CN113504277A - Carbon fiber/gold-plated carbon fiber electrode wrapped with avidin-polluted graphene oxide microstrip as well as preparation method and application of carbon fiber/gold-plated carbon fiber electrode - Google Patents
Carbon fiber/gold-plated carbon fiber electrode wrapped with avidin-polluted graphene oxide microstrip as well as preparation method and application of carbon fiber/gold-plated carbon fiber electrode Download PDFInfo
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Abstract
The invention discloses a carbon fiber/gold-plated carbon fiber electrode wrapped with a graphene oxide microstrip capable of resisting biological protein pollution, which is characterized in that a three-electrode system containing a reference electrode is used, the carbon fiber electrode or the gold-plated carbon fiber electrode is soaked in a graphene oxide dispersion liquid, and a constant positive potential is set for electrodeposition, so that a graphene oxide microstrip electrode modification layer is obtained. The invention also discloses an application of the graphene oxide microstrip modification material in detection in organisms. The graphene oxide microstrip material disclosed by the invention is covered on the active surface of the sensor in a cross winding manner, so that a plurality of active sites can be exposed on the surface of the graphene oxide microstrip material, and the functional activity of the surface of the graphene oxide microstrip material is reserved. The micro-strip material also has the advantages of enriching electropositive molecules and excluding the adsorption of biological protein, can be modified on various biosensors to solve the problem that the sensor is easily polluted by the biological protein when detecting signals in a living body, and has an important effect on realizing the accurate detection of the biosensors in the living body.
Description
Technical Field
The invention belongs to the technical field of analysis, and relates to a carbon fiber/gold-plated carbon fiber electrode wrapped with an avidin-polluted graphene oxide microstrip, and a preparation method and application thereof.
Background
With the development of science and technology and the improvement of living standard of people, the needs of the research of the physiology and pathology of several acute and chronic diseases and the analysis of the drug treatment process are more and more urgent. In addition, in-vivo physiological monitoring of various behavioral processes of a living animal is also a key to further uncovering the fundamental principles of life. Therefore, the implantable sensor is widely applied to in-vivo detection of organs such as brain, heart, limbs, five sense organs and the like of a human body. These sensors are often modified with functionalized molecules and materials on their surface to achieve specific sensing functions. For example, the latest glucose biosensors modify glucose oxidase covalently bound to the electrode surface to specifically recognize glucose and directly generate redox electron transfer. In addition, recently, the development of positive thermal fiber spectroscopy, surface plasmon resonance chip and other methods also rely on surface functional modification of the sensor, and have been gradually perfected and introduced into the market. In recent years, the feasibility of human body communication is further explored by some implanted wireless chip sensors.
However, the development of implantable sensors is still limited by biocompatibility and stability, and especially after the living sensor is implanted into a living animal, a large amount of biological macromolecules are adsorbed on the surface of the living sensor. In particular, adsorption of proteins often results in a decrease in sensor sensitivity and a distortion of the measurement signal. These proteins adsorbed on the sensor also tend to trigger an immune response, which allows the sensor to be encapsulated by immune cells and isolated from the internal environment. Over the past several decades, many hydrophilic materials such as methyl viologen, alkaline hydrolyzed cellulose acetate, zwitterionic phosphorylcholine, etc., have been developed to coat sensor surfaces to prevent biological contamination in vivo, based on the repulsive interaction between the protein hydration layer and the hydrophilic material. However, these materials often completely encapsulate the active surface of the sensor and make it difficult to further modify functional molecules thereon, which makes it difficult for existing anti-biofouling materials to meet the requirements of numerous biosensors with functionalized surfaces, and severely limits the exploration and monitoring of long-term physiopathological processes. Therefore, it is urgent to develop a novel material having good anti-biological contamination properties while retaining the modification activity of the sensor.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to design and develop a novel carbon fiber electrode or a gold-plated carbon fiber electrode wrapped with a graphene oxide microstrip capable of resisting biological protein pollution. The method has the advantages that the conditions of electrodeposition are accurately controlled by uniformly stirring the graphene oxide dispersion liquid in the constant potential electrodeposition process, graphene oxide micro-strips can be alternately wound and modified on the surface of a gold-plated carbon fiber electrode, wherein gold particles exposed at intervals provide active sites for further modifying functional molecules, and due to the fact that the surface hydrophilicity of the electrodeposited graphene oxide is strong, when a large amount of bovine serum albumin is added into a test solution, the open-circuit potential change of the electrodeposited graphene oxide is extremely small, so that the electrode has remarkable antifouling performance, and meanwhile, the long-term stability is achieved in the aspect of monitoring free-moving animals.
