CN108375617B - A kind of double nanozyme modified carbon fiber composite material, its preparation method and application - Google Patents
A kind of double nanozyme modified carbon fiber composite material, its preparation method and application Download PDFInfo
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- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3271—Amperometric enzyme electrodes for analytes in body fluids, e.g. glucose in blood
- G01N27/3272—Test elements therefor, i.e. disposable laminated substrates with electrodes, reagent and channels
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Abstract
本发明属于纳米材料的合成领域，具体地，涉及一种双纳米酶修饰碳纤维复合材料、制备方法及其在电化学分析中的应用。本发明制备得到的一种负载在碳纤维载体上的金属(及合金)纳米颗粒‑石墨烯量子点组装体的双纳米酶复合材料，利用双纳米酶较大的比表面积、表面丰富的活性位点结构优点和协同催化作用，基于碳纤维电极材料特殊的机械性能和微小尺寸，将负载了双纳米酶复合材料的碳纤维作为柔性纳米复合微电极，用于检测生物组织中活性氧自由基类物质(如过氧化氢的浓度)，灵敏度高、稳定性好。
The invention belongs to the field of nanomaterial synthesis, and in particular relates to a double nanozyme modified carbon fiber composite material, a preparation method and its application in electrochemical analysis. The double-nanozyme composite material of metal (and alloy) nanoparticle-graphene quantum dot assemblies supported on a carbon fiber carrier prepared by the present invention utilizes the larger specific surface area of the double-nanozyme and the abundant active sites on the surface. Structural advantages and synergistic catalysis, based on the special mechanical properties and tiny size of carbon fiber electrode materials, carbon fibers loaded with dual nanozyme composites are used as flexible nanocomposite microelectrodes to detect reactive oxygen species in biological tissues (such as concentration of hydrogen peroxide), high sensitivity and good stability.
Description
Technical Field
The invention belongs to the field of synthesis of nano materials, and particularly relates to a double-nano-enzyme modified carbon fiber composite material, a preparation method and application thereof in electrochemical analysis.
Background
With the rapid development of science and technology and the improvement of health consciousness of people, people continuously pursue portable, safe and healthy miniature precise medical electronic products, and how to obtain the medical electronic products with the characteristics of miniature, light weight, softness, safety, implantation and the like is urgent. The high-performance nano composite microelectrode material is prepared by introducing the nano material into a flexible microelectrode system, so that the specific surface area of the microelectrode material can be greatly increased and the electrochemical performance and the catalytic activity of the microelectrode material can be improved by utilizing the unique characteristics of quantum confinement effect, surface effect and the like of the loaded nano-sized material besides the physicochemical characteristics of the nano material introduced into an electrode interface, and the microelectrode material can be used for electrochemical biosensing detection; the flexible microelectrode has the advantages of micron or even nanometer level size, good flexibility and mechanical property, capability of being directly used as a non-support electrode without adding other electrode assemblies, capability of following the natural movement of soft tissues around a human body, good application in the detection of the human body, no damage to organic tissues of the human body, and capability of effectively relieving or eliminating discomfort and pain brought to a patient by treatment. Therefore, research and preparation of flexible microelectrodes become a great hotspot of biosensing detection.
In living organisms, the content level of active oxygen free radical substances such as hydrogen peroxide in living organisms is directly related to physiological and pathological activities of biological cells; hydrogen peroxide is also an important component in food, pharmaceutical, environmental analysis. Therefore, the technology for efficiently and accurately detecting the content of the hydrogen peroxide in the organism is researched, and has theoretical significance and practical value for explaining the signal conversion process in cells and developing early diagnosis and intervention methods of diseases. The sensitive element commonly used for constructing the hydrogen peroxide sensor at present is natural enzyme, has the characteristics of high efficiency and single substrate, but is easy to be denatured by environmental change, poor in stability and high in operation cost in the catalysis process.
With the development of nanotechnology and biotechnology, artificially synthesized nano enzyme materials are concerned, the nano enzyme simulates the structure and the function of natural enzyme and has double identities of the enzyme and the nano material, and the nano enzyme has the unique physical and chemical characteristics of the nano material besides the catalytic function of the enzyme, and has good chemical stability and thermal stability, high catalytic activity, low price and easy obtainment, which are different from the natural enzyme and the traditional simulated enzyme. The reported nano material such as noble metal particles have inherent catalytic activity similar to horseradish peroxidase, good electrochemical performance and biocompatibility, can be applied to hydrogen peroxide detection, but the noble metal particles of the nano enzyme used alone are easy to agglomerate to reduce the activity, and the noble metal particles used as the micro electrode have large particle size in the loading process, and the dispersity is not high so that the catalytic performance is low and needs to be improved.
