CN113671004B - Graphene tube/Au nanoparticle microfluidic channel, preparation method thereof and surface acoustic wave biosensor - Google Patents
Graphene tube/Au nanoparticle microfluidic channel, preparation method thereof and surface acoustic wave biosensor Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 197
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 74
- 238000010897 surface acoustic wave method Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000010931 gold Substances 0.000 claims description 84
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 42
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 37
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- CQVDKGFMVXRRAI-UHFFFAOYSA-J Cl[Au](Cl)(Cl)Cl Chemical compound Cl[Au](Cl)(Cl)Cl CQVDKGFMVXRRAI-UHFFFAOYSA-J 0.000 claims description 10
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- 238000005137 deposition process Methods 0.000 claims description 5
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- 238000003780 insertion Methods 0.000 claims description 4
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- 239000001257 hydrogen Substances 0.000 claims description 3
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- 238000001514 detection method Methods 0.000 abstract description 12
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- 239000000243 solution Substances 0.000 description 60
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- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 25
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- 239000002904 solvent Substances 0.000 description 2
- WPLOVIFNBMNBPD-ATHMIXSHSA-N subtilin Chemical compound CC1SCC(NC2=O)C(=O)NC(CC(N)=O)C(=O)NC(C(=O)NC(CCCCN)C(=O)NC(C(C)CC)C(=O)NC(=C)C(=O)NC(CCCCN)C(O)=O)CSC(C)C2NC(=O)C(CC(C)C)NC(=O)C1NC(=O)C(CCC(N)=O)NC(=O)C(CC(C)C)NC(=O)C(NC(=O)C1NC(=O)C(=C/C)/NC(=O)C(CCC(N)=O)NC(=O)C(CC(C)C)NC(=O)C(C)NC(=O)CNC(=O)C(NC(=O)C(NC(=O)C2NC(=O)CNC(=O)C3CCCN3C(=O)C(NC(=O)C3NC(=O)C(CC(C)C)NC(=O)C(=C)NC(=O)C(CCC(O)=O)NC(=O)C(NC(=O)C(CCCCN)NC(=O)C(N)CC=4C5=CC=CC=C5NC=4)CSC3)C(C)SC2)C(C)C)C(C)SC1)CC1=CC=CC=C1 WPLOVIFNBMNBPD-ATHMIXSHSA-N 0.000 description 2
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- WSMQKESQZFQMFW-UHFFFAOYSA-N 5-methyl-pyrazole-3-carboxylic acid Chemical compound CC1=CC(C(O)=O)=NN1 WSMQKESQZFQMFW-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
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- G—PHYSICS
- 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
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
- B01L3/50—Containers for the purpose of retaining a material to be analysed, e.g. test tubes
- B01L3/502—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
- B01L3/5027—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip
- B01L3/502707—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip characterised by the manufacture of the container or its components
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
- B01L3/50—Containers for the purpose of retaining a material to be analysed, e.g. test tubes
- B01L3/502—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
- B01L3/5027—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip
- B01L3/502761—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip specially adapted for handling suspended solids or molecules independently from the bulk fluid flow, e.g. for trapping or sorting beads, for physically stretching molecules
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- G—PHYSICS
- 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
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- 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
- G01N27/3275—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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- Chemical & Material Sciences (AREA)
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- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Electrochemistry (AREA)
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- Engineering & Computer Science (AREA)
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Abstract
The invention provides a graphene tube/Au nanoparticle microfluidic channel, a preparation method thereof and a surface acoustic wave biosensor, and belongs to the technical field of biosensors. The graphene tube/Au nanoparticle microfluidic channel provided by the invention consists of a graphene tube and Au nanoparticles distributed on the inner surface of the graphene tube. In the graphene tube/Au nanoparticle microfluidic channel provided by the invention, graphene has a large specific surface area and has a very strong surface adsorption effect; the Au nano-particles have good biocompatibility, can be combined with biomolecules such as proteins to form active sites, and do not destroy the bioactivity. Therefore, the graphene tube/Au nanoparticle microfluidic channel provided by the invention can have the functions of a microfluidic channel and a sensitive element, can be used for constructing a biosensor, and realizes the detection of amino acids with different concentrations; and the Au nano-particles and the graphene tube are tightly combined, so that the service life of the biosensor is prolonged.
Description
Technical Field
The invention relates to the technical field of biosensors, in particular to a graphene tube/Au nanoparticle microfluidic channel, a preparation method thereof and a surface acoustic wave biosensor.