The invention provides an anti-avidin-polluted graphene oxide microstrip modification material, which consists of graphene oxide, is wound on the surface of a biosensor in a crossing manner, and the surface of the biosensor is exposed with a plurality of active sites and retains the functional activity of the surface.
The graphene oxide microstrip modification material is structurally characterized in that a plurality of active sites for modification are still reserved when the graphene oxide microstrip modification material is crossly wound and modified on the surface of a sensor. The existing anti-biological pollution technology often uses hydrophilic materials to modify and cover the whole sensor surface, so that the sensor surface is difficult to further perform functional modification. When the graphene oxide micro-strip modification material is used for modifying the surface of a carbon fiber electrode after gold plating, a large amount of gold can still be modified with functionalized molecules, such as Ca2+Selective ligands, to obtain Ca resistant to biological contamination2+An ion selective electrode.
The graphene oxide microstrip modification material has the characteristics of strong biological pollution resistance and reservation of the active surface of a sensor. When a large amount of bovine serum albumin (20mg/mL) for testing is added into the testing solution, the cyclic voltammetry peak of the gold-plated carbon fiber electrode modified with the material can still maintain 91.3% of current intensity when the gold-plated carbon fiber electrode detects bioactive molecules such as dopamine. And modifying the electrode with Ca2+Preparation of Ca after ion ligand2+Ion selective electrode and implanted live rat brain 6At day 0, the post-correction sensitivity loss for the electrode was less than 8%.
The invention also provides a preparation method of the carbon fiber electrode or the gold-plated carbon fiber electrode wrapped with the avidin-polluted graphene oxide microstrip, which comprises the following steps:
step (1): and (3) soaking the carbon fiber electrode in chloroauric acid by using a three-electrode system containing a reference electrode, connecting the electrodes by using an electrochemical workstation, and setting constant potential electrodeposition to obtain the gold-plated carbon fiber electrode.
Step (2): and (2) soaking the carbon fiber electrode or the gold-plated carbon fiber electrode prepared in the step (1) in graphene oxide suspension by using a three-electrode system containing a reference electrode, connecting the electrodes by using an electrochemical workstation, and setting constant potential electrodeposition to obtain the carbon fiber electrode or the gold-plated carbon fiber electrode wrapped with the avidin-polluted graphene oxide microstrip.
In the steps (1) and (2), the three-electrode system containing the reference electrode means that the carbon fiber electrode is a working electrode, the silver/silver chloride electrode is a reference electrode, and the platinum wire electrode is an auxiliary electrode.
In the steps (1) and (2), the working electrode serving as the substrate electrode in the three-electrode system can be a microelectrode made of any material with the diameter of 10-30 microns, such as carbon fiber, iridium, platinum-iridium alloy, nickel-chromium alloy, tungsten and the like; preferably a carbon fibre electrode of 10 μm diameter.
In the steps (1) and (2), the reference electrode used in the electrochemical process is an Ag/AgCl electrode, and the auxiliary electrode is a platinum wire electrode.
In step (1) of the present invention, the carbon fiber electrode is preferably immersed in chloroauric acid at room temperature.
Soaking a carbon fiber electrode in a chloroauric acid solution for electrode gold plating, and enabling the active surface of the electrode to be further subjected to functional modification; the preparation steps of the electrode gold plating comprise the steps of electrodeposition, chemical vapor deposition, magnetron sputtering and the like.