Disclosure of Invention
Aiming at the defects or improvement requirements in the prior art, the invention provides a double-nanoenzyme modified carbon fiber composite material, a preparation method and application thereof, in particular to a preparation method and application of a double-nanoenzyme modified carbon fiber electrode based on a noble metal (and alloy) nanoparticle-graphene quantum dot assembly, which fully combines the characteristics and requirements of hydrogen peroxide detection enzyme, redesigns the hydrogen peroxide manual detection enzyme in a targeted manner, compounds the noble metal (and alloy) nanoenzyme and graphene quantum dots, improves the overall process design of the key preparation process, the reaction conditions (such as reactant concentration, reaction time and electrodeposition parameters) of each step and the like, and compared with the prior art, prepares the obtained noble metal (and alloy) -graphene quantum dot assembly, wherein the graphene quantum dots form an assembly structure, the compactness of the catalyst is greatly improved, a larger specific surface area is provided for loading noble metal (and alloy) nano particles, and the catalytic activity of the catalyst is also effectively improved. By utilizing the advantages of large specific surface area and rich surface active site structures of double nanoenzymes and the synergistic catalytic action, the carbon fiber loaded with the double nanoenzyme composite material is used as a flexible microelectrode for detecting active oxygen free radical substances (such as the concentration of hydrogen peroxide) in biological tissues based on the special mechanical properties and small size of a carbon fiber electrode material, and the sensitivity and the stability are high, so that the technical problems of large particle size, low dispersity, easy agglomeration, low catalytic activity and the like of single nanoenzyme precious metal particles in the prior art are solved.
In order to achieve the above object, according to one aspect of the present invention, a double-nanoenzyme modified carbon fiber composite material is provided, which uses carbon fibers as a substrate, the surface of the carbon fibers is loaded with graphene quantum dots and ionic liquid, the graphene quantum dots and the ionic liquid are used as nucleation points, and the nucleation points are loaded with noble metal nanoparticles.
Preferably, the particle size of the graphene quantum dot is not more than 15 nanometers, and the thickness of the graphene quantum dot is 0.5-1.0 nanometer.
Preferably, the noble metal nanoparticles are Pd nanoparticles, Au nanoparticles, Ag nanoparticles, Pt nanoparticles, bimetallic AuPd nanoparticles, or bimetallic PtAu nanoparticles.
Preferably, the ionic liquid is imidazole ionic liquid [ C ] with hydrophilicitynMIM]X (n ═ 2,4,6,8, X is an anion); anions in the imidazole ionic liquid are halide ions and [ NO3]-、[CF3CO]-、[BF4]-And [ CF3SO3]-at least one of.
Further preferably, the ionic liquid is at least one of 1-butyl-3-methylimidazole trifluoromethanesulfonate, 1-butyl-3-methylimidazole tetrafluoroborate and 1-ethyl-3-methylimidazole tetrafluoroborate.
According to another aspect of the invention, a preparation method of a double-nanoenzyme modified carbon fiber composite material is provided, which comprises the following steps:
(1) dispersing graphene quantum dots in an ionic liquid to form a graphene quantum dot-ionic liquid dispersion liquid;
(2) taking the graphene quantum dot-ionic liquid dispersion liquid obtained in the step (1) as an electrolyte, and taking activated carbon fibers as working electrodes for electrodeposition to obtain carbon fibers loaded with the graphene quantum dot assembly, namely the graphene quantum dot assembly/carbon fibers;
(3) and (3) taking the graphene quantum dot assembly/carbon fiber obtained in the step (2) as a working electrode, placing the working electrode in a precursor solution dissolved with noble metal ions for electrodeposition, and depositing noble metal nano particles on the surface of the graphene quantum dot assembly to obtain the noble metal nano particles-graphene quantum dot assembly/carbon fiber.
Preferably, the graphene quantum dot-ionic liquid dispersion liquid in the step (1) is obtained according to the following method: dispersing the dried graphene quantum dots in an ionic liquid, uniformly mixing by an ultrasonic method, and drying the mixed solution to remove moisture, thereby preparing the graphene quantum dot-ionic liquid dispersion liquid.
Preferably, the drying is performed by placing the mixed solution in a vacuum drying oven at 30-40 ℃ for 2-4 days.
Preferably, the concentration of the graphene quantum dots in the graphene quantum dot-ionic liquid dispersion liquid in the step (1) is 1-15 mg/mL.
Preferably, the ionic liquid in the step (1) is imidazole ionic liquid [ C ] with hydrophilicitynMIM]X, wherein n is 2,4,6,8, X is an anion; anions in the imidazole ionic liquid are halide ions and [ NO3]-、[CF3CO]-、[BF4]-And [ CF3SO3]-at least one of.
Further preferably, the ionic liquid is at least one of 1-butyl-3-methylimidazole trifluoromethanesulfonate, 1-butyl-3-methylimidazole tetrafluoroborate and 1-ethyl-3-methylimidazole tetrafluoroborate.
Preferably, the particle size of the graphene quantum dot in the step (1) is not more than 15 nanometers, and the thickness of the graphene quantum dot is 0.5-1.0 nanometer.
Preferably, the carbon fiber in the step (1) is soaked and activated by using a hydrogen peroxide-ethanol mixed solution.
Preferably, the electrodeposition in the step (2) is carried out by utilizing a three-electrode system under the condition of constant potential, the deposition potential is-1.0V to-4.0V, and the deposition time is 1min to 20 min.
Preferably, the electrodeposition in the step (3) is carried out under the condition of constant potential by using a three-electrode system, the deposition potential is-0.3V to-0.1V, and the deposition time is 40s to 100 s.
Preferably, the noble metal nanoparticles in step (3) are Pd nanoparticles, Au nanoparticles, Ag nanoparticles, Pt nanoparticles, bimetallic AuPd nanoparticles or bimetallic PtAu nanoparticles.
Preferably, the precursor solution in step (3) is a soluble metal salt solution.
