CN102608185B - Gold electrode and preparation method thereof - Google Patents
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- CN102608185B CN102608185B CN201210082608.4A CN201210082608A CN102608185B CN 102608185 B CN102608185 B CN 102608185B CN 201210082608 A CN201210082608 A CN 201210082608A CN 102608185 B CN102608185 B CN 102608185B
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Abstract
The invention relates to a gold electrode and a preparation method thereof. A method for forming a self-assembly molecular film on the surface of the gold electrode comprises the following steps: mixing a DNA solution with a first thiol solution to obtain a mixed solution containing DNA and thiol; placing the gold electrode into the mixed solution containing DNA and thiol to form an initial self-assembly molecular film on the surface of the gold electrode; and placing the gold surface on which the initial self-assembly molecular film is formed into a second thiol solution to form a self-assembly molecular film on the surface of the gold electrode. The self-assembly molecular film prepared by using the method for forming the self-assembly molecular film on the surface of the gold electrode, provided by the invention, has high packing density, low defect concentration and stable electrochemical properties.
Description
Technical field
The invention belongs to gold electrode and preparation method thereof.
Background technology
Self assembly molecule film becomes rapidly the research focus in the fields such as material science, microelectronics, biology after occurring the eighties in 20th century.By designing different self assembly molecules, can obtain various function interfaces, for people's scientific research provides new ways and means.The DNA probe molecule adsorption method of DNA biology sensor mainly contains four kinds at present: the nucleic acid molecules of directly absorption process modification, after absorption nucleic acid probe, with mercaptan, fill out punching, absorption mercaptan afterwards by nucleic acid molecules displacement and nucleic acid molecules and mercaptan while mixing and absorption.
Directly on gold electrode, fixed dna nucleic acid molecules is the fixing method of self assembly molecule film the first.This method has very serious defect, and nucleic acid molecules is very chaotic in the absorption situation of gold electrode surfaces, causes the inefficiency of final hydridization reaction.Research discovery DNA base afterwards and the attractive force between gold electrode are due to the effect of nitrogen-Jin chemical bond and tygon (purine)-Jin chemical bond, firmly degree is even taller than sulphur-Jin chemical bond, so nucleic acid probe molecules is easy to " lodging " in gold electrode surfaces.
In order to address this problem, Herne and Tarlov have proposed heavily to fill out as filling agent with MCH, and this method can be incorrect suction type, the not firm nucleic acid molecules of absorption displaces, and can prevent that determined nucleic acid molecular adsorption is to gold electrode surfaces.But this method is also defective.First be exactly reproducibility problems; Secondly this method is affected by the sequence of DNA very.In addition, also have scholar's statement, with MCH, carry out fast processing and cannot remove the wrong nucleic acid probe molecules of absorption completely.
In order to solve DNA base, can be adsorbed on the problem of gold electrode surfaces, someone has proposed first to form the densification method on new surface uniformly before adding DNA nucleic acid probe.Concrete way is exactly before adsorption of DNA nucleic acid probe molecules, first in gold electrode surfaces, to prepare the MCH film of one deck densification.The probe molecule density of self assembly molecule film prepared by this method depends on pore density and the defect concentration of pure MCH film, and these two density are all unpredictable also uncontrollable.And repeated non-constant.
By adsorb recently studied a lot of of mixing self assembly molecule film that alkyl sulfhydryl and DNA nucleic acid probe molecules prepare simultaneously.In mixed solution, the density of the self assembly molecule film that obtains of absorption is decided by an equilibrium process simultaneously, and this makes the molecular film density that finally obtains insensitive to adsorption time, molecular motion, probe sequence.There are a lot of scholars to adopt similar method all to prepare 4～5 * 10
12the self assembly molecule film of molecule/square centimeter.
Yet the method at gold electrode surfaces formation self assembly molecule film still haves much room for improvement at present.
Summary of the invention
The present invention is intended at least one of solve the problems of the technologies described above.