Background
Amino acids are the basic units constituting protein molecules, play an important role in human body through metabolism, and the life activities and health conditions of organisms are closely related to amino acids. At present, the detection methods of amino acid include capillary electrophoresis, high performance liquid chromatography, spectrometry, fluorescence method and the like, and the methods have the defects of time consumption, complex structure and low precision. A surface acoustic wave is an acoustic wave propagating along the surface of an object, and is very sensitive to a perturbation of the surface of the object, so that the surface acoustic wave biosensor has high sensitivity. In addition, the acoustic surface biosensor has the advantages of small volume, low cost and the like.
The micro-fluidic technology is a technology for researching a small amount of fluid by using a micro-channel with a micro size, can be applied to various fields from biology, chemistry, information technology, optics and the like, and has great application prospect in the surface acoustic wave biosensor. However, when the present microfluidic technology is used for the surface acoustic wave biosensor, the sensitive film is often required to be combined into the microfluidic channel, and the microfluidic channel needs to be prepared first, and then the sensitive film is combined with the microfluidic channel to form the sensitive element of the surface acoustic wave biosensor. However, the preparation method of the surface acoustic wave biosensor is complex, and the surface acoustic wave biosensor cannot be suitable for detecting amino acids with different concentrations due to the fact that the sensitive film is not tightly combined with the microfluidic channel, and the service life of the surface acoustic wave biosensor is short.
Therefore, it is desirable to provide a microfluidic channel that can be used in a surface acoustic wave biosensor to detect amino acids at different concentrations and that has a long service life.
Disclosure of Invention
The invention aims to provide a graphene tube/Au nano-particle microfluidic channel, a preparation method thereof and a surface acoustic wave biosensor.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a graphene tube/Au nanoparticle microfluidic channel, which consists of a graphene tube and Au nanoparticles distributed on the inner surface of the graphene tube.
Preferably, the inner diameter of the graphene tube is 0.6-0.8 mm, and the outer diameter of the graphene tube is 0.75-1 mm.
Preferably, the particle size of the Au nanoparticle is 50-300 nm.
The invention also provides a preparation method of the graphene tube/Au nanoparticle microfluidic channel, which comprises the following steps:
(1) Growing graphene on the surface of a tantalum wire by adopting a hot wire chemical vapor deposition method, and then separating the graphene from the tantalum wire to obtain a graphene tube;
(2) Electroplating Au in the graphene tube obtained in the step (1) by adopting a double-electrode system to obtain a graphene tube/Au nano-particle microfluidic channel; the double-electrode system comprises a reference electrode, a counter electrode, an electroplating solution and a working electrode; the reference electrode and the counter electrode are platinum wires, the electroplating solution is tetrachloro-gold acid solution, and the graphene tube is a working electrode.
Preferably, the deposition process parameters of the hot filament chemical vapor deposition method in the step (1) are as follows: the flow rate of the hydrogen is 20-50 sccm, the flow rate of the methane is 10-25 sccm, the output current of the AC filament power supply is 50-100A, the vacuum degree is 30-45 Torr, and the deposition time is 20 min-1 h.
Preferably, the method for assembling the two-electrode system in step (2) comprises: fixing one end of a tantalum wire micro-insertion graphene tube; introducing tetrachloroauric acid solution into the graphene tube by using an injector; then, a platinum wire is parallelly inserted into the graphene tube from the other end of the graphene tube, and the platinum wire and the graphene tube are immersed into tetrachloro-gold acid solution; the platinum wire is not in contact with the graphene tube.
Preferably, the concentration of the tetrachloroauric acid solution is 10 -3 ～10 -1 mol/L。
The invention also provides a surface acoustic wave biosensor, which comprises a substrate, an interdigital electrode arranged on the surface of the substrate and a graphene tube/Au nano-particle microfluidic channel arranged on the surface of the interdigital electrode; the graphene tube/Au nanoparticle microfluidic channel is prepared by the graphene tube/Au nanoparticle microfluidic channel according to the technical scheme or the preparation method according to the technical scheme.
Preferably, the substrate is a piezoelectric single crystal.
Preferably, the material of the interdigital electrode is aluminum, platinum or gold.
The invention provides a graphene tube/Au nanoparticle microfluidic channel, which consists of a graphene tube and Au nanoparticles distributed on the inner surface of the graphene tube. In the graphene tube/Au nanoparticle microfluidic channel provided by the invention, graphene has a large specific surface area and has a very strong surface adsorption effect; the Au nano-particles have good biocompatibility, can be combined with biomolecules such as proteins to form active sites, and do not destroy the bioactivity. Therefore, the graphene tube/Au nanoparticle microfluidic channel provided by the invention can have the functions of a microfluidic channel and a sensitive element, can be used for constructing a biosensor, and realizes the detection of amino acids with different concentrations; and the Au nano-particles and the graphene tube are tightly combined, so that the service life of the biosensor is prolonged. The embodiment data show that the L-lysine solutions with different concentrations are introduced into the graphene tube/Au nano-particle microfluidic channel in the surface acoustic wave biosensor, so that the surface acoustic wave biosensor can be effectively detected, can be recycled for multiple times, and has long service life.
