CN109557160A - The method that self assembly has the preparation of the carbon nanotube of nanometer gold bar and carries out biomolecule detection using it - Google Patents
The method that self assembly has the preparation of the carbon nanotube of nanometer gold bar and carries out biomolecule detection using it Download PDFInfo
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- CN109557160A CN109557160A CN201811638623.6A CN201811638623A CN109557160A CN 109557160 A CN109557160 A CN 109557160A CN 201811638623 A CN201811638623 A CN 201811638623A CN 109557160 A CN109557160 A CN 109557160A
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- G—PHYSICS
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- 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
- B81—MICROSTRUCTURAL TECHNOLOGY
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- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/159—Carbon nanotubes single-walled
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- C01B32/16—Preparation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
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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
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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
Abstract
The invention discloses the methods that self assembly has the preparation of the carbon nanotube of nanometer gold bar and carries out biomolecule detection using it, specific steps are as follows: step 1: preparing single-walled carbon nanotube；Step 2: the preparation micro- gap electrode substrate of carbon nanotube；Step 3: nanometer gold bar is prepared；Step 4: assemble nanometer gold stick；The micro- gap electrode substrate of the carbon nanotube prepared in step 2 is statically placed in nanometer gold bar solution, electrostatic self-assembled is made it through, the electrode base sheet independently installed is taken out, ultrapure water is used；Step 5: the electric interelectrode conductance for assembling nanometer gold bar carbon pipe is measured by probe station and electrochemical workstation and is recorded.Self assembly has the carbon nanotube reaction success rate of nanometer gold bar high, and preparation is convenient, more importantly nanometer gold bar can transversely or longitudinally on the carbon nanotubes, electric current be big for linear array along carbon pipe.Detection biomolecule has high sensitivity, analysis speed fastly and is easy to mass production.
Description
Technical field
There is the preparation of the carbon nanotube of nanometer gold bar the present invention relates to field of nanometer material technology, especially self assembly and utilizes it
The method for carrying out biomolecule detection.
Background technique
As the development and biological product of biotechnology are more and more widely used, the detection method of biomolecule is also
Mature, all kinds of detection techniques are widely used in different biomolecule detection fields already.Just being to rely on these has
The detection means of effect just ensure that the accuracy of China's food, drugs monitoring, ensure that the safety of circulation.
Detection means at this stage is detected both for single creature molecule, and require with fluorescent marker or
The reagent material of the valuableness such as biotinylation kit.At present biomolecule detection the problem is that: first, testing cost is high；Second,
Required detecting instrument is complicated；Third, detection means popularity rate is low, popularizes difficult big.
Summary of the invention
There is the preparation of the carbon nanotube of nanometer gold bar the object of the present invention is to provide self assembly and carries out biology point using it
Son detection method, to solve at this stage biological detection preparation it is inconvenient, at high cost, analyze speed it is limited, not portable, universal
The technical issues of Difficulty.
To achieve the above object, the present invention adopts the following technical scheme: the present invention provides the carbon that self assembly has nanometer gold bar
The preparation of nanotube, specific steps are as follows:
Step 1: preparing single-walled carbon nanotube, specifically includes:
S1, the SiO for being 250nm-550nm by surface thickness2Si substrate be cut into the small pieces of 5mm × 6mm by hand；
S2 carries out ultrasonic cleaning processing with acetone, second alcohol and water；
S3, using ethyl alcohol as carbon source, Fe is catalyst, grows single-walled carbon nanotube in Si substrate surface；Growth temperature is
850℃-950℃；
Step 2: the preparation micro- gap electrode substrate of carbon nanotube；
Step 3: nanometer gold bar is prepared；
Step 4: assemble nanometer gold stick；The micro- gap electrode substrate of the carbon nanotube prepared in step 2 is statically placed in and is received
In the golden stick solution of rice, electrostatic self-assembled is made it through, the electrode base sheet independently installed is taken out, ultrapure water is used；
Step 5: it is measured by probe station and electrochemical workstation and assembles the electric interelectrode conductance of nanometer gold bar carbon pipe simultaneously
Record.
Further, nanometer gold bar is along carbon pipe transversely or longitudinally linear array.
Further, the partial size length of nanometer gold bar is 107.5 ± 7.2nm, 14.7 ± 0.6nm of diameter.