Therefore, after the object of the invention is to adsorb at the same time alkyl sulfhydryl and DNA nucleic acid probe molecules, add a step of heavily filling out, filling agent is used the thiol solution of higher concentration.The step of heavily filling out makes self assembly molecule film form fine and close membrane structure, obtains stable electrochemical properties.
The present invention completes based on following two subsidies, at this, expresses thanks:
1. project of national nature science fund project
Project name: nucleic acid mixing self assembly molecule film property control principle and method research based on electric field induction,
Project approval number: 51105222.
2. the autonomous research topic of tribology National Key Laboratory
Project name: the research of nucleic acid probe mixing self assembly molecule film property control technology,
Project approval number: SKLT10B02.
According to an aspect of the present invention, the invention provides a kind of method that forms self assembly molecule film in gold electrode surfaces.According to embodiments of the invention, the method comprises: DNA solution is mixed with the first thiol solution, to obtain the mixed liquor that contains DNA and mercaptan; Gold electrode is placed in to the mixed liquor that contains DNA and mercaptan, to form elementary self assembly molecule film in gold electrode surfaces; And the gold electrode that surface forms elementary self assembly molecule film is placed in to the second thiol solution, to form self assembly molecule film in gold electrode surfaces.Inventor finds, utilize the method to form self assembly molecule film in gold electrode surfaces, on gold electrode, suction type is incorrect, and adsorbing not firm nucleic acid molecules can be fallen by sulfenyl hexanol (MCH) molecular replacement, thereby can improve the quality of forming film of self assembly molecule film.According to embodiments of the invention, utilize the method at gold electrode surfaces formation self assembly molecule film of the present invention to prepare self assembly molecule film, without complex apparatus, simple, favorable repeatability, and cost is low, the self assembly molecule film arranging density of formation is high, defect concentration is little, electrochemical properties is stable, and quality is very good.
According to embodiments of the invention, of the present invention, in gold electrode surfaces, form in the method for self assembly molecule film, DNA solution can be the TE solution of DNA, the first thiol solution can be the ethanolic solution of MCH.This is because TE solution is alkalescent, and the base of DNA is had to protective effect, and DNA has in TE solution that stability is better, integrality is high, without producing the features such as open loop and phenomenon of rupture; MCH is soluble in ethanol, and ethanolic solution is often used as the lysate of MCH.Due to steric hindrance and Coulomb repulsion, probe molecule density can obviously affect hydridization reaction.Research shows, hydridization reaction is 4 * 10 in probe density
12during molecule/square centimeter, efficiency reaches the highest, and when probe density rises again, hydridization efficiency can sharply decline.Therefore, control accurately probe density very important to detection of nucleic acids.Correspondingly, when gold electrode surfaces forms self assembly molecule film, need the concentration of the strict DNA of control and MCH, prepare the self assembly molecule film of required probe density.In addition,, because the molecular weight of DNA molecular is large, the optimum concentration of the DNA solution adopting in experiment is generally in micro-rank of rubbing.According to some embodiments of the present invention, in DNA solution, the concentration of DNA is 20 micro-rubbing, and in the first thiol solution, the concentration of MCH is that 1 milli rubs.In addition, according to other embodiment of the present invention, the volume ratio of DNA solution and the first thiol solution can be 1: 1～5, and the probe density obtaining thus and optimum probe density value are the most approaching, thereby can improve the quality of formed self assembly molecule film.
DNA molecular is all electronegative, has each other repulsive force, therefore cannot form fine and close molecular film; And in SPB solution, because the cation concentration of solution is high, positive charge can be adsorbed onto on DNA molecular, neutralize the negative charge of its original band, greatly reduce the repulsive force between nucleic acid molecules, thereby can improve the density of DNA molecular film.Therefore,, after DNA solution can being mixed with SPB solution, in order to preparation, form self assembly molecule film.According to embodiments of the invention, of the present invention, in gold electrode surfaces, form in the method for self assembly molecule film, the mixed liquor that contains DNA and mercaptan is by being mixed to get DNA solution, the first thiol solution and SPB solution, and wherein, SPB solution can contain:
The volume ratio of SPB solution, DNA solution and the first thiol solution is 94: 5: 1.Wherein, SPB solution is the phosphate buffer solution of high ionic strength, PH=7.0,200mM PB+400mM K
2sO
4.Thus, gold electrode is placed in after the mixed liquor that contains DNA and mercaptan, can successfully in gold electrode surfaces, forms fine and close elementary self assembly molecule film.