Drawings
FIG. 1 is an SEM image of a cross section of a graphene tube prepared in example 1 of the present invention;
fig. 2 is an SEM image of the internal structure of the graphene tube/Au nanoparticle microfluidic channel prepared in example 1 of the present invention at 2K magnification;
fig. 3 is an SEM image of the internal structure of the graphene tube/Au nanoparticle microfluidic channel prepared in example 1 of the present invention at 20K magnification;
FIG. 4 is a schematic diagram of a biological detection system according to an embodiment of the present invention, wherein: a1 is a network analyzer, A2 is a peristaltic pump, A3 is a carbon nanotube/Au nanoparticle microfluidic channel, A4 is a test fixture, A5 is a delay line type surface acoustic wave device, and A6 is a beaker;
FIG. 5 is a graph showing the change of the center frequency of a device with the concentration of L-tyrosine when the SAW biosensor of example 2 of the present invention detects L-tyrosine;
FIG. 6 is a graph showing the change in the center frequency of a device with the concentration of L-lysine when the SAW biosensor of example 3 of the present invention detects L-lysine.
Detailed Description
The invention provides a graphene tube/Au nanoparticle microfluidic channel, which consists of a graphene tube and Au nanoparticles distributed on the inner surface of the graphene tube.
In the present invention, the inner diameter of the graphene tube is preferably 0.6 to 0.8mm, more preferably 0.7 to 0.8mm; the outer diameter of the graphene tube is preferably 0.75 to 1mm, more preferably 0.9 to 1mm. In the invention, the graphene tube is a hollow tube with inner diameter and outer diameter which are in the above ranges and are composed of graphene, and can form a micro-fluid channel for micro-fluid to pass through, and the sensitivity of the sensor can be improved when the graphene tube is used for a surface acoustic wave biosensor.
In the present invention, the particle diameter of the Au nanoparticle is preferably 50 to 300nm, more preferably 100 to 200nm. In the invention, the Au nano-particles have good biocompatibility, can be combined with biomolecules such as proteins, amino acids and the like to form active sites, and do not destroy the bioactivity. In the invention, when the particle size of the Au nano-particles is in the range, more active sites can be formed in the graphene tube to adsorb amino acids to be detected, and when the Au nano-particles are used for the surface acoustic wave biosensor, the sensitivity of the sensor can be improved.
According to the graphene tube/Au nanoparticle microfluidic channel provided by the invention, graphene has a large specific surface area, has a very strong surface adsorption effect, can adsorb Au nanoparticles, and is tightly combined with the Au nanoparticles; the Au nano-particles have good biocompatibility, can be combined with biomolecules such as proteins to form active sites, and do not destroy the bioactivity. Therefore, the graphene tube/Au nanoparticle microfluidic channel provided by the invention can have the functions of a microfluidic channel and a sensitive element, can be used for constructing a biosensor, realizes the detection of amino acids with different concentrations, and has the advantages of stable structure and long service life.
The invention also provides a preparation method of the graphene tube/Au nanoparticle microfluidic channel, which comprises the following steps:
(1) Growing graphene on the surface of a tantalum wire by adopting a hot wire chemical vapor deposition method, and then separating the graphene from the tantalum wire to obtain a graphene tube;
(2) Electroplating Au in the graphene tube obtained in the step (1) by adopting a double-electrode system to obtain a graphene tube/Au nano-particle microfluidic channel; the double-electrode system comprises a reference electrode, a counter electrode, an electroplating solution and a working electrode; the reference electrode and the counter electrode are platinum wires, the electroplating solution is tetrachloro-gold acid solution, and the graphene tube is a working electrode.
According to the invention, graphene grows on the surface of the tantalum wire by adopting a hot wire chemical vapor deposition method, and then the graphene is separated from the tantalum wire to obtain the graphene tube.
In the present invention, the diameter of the tantalum wire is preferably 0.6 to 0.8mm, more preferably 0.7 to 0.8mm; the length of the tantalum wire is preferably 5to 10cm, more preferably 6 to 8cm. In the invention, the diameter of the tantalum wire determines the inner diameter of the graphene tube.