Further, the step 2 specifically includes:
S1 drips upper PMMA corrosion inhibitor on single-walled carbon nanotube substrate；After spin coating, a few minutes are placed on hot plate；
S2 is got to electron beam on substrate by EBL electron-beam exposure system, and the pattern of the composition of electron beam is electrode
Shape has single carbon pipe across the two poles of the earth, and two interelectrode distances are 1 μm；
Substrate after the completion of exposure is first placed in developer solution and is placed in fixing solution again, electrode pattern is exposed by s3；It is aobvious
The shadow time is 20s-30s, fixing time 20s-30s；
Golden film is plated to substrate surface using vacuum vapour deposition, places the substrate in acetone, expose electrode pattern by s4
The golden film of position can be retained, and the golden film of other positions can be removed as PMMA is dissolved in acetone；
S5, the single-walled carbon nanotube between the golden film being retained and its slit, i.e. group become single single-walled carbon nanotube electricity
Pole.
Further, in the s1 of step 2, PMMA corrosion inhibitor specification is 600K-900K；Spin coating revolving speed be 3500-4000 turn/
Minute；Hot plate temperature is 140 DEG C -160 DEG C.
Further, in the s2 of step 2, two interelectrode distances are 0.4 μm -0.6 μm.
Further, the step 3 specifically includes:
In beaker, HAuCl is added in s14And CTAB, stir to clarify it is transparent after, then by ice MNaBH4Be rapidly injected it is molten
In liquid, the color of solution can go to dark brown by faint yellow, stand, spare as seed solution；
S2, CTAB and NaOL is soluble in water, and stirring is to being completely dissolved；AgNO is then added3Solution stirs to clarify
It is bright；Add HAuCl4Solution and concentrated hydrochloric acid, continue to stir to clarify it is transparent, it is spare as growth-promoting media；
Seed solution obtained in ascorbic acid solution, with s1 is added in s2 in growth-promoting media obtained, stands by s3,
Nanometer gold bar solution can be obtained.
Further, step 4: the time of assemble nanometer gold stick is 5-10min.
Further, the length of carbon nanotube is 100um-50000um.
Another aspect of the present invention, which is provided, carries out biomolecule detection using the carbon nanotube that above-mentioned self assembly has nanometer gold bar
Method, the specific steps are as follows:
The self assembly prepared is had the carbon nanotube of nanometer gold bar, passes through probe station and electrochemical workstation by step 1
Its interelectrode conductance can be measured, connects into line since nanometer gold bar has been assembled in carbon tube wall at this time, it is big for measuring at this time
Electric current is as control；
Step 2, the carbon nanotube that self assembly has nanometer gold bar, which is soaked in higher concentration probes molecular solution, makes it sufficiently
Probe molecule is adsorbed, takes out, with ultrapure water, is dried with nitrogen；Its conductance is measured by probe station and electrochemical workstation；By
In the powerful adsorption capacity in nanometer gold bar surface, nanometer gold bar surface can be lived by probe molecule tight；
Carbon nanotube in step 2 is placed in sample to be tested solution to be measured a period of time, taken out by step 3, with super
Pure water rinsing is dried with nitrogen；
Step 4 places it in a period of time in the solution of iron chloride and thiocarbamide, takes out, with ultrapure water, nitrogen is blown
It is dry；Its conductance is measured by probe station and electrochemical workstation, result is compared with the control electric current that step 1 obtains；
Step 5 obtains conclusion (of pressure testing)；There is target molecule in sample solution, then nanometer gold bar surface-probe molecule is clear
It removes, nanometer gold bar surface is exposed again, current reduction；Without target molecule in sample solution, then probe molecule can not be clear
It removes, nanometer gold bar continuation is wrapped, and electric current is substantially unchanged.
Further, biomolecule is DNA or biological enzyme.
The beneficial effects of the present invention are embodied in:
1, self assembly has the preparation method setting of the carbon nanotube of nanometer gold bar rationally, and reaction success rate is high, and preparation is convenient,
More importantly nanometer gold bar can transversely or longitudinally on the carbon nanotubes, electric current be big for linear array along carbon pipe.In list
Then nanometer gold bar is assembled in single-walled carbon nanotube by Electrostatic Absorption by growth in situ single-walled carbon nanotube on wall carbon nano tube
Wall.Without carrying out substrate transfer to carbon nanotube, nanometer gold bar is fixed without any chemical method, method is simple.