According to embodiments of the invention, of the present invention, in gold electrode surfaces, form in the method for self assembly molecule film, the second thiol solution can contain:
Rub 10 milliliters of MCH of 10 millis
10 milliliters of ethanol
Deionized water complements to 100 milliliters.
Thus, the gold electrode that surface is formed to elementary self assembly molecule film is placed in after the second thiol solution, MCH molecule in the second thiol solution can displace the DNA probe molecule that some suction types are incorrect, absorption is not firm, thereby successfully in gold electrode surfaces, forms the self assembly molecule film that arranging density is high, defect concentration is little, electrochemical properties is stable.
According to embodiments of the invention, of the present invention, in gold electrode surfaces, form in the method for self assembly molecule film, before gold electrode is placed in to the mixed liquor that contains DNA and mercaptan, can, by least one of mechanical buffing and electrochemical polish, to the surface of gold electrode, carry out polishing.This is because self assembly molecule film is to be adsorbed on gold electrode surfaces to form, if gold electrode surfaces roughness is high, can increase considerably self-assembled film defect concentration.Thus, through the gold electrode surfaces of polishing, DNA and mercaptan can be improved in the adsorbance of gold electrode surfaces, thereby arranging density and the electrochemical stability of prepared self assembly molecule film can be improved.
According to embodiments of the invention, of the present invention, in gold electrode surfaces, form in the method for self assembly molecule film, the time that gold electrode is placed in to the mixed liquor that contains DNA and mercaptan is not particularly limited.Due to the self assembling process of alkyl sulfhydryl strong depend on its concentration, and DNA and the concentration of mercaptan in mixed liquor that experiment adopts are micro-rank of rubbing, and the feasibility of considering experiment, therefore, according to concrete examples more of the present invention, gold electrode is placed in mixed liquor 16-20 hour that contains DNA and mercaptan.Thus, can make DNA and mercaptan fully be adsorbed in gold electrode surfaces, thereby can form elementary self assembly molecule film.
According to embodiments of the invention, of the present invention, in gold electrode surfaces, form in the method for self assembly molecule film, the time that the gold electrode that surface is formed to elementary self assembly molecule film is placed in the second thiol solution is not particularly limited.According to concrete examples more of the present invention, the gold electrode that surface is formed to elementary self assembly molecule film is placed in the second thiol solution 2 hours.Thus, can make MCH displace fully the nucleic acid molecules that on the elementary self assembly molecule film of gold electrode surfaces, some suction types are incorrect, absorption is not firm, thereby can form the self assembly molecule film that arranging density is high, defect concentration is little, electrochemical properties is stable.
Particularly, according to embodiments of the invention, the method that forms self assembly molecule film in gold electrode surfaces of the present invention, can comprise the following steps: by the potpourri of DNA and MCH self assembly film forming in clean gold substrate, mixture D NA, MCH solution mix with certain proportion; With higher concentration MCH solution, fill again, be self-assembled into form compact and stable molecular film.
More specifically, according to some embodiments of the present invention, the method that forms self assembly molecule film in gold electrode surfaces of the present invention, can also comprise the following steps:
A) gold electrode is carried out to pre-service: first gold electrode is carried out to mechanical buffing 5min, ultrasonic processing 5min, then it is carried out under olefin(e) acid environment to electrochemical polish, make gold electrode surfaces clean;
B) treated gold electrode is immersed in the mixed liquor that contains DNA and MCH, to form elementary self assembly molecule film on gold electrode;
C) MCH heavily fills out: the gold electrode that surface is formed to elementary self assembly molecule film immerses in the second thiol solution of higher concentration more heavily to be filled out, to form self assembly molecule film in gold electrode surfaces.