The modified active surface material also comprises gold, silver, platinum, an organic monomolecular self-assembly layer and the like; preferably, electrodeposited gold particles.
In the step (1), the concentration of the chloroauric acid is 0.001-0.1M; preferably, it is 0.1M.
In the step (1), the constant potential is set to-0.02 to-0.3V; preferably, -0.2V.
In the step (1), the deposition time is 10-120 seconds; preferably 15 seconds.
In the step (2), the concentration of the graphene oxide suspension is 0.05-2.00 mg/ml; preferably, it is 2.00 mg/mL.
In the step (2), the constant potential is set to be 0.2-1.0V; preferably, it is 0.8V.
In the step (2), the deposition time is set to be 10-60 min; preferably, it is 30 min.
In the step (2), the deposition pool needs to be stirred in the constant potential electrodeposition process, and the stirring process comprises shaking by a shaking table, magnetic stirring, mechanical stirring, ultrasonic treatment and other methods; preferably, magnetic stirring.
In step (2) of the present invention, the carbon fiber electrode or the gold-plated carbon fiber electrode prepared in step (1) is preferably immersed in the graphene oxide suspension at room temperature.
The invention provides a strategy for modifying a sensor by cross winding of a hydrophilic material to resist biological protein pollution for the first time. The method not only can effectively resist the adsorption of the biological protein on the surface of the sensor, but also can reserve an electrode active site which can be further modified.
The invention improves the method for electrodepositing the graphene oxide on the surface of the microelectrode, and accelerates the formation of graphene oxide micro-strips by stirring the graphene oxide dispersion liquid during the constant potential electrodeposition process, and certain gaps are still left among the prepared surface modified graphene oxide micro-strips so that partial active surfaces of the electrodes still retain the potential of further functional modification.
The invention also provides the carbon fiber electrode wrapped with the avidin-polluted graphene oxide microstrip prepared by the method.
The invention also provides a gold-plated carbon fiber electrode wrapped with the avidin-polluted graphene oxide microstrip, which is prepared by the method.
The invention also provides Ca wrapped with the graphene oxide microstrip2+The preparation method of the ion selective electrode comprises the step of soaking the gold-plated carbon fiber electrode wrapped with the graphene oxide microstrip in 0.5-5mM Ca with alkynyl connecting functional groups2+Is obtained after 6 hours in ethanol solution of selective ligand; preferably, the ligand concentration is 1 mM.
The invention also provides Ca formed by the gold-plated carbon fiber electrode wrapped with the avidin-polluted graphene oxide microstrip2+Extracellular Ca to mouse brain after ion selective electrode2+The application of monitoring is continuously tracked.
The beneficial effects of the invention include: according to the invention, graphene oxide micro-strips are uniformly and crosswise wrapped on the surface of a carbon fiber electrode or a gold-plated carbon fiber electrode by using an electrodeposition technology, so that a novel graphene oxide micro-strip modification material capable of resisting biological protein pollution is constructed. The material can still expose active sites on the sensor surface because of the modified sensor surface being intertwined, and therefore can further modify functionalized molecules on these active sites. The graphene oxide microstrip modification material has the advantages of enriching electropositive molecules, rejecting adsorption of biological protein, having strong biological pollution resistance and simultaneously reserving active surface sites of a sensor.
Drawings
Fig. 1 is a scanning electron microscope image of a graphene oxide microstrip modified gold-plated carbon fiber electrode prepared in example 1 of the present invention.
FIG. 2 is a fluorescence image of the gold-plated carbon fiber electrode prepared in example 1 of the present invention after being soaked in 20mg/mL of a solution of bovine serum albumin labeled with fluorescein isothiocyanate for 2 hours. From the figure, it can be seen that a large amount of fluorescence labeled bovine serum albumin (white spots) is adsorbed on the surface of the gold-plated carbon fiber electrode, which proves that the gold-plated electrode is extremely easy to adsorb and deposit protein in a solution containing protein.