2, there is the preparation of the carbon nanotube of nanometer gold bar the present invention provides self assembly and carries out biomolecule inspection using it
The method of survey, since carbon nanotube self-conductive ability is weaker, can be examined delicately using single-walled carbon nanotube as carrier connection electrode
The variation that nanometer gold bar connection disconnects front and back is measured, and then electric signal conversion is realized by the change of self-conductance, is further mentioned
The sensitivity of high single-walled carbon nanotube and Monitoring lower-cut.Preparation cost is cheap, and detection biomolecule has high sensitivity, analysis
The advantages that speed is fast, instrument is simple, at low cost, result is reliable and is able to achieve real-time detection in situ.And it is easy to batch metaplasia
It produces.
3, there is the preparation of the carbon nanotube of nanometer gold bar the present invention provides self assembly and carries out biomolecule inspection using it
The method of survey, by the change of single-walled carbon nanotube middle probe molecule, so that self assembly provided by the invention has nanometer gold bar
Carbon nanotube can be adapted for detecting other different target molecules, and it is high not need to use fluorescent marker and biotinylation kit etc.
Expensive reagent material has universality, can be recycled, relatively cheap, more conducively promotes the use of.
4, carbon nanotube by volume provided by the invention is small, light-weight, easy to carry, significantly reduces the work of testing staff
Weight bearing.
Other features and advantages of the present invention will be illustrated in the following description, and partly becomes from specification
It is clear that understand through the implementation of the invention.The main object of the present invention and further advantage can be by the description
Specifically noted scheme is achieved and obtained.
Detailed description of the invention
The present invention will be further described in detail with reference to the accompanying drawing.
Fig. 1 is the flow chart of the preparation for the carbon nanotube that self assembly has nanometer gold bar；
Fig. 2 is biomolecule detecting method figure；
Curent change schematic diagram when Fig. 3 is detection.
Fig. 4 is the electron microscope for the carbon nanotube that self assembly has nanometer gold bar.
Specific embodiment
Carry out the technical solution that the present invention will be described in detail by the following examples, embodiment below is only exemplary,
It is only capable of for explanation and illustration technical solution of the present invention, and the limitation to technical solution of the present invention cannot be construed to.
Currently, nano material is widely used in the research and development of biological single-walled carbon nanotube.Wherein, gold nanorods
Due to scattering absorption efficiency, large specific surface area, good optical stability, biocompatibility, easy processing system with stronger light
The features such as standby, have been widely used for the multiple fields such as bio-sensing, optical imagery, gene and pharmaceutical carrier, heat cure.It is based on
The biological single-walled carbon nanotube of nanometer gold bar has many advantages, such as low cost, highly sensitive and small size, is widely used in life
Analyte detection field.
Nanometer gold bar is fixed on electrode using package technique by the electrochemica biological single-walled carbon nanotube based on nanometer gold bar
Surface can not only carry multiple indicator molecules, can also increase the effective surface area of electrode, to substantially increase electrification
Learn the sensitivity of detection.
Embodiment 1
As shown in Figure 1, the present invention provides the preparation that self assembly has the carbon nanotube of nanometer gold bar, concrete operation step is such as
Under:
Step 1: preparing single-walled carbon nanotube, specifically includes:
S1, the SiO for being 250nm-550nm by surface thickness2Si substrate be cut into the small pieces of 5mm × 6mm by hand；
S2 carries out ultrasonic cleaning processing with acetone, second alcohol and water；
S3, using ethyl alcohol as carbon source, Fe is catalyst, grows single-walled carbon nanotube in Si substrate surface；Growth temperature is
850℃-950℃；
Step 2: the preparation micro- gap electrode substrate of carbon nanotube；It specifically includes:
S1 drips upper PMMA corrosion inhibitor on single-walled carbon nanotube substrate；After spin coating, a few minutes are placed on hot plate；Specifically
PMMA corrosion inhibitor specification be 600K-900K；Spin coating revolving speed is 3500-4000 revs/min；Hot plate temperature is 140 DEG C -160 DEG C.
S2 is got to electron beam on substrate by EBL electron-beam exposure system, and the pattern of the composition of electron beam is electrode
Shape has single carbon pipe across the two poles of the earth, and two interelectrode distances are 0.5 μm.
Substrate after the completion of exposure is first placed in developer solution and is placed in fixing solution again, electrode pattern is exposed by s3；It is aobvious
The shadow time is 20s-30s, fixing time 20s-30s；
Golden film is plated to substrate surface using vacuum vapour deposition, places the substrate in acetone, expose electrode pattern by s4
The golden film of position can be retained, and the golden film of other positions can be removed as PMMA is dissolved in acetone；
S5, the single-walled carbon nanotube between the golden film being retained and its slit, i.e. group become single single-walled carbon nanotube electricity
Pole.