According to another aspect of the invention, the application of the double-nanoenzyme modified carbon fiber composite material is provided, and the double-nanoenzyme modified carbon fiber composite material is used for preparing a flexible microelectrode.
Preferably, the flexible microelectrode is used for ultrasensitive detection of reactive oxygen species in biological tissue.
In general, compared with the prior art, the above technical solution contemplated by the present invention can achieve the following beneficial effects:
(1) the invention provides a double-nanoenzyme modified carbon fiber composite material, which takes carbon fibers as a substrate, and graphene quantum dots with nanometer sizes are loaded on the surfaces of the carbon fibers, so that the characteristics of the graphene quantum dots, the quantum confinement effect and the surface effect provide large specific surface area and improve the electrochemical performance for the carbon fibers; and then, the graphene quantum dots are used as nucleation points to load noble metals, so that the obtained noble metals are high in dispersion, high in density and small in particle, the catalytic activity and the electrochemical performance of the noble metals are improved to a certain degree, the carbon fiber electrode is modified through the unique structural advantages and the synergistic catalytic action of the graphene quantum dots and the noble metal double nanoenzymes, and the graphene quantum dots and noble metal double nanoenzymes can be used as self-supporting flexible electrode products to be applied to electrochemical analysis.
(2) The invention provides a preparation method of a double-nanoenzyme modified carbon fiber composite material, which comprises the steps of taking carbon fibers as working electrodes, taking dispersion liquid of graphene quantum dots in ionic liquid as electrolyte, carrying out electrodeposition to obtain graphene quantum dot assemblies/carbon fibers, taking the graphene quantum dot assemblies/carbon fibers as the working electrodes, taking the graphene quantum dots as nucleation points, and carrying out electrodeposition to deposit noble metal (or alloy thereof) nanoparticles to obtain the composite material. The preparation method is simple and easy to implement and is easy for large-scale production.
(3) In the composite material prepared by the invention, the graphene quantum dots have larger specific surface area and high activity due to the quantum confinement effect and the surface effect of the nano size; has good chemical inertness, good biocompatibility and low cytotoxicity; the surface of the graphene quantum dot contains hydroxyl, carbonyl and carboxyl groups, so that the graphene quantum dot has good water solubility, shows good dispersion performance in a water phase and an organic solvent, and can be well dispersed in the ionic liquid; due to the aromatic structure and the rich carboxyl groups on the surface, the graphene quantum dots have catalase-like characteristics and can be used as the nano-enzyme catalytic hydrogen peroxide; on the other hand, the noble metal nanoparticles have inherent catalytic activity similar to horseradish peroxidase, good electrochemical performance and biocompatibility, and can be applied to hydrogen peroxide detection; therefore, the graphene quantum dots and the noble metal nanoparticles are called double nanoenzymes, the carbon fibers are modified, the double nanoenzymes sequentially modify the carbon fibers through the special preparation method, and good conditions are provided for modification of the noble metal particle nanoenzymes by virtue of the characteristics of the graphene quantum dots, so that the finally obtained double nanoenzyme modified carbon fiber composite material obtains good effects when applied.
(4) The double-nanoenzyme modified carbon fiber composite material prepared by the invention is used as an active material of a flexible microelectrode and is used for detecting active oxygen free radical substances (such as the concentration of hydrogen peroxide) in biological tissues, compared with the prior art, the detection limit is low (500nM, the signal-to-noise ratio is 3:1), the linear range is wide (1.0 mu M to 18.44mM), the sensitivity is improved to 371 mu Acm-2mM-1The anti-interference capability is strong, and the stability is good.
Drawings
In fig. 1, fig. 1a is a scanning electron microscope image of carbon fibers, fig. 1b is a scanning electron microscope image of graphene quantum dot assemblies/carbon fibers prepared in example 1, and fig. 1c is a scanning electron microscope image of AuPd alloy nanoparticles-graphene quantum dot assemblies/carbon fibers prepared in example 1.
Fig. 2a is a high-resolution transmission electron microscope image of a Graphene Quantum Dot (GQDs) assembly prepared in example 1; FIG. 2b is a transmission electron microscope image of the AuPd Alloy Nanoparticle (ANPs) -Graphene Quantum Dot (GQDs) assembly composite material prepared in example 1; FIG. 2c is an enlarged high resolution TEM image of FIG. 2 b.
FIG. 3 is a graph of Cyclic Voltammetry (CV) of the double nanoenzyme-modified carbon fiber electrode prepared in example 1 in 0.1 mol/liter (mol/L) phosphate buffered saline (pH 7.4) containing different concentrations of hydrogen peroxide, corresponding to hydrogen peroxide solutions of 0(i), 0.002mol/L (ii), 0.005mol/L (iii) and 0.01mol/L (iv), respectively.
FIG. 4a is an Amperometric curve (Amperometric i-t curve) obtained by continuously adding hydrogen peroxide with different concentrations to a PBS buffer solution (pH 7.4) at a potential of 0.05V in example 1 by using a double-nanoenzyme modified carbon fiber electrode as a working electrode of a hydrogen peroxide electrochemical sensor; fig. 4b is a corresponding operating curve of fig. 4 a.
FIG. 5 is an amperometric time curve for real-time detection of hydrogen peroxide release by cancer cells in tumor tissue by inserting a double nanoenzyme-modified carbon fiber microelectrode into surgically excised breast cancer tissue.