According to a further aspect in the invention, the invention provides a kind of gold electrode, its surface is formed with self assembly molecule film.According to embodiments of the invention, this self assembly molecule film is to form in the method for gold electrode surfaces formation self assembly molecule film according to the present invention.Inventor is surprised to find, and it is low that the self assembly molecule film on gold electrode of the present invention and surface thereof has cost, the advantage that arranging density is high, defect concentration is little, electrochemical properties is stable.In addition,, according to embodiments of the invention, the gold electrode that has self assembly molecule film that utilizes the present invention to form, can be easily and effectively as DNA probe or DNA biology sensor.
It should be noted that, the work that gold electricity of the present invention and preparation method thereof is present inventor by arduous creative work and optimization just completes.
Additional aspect of the present invention and advantage in the following description part provide, and part will become obviously from the following description, or recognize by practice of the present invention.
Accompanying drawing explanation
Above-mentioned and/or additional aspect of the present invention and advantage accompanying drawing below combination obviously and is easily understood becoming the description of embodiment, wherein:
Fig. 1: shown according to one embodiment of present invention, while utilizing the method at gold electrode surfaces formation self assembly molecule of the present invention to prepare gold electrode, the graph of a relation of gold electrode surfaces electric weight and time;
Fig. 2: shown according to one embodiment of present invention, while utilizing the method at gold electrode surfaces formation self assembly molecule film of the present invention to prepare gold electrode, the Ru (NH of the volume ratio of DNA and mercaptan and the gold electrode surfaces of acquisition in the mixed liquor that contains DNA and mercaptan
3)
6 3+the graph of a relation of adsorbance; And
Fig. 3: shown according to one embodiment of present invention, while utilizing the method at gold electrode surfaces formation self assembly molecule film of the present invention to prepare gold electrode, the graph of a relation of the probe density of the volume ratio of DNA and mercaptan and the gold electrode surfaces of acquisition in the mixed liquor that contains DNA and mercaptan.
Embodiment
Describe embodiments of the invention below in detail, it should be noted that, these embodiment are only used to illustrate the present invention, and scope of the present invention are not made to any restriction.The all material adopting in the following example is all industrial conventional, is commercially available.
Conventional method:
1. configure solution
The mixed liquor that 1.1 configurations contain DNA and mercaptan
The configuration of the mixed liquor that contains DNA and mercaptan is divided into three steps to be carried out, and first configures SPB solution and (according to Buffer Calculator, calculates PH=7.0,200mMPB+400mMK
2sO
4), the TE solution of DNA, the first thiol solution (1mM), then the TE solution of SPB solution, DNA and the first thiol solution (1mM) are mixed and make solution, concrete configuration process is as follows:
A) first, according to the SPB solution of following recipe configuration 200mL, (according to Buffer Calculator, calculate PH=7.0,200mMPB+400mMK
2sO
4), standby:
B) secondly, according to the TE solution of following recipe configuration DNA, standby:
The instructions of buying according to DNA can first obtain the TE solution of 100 micro-DNA of rubbing, and recycling TE solution is diluted to 20 micro-rubbing;
C) again by following recipe configuration 100mL the first thiol solution (1mM), standby:
Mercaptan (MCH-97%) 14.10 microlitres
Ethanol (CH
3cH
2oH) supply.
Then, by three kinds of solution that obtain above: the TE solution of SPB solution, DNA and the first thiol solution are proportionally configured to the mixed liquor that contains DNA and mercaptan at 94: 5: 1, standby.
1.2 configuration the second thiol solutions:
First, according to following formula, first configure the ethanolic solution (10mM) of 100mL mercaptan, standby:
Mercaptan (MCH-97%) 141.00 microlitres
Ethanol (CH
3cH
2oH) supply;
Then, according to the second thiol solution of following recipe configuration 100mL, standby:
Mercaptan (10mM configuring above) 10mL
Ethanol (CH
3cH
2oH) 10mL
Deionized water is supplied.