Fig. 3 is a fluorescence image of the graphene oxide microstrip modified gold-plated carbon fiber electrode prepared in embodiment 1 of the present invention after being soaked in 20mg/mL bovine serum albumin solution labeled with fluorescein isothiocyanate for 2 hours. It can be seen from the figure that the fluorescent-labeled bovine serum albumin is hardly observed to adhere to the electrode surface.
Fig. 4 is a cyclic voltammetry curve obtained by the graphene oxide microstrip modified gold-plated carbon fiber electrode prepared in embodiment 1 of the present invention in a 10 μ M dopamine solution. The solid line is the normal test curve and the dotted line is the test curve after the electrode has been soaked in 20mg/mL bovine serum albumin for 2 h. It can be seen from the figure that even after soaking in bovine serum albumin, the graphene oxide microstrip modified gold-plated carbon fiber electrode still has 91.3% of the current intensity of the un-soaked electrode.
Fig. 5 is a contact angle diagram of electrodeposited graphene oxide on the surface of a glassy carbon electrode in example 1 of the present invention. The contact angle was calculated to be 25 °, demonstrating the highly hydrophilic nature of electrodeposited graphene oxide.
FIG. 6 shows Ca of modified (A) and unmodified (B) electrodeposited graphene oxide microstrip of example 2 of the present invention2+The ion selective electrode was added to 9.9mL of the test solution in 100. mu.L volume of 10mM CaCl2After the solution and 100mg of bovine serum albumin were continuously added 3 times, the change of the electrode signal when the solution totally accumulates 30mg/ml of bovine serum albumin was tested. From the figure, Ca modifying (A) electrodeposited graphene oxide microstrip can be seen2+The signal of the ion-selective electrode is reduced by only 5.7%, while the Ca of the unmodified (B) graphene oxide microstrip2+The signal of the ion selective electrode decreased by 31.6%. Evidence of Ca2+The protein resistance of the ion selective electrode is greatly improved after the modification of the electrodeposited graphene oxide microstrip.
FIG. 7 shows Ca coated with graphene oxide micro-strips in example 3 of the present invention2+Statistical plots of sensitivity changes over 60 days after ion selective electrode implantation into a living body. As can be seen from the figure, the sensitivity of the electrode was greater than 92% of the initial value even after 60 days of implantation into the living body.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples and the accompanying drawings. The procedures, conditions, experimental methods and the like for carrying out the present invention are general knowledge and common general knowledge in the art except for the contents specifically mentioned below, and the present invention is not particularly limited.
Example 1
(1) Preparing a gold-plated carbon fiber electrode: using a three-electrode system containing a reference electrode, the carbon fiber electrode was immersed in 0.1M chloroauric acid at room temperature. Connecting the electrodes by using an electrochemical workstation, and setting a constant potential of-0.2V for electrodeposition for 15 seconds to obtain the gold-plated carbon fiber electrode.
(2) Preparing a carbon fiber electrode or a gold-plated carbon fiber electrode wrapped with a graphene oxide microstrip: and soaking the carbon fiber electrode or the gold-plated carbon fiber electrode prepared in the way in a graphene oxide suspension of 2.00mg/mL at room temperature by using a three-electrode system containing a reference electrode. Connecting the electrodes by using an electrochemical workstation, and setting a constant potential of 0.8V for electrodeposition for 30min to obtain the carbon fiber electrode or the gold-plated carbon fiber electrode wrapped with the graphene oxide micro-strip.
Fig. 1 is a scanning electron microscope image of a graphene oxide microstrip modified gold-plated carbon fiber electrode prepared in embodiment 1 of the present invention.