Fig. 6 is a scanning electron microscope image of the AuPd alloy nanoparticle/graphene quantum dot assembly modified carbon fiber prepared in example 1.
Fig. 7 is a scanning electron microscope image of AuPd alloy nanoparticle/carbon fiber electrodes prepared in comparative example 1 at different magnifications.
FIG. 8 is a graph of Cyclic Voltammetry (CV) of the graphene quantum dot/carbon fiber electrode prepared in comparative example 2 in 0.1mol/L phosphate buffered saline solution containing hydrogen peroxide at different concentrations, corresponding to hydrogen peroxide solutions of 0(i), 0.002mol/L (ii), 0.005mol/L (iii) and 0.01mol/L (iv), respectively.
FIG. 9 is a comparison graph of cyclic voltammetry CV of the dual nanoenzyme-modified carbon fiber electrodes (AuPd-ANPs/GODs/ACF), AuPd alloy nanoparticles/carbon fiber electrodes (AuPd-ANPs/ACF) and graphene quantum dots/carbon fiber electrodes (GODs/ACF) prepared in example 1, comparative example 1 and comparative example 2, respectively, in 0.1mol/L phosphate buffered saline containing 0.01mol/L hydrogen peroxide.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention provides a method for modifying carbon fibers by using a double-nanoenzyme composite material based on a noble metal (and alloy) nanoparticle-graphene quantum dot assembly, which comprises the following steps:
(1) dispersing graphene quantum dots in an ionic liquid to form a graphene quantum dot-ionic liquid dispersion liquid;
(2) and (2) taking the graphene quantum dot-ionic liquid dispersion liquid obtained in the step (1) as an electrolyte, activating carbon fibers and taking the activated carbon fibers as a working electrode for electrodeposition to obtain carbon fibers loaded with the graphene quantum dot assembly, namely the graphene quantum dot assembly/carbon fibers.
(3) And (3) taking the graphene quantum dot assembly/carbon fiber obtained in the step (2) as a working electrode, putting the working electrode in a precursor solution dissolved with noble metal ions for electrodeposition, and depositing a layer of highly dispersed and high-density noble metal (and alloy) nanoparticles on the surface of the graphene quantum dot assembly, namely the noble metal (and alloy) nanoparticles-graphene quantum dot assembly/carbon fiber.
Preparing the graphene quantum dot-ionic liquid dispersion liquid in the step (1), namely dispersing dried graphene quantum dots in ionic liquid, uniformly mixing by an ultrasonic method to obtain a yellow mixed liquid, and drying the mixed liquid to remove water, so as to prepare the graphene quantum dot-ionic liquid dispersion liquid; preferably, the drying is to dry the dispersion in a vacuum drying oven at 30-40 ℃ for 2-4 days. The concentration of the graphene quantum dots in the graphene quantum dot-ionic liquid dispersion liquid in the step (1) is 1mg/mL-15 mg/mL; the ionic liquid in the step (1) is an ionic liquid which can be mutually soluble and stably exists with the graphene quantum dot-ionic liquid dispersion liquid; preferably, the ionic liquid is imidazole ionic liquid [ C ] with hydrophilicitynMIM]X (n ═ 2,4,6,8, X is an anion); anions in the imidazole ionic liquid are halide ions and [ NO3]-、[CF3CO]-、[BF4]-And [ CF3SO3]-At least one of; preferably, the ionic liquid is at least one of 1-butyl-3-methylimidazole trifluoromethanesulfonate, 1-butyl-3-methylimidazole tetrafluoroborate and 1-ethyl-3-methylimidazole tetrafluoroborate. The graphene quantum dots in the step (1) are prepared by a bottom-up method, the particle size is not more than 15nm, the thickness is only 0.5-1.0 nm, and the nano-sized quantum confinement effect and the surface effect have larger specific surface area and high activity; has good chemical inertness, good biocompatibility and low cytotoxicity; the surface of the graphene quantum dot contains hydroxyl, carbonyl and carboxyl groups, so that the graphene quantum dot has good water solubility, shows good dispersion performance in a water phase and an organic solvent, and can be well dispersed in an ionic liquid; due to the aromatic structure and the rich carboxyl groups on the surface, the graphene quantum dots have catalase-like characteristics and can be used as the nano-enzyme catalytic hydrogen peroxide.
And (3) carrying out electrodeposition in the step (2) to obtain the carbon fiber loaded with the graphene quantum dots, wherein the electrodeposition is carried out under the condition of constant potential by using a three-electrode system, the deposition potential is-1.0V to-4.0V, and the deposition time is 1min to 20 min. In the step (2), the carbon fiber is activated by soaking the carbon fiber in a hydrogen peroxide-ethanol mixed solution for 48 hours (h) in a drying oven at the temperature of 60 ℃ to obtain the activated carbon fiber; the volume ratio of the hydrogen peroxide-ethanol mixed solution is preferably 1:1, preferably, the activating solution can be replaced once in 24 hours, and the concentration of hydrogen peroxide in the mixed solution is not lower than 30 percent, and the concentration of ethanol is not lower than 90 percent.
