫描，扫描速率为20mV s-1，扫描范围为0V至0.7V。Prepare 60 mL of 0.1 mol/L sodium hydroxide solution, use argon to remove all oxygen from the sodium hydroxide solution, add 10 mmol/L eugenol to obtain electrolyte B, and acid-treat carbon nanotube fibers after depositing platinum nanoparticles. As the working electrode, the silver-silver chloride electrode is used as the reference electrode, and the platinum electrode is used as the counter electrode. The three electrodes are immersed in electrolyte B, and the working electrode is scanned for 10 cycles using cyclic voltammetry. The scan rate is 20mV s-1 and the scanning range is 0V to 0.7V.
在此步骤中，丁香酚被电化学聚合在工作电极表面，形成聚丁香酚薄膜，此过程实现了聚丁香酚在沉积铂纳米颗粒后的酸处理碳纳米管纤维表面的沉积，得到沉积铂纳米颗粒以及聚丁香酚后的酸处理碳纳米管纤维。In this step, eugenol is electrochemically polymerized on the surface of the working electrode to form a polyeugenol film. This process realizes the deposition of polyeugenol on the acid-treated carbon nanotube fiber surface after depositing platinum nanoparticles, and obtains deposited platinum nanoparticles. particles as well as acid-treated carbon nanotube fibers after polyeugenol.
准备全氟磺酸型聚合物溶液，并将全氟磺酸型聚合物溶液稀释到5wt％，取5μL稀释后的全氟磺酸型聚合物溶液均匀涂覆在沉积铂纳米颗粒以及聚丁香酚后的酸处理碳纳米管纤维表面，全氟磺酸型聚合物溶液干燥后形成全氟磺酸薄膜，得到酸处理碳纳米管一氧化氮传感纤维。其中wt％是重量(质量)百分数的单位,表示重量比及一种物质占混合物的比重。Prepare a perfluorosulfonic acid polymer solution and dilute the perfluorosulfonic acid polymer solution to 5wt%. Take 5 μL of the diluted perfluorosulfonic acid polymer solution and apply it evenly on the deposited platinum nanoparticles and polyeugenol. After acid-treating the surface of the carbon nanotube fiber, the perfluorosulfonic acid polymer solution is dried to form a perfluorosulfonic acid film, and the acid-treated carbon nanotube nitric oxide sensing fiber is obtained. Among them, wt% is the unit of weight (mass) percentage, which represents the weight ratio and the proportion of a substance in the mixture.
如图2所示，为酸处理碳纳米管一氧化氮传感纤维的结构示意图。As shown in Figure 2, it is a schematic structural diagram of acid-treated carbon nanotube nitric oxide sensing fiber.
根据上述步骤制备的酸处理碳纳米管一氧化氮传感纤维具有优异的比表面积和丰富的含氧官能团，增强了传感纤维对一氧化氮的吸附能力。由此可知，酸处理碳纳米管一氧化氮传感纤维对一氧化氮的吸附能力分别比碳纤维和铂丝高出11倍和13倍。The acid-treated carbon nanotube nitric oxide sensing fiber prepared according to the above steps has excellent specific surface area and abundant oxygen-containing functional groups, which enhances the adsorption capacity of the sensing fiber for nitric oxide. It can be seen that the acid-treated carbon nanotube nitric oxide sensing fiber has a nitric oxide adsorption capacity that is 11 times and 13 times higher than that of carbon fiber and platinum wire respectively.
如图3所示，为酸处理碳纳米管一氧化氮传感纤维的一氧化氮吸附能力示意图，如图4所示，为酸处理碳纳米管一氧化氮传感纤维的性能示意图。根据上述步骤制备的酸处理碳纳米管一氧化氮传感纤维灵敏度达到了3245pA·nM-1，且检测下限达到了0.1nmol/L，均优异于迄今为止报道的颅内一氧化氮传感。As shown in Figure 3, it is a schematic diagram of the nitric oxide adsorption capacity of acid-treated carbon nanotube nitric oxide sensing fibers. As shown in Figure 4, it is a schematic diagram of the performance of acid-treated carbon nanotube nitric oxide sensing fibers. The acid-treated carbon nanotube nitric oxide sensing fiber prepared according to the above steps has a sensitivity of 3245pA·nM-1 and a lower detection limit of 0.1nmol/L, both of which are superior to intracranial nitric oxide sensing reported so far.
如图5所示，为制备的酸处理碳纳米管一氧化氮传感纤维的生物相容性示意图，根据上述步骤制备的酸处理碳纳米管一氧化氮传感纤维的力学性能与脑组织相匹配，相比于刚性的碳纤维和铂丝，酸处理碳纳米管一氧化氮传感纤维在植入后不会引发严重的神经炎症反应和iNOS的过度表达，进而不会影响一氧化氮检测信号的准确性。As shown in Figure 5, it is a schematic diagram of the biocompatibility of the acid-treated carbon nanotube nitric oxide sensing fiber prepared according to the above steps. The mechanical properties of the acid-treated carbon nanotube nitric oxide sensing fiber prepared according to the above steps are similar to those of brain tissue. Matching, compared with rigid carbon fibers and platinum wires, acid-treated carbon nanotube nitric oxide sensing fibers will not trigger severe neuroinflammatory reactions and overexpression of iNOS after implantation, and will not affect the nitric oxide detection signal. accuracy.
其中，iNOS为在损伤后诱导表达的诱导型一氧化氮合酶。一氧化氮合酶(NOS)属于神经系统，其同功酶有三种亚型，即在正常状态下表达的神经元型一氧化氮合酶(nNOS)和内皮型一氧化氮合酶(eNOS)以及在损伤后诱导表达的诱导型一氧化氮合酶(iNOS)。Among them, iNOS is an inducible nitric oxide synthase whose expression is induced after injury. Nitric oxide synthase (NOS) belongs to the nervous system, and its isoenzyme has three subtypes, namely neuronal nitric oxide synthase (nNOS) and endothelial nitric oxide synthase (eNOS) expressed under normal conditions. and inducible nitric oxide synthase (iNOS), whose expression is induced after injury.
制备酸处理碳纳米管银-氯化银传感纤维：Preparation of acid-treated carbon nanotube silver-silver chloride sensing fiber:
将碳纳米管纤维浸泡在20mL浓度为98％的硝酸溶液中，并在25℃下静置12小时后，再用去离子水洗涤碳纳米管纤维，在洗涤结束后对碳纳米管纤维进行干燥，得到酸处理碳纳米管纤维；Soak the carbon nanotube fiber in 20 mL of 98% nitric acid solution, and let it stand at 25°C for 12 hours. Then wash the carbon nanotube fiber with deionized water, and dry the carbon nanotube fiber after washing. , obtain acid-treated carbon nanotube fibers;
配置0.1mol/L硝酸银-0.1mol/L硝酸钾溶液得到电解液C，酸处理碳纳米管纤维作为工作电极，银-氯化银电极作为参比电极，铂电极作为对电极，将三个电极浸入电解液C中，用循环伏安法对工作电极进行循环次数为14次的扫描，扫描速率为0.1V s-1，扫描范围为-0.9V至0.9V。Configure 0.1mol/L silver nitrate-0.1mol/L potassium nitrate solution to obtain electrolyte C. The acid-treated carbon nanotube fiber is used as the working electrode, the silver-silver chloride electrode is used as the reference electrode, and the platinum electrode is used as the counter electrode. Three The electrode was immersed in electrolyte C, and the working electrode was scanned for 14 cycles using cyclic voltammetry, with a scan rate of 0.1V s-1 and a scan range of -0.9V to 0.9V.
在此过程中，硝酸银中的银元素被还原，形成银颗粒，从而将银电化学沉积到酸处理碳纳米管纤维表面，得到镀银后的碳纳米管纤维。During this process, the silver element in silver nitrate is reduced to form silver particles, thereby electrochemically depositing silver onto the surface of acid-treated carbon nanotube fibers to obtain silver-plated carbon nanotube fibers.