Step 3: nanometer gold bar is prepared；It specifically includes:
S1, in 50mL beaker, be added 5mL 0.5mM HAuCl4 and 5mL 0.2M CTAB, stir to clarify it is transparent after,
Then by ice 0.6mL 0.01MNaBH4Be rapidly injected in solution, the color of solution can go to dark brown by faint yellow, stand
30min, it is spare as seed solution；
7g CTAB and 1.234g NaOL are dissolved in 250mL water by s2, and stirring is to being completely dissolved；24mL is then added
4mM AgNO3Solution stirs to clarify transparent；250mL 1mM HAuCl4 solution and 4.8mL concentrated hydrochloric acid are added, continues to stir
It is spare as growth-promoting media to clear；
1.25mL 0.064M ascorbic acid solution is added in s2 by s3 with the seed solution synthesized in 0.8mL s1
Growth-promoting media stands 12h, nanometer gold bar solution can be obtained.
Step 4: assemble nanometer gold stick；The micro- gap electrode substrate of the carbon nanotube prepared in step 2 is statically placed in and is received
In the golden stick solution of rice, electrostatic self-assembled is made it through, the electrode base sheet independently installed is taken out, ultrapure water is used；Group accommodates
The time of the golden stick of rice is 5-10min.Referring to as shown in Figure 4.
Step 5: it is measured by probe station and electrochemical workstation and assembles the electric interelectrode conductance of nanometer gold bar carbon pipe simultaneously
Record.Nanometer gold bar is along carbon pipe transversely or longitudinally linear array.The partial size length of nanometer gold bar is 107.5 ± 7.2nm, directly
14.7 ± 0.6nm. of diameter
Due to preparing micro- gap electrode by EBL method, the distance of two interpolars can accomplish minimum (less than 1 μm), thus electricity
The golden stick number of interpolar also seldom (by taking a length of 100nm gold stick as an example, as a length of 500nm of slit or so between electrode, only needs 5-6
A gold stick joins end to end and can be connected to electrode).So the probe score removed needed on each device is also less, it is required
Target molecule number is also less.It is more conducive to the detection of low concentration intentional molecule in this way.
Following experimental data is provided according to above-mentioned steps:
The parameters detail of embodiment 1-4
Note: NaOL is enuatrol, a kind of surfactant.
There is the carbon nanotube of nanometer gold bar to be given birth to using above-mentioned self assembly as shown in Fig. 2, another aspect of the present invention is provided
The method of object Molecular Detection, biomolecule are DNA or biological enzyme, and solution of the substrate containing probe molecule is handled, nanometer is made
Probe molecule is sufficiently adsorbed on golden stick surface, then places the substrate in sample to be tested solution.
Step 1, before any processing, can measure self assembly by probe station and electrochemical workstation has nanogold
The interelectrode conductance of the carbon nanotube of stick connects into line since nanometer gold bar has been assembled in carbon tube wall at this time, measures at this time
For high current, as control.
Step 2, the carbon nanotube that self assembly has nanometer gold bar, which is soaked in higher concentration probes molecular solution, makes it sufficiently
Probe molecule is adsorbed, takes out, with ultrapure water, is dried with nitrogen；Its conductance is measured by probe station and electrochemical workstation；By
In the powerful adsorption capacity in nanometer gold bar surface, nanometer gold bar surface can be lived by probe molecule tight.
Carbon nanotube in step 2 is placed in sample to be tested solution to be measured a period of time, taken out by step 3, with super
Pure water rinsing is dried with nitrogen；
Step 4 places it in a period of time in the solution of iron chloride and thiocarbamide, takes out, with ultrapure water, nitrogen is blown
It is dry；Its conductance is measured by probe station and electrochemical workstation, result is compared with the control electric current that step 1 obtains；
Step 5 obtains conclusion (of pressure testing)；There is target molecule in sample solution, then nanometer gold bar surface-probe molecule is clear
It removes, nanometer gold bar surface is exposed again；Without target molecule in sample solution, then probe molecule can not be removed, nanogold
Stick continuation is wrapped.
Only when nanometer gold bar surface is under exposed state, nanometer gold bar can just be chlorinated iron and the molten liquid etching of thiocarbamide
Become smaller to connection and disconnects.By the test to electric interelectrode conductance ability, complete to fail to complete to carve for low current between the electrode of etching
It is high current between the electrode of erosion.Electric electrode current becomes smaller, and illustrates that nanometer gold bar completes etching, i.e., contains target point in sample solution
Son converts detection to the electric signal of target molecule to realize.