In the step (3), a layer of high-dispersion and high-density noble metal (and alloy) nano particles is deposited on the surface of the graphene quantum dot assembly, the deposition is carried out under the condition of constant potential by using a three-electrode system, the deposition potential is-0.3V to-0.1V, and the deposition time is 40s to 100 s. The metal particles or metal oxide particles in step (3) are nano materials with catalytic activity, preferably at least one of Pd nanoparticles, Au nanoparticles, Ag nanoparticles, Pt nanoparticles, bimetallic AuPd nanoparticles, bimetallic PtAu nanoparticles, and bimetallic PtPd nanoparticles. And (4) the precursor solution dissolved with the noble metal ions in the step (3) is a soluble metal salt solution.
The double-nanoenzyme modified carbon fiber composite material prepared by the method can be used as a flexible nano composite microelectrode for ultrasensitive detection of active oxygen in biological tissues.
Through the technical scheme, compared with the prior art, the graphene quantum dots form an assembly structure, the density of the assembly structure is greatly improved, a larger specific surface area is provided for loading noble metal (and alloy) nanoparticles, and the catalytic activity of the assembly structure is effectively improved. By utilizing the advantages of large specific surface area and abundant active site structures on the surface of the double nanoenzymes and the synergistic catalytic action, the carbon fiber loaded with the double nanoenzyme composite material is used as a flexible microelectrode for detecting active oxygen free radical substances (such as the concentration of hydrogen peroxide) in biological tissues based on the special mechanical properties and the small size of the carbon fiber electrode material, and the flexible microelectrode is high in sensitivity and good in stability.
The high-performance flexible nano composite microelectrode material can be prepared, and the noble metal (and alloy) nanoparticle-graphene quantum dot assembly/carbon fiber prepared by the preparation method can be used as a flexible microelectrode for detecting the concentration of active oxygen radicals such as hydrogen peroxide in biological tissues. The graphene quantum dots have a large specific surface area and high activity due to the special quantum confinement effect and the surface effect, and more importantly, the graphene quantum dots have catalase-like characteristics due to the planar polycyclic aromatic hydrocarbon structure and the rich carboxyl groups on the surface, and can also be used as a novel nanoenzyme for hydrogen peroxide detection. The nano material metal particles or metal oxide particles are common catalytic hydrogen peroxide nanoenzyme, have inherent catalytic activity similar to horseradish peroxidase, and have good electrochemical performance and biocompatibility. The ionic liquid is used as electrolyte to deposit the graphene quantum dots, the graphene quantum dots can provide a larger driving force to deposit under a more negative potential to form an assembly structure, the interference of hydrogen evolution reaction in common aqueous solution does not exist in the electrodeposition process, and ionic liquid molecules can be adsorbed on the graphene quantum dot nano layer and act synergistically with the graphene quantum dots to provide more nucleation sites for the subsequent in-situ growth of noble metal (and alloy) nano particles on the surface of the graphene quantum dots. The graphene quantum dot assembly loaded with the noble metal (and alloy) nano particles can be used as a double-nano enzyme catalysis system, and the unique structural advantage and the synergistic effect of the graphene quantum dot assembly can obviously improve the catalysis performance of the system. The method has the advantages of simple and stable operation, easily obtained raw materials and high reaction efficiency, and has great innovative significance for preparing the flexible nano composite microelectrode and applying the flexible nano composite microelectrode to a biomedical detection system.
Compared with the prior art, the preparation method is simple and efficient to operate, the prepared material is high in catalytic activity (the unique structure and the synergistic catalytic effect of the double-nanoenzyme), low in synthesis cost (the precursor material is low in cost, the electrolyte ionic liquid can be recycled, and the micro-morphology (such as a nano structure) of the prepared material is accurate and controllable, and the prepared flexible nano composite microelectrode has good electrocatalytic activity and can be used as an electrode material of an electrochemical sensor for measuring the concentration of active oxygen radicals (such as hydrogen peroxide) in biological tissues.
The following are examples:
example 1
(1) Selecting ionic liquid 1-butyl-3-methylimidazole trifluoromethanesulfonate to prepare the graphene quantum dot-ionic liquid dispersion liquid with the concentration of 10 mg/ml: uniformly mixing 30mg of dried graphene quantum dots and 3ml of 1-butyl-3-methylimidazole trifluoromethanesulfonate by an ultrasonic method, then placing the mixed solution in a vacuum drying oven at 30 ℃ for 3 days, and removing water.
(2) Activating carbon fibers: respectively ultrasonically cleaning carbon fibers for 3 times by using acetone, ethanol and deionized water, drying, soaking the dried carbon fibers in a hydrogen peroxide-ethanol mixed solution (the volume ratio is 1:1) in a 60 ℃ drying oven for 48 hours, changing the mixed solution once for 24 hours, soaking and washing the carbon fibers by using the deionized water, and freeze-drying to obtain the activated carbon fibers.
(3) And (3) electrodepositing the graphene quantum dots: and (2) taking the activated carbon fiber as a working electrode, a platinum mesh electrode as an auxiliary electrode and a silver/silver chloride electrode as a reference electrode, placing the activated carbon fiber into the graphene quantum dot-ionic liquid dispersion liquid of 10mg/ml prepared in the step (1), and performing electrodeposition for 10min under a constant potential of-3V to prepare the graphene quantum dot modified carbon fiber, namely the graphene quantum dot/carbon fiber electrode.