In the invention, the hot wire chemical vapor deposition takes a tantalum wire as a hot wire and a supporting template for depositing the graphene tube, and the graphene tube is grown on the surface of the supporting template by adopting a hot wire chemical vapor deposition method.
The tantalum wire is preferably cleaned before hot wire chemical vapor deposition. The method for cleaning the tantalum wire is not particularly limited, and the method for cleaning the tantalum wire is well known to those skilled in the art, and can be used for removing pollutants on the surface of the tantalum wire. In the invention, the method for cleaning the tantalum wire is preferably to polish the tantalum wire with 100-300 mesh sand paper for removing surface oxides and impurities; respectively ultrasonic cleaning in ultrapure water, absolute ethanol and ultrapure water for 5-10 min, and drying at room temperature. In the invention, when the tantalum wire is cleaned by the method, the pollutants on the surface of the tantalum wire can be removed, and meanwhile, the surface of the tantalum wire can be roughened so as to attach the modified particles.
In the invention, the deposition process parameters of the hot wire chemical vapor deposition method are as follows: the flow rate of the hydrogen gas is preferably 20 to 50sccm, more preferably 30 to 40sccm; the methane flow rate is preferably 10 to 25sccm, more preferably 15 to 20sccm; the output current of the AC filament power supply is preferably 50-100A, more preferably 60-80A; the vacuum degree is preferably 30 to 45Torr, more preferably 35 to 40Torr; the deposition time period is preferably 20min to 1h, more preferably 30min to 50min. In the invention, when the deposition process parameters of the hot wire chemical vapor deposition method are in the above range, a more continuous graphene layer can be formed on the surface of the tantalum wire.
After the hot wire chemical vapor deposition is completed, the graphene and the tantalum wire are separated to obtain the graphene tube. The method for separating the graphene from the tantalum wire is not particularly limited, and the graphene and the tantalum wire can be separated by adopting a method well known to a person skilled in the art.
After the graphene tube is obtained, au is electroplated in the graphene tube by adopting a double-electrode system, so that the graphene tube/Au nanoparticle microfluidic channel is obtained.
In the present invention, the dual electrode system preferably includes a reference electrode and a counter electrode, a plating solution, and a working electrode; the reference electrode and the counter electrode are preferably platinum wires, the electroplating solution is preferably tetrachloroauric acid solution, and the graphene tube is a working electrode.
In the present invention, the outer diameter of the platinum wire is preferably lower than the inner diameter of the graphene tube. In the invention, the platinum wire is used as a reference electrode and a counter electrode, and is inserted into the graphene tube when electroplating is performed, and the platinum wire can be prevented from contacting the graphene tube to cause short circuit when the outer diameter of the platinum wire is lower than the inner diameter of the graphene tube.
In the present invention, the concentration of the tetrachloroauric acid solution is preferably 10 -3 ～10 -1 mol/L, more preferably 10 -2 ～10 -1 mol/L. In the invention, when the concentration of the tetrachloroauric acid solution is in the above range, the Au nano-particles which are uniformly distributed and not stacked are more favorable to be formed inside the graphene tube.
In the present invention, the length of the graphene tube is preferably 10 to 20mm, more preferably 15 to 20mm. In the invention, when the length of the graphene tube is in the above range, the operation of electroplating is facilitated.
In the present invention, the assembly method of the dual electrode system preferably includes: fixing one end of a tantalum wire micro-insertion graphene tube; introducing tetrachloroauric acid solution into the graphene tube by using an injector; then, a platinum wire is parallelly inserted into the graphene tube from the other end of the graphene tube, and the platinum wire and the graphene tube are immersed into tetrachloro-gold acid solution; the platinum wire is not in contact with the graphene tube.
In the invention, the graphene tube is brittle and is easy to damage when being directly used as a working electrode to be connected with a circuit. According to the invention, one end of the graphene tube is slightly inserted into the tantalum wire to be fixed, and then the tantalum wire is connected with the circuit, so that the operation problem of electroplating interruption caused by graphene breakage when the circuit is directly connected with the graphene tube can be prevented, and further the smooth electroplating is promoted.
According to the invention, the tetra-chloroauric acid solution is introduced into the graphene tube by the injector, so that the electroplating solution can be filled when the platinum wire is inserted into the graphene tube, and the inside of the graphene tube is filled with the electroplating solution at the beginning of electroplating, so that uniform Au particles can be formed in the graphene tube.
In the invention, the platinum wire is inserted into the graphene tube from the other end of the graphene tube in parallel, so that Au particles can be distributed in the graphene tube during electroplating.