FIG. 2 is a fluorescence image of the gold-plated carbon fiber electrode prepared in example 1 of the present invention after being soaked in 20mg/mL of a solution of bovine serum albumin labeled with fluorescein isothiocyanate for 2 hours. From the figure, it can be seen that a large amount of fluorescence labeled bovine serum albumin (white spots) is adsorbed on the surface of the gold-plated carbon fiber electrode, which proves that the gold-plated electrode is extremely easy to adsorb and deposit protein in a solution containing protein.
Fig. 3 is a fluorescence image of the graphene oxide microstrip modified gold-plated carbon fiber electrode prepared in embodiment 1 of the present invention after being soaked in 20mg/mL bovine serum albumin solution labeled with fluorescein isothiocyanate for 2 hours. It can be seen from the figure that the fluorescent-labeled bovine serum albumin is hardly observed to adhere to the electrode surface. The excellent resistance effect of the coated graphene oxide micro-strip to protein adsorption is proved.
Fig. 4 is a cyclic voltammetry curve obtained by the graphene oxide microstrip modified gold-plated carbon fiber electrode prepared in embodiment 1 of the present invention in a 10 μ M dopamine solution. The solid line is the normal test curve and the dotted line is the test curve after the electrode has been soaked in 20mg/mL bovine serum albumin for 2 h. It can be seen from the figure that even after soaking in bovine serum albumin, the graphene oxide microstrip modified gold-plated carbon fiber electrode still has 91.3% of the current intensity of the un-soaked electrode. The graphene oxide microstrip modified gold-plated carbon fiber electrode is proved to still maintain excellent sensitivity when bioactive molecules are detected after protein soaking.
Fig. 5 is a contact angle diagram of electrodeposited graphene oxide on the surface of a glassy carbon electrode in example 1 of the present invention. The contact angle was calculated to be 25 °, demonstrating the highly hydrophilic nature of electrodeposited graphene oxide. The hydrophilicity is beneficial to generating the effect of repelling a protein hydration layer, and the protein adsorption resistance effect of the graphene oxide micro-strip is ensured.
Example 2
Ca wrapped with graphene oxide micro-strips2+Preparation of ion-selective electrode: the gold-plated carbon fiber electrode wrapped with graphene oxide micro-strips in example 1 was immersed in Ca with 1mM alkynyl linker functional groups2+The Ca coated with the graphene oxide micro-strips is obtained after 6 hours in the ethanol solution of the selective ligand2+An ion selective electrode.
FIG. 6 shows Ca of electrodeposited graphene oxide microstrip with (A) and unmodified (B) modified in example 2 of the present invention2+The ion selective electrode was added to 9.9mL of the test solution in 100. mu.L volume of 10mM CaCl2After the solution and 100mg of bovine serum albumin were continuously added 3 times, the change of the electrode signal when the solution totally accumulates 30mg/ml of bovine serum albumin was tested. From the figure, Ca modifying (A) electrodeposited graphene oxide microstrip can be seen2+The signal of the ion-selective electrode is reduced by only 5.7%, while the Ca of the unmodified (B) graphene oxide microstrip2+The signal of the ion selective electrode decreased by 31.6%. Evidence of Ca2+The protein resistance of the ion selective electrode is greatly improved after the modification of the electrodeposited graphene oxide microstrip.
Example 3
Coated aerobic stones prepared in example 2 of the inventionCa of graphene microstrip2+Study of avidin contamination after long-term in vivo implantation of ion selective electrodes.
FIG. 7 shows Ca coated with graphene oxide micro-strips in example 3 of the present invention2+Statistical plots of sensitivity changes over 60 days after ion selective electrode implantation into a living body. As can be seen from the figure, the sensitivity of the electrode was greater than 92% of the initial value even after 60 days of implantation into the living body. The graphene oxide microstrip provided by the invention can retain the active modification site of the sensor, and Ca is successfully modified2+Selective ligands, Ca encapsulating graphene oxide micro-strips have also been demonstrated2+The ion selective electrode can still maintain high sensitivity in long-term biological contamination.