(4) Electrodeposition of active bimetallic AuPd nanoparticles: placing graphene quantum dots/carbon fibers as a working electrode, a platinum mesh electrode as an auxiliary electrode, a silver/silver chloride electrode as a reference electrode in 10ml of HAuCl containing 1.5mM4、0.3mMK2PdCl4And 0.1M NaNO3In the mixed solution, the AuPd alloy nano particles/graphene quantum dot assemblies/carbon fiber electrodes are prepared by electro-deposition for 60s under the condition of constant potential of-0.2V.
(5) Electrochemical analysis application: the prepared AuPd alloy nano-particles/graphene quantum dot assembly/carbon fibers are used as flexible nano-composite microelectrodes and applied to hydrogen peroxide electrochemical sensors.
In fig. 1, fig. 1a is a scanning electron microscope image of carbon fibers, fig. 1b is a scanning electron microscope image of graphene quantum dot assemblies/carbon fibers prepared in example 1, and fig. 1c is a scanning electron microscope image of AuPd alloy nanoparticles-graphene quantum dot assemblies/carbon fibers prepared in example 1.
Fig. 2a is a high-resolution transmission electron microscope image of the Graphene Quantum Dot (GQDs) assembly prepared in example 1, and it can be seen that the graphene quantum dot assembly has an obvious structure; fig. 2b is a transmission electron microscope image of the AuPd Alloy Nanoparticle (ANPs) -Graphene Quantum Dot (GQDs) assembly composite material prepared in example 1, and it can be seen that AuPd alloy nanoparticles are uniformly and densely distributed on the graphene quantum dot sheet layer. FIG. 2c is an enlarged high resolution TEM image of FIG. 2 b.
FIG. 3 is a graph of Cyclic Voltammetry (CV) of the double nanoenzyme-modified carbon fiber electrode prepared in example 1 in 0.1 mol/liter (mol/L) phosphate buffered saline (pH 7.4) containing different concentrations of hydrogen peroxide, corresponding to hydrogen peroxide solutions of 0(i), 0.002mol/L (ii), 0.005mol/L (iii), and 0.01mol/L (iv), respectively; it can be seen that in the buffer solution containing hydrogen peroxide, the double-nanoenzyme modified microelectrode has an obvious reduction peak at the potential of 0.05V, which corresponds to the electrochemical reduction of hydrogen peroxide, and the current density of the reduction peak is increased with the increasing of the concentration of hydrogen peroxide, which indicates that the electrode material has excellent electrocatalytic activity for the reduction of hydrogen peroxide.
FIG. 4a is an Amperometric curve (Amperometric i-t curve) obtained by continuously adding hydrogen peroxide with different concentrations to a PBS buffer solution (pH 7.4) at a potential of 0.05V in example 1 by using a double-nanoenzyme modified carbon fiber electrode as a working electrode of a hydrogen peroxide electrochemical sensor; the curve presents a regular staircase shape; when the ampere response current reaches 90%, the response time is less than 4s, and the detection limit is as low as 500nM (the signal-to-noise ratio is 3); FIG. 4b is a graph showing the operation curve corresponding to FIG. 4a, wherein the sensitivity of the electrode for detecting hydrogen peroxide is 371 μ A cm-2mM-1The linear range was 1.0. mu.M to 18.44 mM.
FIG. 5 is an amperometric time curve for detecting the release of hydrogen peroxide from cancer cells in tumor tissue in real time by inserting a double nanoenzyme-modified carbon fiber microelectrode (microelectrode in the figure) into surgically excised breast cancer tissue. The release of hydrogen peroxide from MCF-7 cells under stimulation by N-formylmethionyl-leucyl-phenylalanine (fMLP) resulted in an increase in current density of 1.27. mu.A cm-2。
Fig. 6 is a scanning electron microscope image of the AuPd alloy nanoparticle/graphene quantum dot assembly modified carbon fiber prepared in example 1.
Comparative example 1
(1) Selecting ionic liquid 1-butyl-3-methylimidazole trifluoromethanesulfonate to prepare the graphene quantum dot-ionic liquid dispersion liquid with the concentration of 10 mg/ml: uniformly mixing 30mg of dried graphene quantum dots and 3ml of 1-butyl-3-methylimidazole trifluoromethanesulfonate by an ultrasonic method, then placing the mixed solution in a vacuum drying oven at 30 ℃ for 3 days, and removing water.
(2) Activating carbon fibers: respectively ultrasonically cleaning carbon fibers for 3 times by using acetone, ethanol and deionized water, drying, soaking the dried carbon fibers in a hydrogen peroxide-ethanol mixed solution (the volume ratio is 1:1) in a 60 ℃ drying oven for 48 hours, changing the mixed solution once for 24 hours, soaking and washing the carbon fibers by using the deionized water, and freeze-drying to obtain the activated carbon fibers.
(3) Electrodeposition of active bimetallic AuPd nanoparticles: the activated carbon fiber is directly used as a working electrode, a platinum mesh electrode is used as an auxiliary electrode, a silver/silver chloride electrode is used as a reference electrode, and the activated carbon fiber is placed in 10ml of HAuCl containing 1.5mM4、0.3mMK2PdCl4And 0.1M NaNO3In the mixed solution, the AuPd alloy nano-particle/carbon fiber electrode is prepared by electro-deposition for 60s under the condition of constant potential of-0.2V.
(4) Electrochemical analysis application: the prepared AuPd alloy nano particles/carbon fibers are used as a contrast experiment and are applied to a hydrogen peroxide electrochemical sensor as a microelectrode.