配置0.1mmol/L盐酸-0.01mol/L氯化钾溶液作为电解液D，镀银后的碳纳米管纤维作为工作电极，银-氯化银电极作为参比电极，铂电极作为对电极，将三个电极浸入电解液D中，用循环伏安法对工作电极进行循环次数为4次的扫描，扫描速率为0.05V s-1，扫描范围为-0.15V至1.05V，对镀银后的酸处理碳纳米管纤维进行氯化，得到银-氯化银酸处理碳纳米管纤维；Configure 0.1mmol/L hydrochloric acid-0.01mol/L potassium chloride solution as electrolyte D, silver-plated carbon nanotube fiber as the working electrode, silver-silver chloride electrode as the reference electrode, and platinum electrode as the counter electrode. Three electrodes were immersed in electrolyte D, and the working electrode was scanned for 4 cycles using cyclic voltammetry. The scanning rate was 0.05V s-1 and the scanning range was -0.15V to 1.05V. After silver plating, the Acid-treated carbon nanotube fibers are chlorinated to obtain silver-silver chloride acid-treated carbon nanotube fibers;
将1mg聚乙烯醇缩丁醛树脂、1mg氯化钠、1mg聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物和1mg的MWCNT(碳纳米管)溶解于1ml甲醇中，得到PVB(聚乙烯醇缩丁醛酯)混合溶液；取1滴PVB混合溶液均匀涂覆到银-氯化银酸处理碳纳米管纤维表面，制备得到酸处理碳纳米管银-氯化银传感纤维。Dissolve 1 mg polyvinyl butyral resin, 1 mg sodium chloride, 1 mg polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and 1 mg MWCNT (carbon nanotube) in 1 ml methanol , obtain a PVB (polyvinyl butyral ester) mixed solution; take 1 drop of the PVB mixed solution and evenly coat it on the surface of the silver-silver chloride acid-treated carbon nanotube fiber to prepare the acid-treated silver-chlorinated carbon nanotube Silver sensing fiber.
制备基于酸处理碳纳米管纤维的颅内一氧化氮传感器：Preparation of intracranial nitric oxide sensor based on acid-treated carbon nanotube fibers:
酸处理碳纳米管一氧化氮传感纤维和酸处理碳纳米管银-氯化银传感纤维的传感部位平行排列，并具有一定的轴向位移差。两根纤维的一端用旋转电机轴固定，另一端用胶带固定，电机以50rad·min-1的转速运行，将两根纤维缠绕在一起，形成螺旋结构，得到基于酸处理碳纳米管纤维的颅内一氧化氮电化学传感器。The sensing parts of the acid-treated carbon nanotube nitric oxide sensing fiber and the acid-treated carbon nanotube silver-silver chloride sensing fiber are arranged in parallel and have a certain axial displacement difference. One end of the two fibers is fixed with a rotating motor shaft, and the other end is fixed with a tape. The motor runs at a speed of 50rad·min-1 , and the two fibers are wound together to form a spiral structure, and a skull based on acid-treated carbon nanotube fibers is obtained. Internal nitric oxide electrochemical sensor.
作为本实施例的另一种实现方式，上述步骤中的电机也可以25rad·min-1、75rad·min-1、100rad·min-1、200rad·min-1的速度运行，将纤维束缠绕在一起。As another implementation of this embodiment, the motor in the above steps can also run at a speed of 25rad·min-1 , 75rad·min-1 , 100rad·min-1 , or 200rad·min-1 to wind the fiber bundle around Together.
在实际应用中，如图6至图9所示，为基于酸处理碳纳米管纤维的颅内新型电化学一氧化氮传感器的应用示例示意图。In practical applications, Figures 6 to 9 are schematic diagrams of application examples of a new intracranial electrochemical nitric oxide sensor based on acid-treated carbon nanotube fibers.
其中，如图6所示，为传感器植入到大鼠脑部的示意图。如图7所示，为各一氧化氮传感器检测大脑中一氧化氮浓度的变化比较示意图。在大鼠脑中局部注射L-精氨酸以刺激一氧化氮的产生，相比于基于碳纤维和铂丝的一氧化氮传感器，基于酸处理碳纳米管纤维的颅内新型电化学一氧化氮传感器成功地检测到大脑中一氧化氮浓度的变化。Among them, as shown in Figure 6, it is a schematic diagram of the sensor being implanted into the brain of a rat. As shown in Figure 7, it is a schematic diagram comparing the changes in nitric oxide concentration detected by each nitric oxide sensor in the brain. Novel intracranial electrochemical nitric oxide sensor based on acid-treated carbon nanotube fibers compared to carbon fiber and platinum wire-based nitric oxide sensors after local injection of L-arginine in the rat brain to stimulate nitric oxide production The sensor successfully detected changes in nitric oxide concentrations in the brain.
如图8至图9所示所示，进一步使用一氧化氮传感器，在大鼠缺血性脑卒中模型中，研究了大脑皮质中一氧化氮浓度的变化。如图8所示，为颅内电化学一氧化氮传感器植入大鼠脑部后检测到脑卒中疾病模型中一氧化氮浓度的变化示意图，基于酸处理碳纳米管纤维的颅内新型电化学一氧化氮传感器显示出快速且准确的响应电流，严重缺血性脑卒中组中大脑皮质中一氧化氮浓度显著增加，而轻度缺血性脑卒中组中一氧化氮浓度变化较小。如图9所示，为颅内电化学一氧化氮传感器植入大鼠脑部后检测到脑卒中疾病模型中的大鼠的行为学示意图，进行严重缺血性脑卒中实验的大鼠的总移动距离和粪便数量高于进行轻度缺血性脑卒中实验的大鼠，与大脑皮质中的一氧化氮变化一致。该示例可进一步表明基于酸处理碳纳米管纤维的颅内新型电化学一氧化氮传感器在脑科学研究方面的潜力。As shown in Figures 8 to 9, a nitric oxide sensor was further used to study changes in nitric oxide concentration in the cerebral cortex in a rat ischemic stroke model. As shown in Figure 8, it is a schematic diagram of the changes in nitric oxide concentration detected in the stroke model after the intracranial electrochemical nitric oxide sensor was implanted in the rat brain. A new intracranial electrochemical sensor based on acid-treated carbon nanotube fibers. The nitric oxide sensor showed a fast and accurate response current, and the nitric oxide concentration in the cerebral cortex increased significantly in the severe ischemic stroke group, while the nitric oxide concentration changed less in the mild ischemic stroke group. As shown in Figure 9, it is a schematic diagram of the behavior of rats in a stroke disease model after an intracranial electrochemical nitric oxide sensor was implanted in the rat brain. The overall behavior of rats undergoing severe ischemic stroke experiments is shown in Figure 9. Movement distance and feces count were higher than in rats undergoing mild ischemic stroke experiments, consistent with changes in nitric oxide in the cerebral cortex. This example may further demonstrate the potential of novel intracranial electrochemical nitric oxide sensors based on acid-treated carbon nanotube fibers for brain science research.
实施例2Example 2
本实施例公开一种颅内一氧化氮电化学传感的制备方法，包括以下步骤，This embodiment discloses a preparation method for intracranial nitric oxide electrochemical sensing, which includes the following steps:
制备酸处理碳纳米管一氧化氮传感纤维：Preparation of acid-treated carbon nanotube nitric oxide sensing fibers:
将碳纳米管纤维浸泡在20mL的浓度为98％的硝酸溶液中，并在25℃静置12小时后，静置完毕后用去离子水进行洗涤，洗涤完毕后进行干燥，得到酸处理碳纳米管纤维；Soak the carbon nanotube fiber in 20 mL of nitric acid solution with a concentration of 98%, and let it stand at 25°C for 12 hours. After the rest is completed, it is washed with deionized water and dried after the washing is completed to obtain the acid-treated carbon nanotube fiber. tube fiber;
通过配置1×10-3mol/L氯铂酸钾-0.1mol/L氯化钾溶液，得到电解液A。将得到的酸处理碳纳米管纤维作为工作电极，银-氯化银电极作为参比电极，铂电极作为对电极，将三个电极浸入电解液A中，通过恒电位极化法在工作电极上交替施加0.5V和-0.7V的电压，总共持续10秒，并重复该过程100次。Electrolyte solution A is obtained by preparing a 1×10-3 mol/L potassium chloroplatinate-0.1 mol/L potassium chloride solution. The obtained acid-treated carbon nanotube fiber was used as the working electrode, the silver-silver chloride electrode was used as the reference electrode, and the platinum electrode was used as the counter electrode. The three electrodes were immersed in the electrolyte A, and the electrodes were polarized on the working electrode through the constant potential polarization method. Apply voltages of 0.5V and -0.7V alternately for a total of 10 seconds, and repeat the process 100 times.
在此步骤中，氯铂酸钾中的铂元素被还原，形成铂纳米颗粒，从而实现铂纳米颗粒在酸处理碳纳米管纤维表面的沉积，得到沉积铂纳米颗粒后的酸处理碳纳米管纤维。In this step, the platinum element in potassium chloroplatinate is reduced to form platinum nanoparticles, thereby realizing the deposition of platinum nanoparticles on the surface of the acid-treated carbon nanotube fiber, and obtaining the acid-treated carbon nanotube fiber after depositing the platinum nanoparticles. .