In the invention, the platinum wire is not contacted with the graphene tube, so that the occurrence of short circuit can be prevented.
In the present invention, the depth of the platinum wire immersed in the tetrachloroauric acid solution is preferably 8 to 18mm, more preferably 10 to 15mm. In the invention, when the depth of immersing the platinum wire and the graphene tube in the tetrachloroauric acid solution is within the range, au particles can be more uniform.
In the invention, a tetrachloroauric acid solution is preferably introduced into the graphene tube by a syringe in the electroplating process. According to the invention, au nano particles are formed in the graphene tube along with gold ions in the electroplating process, the concentration of the tetrachloroauric acid solution in the graphene tube is reduced, and the electroplating efficiency is reduced due to the change of the concentration of the tetrachloroauric acid solution in the graphene tube can be prevented by introducing the tetrachloroauric acid solution into the graphene tube, and meanwhile, the even distribution of the Au nano particles in the graphene tube can be promoted.
In the present invention, the plating is preferably Au plating within the graphene tube using an electrochemical workstation step method.
In the present invention, the electroplating of Au inside the graphene tube using the electrochemical workstation step method is preferably divided into three stages:
in stage 1, the plating potential is preferably-3 to 0V, more preferably-2 to 0V; the deposition time is preferably 0to 2s, more preferably 1to 2s;
in stage 2, the plating potential is preferably 0to 3V, more preferably 1to 2V; the deposition time is preferably 2 to 8 seconds, more preferably 4 to 6 seconds;
in the 3 rd stage, the plating potential is preferably-2 to 1V, more preferably-1 to 0V; the deposition time is preferably 0to 2s, more preferably 1to 2s;
the number of electroplating turns is preferably 20 to 50 turns, more preferably 30 to 40 turns;
the sensitivity is preferably 1X 10 -3 ～1×10 -1 More preferably 1X 10 -2 ～1×10 -1 ；
Injecting tetrachloro-gold acid solution into the graphene tube by using an injector after each electroplating for 3-6 min;
the plating of Au in the graphene tube using the electrochemical workstation step method is preferably repeated 3 to 8 times, more preferably 4 to 6 times.
In the invention, after each electroplating, the tetrachloro-gold acid solution is injected into the graphene tube by a syringe, so that the interior of the graphene tube can be filled with the tetrachloro-gold acid solution. According to the invention, the graphene tube is preferably taken down when the tetrachloroaurate solution is introduced into the graphene tube by using the injector, so that the injection of the tetrachloroaurate solution is facilitated.
The preparation method provided by the invention can form Au particles which are uniformly distributed and not stacked on the surface of the graphene.
The invention also provides a surface acoustic wave biosensor, which comprises a substrate, an interdigital electrode arranged on the surface of the substrate and a graphene tube/Au nano-particle microfluidic channel arranged on the surface of the interdigital electrode; the graphene tube/Au nanoparticle microfluidic channel is prepared by the graphene tube/Au nanoparticle microfluidic channel according to the technical scheme or the preparation method according to the technical scheme.
In the present invention, the substrate is preferably a piezoelectric single crystal; the piezoelectric single crystal is preferably lithium niobate, quartz, bismuth germanate, or lithium tantalate. In the invention, the substrate plays a role of supporting the interdigital electrode and the graphene tube/Au nanoparticle microfluidic channel.
In the present invention, the material of the interdigital electrode is preferably aluminum, platinum or gold. In the present invention, the interdigital electrode can improve the sensitivity of the sensor when made of the above-mentioned material.
The method for preparing the surface acoustic wave biosensor is not particularly limited, and the method for preparing the surface acoustic wave biosensor is well known to those skilled in the art.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The medicine purchase sources in the embodiment of the invention are as follows:
the purchase of 3-hydroxychlorogold acid hydrate was made by alfa elsha (china) chemical company;
the model number of the electrochemical workstation is 660e, which is purchased from Shanghai Chen instruments Co., ltd;
the anhydrous disodium hydrogen phosphate is purchased from a metallocene chemical reagent factory in Tianjin;
the anhydrous sodium dihydrogen phosphate is purchased from a metallocene chemical reagent factory in Tianjin;
the pH meter model is PhS-3C, which is purchased from Shanghai instrument and electrosurgery instruments Co., ltd;
the L-lysine is purchased from the light-recovery fine chemical engineering institute of Tianjin;
l-tyrosine is purchased from the light-recovery fine chemical engineering institute of Tianjin.
In the following examples, the length of the working electrode, the reference electrode and the counter electrode inserted into the measured liquid was 15mm and the distance between the working electrode, the reference electrode and the counter electrode was 15mm when the time-current curve was measured using a two-electrode system.