Fig. 7 is a scanning electron microscope image of AuPd alloy nanoparticle/carbon fiber electrode prepared in comparative example 1 at different magnifications, which shows that single nanoenzyme alloy particles are directly deposited on carbon fibers, and are easy to agglomerate, and that the deposited alloy particles are large, have small specific surface area, are sparse, and have insufficient catalytic activity.
Comparative example 2
(1) Selecting ionic liquid 1-butyl-3-methylimidazole trifluoromethanesulfonate to prepare the graphene quantum dot-ionic liquid dispersion liquid with the concentration of 10 mg/ml: uniformly mixing 30mg of dried graphene quantum dots and 3ml of 1-butyl-3-methylimidazole trifluoromethanesulfonate by an ultrasonic method, then placing the mixed solution in a vacuum drying oven at 30 ℃ for 3 days, and removing water.
(2) Activating carbon fibers: respectively ultrasonically cleaning carbon fibers for 3 times by using acetone, ethanol and deionized water, drying, soaking the dried carbon fibers in a hydrogen peroxide-ethanol mixed solution (the volume ratio is 1:1) in a 60 ℃ drying oven for 48 hours, changing the mixed solution once for 24 hours, soaking and washing the carbon fibers by using the deionized water, and freeze-drying to obtain the activated carbon fibers.
(3) And (3) electrodepositing the graphene quantum dots: and (2) taking the activated carbon fiber as a working electrode, a platinum mesh electrode as an auxiliary electrode and a silver/silver chloride electrode as a reference electrode, placing the activated carbon fiber into the graphene quantum dot-ionic liquid dispersion liquid of 10mg/ml prepared in the step (1), and performing electrodeposition for 10min under a constant potential of-3V to prepare the graphene quantum dot modified carbon fiber, namely the graphene quantum dot/carbon fiber electrode.
(4) Electrochemical analysis application: the prepared graphene quantum dot/carbon fiber electrode is used as a contrast experiment and is applied to a hydrogen peroxide electrochemical sensor as a microelectrode.
FIG. 8 is a graph of Cyclic Voltammetry (CV) of the graphene quantum dot/carbon fiber electrode prepared in comparative example 2 in 0.1mol/L phosphate buffered saline solution containing hydrogen peroxide at different concentrations, corresponding to hydrogen peroxide solutions of 0(i), 0.002mol/L (ii), 0.005mol/L (iii) and 0.01mol/L (iv), respectively; it can be seen that the graphene quantum dot/carbon fiber electrode has a weak reduction peak at-0.35V, the peak current intensity is slowly increased along with the increase of the hydrogen peroxide concentration, but the catalytic activity is small, and the requirement of the hydrogen peroxide sensor is not satisfied.
FIG. 9 is a comparison graph of cyclic voltammetry CV of the dual nanoenzyme-modified carbon fiber electrodes (AuPd-ANPs/GODs/ACF), AuPd alloy nanoparticles/carbon fiber electrodes (AuPd-ANPs/ACF) and graphene quantum dots/carbon fiber electrodes (GODs/ACF) prepared in example 1, comparative example 1 and comparative example 2, respectively, in 0.1mol/L phosphate buffered saline solution containing 0.01mol/L hydrogen peroxide; therefore, the peak current response of the double-nanoenzyme modified carbon fiber electrode is most obvious, the catalytic performance of the double-nanoenzyme modified carbon fiber electrode is obviously superior to that of an AuPd alloy nanoparticle/carbon fiber electrode and a graphene quantum dot/carbon fiber electrode, and the double-nanoenzyme synergistic effect is shown to promote the electrochemical performance of the electrode to be improved.
Example 2
The method comprises the following steps:
(1) selecting an ionic liquid 1-ethyl-3-methylimidazole tetrafluoroborate to prepare a graphene quantum dot-ionic liquid dispersion liquid with the concentration of 5 mg/ml: uniformly mixing 15mg of dried graphene quantum dots and 3ml of 1-ethyl-3-methylimidazole tetrafluoroborate by an ultrasonic method, then placing the mixed solution in a vacuum drying oven at 30 ℃ for 3 days, and removing water.
(2) Activating carbon fibers: respectively ultrasonically cleaning carbon fibers for 3 times by using acetone, ethanol and deionized water, drying, soaking the dried carbon fibers in a hydrogen peroxide-ethanol mixed solution (the volume ratio is 1:1) in a 60 ℃ drying oven for 48 hours, changing the mixed solution once for 24 hours, soaking and washing the carbon fibers by using the deionized water, and freeze-drying to obtain the activated carbon fibers.
(3) And (3) electrodepositing the graphene quantum dots: and (2) taking the activated carbon fiber as a working electrode, a platinum mesh electrode as an auxiliary electrode and a silver/silver chloride electrode as a reference electrode, placing the activated carbon fiber into the 5mg/ml graphene quantum dot-ionic liquid dispersion liquid prepared in the step (1), and performing electrodeposition for 5min under a constant potential of-4V to prepare the graphene quantum dot modified carbon fiber, namely the graphene quantum dot assembly/carbon fiber electrode.