配置60mL的0.1mol/L的氢氧化钠溶液，用氩气将氢氧化钠溶液的氧气除尽，加入5mmol/L的丁香酚得到电解液B，沉积铂纳米颗粒后的酸处理碳纳米管纤维作为工作电极，银-氯化银电极作为参比电极，铂电极作为对电极，将三个电极浸入电解液B中，用循环伏安法对工作电极进行循环次数为10次的扫描，扫描速率为20mV s-1，扫描范围为0V至0.7V。Prepare 60 mL of 0.1 mol/L sodium hydroxide solution, use argon to remove all oxygen from the sodium hydroxide solution, add 5 mmol/L eugenol to obtain electrolyte B, and acid-treat carbon nanotube fibers after depositing platinum nanoparticles. As the working electrode, the silver-silver chloride electrode is used as the reference electrode, and the platinum electrode is used as the counter electrode. The three electrodes are immersed in electrolyte B, and the working electrode is scanned for 10 cycles using cyclic voltammetry. The scan rate is 20mV s-1 and the scanning range is 0V to 0.7V.
在此步骤中，丁香酚被电化学聚合在工作电极表面，形成聚丁香酚薄膜，此过程实现了聚丁香酚在沉积铂纳米颗粒后的酸处理碳纳米管纤维表面的沉积，得到沉积铂纳米颗粒以及聚丁香酚后的酸处理碳纳米管纤维。In this step, eugenol is electrochemically polymerized on the surface of the working electrode to form a polyeugenol film. This process realizes the deposition of polyeugenol on the acid-treated carbon nanotube fiber surface after depositing platinum nanoparticles, and obtains deposited platinum nanoparticles. particles as well as acid-treated carbon nanotube fibers after polyeugenol.
准备全氟磺酸型聚合物溶液，并将全氟磺酸型聚合物溶液稀释到2.5wt％，取5μL稀释后的全氟磺酸型聚合物溶液均匀涂覆在沉积铂纳米颗粒以及聚丁香酚后的酸处理碳纳米管纤维表面，干燥后形成薄膜，得到酸处理碳纳米管一氧化氮传感纤维。Prepare a perfluorosulfonic acid polymer solution and dilute the perfluorosulfonic acid polymer solution to 2.5wt%. Take 5 μL of the diluted perfluorosulfonic acid polymer solution and apply it evenly on the deposited platinum nanoparticles and polyclove. The surface of the carbon nanotube fiber is treated with acid after phenol, and a thin film is formed after drying to obtain the acid-treated carbon nanotube nitric oxide sensing fiber.
如图2所示，为酸处理碳纳米管一氧化氮传感纤维的结构示意图。As shown in Figure 2, it is a schematic structural diagram of acid-treated carbon nanotube nitric oxide sensing fiber.
根据上述步骤制备的酸处理碳纳米管一氧化氮传感纤维具有优异的比表面积和丰富的含氧官能团，增强了传感纤维对一氧化氮的吸附能力。由此可知，酸处理碳纳米管一氧化氮传感纤维对一氧化氮的吸附能力分别比碳纤维和铂丝高出11倍和13倍。The acid-treated carbon nanotube nitric oxide sensing fiber prepared according to the above steps has excellent specific surface area and abundant oxygen-containing functional groups, which enhances the adsorption capacity of the sensing fiber for nitric oxide. It can be seen that the acid-treated carbon nanotube nitric oxide sensing fiber has a nitric oxide adsorption capacity that is 11 times and 13 times higher than that of carbon fiber and platinum wire respectively.
如图3所示，为酸处理碳纳米管一氧化氮传感纤维的一氧化氮吸附能力示意图，如图4所示，为酸处理碳纳米管一氧化氮传感纤维的性能示意图。根据上述步骤制备的酸处理碳纳米管一氧化氮传感纤维灵敏度达到了3245pA·nM-1，且检测下限达到了0.1nmol/L，均优异于迄今为止报道的颅内一氧化氮传感。As shown in Figure 3, it is a schematic diagram of the nitric oxide adsorption capacity of acid-treated carbon nanotube nitric oxide sensing fibers. As shown in Figure 4, it is a schematic diagram of the performance of acid-treated carbon nanotube nitric oxide sensing fibers. The acid-treated carbon nanotube nitric oxide sensing fiber prepared according to the above steps has a sensitivity of 3245pA·nM-1 and a lower detection limit of 0.1nmol/L, both of which are superior to intracranial nitric oxide sensing reported so far.
如图5所示，为制备的酸处理碳纳米管一氧化氮传感纤维的生物相容性示意图，根据上述步骤制备的酸处理碳纳米管一氧化氮传感纤维的力学性能与脑组织相匹配，相比于刚性的碳纤维和铂丝，酸处理碳纳米管一氧化氮传感纤维在植入后不会引发严重的神经炎症反应和iNOS的过度表达，进而不会影响一氧化氮检测信号的准确性。As shown in Figure 5, it is a schematic diagram of the biocompatibility of the acid-treated carbon nanotube nitric oxide sensing fiber prepared according to the above steps. The mechanical properties of the acid-treated carbon nanotube nitric oxide sensing fiber prepared according to the above steps are similar to those of brain tissue. Matching, compared with rigid carbon fibers and platinum wires, acid-treated carbon nanotube nitric oxide sensing fibers will not trigger severe neuroinflammatory reactions and overexpression of iNOS after implantation, and will not affect the nitric oxide detection signal. accuracy.
制备酸处理碳纳米管银-氯化银传感纤维：Preparation of acid-treated carbon nanotube silver-silver chloride sensing fiber:
将碳纳米管纤维浸泡在20mL浓度为98％的硝酸溶液中，并在25℃静置12小时后，再用去离子水洗涤碳纳米管纤维，在洗涤结束后对碳纳米管纤维进行干燥，得到酸处理碳纳米管纤维；Soak the carbon nanotube fiber in 20 mL of 98% nitric acid solution, and let it stand at 25°C for 12 hours. Then wash the carbon nanotube fiber with deionized water, and dry the carbon nanotube fiber after washing. Obtain acid-treated carbon nanotube fibers;
配置0.1mol/L硝酸银-0.1mol/L硝酸钾溶液得到电解液C，酸处理碳纳米管纤维作为工作电极，银-氯化银电极作为参比电极，铂电极作为对电极，将三个电极浸入电解液C中，用循环伏安法对工作电极进行循环次数为14次的扫描，扫描速率为0.1V s-1，扫描范围为-0.9V至0.9V。Configure 0.1mol/L silver nitrate-0.1mol/L potassium nitrate solution to obtain electrolyte C. The acid-treated carbon nanotube fiber is used as the working electrode, the silver-silver chloride electrode is used as the reference electrode, and the platinum electrode is used as the counter electrode. Three The electrode was immersed in electrolyte C, and the working electrode was scanned for 14 cycles using cyclic voltammetry, with a scan rate of 0.1V s-1 and a scan range of -0.9V to 0.9V.
在此过程中，硝酸银中的银元素被还原，形成银颗粒，从而将银电化学沉积到酸处理碳纳米管纤维上，得到镀银后的碳纳米管纤维。During this process, the silver element in silver nitrate is reduced to form silver particles, thereby electrochemically depositing silver onto the acid-treated carbon nanotube fibers to obtain silver-plated carbon nanotube fibers.
配置0.1mmol/L盐酸-0.01mol/L氯化钾溶液作为电解液D，镀银后的碳纳米管纤维作为工作电极，银-氯化银电极作为参比电极，铂电极作为对电极，将三个电极浸入电解液D中，用循环伏安法对工作电极进行循环次数为4次的扫描，扫描速率为0.05V s-1，扫描范围为-0.15V至1.05V。对镀银后的酸处理碳纳米管纤维进行氯化，得到银-氯化银酸处理碳纳米管纤维；Configure 0.1mmol/L hydrochloric acid-0.01mol/L potassium chloride solution as electrolyte D, silver-plated carbon nanotube fiber as the working electrode, silver-silver chloride electrode as the reference electrode, and platinum electrode as the counter electrode. Three electrodes were immersed in electrolyte D, and the working electrode was scanned for 4 cycles using cyclic voltammetry. The scan rate was 0.05V s-1 and the scan range was -0.15V to 1.05V. Chloride the silver-plated acid-treated carbon nanotube fibers to obtain silver-silver chloride acid-treated carbon nanotube fibers;
将1mg聚乙烯醇缩丁醛树脂、1mg氯化钠、1mg聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物和1mg的MWCNT(碳纳米管)溶解于1ml甲醇中，得到PVB(聚乙烯醇缩丁醛酯)混合溶液；取1滴PVB混合溶液涂覆到银-氯化银酸处理碳纳米管纤维上，制备得到酸处理碳纳米管银-氯化银传感纤维。Dissolve 1 mg polyvinyl butyral resin, 1 mg sodium chloride, 1 mg polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and 1 mg MWCNT (carbon nanotube) in 1 ml methanol , obtain a PVB (polyvinyl butyral ester) mixed solution; take 1 drop of the PVB mixed solution and coat it on the silver-silver chloride acid-treated carbon nanotube fiber to prepare acid-treated silver carbon nanotube-silver chloride Sensing fibers.