2. prepare gold electrode:
1. the method that adopts mechanical buffing and electrochemical polish (carrying out CV scanning under olefin(e) acid environment) to combine cleans up gold electrode surfaces, is then stored in deionized water;
2. the mixed liquor that contains DNA and mercaptan that gold electrode is placed in to above-mentioned acquisition is cultivated 16-20 hour, to form elementary self assembly molecule film in gold electrode surfaces;
3. the gold electrode that utilizes deionized water that surface is formed to elementary self assembly molecule film rinses, and then this gold electrode is placed in to the second thiol solution cultivates 2 hours, to form self assembly molecule film in gold electrode surfaces.
Example 1:
According to conventional method, prepare gold electrode, wherein, the mixed liquor that contains DNA and mercaptan that respectively gold electrode is placed in to above-mentioned acquisition is cultivated 16-20 hour, and the DNA, the first thiol solution that wherein contain in the mixed liquor of DNA and mercaptan mixed with 1: 10.Then, adopt timing coulometry, according to following steps, measure and calculate the Ru (NH of the gold electrode surfaces of preparation
3)
6 3+adsorbance, the potential range that wherein adopted is-300mv～-800mv that Measuring Time is 500ms:
First the gold electrode of preparation is placed in to blank solution, PH=7.4, in the Tris-HCl solution of 10mM, measures the first curve to it; Then to adding concentration in above-mentioned blank solution, be, 100 micro-Ru (NH that rub
3)
6 3+solution (negative charge of each phosphate group band of DNA, its can with Ru (NH
3)
6 3+there is suction-operated), and it is measured to the second curve; Then, based on aforementioned two curves, make the tangent line of two curves and obtain intercept, by the poor Ru (NH that tries to achieve of intercept
3)
6 3+adsorbance Γ
0(unit: mol/cm
2), then by the formula Q=2nFAC of timing coulometry
*(Dt/ π)
1/2+ Q
d1+ nFA Γ
0(wherein n is the electron number that redox is shifted, and F is Faraday constant, and A is that gold electrode surfaces is long-pending, C
*for Ru (NH
3)
6 3+body solubility, D is Ru (NH
3)
6 3+coefficient of diffusion, t is the time, Q
d1for the electric weight of electrostatic double layer, Γ
0adsorbance for adsorbate) calculate the electric weight of gold electrode surfaces, and take respectively gold electrode surfaces electric weight and time as the mapping of transverse and longitudinal coordinate, the results are shown in Figure 1.Fig. 1 has shown while utilizing the method at gold electrode surfaces formation self assembly molecule of the present invention to prepare gold electrode, the graph of a relation of gold electrode surfaces electric weight and time.As shown in Figure 1, the electric weight Q that ordinate is gold electrode surfaces, the square root t that horizontal ordinate is the time
1/2.It should be noted that, due to reasons such as instruments, the Q-t that experiment obtains
1/2curve is not a straight line, pretends its tangent line and asks it.
Example 2:
Ru (the NH of the prepared according to the methods of the invention gold electrode surfaces obtaining based on example 1
3)
6 3+adsorbance, in the mixed liquor that can obtain containing DNA and mercaptan, the volume ratio of DNA and mercaptan is respectively 1: 10,1: 5,1: 1 o'clock corresponding adsorbance Γ
0thereby, can access the Ru (NH of DNA and the volume ratio of mercaptan and the gold electrode surfaces of acquisition in the mixed liquor that contains DNA and mercaptan
3)
6 3+adsorbance Γ
0relation, and with its corresponding surface, form elementary self assembly molecule film gold electrode adsorbance in contrast, make the Ru (NH of DNA and the volume ratio of mercaptan and the gold electrode surfaces of acquisition in the mixed liquor that contains DNA and mercaptan
3)
6 3+adsorbance Γ
0graph of a relation, the results are shown in Figure 2.As shown in Figure 2, the Ru (NH that ordinate is gold electrode surfaces
3)
6 3+adsorbance Γ
0(unit: mol/cm
2); Horizontal ordinate is DNA:MCH, the volume ratio of DNA and mercaptan in the mixed liquor that represents to contain DNA and mercaptan; Red line is that DNA+MCH+ heavily fills out, and represents the resulting gold electrode of method at gold electrode surfaces formation self assembly molecule film according to the embodiment of the present invention, the Ru (NH that it is surperficial