Single-walled carbon nanotube provided by the invention using nanometer gold bar etching condition electric signal transition detection biomolecule,
It is connected between electrode by single single-walled carbon nanotube, carbon nanotube itself has certain conductive capability, and the etching of nanometer gold bar is led
Cause carbon nanotube conductance reduced capability, can sensitively by electric signal conversion capture, further improve sensitivity with
Monitoring lower-cut, while can be carried out and recycle.
Further, the present invention constructs the single-walled carbon nanotube carbon an of overlength, and the length of nanotube is 100um-
50000um.(carbon nanotube is grown on substrate, and length reaches hundreds of microns to several centimeters), thus may be implemented device and
Connection uses, and to same sample, can detect multiple and different target molecules simultaneously, after detection, nanometer gold bar can be again
Assembling is recycled.
The present invention also provides the methods that the carbon nanotube for having nanometer gold bar using self assembly carries out biomolecule detection:
The object of detection be can be the biomolecule of DNA or biological enzyme etc, specific detection example: for example I
Can design the nucleic acid sequence of probe molecule, to detect the target nucleic acid molecules of particular sequence.For example, probe molecule
Are as follows: (5 ' → 3 ') CCACATCATCCATATAGCT.It can detect target molecule sequence AGCTATATGGATGATGTGG.
The carbon nanotube for having nanometer gold bar using self assembly is made in embodiment 1, partial size length is about 108.7nm, diameter
About 15.1nm.Its interelectrode conductance can be measured by probe station and electrochemical workstation, due to nanometer gold bar at this time
It is assembled in carbon tube wall and connects into line, measuring at this time is high current, which reads shown in Figure 3, Imax=1.6A,
Imax is as control.
Being soaked in higher concentration probes molecular solution makes it sufficiently adsorb probe molecule, and measurement conductance is about Imax.
Single-walled carbon nanotube substrate is placed in 3h in 0.05mM iron chloride and 1mM thiourea solution.It takes out and uses and be dried with nitrogen, measurement electricity
It leads.Conclusion: single-walled carbon nanotube substrate, which detects target molecule, has high sensitivity.If interelectrode conductance is not obvious
Variation, illustrate there is no target molecule in sample, (Imax=1.6A).If electric interelectrode conductance is obviously reduced, illustrate to test sample
There is target molecule (I in productMIX=0.02A).
Present invention offer self assembly has the preparation of the carbon nanotube of nanometer gold bar and it is utilized to carry out biomolecule detection
Method successfully constructs single-walled carbon nanotube and nanometer gold bar assembling device, by the condition that is etched using nanometer gold bar as
Detect the switch of target biological molecules.Since single-walled carbon nanotube itself has certain conductive capability, when nanometer gold bar is etched
Afterwards, reduced conductance can be detected by single-walled carbon nanotube, thus have higher sensitivity.
The foregoing is merely the preferable specific embodiments of the present invention, but scope of protection of the present invention is not limited thereto,
The change or replacement that anyone skilled in the art is expected in the technical scope disclosed by the present invention should all be contained
Lid is within protection scope of the present invention.
Claims (10)
1. the preparation that self assembly has the carbon nanotube of nanometer gold bar, it is characterised in that: specific steps are as follows:
Step 1: preparing single-walled carbon nanotube, specifically includes:
S1, the SiO for being 250nm-550nm by surface thickness2Si substrate be cut into the small pieces of 5mm × 6mm by hand；
S2 carries out ultrasonic cleaning processing with acetone, second alcohol and water；
S3, using ethyl alcohol as carbon source, Fe is catalyst, grows single-walled carbon nanotube in Si substrate surface；Growth temperature is 850
℃-950℃；
Step 2: the preparation micro- gap electrode substrate of carbon nanotube；
Step 3: nanometer gold bar is prepared；
Step 4: assemble nanometer gold stick；The micro- gap electrode substrate of the carbon nanotube prepared in step 2 is statically placed in nanogold
In stick solution, electrostatic self-assembled is made it through, the electrode base sheet independently installed is taken out, ultrapure water is used；
Step 5: the electric interelectrode conductance for assembling nanometer gold bar carbon pipe is measured by probe station and electrochemical workstation and is remembered
Record.
2. the preparation that self assembly as described in claim 1 has the carbon nanotube of nanometer gold bar, which is characterized in that nanometer gold bar edge
Carbon pipe transversely or longitudinally linear array.