制备基于酸处理碳纳米管纤维的颅内一氧化氮传感器：Preparation of intracranial nitric oxide sensor based on acid-treated carbon nanotube fibers:
酸处理碳纳米管一氧化氮传感纤维和酸处理碳纳米管银-氯化银传感纤维的传感部位平行排列，并具有一定的轴向位移差。两根纤维的一端用旋转电机轴固定，另一端用胶带固定，电机以50rad·min-1的转速运行，将两根纤维缠绕在一起，形成螺旋结构，得到基于酸处理碳纳米管纤维的颅内新型电化学一氧化氮传感器。The sensing parts of the acid-treated carbon nanotube nitric oxide sensing fiber and the acid-treated carbon nanotube silver-silver chloride sensing fiber are arranged in parallel and have a certain axial displacement difference. One end of the two fibers is fixed with a rotating motor shaft, and the other end is fixed with a tape. The motor runs at a speed of 50rad·min-1 , and the two fibers are wound together to form a spiral structure, and a skull based on acid-treated carbon nanotube fibers is obtained. New electrochemical nitric oxide sensor.
作为本实施例的另一种实现方式，上述步骤中的电机也可以25rad·min-1、75rad·min-1、100rad·min-1、200rad·min-1的速度运行，将纤维束缠绕在一起。As another implementation of this embodiment, the motor in the above steps can also run at a speed of 25rad·min-1 , 75rad·min-1 , 100rad·min-1 , or 200rad·min-1 to wind the fiber bundle around Together.
实施例3Example 3
本实施例公开一种颅内一氧化氮电化学传感的制备方法，包括以下步骤，This embodiment discloses a preparation method for intracranial nitric oxide electrochemical sensing, which includes the following steps:
制备酸处理碳纳米管一氧化氮传感纤维：Preparation of acid-treated carbon nanotube nitric oxide sensing fibers:
将碳纳米管纤维浸泡在20mL的浓度为98％的硝酸溶液中，并在25℃静置12小时后，静置完毕后用去离子水进行洗涤，洗涤完毕后进行干燥，得到酸处理碳纳米管纤维；Soak the carbon nanotube fiber in 20 mL of nitric acid solution with a concentration of 98%, and let it stand at 25°C for 12 hours. After the rest is completed, it is washed with deionized water and dried after the washing is completed to obtain the acid-treated carbon nanotube fiber. tube fiber;
通过配置1×10-3mol/L氯铂酸钾-0.1mol/L氯化钾溶液，得到电解液A。将得到的酸处理碳纳米管纤维作为工作电极，银-氯化银电极作为参比电极，铂电极作为对电极，将三个电极浸入电解液A中，通过恒电位极化法在工作电极上交替施加0.5V和-0.7V的电压，持续10秒，并重复该过程150次。Electrolyte solution A is obtained by preparing a 1×10-3 mol/L potassium chloroplatinate-0.1 mol/L potassium chloride solution. The obtained acid-treated carbon nanotube fiber was used as the working electrode, the silver-silver chloride electrode was used as the reference electrode, and the platinum electrode was used as the counter electrode. The three electrodes were immersed in the electrolyte A, and the electrodes were polarized on the working electrode through the constant potential polarization method. Apply voltages of 0.5V and -0.7V alternately for 10 seconds, and repeat the process 150 times.
在此步骤中，氯铂酸钾中的铂元素被还原，形成铂纳米颗粒，从而实现铂纳米颗粒在酸处理碳纳米管纤维表面的沉积，得到沉积铂纳米颗粒后的酸处理碳纳米管纤维。In this step, the platinum element in potassium chloroplatinate is reduced to form platinum nanoparticles, thereby realizing the deposition of platinum nanoparticles on the surface of the acid-treated carbon nanotube fiber, and obtaining the acid-treated carbon nanotube fiber after depositing the platinum nanoparticles. .
配置60mL的0.1mol/L的氢氧化钠溶液，用氩气将氢氧化钠溶液的氧气除尽，加入15mmol/L的丁香酚得到电解液B。沉积铂纳米颗粒后的酸处理碳纳米管纤维作为工作电极，银-氯化银电极作为参比电极，铂电极作为对电极，将三个电极浸入电解液B中，用循环伏安法对工作电极进行循环次数为10次的扫描，扫描速率为20mV s-1，扫描范围为0V至0.7V。Prepare 60 mL of 0.1 mol/L sodium hydroxide solution, use argon to remove all oxygen from the sodium hydroxide solution, and add 15 mmol/L eugenol to obtain electrolyte B. The acid-treated carbon nanotube fiber after depositing platinum nanoparticles was used as the working electrode, the silver-silver chloride electrode was used as the reference electrode, and the platinum electrode was used as the counter electrode. The three electrodes were immersed in electrolyte B, and the work was performed using cyclic voltammetry. The electrode is scanned for 10 cycles, the scan rate is 20mV s-1 , and the scan range is 0V to 0.7V.
在此步骤中，丁香酚被电化学聚合在工作电极表面，形成聚丁香酚薄膜，此过程实现了聚丁香酚在沉积铂纳米颗粒后的酸处理碳纳米管纤维表面的沉积，得到沉积铂纳米颗粒以及聚丁香酚后的酸处理碳纳米管纤维。In this step, eugenol is electrochemically polymerized on the surface of the working electrode to form a polyeugenol film. This process realizes the deposition of polyeugenol on the acid-treated carbon nanotube fiber surface after depositing platinum nanoparticles, and obtains deposited platinum nanoparticles. particles as well as acid-treated carbon nanotube fibers after polyeugenol.
准备全氟磺酸型聚合物溶液，并将全氟磺酸型聚合物溶液稀释到1.5wt％，取5μL稀释后的全氟磺酸型聚合物溶液均匀涂覆在沉积铂纳米颗粒以及聚丁香酚后的酸处理碳纳米管纤维表面，全氟磺酸型聚合物溶液干燥后形成全氟磺酸薄膜，得到酸处理碳纳米管一氧化氮传感纤维。Prepare the perfluorosulfonic acid polymer solution and dilute the perfluorosulfonic acid polymer solution to 1.5wt%. Take 5 μL of the diluted perfluorosulfonic acid polymer solution and apply it evenly on the deposited platinum nanoparticles and polyclove. The surface of the carbon nanotube fiber is treated with acid after phenol, and the perfluorosulfonic acid polymer solution is dried to form a perfluorosulfonic acid film, thereby obtaining the acid-treated carbon nanotube nitric oxide sensing fiber.
如图2所示，为酸处理碳纳米管一氧化氮传感纤维的结构示意图。As shown in Figure 2, it is a schematic structural diagram of acid-treated carbon nanotube nitric oxide sensing fiber.
根据上述步骤制备的酸处理碳纳米管一氧化氮传感纤维具有优异的比表面积和丰富的含氧官能团，增强了传感纤维对一氧化氮的吸附能力。由此可知，酸处理碳纳米管一氧化氮传感纤维对一氧化氮的吸附能力分别比碳纤维和铂丝高出11倍和13倍。The acid-treated carbon nanotube nitric oxide sensing fiber prepared according to the above steps has excellent specific surface area and abundant oxygen-containing functional groups, which enhances the adsorption capacity of the sensing fiber for nitric oxide. It can be seen that the acid-treated carbon nanotube nitric oxide sensing fiber has a nitric oxide adsorption capacity that is 11 times and 13 times higher than that of carbon fiber and platinum wire respectively.
如图3所示，为酸处理碳纳米管一氧化氮传感纤维的一氧化氮吸附能力示意图，如图4所示，为酸处理碳纳米管一氧化氮传感纤维的性能示意图。根据上述步骤制备的酸处理碳纳米管一氧化氮传感纤维灵敏度达到了3245pA·nM-1，且检测下限达到了0.1nmol/L，均优异于迄今为止报道的颅内一氧化氮传感。As shown in Figure 3, it is a schematic diagram of the nitric oxide adsorption capacity of acid-treated carbon nanotube nitric oxide sensing fibers. As shown in Figure 4, it is a schematic diagram of the performance of acid-treated carbon nanotube nitric oxide sensing fibers. The acid-treated carbon nanotube nitric oxide sensing fiber prepared according to the above steps has a sensitivity of 3245pA·nM-1 and a lower detection limit of 0.1nmol/L, both of which are superior to intracranial nitric oxide sensing reported so far.