(III) a preparation method of a graphene tube/Au nanoparticle microfluidic channel:
(1) Cleaning tantalum wires: tantalum wires of 0.60mm diameter and 8cm length were prepared. Polishing tantalum wires with 180-mesh sand paper to remove surface oxides and impurities, respectively ultrasonically cleaning the tantalum wires in ultrapure water, absolute ethyl alcohol and ultrapure water for 10min, and drying at room temperature;
(2) Preparing a graphene tube by hot wire chemical vapor deposition: and (3) growing a graphene tube on the surface of the tantalum wire cleaned in the step (1) by adopting a hot wire chemical vapor deposition method, wherein the deposition process parameters are as follows: the hydrogen flow is 50sccm, the methane flow is 25sccm, the output current of an alternating-current filament power supply is 100A, the vacuum degree is 41Torr, and the deposition time is 40min;
(3) Cutting a tantalum wire at one end, extracting a graphene tube, dividing the graphene tube into 17mm lengths, electroplating Au by adopting a double-electrode system, and taking the graphene tube as a working electrode, wherein the working electrode is firstly connected with the tantalum wire, then a section of the graphene tube is slightly inserted into the tantalum wire to be fixed, a platinum wire is used as a reference electrode and a counter electrode, the graphene tube is inserted onto the platinum wire, the immersion depth of the platinum wire and the graphene tube into a tetrachloro-gold solution is consistent, and the immersion lengths of the platinum wire and the graphene tube are all 15mm;
(4) The solution of tetrachloroauric acid (concentration 10) was introduced into the graphene tube using a syringe -2 mol/L), then the graphene tube is inserted on the tantalum wire, au is electroplated by using an electrochemical workstation step method, and the electroplating is divided into three stages:
stage 1, electroplating potential is-2V, and deposition time is 1s;
2, electroplating potential is 2V, and deposition time is 5s;
stage 3, electroplating potential is-1V, and deposition time is 1s;
the plating turns are 43 turns, and the sensitivity is 1 multiplied by 10 -2 After each electroplating time for 5min, taking down the graphene tube;
(5) Repeating the step (4) for 6 times, and co-electroplating Au for 30min.
Testing the graphene tube prepared in the embodiment by adopting a scanning electron microscope, and obtaining an SEM (scanning electron microscope) diagram of the cross section of the graphene tube as shown in figure 1;
the graphene tube/Au nanoparticle microfluidic channel prepared in this example was tested by using a scanning electron microscope, and an SEM image with an internal structure enlarged by 2K times was obtained as shown in FIG. 2;
the graphene tube/Au nanoparticle microfluidic channel prepared in this example was tested using a scanning electron microscope, and an SEM image of the internal structure thereof magnified 20K times was obtained as shown in fig. 3.
As can be seen from fig. 1, the graphene tube prepared by the method is a graphene tube with uniform thickness, and is assembled by multiple layers of graphene in a tube layer.
As can be seen from fig. 2 and 3, au nanoparticles are attached to the inner surface of the graphene tube/Au nanoparticle microfluidic channel prepared by the method, and the Au nanoparticles are not agglomerated and are uniformly distributed on the inner surface of the graphene tube.
Example 2
The graphene tube/Au nanoparticle microfluidic channel prepared in example 1 was assembled into a surface acoustic wave biosensor, using the graphene tube/Au nanoparticle microfluidic channel as a delay line type surface acoustic wave device, using quartz as a base material, and Al metal as an interdigital electrode.
The surface acoustic wave biosensor obtained by the embodiment is constructed into a biological detection system for detecting L-tyrosine, and the specific process is as follows:
step 1, a biological detection system is shown in fig. 4;
step 2, weighing 0.0906g of L-tyrosine, pouring into a 10mL volumetric flask, and preparing into 5×10 concentration by using PBS with pH of 7.4 as solvent -2 The L-tyrosine solution with mol/L is diluted into 1X 10 by a proper liquid-transferring gun -2 mol/L、3×10 -2 mol/L、1×10 -3 mol/L、3×10 -3 mol/L、5×10 - 3 L-tyrosine solution with mol/L of each concentration; then 0.4g of NaOH is weighed and poured into a volumetric flask of 10mL, the volume is fixed by ultrapure water to prepare 1mol/L NaOH solution, and then the NaOH solution is diluted into 0.5mol/L solution.