(4) Electrodeposition of active component Au nanoparticles: placing graphene quantum dots/carbon fibers as a working electrode, a platinum mesh electrode as an auxiliary electrode, a silver/silver chloride electrode as a reference electrode in 10ml of HAuCl containing 1.5mM4And 0.1M NaNO3In the mixed solution, the Au nano-particle-graphene quantum dot assembly/carbon fiber electrode is prepared by electro-deposition for 40s under the condition of constant potential of-0.1V.
(5) Sensing applications: the prepared Au nanoparticle-graphene quantum dot assembly/carbon fiber electrode is used as a flexible nano composite microelectrode and applied to a hydrogen peroxide electrochemical sensor.
Example 3
The method comprises the following steps:
(1) selecting an ionic liquid 1-butyl-3-methylimidazole tetrafluoroborate to prepare a graphene quantum dot-ionic liquid dispersion liquid with the concentration of 15 mg/ml: uniformly mixing 45mg of dried graphene quantum dots and 3ml of 1-butyl-3-methylimidazole tetrafluoroborate by an ultrasonic method, then placing the mixed solution in a vacuum drying oven at 30 ℃ for 3 days, and removing water.
(2) Activating carbon fibers: respectively ultrasonically cleaning carbon fibers for 3 times by using acetone, ethanol and deionized water, drying, soaking the dried carbon fibers in a hydrogen peroxide-ethanol mixed solution (the volume ratio is 1:1) in a 60 ℃ drying oven for 48 hours, changing the mixed solution once for 24 hours, soaking and washing the carbon fibers by using the deionized water, and freeze-drying to obtain the activated carbon fibers.
(3) And (3) electrodepositing the graphene quantum dots: and (2) taking the activated carbon fiber as a working electrode, a platinum mesh electrode as an auxiliary electrode and a silver/silver chloride electrode as a reference electrode, placing the activated carbon fiber into the 5mg/ml graphene quantum dot-ionic liquid dispersion liquid prepared in the step (1), and performing electrodeposition for 15min at a constant potential of-1.5V to prepare the carbon fiber modified by the graphene quantum dot assembly, namely the graphene quantum dot assembly/carbon fiber electrode.
(4) Electrodeposition of active ingredient Pd nanoparticles: placing graphene quantum dots/carbon fibers as a working electrode, a platinum mesh electrode as an auxiliary electrode, a silver/silver chloride electrode as a reference electrode in 10ml of solution containing 0.3mM K2PdCl4And 0.1M NaNO3In the mixed solution, the Pd nano-particles-graphene quantum dot assembly/carbon fiber electrode is prepared by electrodeposition for 100s under the condition of constant potential of-0.3V.
(5) Electrochemical analysis application: the prepared Pd nano-particle-graphene quantum dot assembly/carbon fiber electrode is used as a flexible nano composite microelectrode and applied to a hydrogen peroxide electrochemical sensor.
The above specific embodiments are data selected during specific operations within the condition selection range of the scheme provided by the present invention, and the preparation of the microelectrode provided by the present invention can be realized by using the above raw materials and reaction conditions listed in the present invention, such as the type of the ionic liquid, the concentration of the graphene quantum dots in the ionic liquid, the electrodeposition potential and time, examples in selecting modified active substances, and upper and lower limit values, and therefore, the details are not repeated.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104851615A (en) * | 2015-03-27 | 2015-08-19 | 上海大学 | Electrophoresis method for controllably preparing graphene quantum dot high-capacitance three-dimensional electrode |
| CN106018517A (en) * | 2016-05-16 | 2016-10-12 | 常州大学 | Preparation of tartaric acid-graphene quantum dot composite film modified electrode and application in tryptophan enantiomer recognition |
-
2018
- 2018-02-09 CN CN201810135110.7A patent/CN108375617B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104851615A (en) * | 2015-03-27 | 2015-08-19 | 上海大学 | Electrophoresis method for controllably preparing graphene quantum dot high-capacitance three-dimensional electrode |
| CN106018517A (en) * | 2016-05-16 | 2016-10-12 | 常州大学 | Preparation of tartaric acid-graphene quantum dot composite film modified electrode and application in tryptophan enantiomer recognition |
Non-Patent Citations (5)
| Title |
|---|
| Au-Pd nanoparticles supported on carbon fiber cloth as the electrocatalyst for H2O2 electroreduction in acid medium;Fan Yang 等;《Journal of Power Sources》;20130129;第233卷;全文 * |
| Jiangbo Xi 等.Pd Nanoparticles Decorated N-Doped Graphene Quantum Dots@N-Doped Carbon Hollow Nanospheres with High Electrochemical Sensing Performance in Cancer Detection.《ACS Applied Materials & Interfaces》.2016,第8卷 * |
| Lu Wang 等.PtAu alloy nanoflowers on 3D porous ionic liquid functionalized graphene-wrapped activated carbon fiber as a flexible microelectrode for near-cell detection of cancer.《NPG Asia Materials》.2016,第8卷 * |
| Pd Nanoparticles Decorated N-Doped Graphene Quantum Dots@N-Doped Carbon Hollow Nanospheres with High Electrochemical Sensing Performance in Cancer Detection;Jiangbo Xi 等;《ACS Applied Materials & Interfaces》;20160809;第8卷;第22563-22570页 * |
| PtAu alloy nanoflowers on 3D porous ionic liquid functionalized graphene-wrapped activated carbon fiber as a flexible microelectrode for near-cell detection of cancer;Lu Wang 等;《NPG Asia Materials》;20161216;第8卷;第1-9页 * |
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