如图5所示，为制备的酸处理碳纳米管一氧化氮传感纤维的生物相容性示意图，根据上述步骤制备的酸处理碳纳米管一氧化氮传感纤维的力学性能与脑组织相匹配，相比于刚性的碳纤维和铂丝，酸处理碳纳米管一氧化氮传感纤维在植入后不会引发严重的神经炎症反应和iNOS的过度表达，进而不会影响一氧化氮检测信号的准确性。As shown in Figure 5, it is a schematic diagram of the biocompatibility of the acid-treated carbon nanotube nitric oxide sensing fiber prepared according to the above steps. The mechanical properties of the acid-treated carbon nanotube nitric oxide sensing fiber prepared according to the above steps are similar to those of brain tissue. Matching, compared with rigid carbon fibers and platinum wires, acid-treated carbon nanotube nitric oxide sensing fibers will not trigger severe neuroinflammatory reactions and overexpression of iNOS after implantation, and will not affect the nitric oxide detection signal. accuracy.
制备酸处理碳纳米管银-氯化银传感纤维：Preparation of acid-treated carbon nanotube silver-silver chloride sensing fiber:
将碳纳米管纤维浸泡在20mL浓度为98％的硝酸溶液中，并在25℃静置12小时后，再用去离子水洗涤碳纳米管纤维，在洗涤结束后对碳纳米管纤维进行干燥，得到酸处理碳纳米管纤维；Soak the carbon nanotube fiber in 20 mL of 98% nitric acid solution, and let it stand at 25°C for 12 hours. Then wash the carbon nanotube fiber with deionized water, and dry the carbon nanotube fiber after washing. Obtain acid-treated carbon nanotube fibers;
配置0.1mol/L硝酸银-0.1mol/L硝酸钾溶液得到电解液C，酸处理碳纳米管纤维作为工作电极，银-氯化银电极作为参比电极，铂电极作为对电极，将三个电极浸入电解液C中，用循环伏安法对工作电极进行循环次数为14次的扫描，扫描速率为0.1V s-1，扫描范围为-0.9V至0.9V。Configure 0.1mol/L silver nitrate-0.1mol/L potassium nitrate solution to obtain electrolyte C. The acid-treated carbon nanotube fiber is used as the working electrode, the silver-silver chloride electrode is used as the reference electrode, and the platinum electrode is used as the counter electrode. Three The electrode was immersed in electrolyte C, and the working electrode was scanned for 14 cycles using cyclic voltammetry, with a scan rate of 0.1V s-1 and a scan range of -0.9V to 0.9V.
在此过程中，硝酸银中的银元素被还原，形成银颗粒，从而将银电化学沉积到酸处理碳纳米管纤维上，得到镀银后的碳纳米管纤维。During this process, the silver element in silver nitrate is reduced to form silver particles, thereby electrochemically depositing silver onto the acid-treated carbon nanotube fibers to obtain silver-plated carbon nanotube fibers.
配置0.1mmol/L盐酸-0.01mol/L氯化钾溶液作为电解液D，镀银后的碳纳米管纤维作为工作电极，银-氯化银电极作为参比电极，铂电极作为对电极，将三个电极浸入电解液D中，用循环伏安法对工作电极进行循环次数为4次的扫描，扫描速率为0.05V s-1，扫描范围为-0.15V至1.05V。对镀银后的酸处理碳纳米管纤维进行氯化，得到银-氯化银酸处理碳纳米管纤维；Configure 0.1mmol/L hydrochloric acid-0.01mol/L potassium chloride solution as electrolyte D, silver-plated carbon nanotube fiber as the working electrode, silver-silver chloride electrode as the reference electrode, and platinum electrode as the counter electrode. Three electrodes were immersed in electrolyte D, and the working electrode was scanned for 4 cycles using cyclic voltammetry. The scan rate was 0.05V s-1 and the scan range was -0.15V to 1.05V. Chloride the silver-plated acid-treated carbon nanotube fibers to obtain silver-silver chloride acid-treated carbon nanotube fibers;
将1mg聚乙烯醇缩丁醛树脂、1mg氯化钠、1mg聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物和1mg的MWCNT溶解于1ml甲醇中，得到PVB混合溶液；取1滴PVB混合溶液涂覆到银-氯化银酸处理碳纳米管纤维上，制备得到酸处理碳纳米管银-氯化银传感纤维。Dissolve 1 mg of polyvinyl butyral resin, 1 mg of sodium chloride, 1 mg of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and 1 mg of MWCNT in 1 ml of methanol to obtain a PVB mixture solution; apply 1 drop of the PVB mixed solution onto the silver-silver chloride acid-treated carbon nanotube fiber to prepare an acid-treated carbon nanotube silver-silver chloride sensing fiber.
制备基于酸处理碳纳米管纤维的颅内一氧化氮传感器：Preparation of intracranial nitric oxide sensor based on acid-treated carbon nanotube fibers:
酸处理碳纳米管一氧化氮传感纤维和酸处理碳纳米管银-氯化银传感纤维的传感部位平行排列，并具有一定的轴向位移差。两根纤维的一端用旋转电机轴固定，另一端用胶带固定，电机以50rad·min-1的转速运行，将两根纤维缠绕在一起，形成螺旋结构，得到基于酸处理碳纳米管纤维的颅内新型电化学一氧化氮传感器。The sensing parts of the acid-treated carbon nanotube nitric oxide sensing fiber and the acid-treated carbon nanotube silver-silver chloride sensing fiber are arranged in parallel and have a certain axial displacement difference. One end of the two fibers is fixed with a rotating motor shaft, and the other end is fixed with a tape. The motor runs at a speed of 50rad·min-1 , and the two fibers are wound together to form a spiral structure, and a skull based on acid-treated carbon nanotube fibers is obtained. New electrochemical nitric oxide sensor.
作为本实施例的另一种实现方式，上述步骤中的电机也可以25rad·min-1、75rad·min-1、100rad·min-1、200rad·min-1的速度运行，将纤维束缠绕在一起。As another implementation of this embodiment, the motor in the above steps can also run at a speed of 25rad·min-1 , 75rad·min-1 , 100rad·min-1 , or 200rad·min-1 to wind the fiber bundle around Together.
实施例4Example 4
本实施例公开一种颅内一氧化氮电化学传感的制备方法，包括以下步骤，This embodiment discloses a preparation method for intracranial nitric oxide electrochemical sensing, which includes the following steps:
制备酸处理碳纳米管一氧化氮传感纤维：Preparation of acid-treated carbon nanotube nitric oxide sensing fibers:
将碳纳米管纤维浸泡在20mL的浓度为98％的硝酸溶液中，并在25℃静置12小时后，静置完毕后用去离子水进行洗涤，洗涤完毕后进行干燥，得到酸处理碳纳米管纤维；Soak the carbon nanotube fiber in 20 mL of nitric acid solution with a concentration of 98%, and let it stand at 25°C for 12 hours. After the rest is completed, it is washed with deionized water and dried after the washing is completed to obtain the acid-treated carbon nanotube fiber. tube fiber;
通过配置1×10-3mol/L氯铂酸钾-0.1mol/L氯化钾溶液，得到电解液A。将得到的酸处理碳纳米管纤维作为工作电极，银-氯化银电极作为参比电极，铂电极作为对电极，将三个电极浸入电解液A中，通过恒电位极化法在工作电极上交替施加0.5V和-0.7V的电压，持续10秒，并重复该过程150次。Electrolyte solution A is obtained by preparing a 1×10-3 mol/L potassium chloroplatinate-0.1 mol/L potassium chloride solution. The obtained acid-treated carbon nanotube fiber was used as the working electrode, the silver-silver chloride electrode was used as the reference electrode, and the platinum electrode was used as the counter electrode. The three electrodes were immersed in the electrolyte A, and the electrodes were polarized on the working electrode through the constant potential polarization method. Apply voltages of 0.5V and -0.7V alternately for 10 seconds, and repeat the process 150 times.
在此步骤中，氯铂酸钾中的铂元素被还原，形成铂纳米颗粒，从而实现铂纳米颗粒在酸处理碳纳米管纤维表面的沉积，得到沉积铂纳米颗粒后的酸处理碳纳米管纤维。In this step, the platinum element in potassium chloroplatinate is reduced to form platinum nanoparticles, thereby realizing the deposition of platinum nanoparticles on the surface of the acid-treated carbon nanotube fiber, and obtaining the acid-treated carbon nanotube fiber after depositing the platinum nanoparticles. .