Step 3, introducing PBS solution into the microfluidic channel of the graphene tube for Au plating by using a peristaltic pump, placing the microfluidic channel on a delay line type surface acoustic wave device, testing the center frequency of the microfluidic channel by using a network analyzer, and introducing 1X 10 into the microfluidic channel of the graphene tube for Au plating by using the peristaltic pump -3 And (3) placing the L-tyrosine solution of mol/L into a 37 ℃ incubator, incubating for half an hour, and then placing the incubator on an interdigital of a surface acoustic wave device to record the center frequency at the moment.
Step 4, using 0.5mol/L NaOH solution, sequentially introducing ultrapure water into the Au-plated micro-fluid channels of the graphene tube respectively, cleaning the Au-plated micro-fluid channels, then introducing PBS solution, then placing the PBS solution on the interdigital of the SAW device to record the center frequency at the moment, and then introducing the Au-plated micro-fluid channels of the graphene tube into the Au-plated micro-fluid channels with the concentration of 5 multiplied by 10 -3 The mol/L-tyrosine solution is placed in an incubator at 37 ℃ as in step 2, incubated for half an hour, and then placed on the interdigital surface acoustic wave device to record the center frequency at the moment.
And 5, repeating the operation of the step 3 to clean, and then introducing a higher-concentration L-tyrosine solution to test, so that the steps are repeated until all concentration tests are finished.
In this example, PBS buffer was prepared from 0.1mol/L anhydrous sodium dihydrogen phosphate and 0.1mol/L anhydrous disodium hydrogen phosphate at a rate of 19:81, the PBS buffer solutions prepared in different proportions have different pH values, the pH value of the PBS buffer solution prepared in the proportion is 7.4, and the pH value of the obtained PBS buffer solution is detected by a pH meter.
The center frequency of the device as a function of L-tyrosine concentration when using a saw biosensor to detect L-tyrosine is shown in fig. 5.
As can be seen from FIG. 5, the surface acoustic wave biosensor prepared by the invention can sensitively detect L-tyrosine with different concentrations, has a wide detection range, and can be suitable for detecting amino acids with different concentrations. In addition, the graphene tube can be used without being damaged by people, and the graphene tube has excellent accuracy after being recycled for a plurality of times.
Example 3
The graphene tube/Au nanoparticle microfluidic channel prepared in example 1 was assembled into a surface acoustic wave biosensor, using the graphene tube/Au nanoparticle microfluidic channel as a delay line type surface acoustic wave device, using quartz as a base material, and Al metal as an interdigital electrode.
The surface acoustic wave biosensor obtained in the embodiment is constructed into a biological detection system for detecting L-lysine, and the specific process is as follows:
step 1, a biological detection system is shown in fig. 4;
step 2, weighing 0.0731g of L-lysine, pouring the L-lysine into a 10mL volumetric flask, and preparing the solution into a concentration of 5X 10 by using PBS with pH of 7.4 as a solvent -2 The L-lysine solution of mol/L is diluted to 1X 10 by using a proper pipette -2 mol/L、3×10 -2 mol/L、1×10 -3 mol/L、3×10 -3 mol/L、5×10 - 3 L-lysine solution with mol/L concentration; then 0.4g of NaOH is weighed and poured into a volumetric flask of 10mL, the volume is fixed by ultrapure water to prepare 1mol/L NaOH solution, and then the NaOH solution is diluted into 0.5mol/L solution.
Step 3, introducing PBS solution into the microfluidic channel of the graphene tube for Au plating by using a peristaltic pump, placing the microfluidic channel on a delay line type surface acoustic wave device, testing the center frequency of the microfluidic channel by using a network analyzer, and introducing 1X 10 into the microfluidic channel of the graphene tube for Au plating by using the peristaltic pump -3 And (3) placing the L-lysine solution with mol/L into a 37 ℃ incubator, incubating for half an hour, and placing the incubator on an interdigital of a surface acoustic wave device to record the center frequency at the moment.
Step 4, using 0.5mol/L NaOH solution, sequentially introducing ultrapure water into the Au-plated micro-fluid channels of the graphene tube respectively, cleaning the Au-plated micro-fluid channels, then introducing PBS solution, then placing the PBS solution on the interdigital of the SAW device to record the center frequency at the moment, and then introducing the Au-plated micro-fluid channels of the graphene tube into the Au-plated micro-fluid channels with the concentration of 5 multiplied by 10 -3 The mol/L-lysine solution was placed in an incubator at 37℃as in step 2, incubated for half an hour, and then placed on an interdigital surface acoustic wave device to record the center frequency at that time.
And 5, repeating the operation of the step 3 to clean, and then introducing a higher-concentration L-lysine solution to test, so that the steps are repeated until all concentration tests are finished.
In this example, the PBS buffer solution was prepared in the same manner as in example 2.