3. the preparation that self assembly as described in claim 1 has the carbon nanotube of nanometer gold bar, which is characterized in that nanometer gold bar
Partial size length is 107.5 ± 7.2nm, 14.7 ± 0.6nm of diameter.
4. the preparation that self assembly as described in claim 1 has the carbon nanotube of nanometer gold bar, which is characterized in that the step 2
It specifically includes:
S1 drips upper PMMA corrosion inhibitor on single-walled carbon nanotube substrate；After spin coating, a few minutes are placed on hot plate；
S2 is got to electron beam on substrate by EBL electron-beam exposure system, and the pattern of the composition of electron beam is electrode shape,
There is single carbon pipe across the two poles of the earth, two interelectrode distances are 1 μm；
Substrate after the completion of exposure is first placed in developer solution and is placed in fixing solution again, electrode pattern is exposed by s3；When development
Between be 20s-30s, fixing time 20s-30s；
Golden film is plated to substrate surface using vacuum vapour deposition, placed the substrate in acetone, exposes the position of electrode pattern by s4
Golden film can be retained, the golden films of other positions can be removed as PMMA is dissolved in acetone；
S5, the single-walled carbon nanotube between the golden film being retained and its slit, i.e. group become single single pipe electrode.
5. the preparation that self assembly as claimed in claim 4 has the carbon nanotube of nanometer gold bar, which is characterized in that the s1 of step 2
In, PMMA corrosion inhibitor specification is 600K-900K；Spin coating revolving speed is 3500-4000 revs/min；Hot plate temperature is 140 DEG C -160
℃。
6. the preparation that self assembly as claimed in claim 4 has the carbon nanotube of nanometer gold bar, which is characterized in that the s2 of step 2
In, two interelectrode distances are 0.4 μm -0.6 μm.
7. the preparation that self assembly as described in claim 1 has the carbon nanotube of nanometer gold bar, which is characterized in that the step 3
It specifically includes:
In beaker, HAuCl is added in s14And CTAB, stir to clarify it is transparent after, ice MNaBH4 is then rapidly injected solution
In, the color of solution can go to dark brown by faint yellow, stand, spare as seed solution；
S2, CTAB and NaOL is soluble in water, and stirring is to being completely dissolved；AgNO is then added3Solution stirs to clarify transparent；Again
HAuCl is added4Solution and concentrated hydrochloric acid, continue to stir to clarify it is transparent, it is spare as growth-promoting media；
Seed solution obtained in ascorbic acid solution, with s1 is added in s2 in growth-promoting media obtained, stands by s3
Obtain nanometer gold bar solution.
8. the preparation that self assembly as described in claim 1 has the carbon nanotube of nanometer gold bar, which is characterized in that carbon nanotube
Length is 100um-50000um.
9. thering is the carbon nanotube of nanometer gold bar to carry out biomolecule inspection using self assembly such as of any of claims 1-8
The method of survey, which is characterized in that specific step is as follows:
The self assembly prepared is had the carbon nanotube of nanometer gold bar, is measured by probe station and electrochemical workstation by step 1
Its interelectrode conductance connects into line since nanometer gold bar has been assembled in carbon tube wall, and measuring at this time is high current as control；
Step 2, the carbon nanotube that self assembly has nanometer gold bar, which is soaked in higher concentration probes molecular solution, adsorbs it sufficiently
Probe molecule takes out, with ultrapure water, is dried with nitrogen；Its conductance is measured by probe station and electrochemical workstation；Due to receiving
The powerful adsorption capacity in rice golden stick surface, nanometer gold bar surface can be lived by probe molecule tight；
Carbon nanotube in step 2 is placed in a period of time in sample to be tested solution to be measured, takes out, use ultrapure water by step 3
It rinses, is dried with nitrogen；
Step 4 places it in a period of time in the solution of iron chloride and thiocarbamide, takes out, with ultrapure water, be dried with nitrogen；It is logical
It crosses probe station and electrochemical workstation measures its conductance, result is compared with the control electric current that step 1 obtains；
Step 5 obtains conclusion (of pressure testing)；There is target molecule in sample solution, then nanometer gold bar surface-probe molecule is removed, and is received
Rice golden stick surface is exposed again, current reduction；Without target molecule in sample solution, then probe molecule can not be removed, and receive
The golden stick continuation of rice is wrapped, and electric current is substantially unchanged.
10. method as claimed in claim 9, which is characterized in that biomolecule is DNA or biological enzyme.
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