配置60mL的0.1mol/L的氢氧化钠溶液，用氩气将氢氧化钠溶液的氧气除尽，加入15mmol/L的丁香酚得到电解液B，沉积铂纳米颗粒后的酸处理碳纳米管纤维作为工作电极，银-氯化银电极作为参比电极，铂电极作为对电极，将三个电极浸入电解液B中，用循环伏安法对工作电极进行循环次数为10次的扫描，扫描速率为20mV s-1，扫描范围为0V至0.7V。Prepare 60 mL of 0.1 mol/L sodium hydroxide solution, use argon to remove all oxygen from the sodium hydroxide solution, add 15 mmol/L eugenol to obtain electrolyte B, and acid-treat carbon nanotube fibers after depositing platinum nanoparticles. As the working electrode, the silver-silver chloride electrode is used as the reference electrode, and the platinum electrode is used as the counter electrode. The three electrodes are immersed in electrolyte B, and the working electrode is scanned for 10 cycles using cyclic voltammetry. The scan rate is 20mV s-1 and the scanning range is 0V to 0.7V.
在此步骤中，丁香酚被电化学聚合在工作电极表面，形成聚丁香酚薄膜，此过程实现了聚丁香酚在沉积铂纳米颗粒后的酸处理碳纳米管纤维表面的沉积，得到沉积铂纳米颗粒以及聚丁香酚后的酸处理碳纳米管纤维。In this step, eugenol is electrochemically polymerized on the surface of the working electrode to form a polyeugenol film. This process realizes the deposition of polyeugenol on the acid-treated carbon nanotube fiber surface after depositing platinum nanoparticles, and obtains deposited platinum nanoparticles. particles as well as acid-treated carbon nanotube fibers after polyeugenol.
准备全氟磺酸型聚合物溶液，并将全氟磺酸型聚合物溶液稀释到1.5wt％，取5μL稀释后的全氟磺酸型聚合物溶液均匀涂覆在沉积铂纳米颗粒以及聚丁香酚后的酸处理碳纳米管纤维表面，干燥后形成薄膜，得到酸处理碳纳米管一氧化氮传感纤维。Prepare the perfluorosulfonic acid polymer solution and dilute the perfluorosulfonic acid polymer solution to 1.5wt%. Take 5 μL of the diluted perfluorosulfonic acid polymer solution and apply it evenly on the deposited platinum nanoparticles and polyclove. The surface of the carbon nanotube fiber is treated with acid after phenol, and a thin film is formed after drying to obtain the acid-treated carbon nanotube nitric oxide sensing fiber.
如图2所示，为酸处理碳纳米管一氧化氮传感纤维的结构示意图。As shown in Figure 2, it is a schematic structural diagram of acid-treated carbon nanotube nitric oxide sensing fiber.
根据上述步骤制备的酸处理碳纳米管一氧化氮传感纤维具有优异的比表面积和丰富的含氧官能团，增强了传感纤维对一氧化氮的吸附能力。由此可知，酸处理碳纳米管一氧化氮传感纤维对一氧化氮的吸附能力分别比碳纤维和铂丝高出11倍和13倍。The acid-treated carbon nanotube nitric oxide sensing fiber prepared according to the above steps has excellent specific surface area and abundant oxygen-containing functional groups, which enhances the adsorption capacity of the sensing fiber for nitric oxide. It can be seen that the acid-treated carbon nanotube nitric oxide sensing fiber has a nitric oxide adsorption capacity that is 11 times and 13 times higher than that of carbon fiber and platinum wire respectively.
如图3所示，为酸处理碳纳米管一氧化氮传感纤维的一氧化氮吸附能力示意图，如图4所示，为酸处理碳纳米管一氧化氮传感纤维的性能示意图。根据上述步骤制备的酸处理碳纳米管一氧化氮传感纤维灵敏度达到了3245pA·nM-1，且检测下限达到了0.1nmol/L，均优异于迄今为止报道的颅内一氧化氮传感。As shown in Figure 3, it is a schematic diagram of the nitric oxide adsorption capacity of acid-treated carbon nanotube nitric oxide sensing fibers. As shown in Figure 4, it is a schematic diagram of the performance of acid-treated carbon nanotube nitric oxide sensing fibers. The acid-treated carbon nanotube nitric oxide sensing fiber prepared according to the above steps has a sensitivity of 3245pA·nM-1 and a lower detection limit of 0.1nmol/L, both of which are superior to intracranial nitric oxide sensing reported so far.
如图5所示，为制备的酸处理碳纳米管一氧化氮传感纤维的生物相容性示意图，根据上述步骤制备的酸处理碳纳米管一氧化氮传感纤维的力学性能与脑组织相匹配，相比于刚性的碳纤维和铂丝，酸处理碳纳米管一氧化氮传感纤维在植入后不会引发严重的神经炎症反应和iNOS的过度表达，进而不会影响一氧化氮检测信号的准确性。As shown in Figure 5, it is a schematic diagram of the biocompatibility of the acid-treated carbon nanotube nitric oxide sensing fiber prepared according to the above steps. The mechanical properties of the acid-treated carbon nanotube nitric oxide sensing fiber prepared according to the above steps are similar to those of brain tissue. Matching, compared with rigid carbon fibers and platinum wires, acid-treated carbon nanotube nitric oxide sensing fibers will not trigger severe neuroinflammatory reactions and overexpression of iNOS after implantation, and will not affect the nitric oxide detection signal. accuracy.
制备酸处理碳纳米管银-氯化银传感纤维：Preparation of acid-treated carbon nanotube silver-silver chloride sensing fiber:
将碳纳米管纤维浸泡在20mL浓度为98％的硝酸溶液中，并在25℃静置12小时后，再用去离子水洗涤碳纳米管纤维，在洗涤结束后对碳纳米管纤维进行干燥，得到酸处理碳纳米管纤维；Soak the carbon nanotube fiber in 20 mL of 98% nitric acid solution, and let it stand at 25°C for 12 hours. Then wash the carbon nanotube fiber with deionized water, and dry the carbon nanotube fiber after washing. Obtain acid-treated carbon nanotube fibers;
配置2.5mol/L硝酸银-2.5mol/L硝酸钾溶液得到电解液C，酸处理碳纳米管纤维作为工作电极，银-氯化银电极作为参比电极，铂电极作为对电极，将三个电极浸入电解液C中，用循环伏安法对工作电极进行循环次数为14次的扫描，扫描速率为0.1V s-1，扫描范围为-0.9V至0.9V。Configure 2.5mol/L silver nitrate-2.5mol/L potassium nitrate solution to obtain electrolyte C. The acid-treated carbon nanotube fiber is used as the working electrode, the silver-silver chloride electrode is used as the reference electrode, and the platinum electrode is used as the counter electrode. Three The electrode was immersed in electrolyte C, and the working electrode was scanned for 14 cycles using cyclic voltammetry, with a scan rate of 0.1V s-1 and a scan range of -0.9V to 0.9V.
在此过程中，硝酸银中的银元素被还原，形成银颗粒，从而将银电化学沉积到酸处理碳纳米管纤维上，得到镀银后的碳纳米管纤维。During this process, the silver element in silver nitrate is reduced to form silver particles, thereby electrochemically depositing silver onto the acid-treated carbon nanotube fibers to obtain silver-plated carbon nanotube fibers.
配置2.5mmol/L盐酸-2.5mol/L氯化钾溶液作为电解液D，镀银后的碳纳米管纤维作为工作电极，银-氯化银电极作为参比电极，铂电极作为对电极，将三个电极浸入电解液D中，用循环伏安法对工作电极进行循环次数为4次的扫描，扫描速率为0.05V s-1，扫描范围为-0.15V至1.05V。对镀银后的酸处理碳纳米管纤维进行氯化，得到银-氯化银酸处理碳纳米管纤维；Configure 2.5mmol/L hydrochloric acid-2.5mol/L potassium chloride solution as electrolyte D, silver-plated carbon nanotube fiber as the working electrode, silver-silver chloride electrode as the reference electrode, and platinum electrode as the counter electrode. Three electrodes were immersed in electrolyte D, and the working electrode was scanned for 4 cycles using cyclic voltammetry. The scan rate was 0.05V s-1 and the scan range was -0.15V to 1.05V. Chloride the silver-plated acid-treated carbon nanotube fibers to obtain silver-silver chloride acid-treated carbon nanotube fibers;
将100mg聚乙烯醇缩丁醛树脂、50mg氯化钠、50mg聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物和5mg的MWCNT溶解于1ml甲醇中，得到PVB混合溶液；取1滴PVB混合溶液涂覆到银-氯化银酸处理碳纳米管纤维上，制备得到酸处理碳纳米管银-氯化银传感纤维。Dissolve 100 mg polyvinyl butyral resin, 50 mg sodium chloride, 50 mg polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and 5 mg MWCNT in 1 ml methanol to obtain a PVB mixture solution; apply 1 drop of the PVB mixed solution onto the silver-silver chloride acid-treated carbon nanotube fiber to prepare an acid-treated carbon nanotube silver-silver chloride sensing fiber.