Example 4
The electrodeposited graphene oxide micro-strip contaminated by avidin needs to maintain deposition conditions of positive potential and rapid stirring in the preparation process. If the potential is too high (> 1.0V) in the deposition process, the phenomenon of too fast adsorption can occur, and the density of the modified graphene oxide microstrip is too high. Whereas if the potential is too low (< 0.6V), it is difficult to form a stripe smoothly. Also, if stirring is not performed during deposition, graphene oxide is hardly adsorbed on the surface of the electrode to form a stripe.
The protection of the present invention is not limited to the above embodiments. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept, which is set forth in the following claims.
Claims (11)
1. The graphene oxide microstrip modification material is characterized by being composed of graphene oxide, and being wound on the surface of a biosensor in a crossed manner, so that active sites for modification are reserved on the surface of the biosensor.
2. A preparation method of a carbon fiber electrode/gold-plated carbon fiber electrode wrapped with an avidin-polluted graphene oxide microstrip is characterized by comprising the following steps:
step (1): soaking a carbon fiber electrode in a chloroauric acid solution by using a three-electrode system containing a reference electrode; connecting an electrode by using an electrochemical workstation, and setting constant potential electrodeposition to obtain a gold-plated carbon fiber electrode;
step (2): soaking a carbon fiber electrode or the gold-plated carbon fiber electrode obtained in the step (1) in a graphene oxide suspension by using a three-electrode system containing a reference electrode; connecting the electrodes by using an electrochemical workstation, and setting constant potential electrodeposition to obtain the carbon fiber electrode/gold-plated carbon fiber electrode wrapped with the avidin-polluted graphene oxide microstrip.
3. The preparation method according to claim 2, wherein in step (1) or step (2), the working electrode as the base electrode in the three-electrode system containing the reference electrode is a microelectrode made of any material with a diameter of 10-30 μm, including carbon fiber, iridium, platinum-iridium alloy, nickel-chromium alloy and tungsten.
4. The method according to claim 2, wherein in the step (1), the carbon fiber electrode is immersed in a chloroauric acid solution to perform electrode gold plating; the preparation steps of the electrode gold plating comprise electrodeposition, chemical vapor deposition and magnetron sputtering.
5. The method of claim 2, wherein in step (1) or step (2), the reference electrode-containing three-electrode system comprises: the carbon fiber electrode is a working electrode, the Ag/AgCl electrode is a reference electrode, and the platinum wire electrode is an auxiliary electrode.
6. The method according to claim 2, wherein in the step (1), the concentration of the chloroauric acid solution is 0.001 to 0.1M; the constant potential is set to-0.02 to-0.3V; the deposition time is 10-120 seconds.
7. The preparation method according to claim 2, wherein in the step (2), the concentration of the graphene oxide suspension is 0.05-2.00 mg/mL; the constant potential is set to be 0.2-1.0V; the deposition time is 10-60 min; in the constant potential electrodeposition process, the sedimentation tank needs to be stirred, and the stirring method comprises shaking by a shaking table, magnetic stirring, mechanical stirring and ultrasonic treatment.
8. A carbon fiber electrode/gold-plated carbon fiber electrode coated with an avidin-contaminated graphene oxide microstrip prepared by the method of any one of claims 2 to 7.
9. Ca wrapped with graphene oxide microstrip polluted by avidin2+The preparation method of the ion selective electrode is characterized in that the Ca coated with the graphene oxide microstrip2+Ion selective electrode by immersing the gold-plated carbon fiber electrode coated with an avidin-contaminated graphene oxide microstrip of claim 8 in a concentration of 0.5-5mM Ca with an alkynyl linking functional group2+Obtained after 6 hours in ethanol solution of the selective ligand.
10. Ca coated with avidin-contaminated graphene oxide microstrip prepared by the preparation method of claim 92+An ion selective electrode.
11. Ca coated with avidin-contaminated graphene oxide microstrip according to claim 102+Ion-selective electrode for extra-cellular Ca in mouse brain2+Applications in continuous follow-up monitoring.
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