The center frequency of the device as a function of the concentration of L-lysine when L-lysine was detected using a SAW biosensor is shown in FIG. 6.
As can be seen from FIG. 6, the surface acoustic wave biosensor prepared by the invention can sensitively detect L-lysine with different concentrations, has a wide detection range, and can be suitable for detecting amino acids with different concentrations.
According to the embodiment, the surface acoustic wave biosensor prepared by the invention takes the graphene tube/Au nano particle micro-fluid channel as a micro-fluid channel and a sensitive element, so that the micro-fluid channel and the sensitive element can be integrated, and the preparation method is simple; and the obtained graphene tube/Au nanoparticle microfluidic channel has stable structure, can be suitable for amino acid detection in a wide concentration range, and has long service life.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. A graphene tube/Au nanoparticle microfluidic channel consists of a graphene tube and Au nanoparticles distributed on the inner surface of the graphene tube;
the preparation method of the graphene tube/Au nanoparticle microfluidic channel comprises the following steps:
(1) Growing graphene on the surface of a tantalum wire by adopting a hot wire chemical vapor deposition method, and then separating the graphene from the tantalum wire to obtain a graphene tube;
(2) Electroplating Au in the graphene tube obtained in the step (1) by adopting a double-electrode system to obtain a graphene tube/Au nano-particle microfluidic channel; the double-electrode system comprises a reference electrode, a counter electrode, an electroplating solution and a working electrode; the reference electrode and the counter electrode are platinum wires, the electroplating solution is tetrachloroauric acid solution, and the graphene tube is a working electrode;
the assembly method of the double-electrode system in the step (2) comprises the following steps: fixing one end of a tantalum wire micro-insertion graphene tube; introducing tetrachloroauric acid solution into the graphene tube by using an injector; then, a platinum wire is parallelly inserted into the graphene tube from the other end of the graphene tube, and the platinum wire and the graphene tube are immersed into tetrachloro-gold acid solution; the platinum wire is not in contact with the graphene tube.
2. The graphene tube/Au nanoparticle microfluidic channel of claim 1, wherein the inner diameter of the graphene tube is 0.6-0.8 mm and the outer diameter of the graphene tube is 0.75-1 mm.
3. The graphene tube/Au nanoparticle microfluidic channel of claim 1, wherein the Au nanoparticles have a particle size of 50-300 nm.
4. A method of preparing a graphene tube/Au nanoparticle microfluidic channel according to any one of claims 1to 3, comprising the steps of:
(1) Growing graphene on the surface of a tantalum wire by adopting a hot wire chemical vapor deposition method, and then separating the graphene from the tantalum wire to obtain a graphene tube;
(2) Electroplating Au in the graphene tube obtained in the step (1) by adopting a double-electrode system to obtain a graphene tube/Au nano-particle microfluidic channel; the double-electrode system comprises a reference electrode, a counter electrode, an electroplating solution and a working electrode; the reference electrode and the counter electrode are platinum wires, the electroplating solution is tetrachloroauric acid solution, and the graphene tube is a working electrode;
the assembly method of the double-electrode system in the step (2) comprises the following steps: fixing one end of a tantalum wire micro-insertion graphene tube; introducing tetrachloroauric acid solution into the graphene tube by using an injector; then, a platinum wire is parallelly inserted into the graphene tube from the other end of the graphene tube, and the platinum wire and the graphene tube are immersed into tetrachloro-gold acid solution; the platinum wire is not in contact with the graphene tube.
5. The method according to claim 4, wherein the hot filament chemical vapor deposition method in the step (1) comprises the following deposition process parameters: the flow rate of the hydrogen is 20-50 sccm, the flow rate of the methane is 10-25 sccm, the output current of the AC filament power supply is 50-100A, the vacuum degree is 30-45 Torr, and the deposition time is 20 min-1 h.
6. The method according to claim 4, wherein the concentration of the tetrachloroauric acid solution is 10 -3 ～10 - 1 mol/L。
7. A surface acoustic wave biosensor comprises a substrate, an interdigital electrode arranged on the surface of the substrate and a graphene tube/Au nano-particle microfluidic channel arranged on the surface of the interdigital electrode; the graphene tube/Au nanoparticle microfluidic channel is prepared by the graphene tube/Au nanoparticle microfluidic channel according to any one of claims 1to 3 or the preparation method according to any one of claims 4 to 6.
8. The saw biosensor of claim 7, wherein the substrate is a piezoelectric single crystal.
9. The surface acoustic wave biosensor of claim 7, wherein the interdigital electrode is made of aluminum, platinum, or gold.
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