制备基于酸处理碳纳米管纤维的颅内一氧化氮传感器：Preparation of intracranial nitric oxide sensor based on acid-treated carbon nanotube fibers:
酸处理碳纳米管一氧化氮传感纤维和酸处理碳纳米管银-氯化银传感纤维的传感部位平行排列，并具有一定的轴向位移差。两根纤维的一端用旋转电机轴固定，另一端用胶带固定，电机以50rad·min-1的转速运行，将两根纤维缠绕在一起，形成螺旋结构，得到基于酸处理碳纳米管纤维的颅内新型电化学一氧化氮传感器。The sensing parts of the acid-treated carbon nanotube nitric oxide sensing fiber and the acid-treated carbon nanotube silver-silver chloride sensing fiber are arranged in parallel and have a certain axial displacement difference. One end of the two fibers is fixed with a rotating motor shaft, and the other end is fixed with a tape. The motor runs at a speed of 50rad·min-1 , and the two fibers are wound together to form a spiral structure, and a skull based on acid-treated carbon nanotube fibers is obtained. New electrochemical nitric oxide sensor.
作为本实施例的另一种实现方式，上述步骤中的电机也可以25rad·min-1、75rad·min-1、100rad·min-1、200rad·min-1的速度运行，将纤维束缠绕在一起。As another implementation of this embodiment, the motor in the above steps can also run at a speed of 25rad·min-1 , 75rad·min-1 , 100rad·min-1 , or 200rad·min-1 to wind the fiber bundle around Together.
实施例5Example 5
本实施例公开一种颅内一氧化氮电化学传感的制备方法，包括以下步骤，This embodiment discloses a preparation method for intracranial nitric oxide electrochemical sensing, which includes the following steps:
制备酸处理碳纳米管一氧化氮传感纤维：Preparation of acid-treated carbon nanotube nitric oxide sensing fibers:
将碳纳米管纤维浸泡在20mL的浓度为98％的硝酸溶液中，并在25℃静置12小时后，静置完毕后用去离子水进行洗涤，洗涤完毕后进行干燥，得到酸处理碳纳米管纤维；Soak the carbon nanotube fiber in 20 mL of nitric acid solution with a concentration of 98%, and let it stand at 25°C for 12 hours. After the rest is completed, it is washed with deionized water and dried after the washing is completed to obtain the acid-treated carbon nanotube fiber. tube fiber;
通过配置1×10-3mol/L氯铂酸钾-0.1mol/L氯化钾溶液，得到电解液A。将得到的酸处理碳纳米管纤维作为工作电极，银-氯化银电极作为参比电极，铂电极作为对电极，将三个电极浸入电解液A中，通过恒电位极化法在工作电极上交替施加0.5V至-0.7V的电压，持续10秒，并重复该过程150次。Electrolyte solution A is obtained by preparing a 1×10-3 mol/L potassium chloroplatinate-0.1 mol/L potassium chloride solution. The obtained acid-treated carbon nanotube fiber was used as the working electrode, the silver-silver chloride electrode was used as the reference electrode, and the platinum electrode was used as the counter electrode. The three electrodes were immersed in the electrolyte A, and the electrodes were polarized on the working electrode through the constant potential polarization method. Apply voltages from 0.5V to -0.7V alternately for 10 seconds and repeat the process 150 times.
在此步骤中，氯铂酸钾中的铂元素被还原，形成铂纳米颗粒，从而实现铂纳米颗粒在酸处理碳纳米管纤维表面的沉积，得到沉积铂纳米颗粒后的酸处理碳纳米管纤维。In this step, the platinum element in potassium chloroplatinate is reduced to form platinum nanoparticles, thereby realizing the deposition of platinum nanoparticles on the surface of the acid-treated carbon nanotube fiber, and obtaining the acid-treated carbon nanotube fiber after depositing the platinum nanoparticles. .
配置60mL的0.1mol/L的氢氧化钠溶液，用氩气将氢氧化钠溶液的氧气除尽，加入15mmol/L的丁香酚得到电解液B，沉积铂纳米颗粒后的酸处理碳纳米管纤维作为工作电极，银-氯化银电极作为参比电极，铂电极作为对电极，将三个电极浸入电解液B中，用循环伏安法对工作电极进行循环次数为10次的扫描，扫描速率为20mV s-1，扫描范围为0V至0.7V。Prepare 60 mL of 0.1 mol/L sodium hydroxide solution, use argon to remove all oxygen from the sodium hydroxide solution, add 15 mmol/L eugenol to obtain electrolyte B, and acid-treat carbon nanotube fibers after depositing platinum nanoparticles. As the working electrode, the silver-silver chloride electrode is used as the reference electrode, and the platinum electrode is used as the counter electrode. The three electrodes are immersed in electrolyte B, and the working electrode is scanned for 10 cycles using cyclic voltammetry. The scan rate is 20mV s-1 and the scanning range is 0V to 0.7V.
在此步骤中，丁香酚被电化学聚合在工作电极表面，形成聚丁香酚薄膜，此过程实现了聚丁香酚在沉积铂纳米颗粒后的酸处理碳纳米管纤维表面的沉积，得到沉积铂纳米颗粒以及聚丁香酚后的酸处理碳纳米管纤维。In this step, eugenol is electrochemically polymerized on the surface of the working electrode to form a polyeugenol film. This process realizes the deposition of polyeugenol on the acid-treated carbon nanotube fiber surface after depositing platinum nanoparticles, and obtains deposited platinum nanoparticles. particles as well as acid-treated carbon nanotube fibers after polyeugenol.
准备全氟磺酸型聚合物溶液，并将全氟磺酸型聚合物溶液稀释到1.5wt％，取5μL稀释后的全氟磺酸型聚合物溶液均匀涂覆在沉积铂纳米颗粒以及聚丁香酚后的酸处理碳纳米管纤维表面，干燥后形成薄膜，得到酸处理碳纳米管一氧化氮传感纤维。Prepare the perfluorosulfonic acid polymer solution and dilute the perfluorosulfonic acid polymer solution to 1.5wt%. Take 5 μL of the diluted perfluorosulfonic acid polymer solution and apply it evenly on the deposited platinum nanoparticles and polyclove. The surface of the carbon nanotube fiber is treated with acid after phenol, and a thin film is formed after drying to obtain the acid-treated carbon nanotube nitric oxide sensing fiber.
如图2所示，为酸处理碳纳米管一氧化氮传感纤维的结构示意图。As shown in Figure 2, it is a schematic structural diagram of acid-treated carbon nanotube nitric oxide sensing fiber.
根据上述步骤制备的酸处理碳纳米管一氧化氮传感纤维具有优异的比表面积和丰富的含氧官能团，增强了传感纤维对一氧化氮的吸附能力。由此可知，酸处理碳纳米管一氧化氮传感纤维对一氧化氮的吸附能力分别比碳纤维和铂丝高出11倍和13倍。The acid-treated carbon nanotube nitric oxide sensing fiber prepared according to the above steps has excellent specific surface area and abundant oxygen-containing functional groups, which enhances the adsorption capacity of the sensing fiber for nitric oxide. It can be seen that the acid-treated carbon nanotube nitric oxide sensing fiber has a nitric oxide adsorption capacity that is 11 times and 13 times higher than that of carbon fiber and platinum wire respectively.
如图3所示，为酸处理碳纳米管一氧化氮传感纤维的一氧化氮吸附能力示意图，如图4所示，为酸处理碳纳米管一氧化氮传感纤维的性能示意图。根据上述步骤制备的酸处理碳纳米管一氧化氮传感纤维灵敏度达到了3245pA·nM-1，且检测下限达到了0.1nmol/L，均优异于迄今为止报道的颅内一氧化氮传感。As shown in Figure 3, it is a schematic diagram of the nitric oxide adsorption capacity of acid-treated carbon nanotube nitric oxide sensing fibers. As shown in Figure 4, it is a schematic diagram of the performance of acid-treated carbon nanotube nitric oxide sensing fibers. The acid-treated carbon nanotube nitric oxide sensing fiber prepared according to the above steps has a sensitivity of 3245pA·nM-1 and a lower detection limit of 0.1nmol/L, both of which are superior to intracranial nitric oxide sensing reported so far.
如图5所示，为制备的酸处理碳纳米管一氧化氮传感纤维的生物相容性示意图，根据上述步骤制备的酸处理碳纳米管一氧化氮传感纤维的力学性能与脑组织相匹配，相比于刚性的碳纤维和铂丝，酸处理碳纳米管一氧化氮传感纤维在植入后不会引发严重的神经炎症反应和iNOS的过度表达，进而不会影响一氧化氮检测信号的准确性。As shown in Figure 5, it is a schematic diagram of the biocompatibility of the acid-treated carbon nanotube nitric oxide sensing fiber prepared according to the above steps. The mechanical properties of the acid-treated carbon nanotube nitric oxide sensing fiber prepared according to the above steps are similar to those of brain tissue. Matching, compared with rigid carbon fibers and platinum wires, acid-treated carbon nanotube nitric oxide sensing fibers will not trigger severe neuroinflammatory reactions and overexpression of iNOS after implantation, and will not affect the nitric oxide detection signal. accuracy.
制备酸处理碳纳米管银-氯化银传感纤维：Preparation of acid-treated carbon nanotube silver-silver chloride sensing fiber:
将碳纳米管纤维浸泡在20mL浓度为98％的硝酸溶液中，并在25℃静置12小时后，再用去离子水洗涤碳纳米管纤维，在洗涤结束后对碳纳米管纤维进行干燥，得到酸处理碳纳米管纤维；Soak the carbon nanotube fiber in 20 mL of 98% nitric acid solution, and let it stand at 25°C for 12 hours. Then wash the carbon nanotube fiber with deionized water, and dry the carbon nanotube fiber after washing. Obtain acid-treated carbon nanotube fibers;
配置5mol/L硝酸银-5mol/L硝酸钾溶液得到电解液C，酸处理碳纳米管纤维作为工作电极，银-氯化银电极作为参比电极，铂电极作为对电极，将三个电极浸入电解液C中，用循环伏安法对工作电极进行循环次数为14次的扫描，扫描速率为0.1V s-1，扫描范围为-0.9V至0.9V。Configure 5mol/L silver nitrate-5mol/L potassium nitrate solution to obtain electrolyte C. The acid-treated carbon nanotube fiber is used as the working electrode, the silver-silver chloride electrode is used as the reference electrode, and the platinum electrode is used as the counter electrode. Immerse the three electrodes In electrolyte C, the working electrode was scanned for 14 cycles using cyclic voltammetry, with a scan rate of 0.1V s-1 and a scan range of -0.9V to 0.9V.
在此过程中，硝酸银中的银元素被还原，形成银颗粒，从而将银电化学沉积到酸处理碳纳米管纤维上，得到镀银后的碳纳米管纤维。During this process, the silver element in silver nitrate is reduced to form silver particles, thereby electrochemically depositing silver onto the acid-treated carbon nanotube fibers to obtain silver-plated carbon nanotube fibers.
配置5mmol/L盐酸-5mol/L氯化钾溶液作为电解液D，镀银后的碳纳米管纤维作为工作电极，银-氯化银电极作为参比电极，铂电极作为对电极，将三个电极浸入电解液D中，用循环伏安法对工作电极进行循环次数为4次的扫描，扫描速率为0.05V s-1，扫描范围为-0.15V至1.05V。对镀银后的酸处理碳纳米管纤维进行氯化，得到银-氯化银酸处理碳纳米管纤维；Configure 5mmol/L hydrochloric acid-5mol/L potassium chloride solution as electrolyte D, silver-plated carbon nanotube fiber as the working electrode, silver-silver chloride electrode as the reference electrode, and platinum electrode as the counter electrode. Three The electrode was immersed in electrolyte D, and the working electrode was scanned for 4 cycles using cyclic voltammetry, with a scan rate of 0.05V s-1 and a scan range of -0.15V to 1.05V. Chloride the silver-plated acid-treated carbon nanotube fibers to obtain silver-silver chloride acid-treated carbon nanotube fibers;
将200mg聚乙烯醇缩丁醛树脂、100mg氯化钠、100mg聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物和10mg的MWCNT(碳纳米管)溶解于1ml甲醇中，得到PVB(聚乙烯醇缩丁醛酯)混合溶液；取1滴PVB混合溶液涂覆到银-氯化银酸处理碳纳米管纤维上，制备得到酸处理碳纳米管银-氯化银传感纤维。Dissolve 200 mg polyvinyl butyral resin, 100 mg sodium chloride, 100 mg polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and 10 mg MWCNT (carbon nanotube) in 1 ml methanol , obtain a PVB (polyvinyl butyral ester) mixed solution; take 1 drop of the PVB mixed solution and coat it on the silver-silver chloride acid-treated carbon nanotube fiber to prepare acid-treated silver carbon nanotube-silver chloride Sensing fibers.
制备基于酸处理碳纳米管纤维的颅内一氧化氮传感器：Preparation of intracranial nitric oxide sensor based on acid-treated carbon nanotube fibers:
酸处理碳纳米管一氧化氮传感纤维和酸处理碳纳米管银-氯化银传感纤维的传感部位平行排列，并具有一定的轴向位移差。两根纤维的一端用旋转电机轴固定，另一端用胶带固定，电机以50rad·min-1的转速运行，将两根纤维缠绕在一起，形成螺旋结构，得到基于酸处理碳纳米管纤维的颅内新型电化学一氧化氮传感器。The sensing parts of the acid-treated carbon nanotube nitric oxide sensing fiber and the acid-treated carbon nanotube silver-silver chloride sensing fiber are arranged in parallel and have a certain axial displacement difference. One end of the two fibers is fixed with a rotating motor shaft, and the other end is fixed with a tape. The motor runs at a speed of 50rad·min-1 , and the two fibers are wound together to form a spiral structure, and a skull based on acid-treated carbon nanotube fibers is obtained. New electrochemical nitric oxide sensor.
作为本实施例的另一种实现方式，上述步骤中的电机也可以25rad·min-1、75rad·min-1、100rad·min-1、200rad·min-1的速度运行，将纤维束缠绕在一起。As another implementation of this embodiment, the motor in the above steps can also run at a speed of 25rad·min-1 , 75rad·min-1 , 100rad·min-1 , or 200rad·min-1 to wind the fiber bundle around Together.
以上示意性地对本发明创造及其实施方式进行了描述，该描述没有限制性，在不背离本发明的精神或者基本特征的情况下，能够以其他的具体形式实现本发明。附图中所示的也只是本发明创造的实施方式之一，实际的结构并不局限于此，权利要求中的任何附图标记不应限制所涉及的权利要求。所以，如果本领域的普通技术人员受其启示，在不脱离本创造宗旨的情况下，不经创造性的设计出与该技术方案相似的结构方式及实施例，均应属于本专利的保护范围。此外，“包括”一词不排除其他元件或步骤，在元件前的“一个”一词不排除包括“多个”该元件。产品权利要求中陈述的多个元件也可以由一个元件通过软件或者硬件来实现。第一，第二等词语用来表示名称，而并不表示任何特定的顺序。The invention and its implementation have been schematically described above. This description is not limiting. The invention can be implemented in other specific forms without departing from the spirit or basic characteristics of the invention. What is shown in the drawings is only one embodiment of the present invention, and the actual structure is not limited thereto. Any reference signs in the claims shall not limit the claims involved. Therefore, if a person of ordinary skill in the art is inspired by the invention and without deviating from the purpose of the invention, can design a similar structural method and embodiment to the technical solution without creativity, they shall all fall within the protection scope of this patent. Furthermore, the word "comprising" does not exclude other elements or steps, and the word "a" before an element does not exclude the inclusion of "a plurality" of that element. Multiple elements stated in a product claim may also be implemented by one element through software or hardware. Words such as first and second are used to indicate names and do not indicate any specific order.
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| US20070243124A1 (en)* | 2004-10-01 | 2007-10-18 | University Of Texas At Dallas | Polymer-Free Carbon Nanotube Assemblies (Fibers, Ropes, Ribbons, Films) |
| US20090198117A1 (en)* | 2008-01-29 | 2009-08-06 | Medtronic Minimed, Inc. | Analyte sensors having nanostructured electrodes and methods for making and using them |
| US20160058316A1 (en)* | 2013-04-12 | 2016-03-03 | William Marsh Rice University | Strong, conductive carbon nanotube electrodes |
| CN115844386A (en)* | 2022-11-16 | 2023-03-28 | 哈尔滨工业大学（深圳） | Flexible sensor and preparation method and application thereof |
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