3)
6 3+the relation curve of the volume ratio of DNA and mercaptan in adsorbance and the mixed liquor that contains DNA and mercaptan; And blue line is DNA+MCH, when the expression method at gold electrode surfaces formation self assembly molecule film according to the present invention is prepared gold electrode, heavily do not fill out step, only in gold electrode surfaces, form elementary self assembly molecule film, the gold electrode that surface is not formed to elementary self assembly molecule film is placed in the second thiol solution, the Ru (NH of the gold electrode surfaces obtaining thus
3)
6 3+the relation curve of the volume ratio of DNA and mercaptan in adsorbance and the mixed liquor that contains DNA and mercaptan.As shown in Figure 2, when the volume ratio of DNA and mercaptan is identical in the mixed liquor that contains DNA and mercaptan, after heavily filling out, in gold electrode surfaces, form the gold electrode of self assembly molecule film, than the gold electrode that only forms elementary self assembly molecule film on surface to Ru (NH
3)
6 3+adsorbance Γ
0height, shows that the gold electrode that surface is formed to elementary self assembly molecule film is placed in the second thiol solution, can significantly increase gold electrode surfaces to Ru (NH
3)
6 3+adsorbance.
Example 3:
According to formula Γ
dNA=Γ
0(z/m) N
a, the Ru (NH of DNA and the volume ratio of mercaptan and the gold electrode surfaces of acquisition in the resulting mixed liquor that contains DNA and mercaptan in example 2
3)
6 3+adsorbance Γ
0graph of a relation in, the corresponding adsorbance Γ of the mixed liquor that contains DNA and mercaptan of different proportion
0, try to achieve the density Γ of DNA probe
dNA, Γ wherein
dNAdensity (unit: individual/cm for DNA probe
2), m is base number, z is the electrically charged number of adion.Then the density based on DNA probe, draws and the graph of a relation of the probe density of DNA and the volume ratio of mercaptan and the gold electrode surfaces of acquisition in the mixed liquor that contains DNA and mercaptan the results are shown in Figure 3.As shown in Figure 3, the probe density that ordinate is gold electrode surfaces (unit: individual/cm
2); Horizontal ordinate is DNA:MCH, the volume ratio of DNA and mercaptan in the mixed liquor that represents to contain DNA and mercaptan; Red line is that DNA+MCH+ heavily fills out, expression forms the resulting gold electrode of method of self assembly molecule film according to the embodiment of the present invention in gold electrode surfaces, the relation curve of the volume ratio of DNA and mercaptan in its surperficial probe density and the mixed liquor that contains DNA and mercaptan; And blue line is DNA+MCH, when the expression method at gold electrode surfaces formation self assembly molecule film according to the present invention is prepared gold electrode, heavily do not fill out step, only in gold electrode surfaces, form elementary self assembly molecule film, the gold electrode that surface is not formed to elementary self assembly molecule film is placed in the second thiol solution, the relation curve of the volume ratio of DNA and mercaptan in the probe density of the gold electrode surfaces obtaining thus and the mixed liquor that contains DNA and mercaptan.As shown in Figure 3, when in the mixed liquor that contains DNA and mercaptan, the volume ratio of DNA and mercaptan is identical, after heavily filling out, in gold electrode surfaces, form the gold electrode of self assembly molecule film, the probe density of gold electrode surfaces that specific surface forms elementary self assembly molecule film is high, show that the gold electrode that surface is formed to elementary self assembly molecule film is placed in the second thiol solution, can significantly increase the probe density of gold electrode surfaces.
In the description of this instructions, the description of reference term " embodiment ", " some embodiment ", " example ", " concrete example " or " some examples " etc. means to be contained at least one embodiment of the present invention or example in conjunction with specific features, structure, material or the feature of this embodiment or example description.In this manual, the schematic statement of above-mentioned term is not necessarily referred to identical embodiment or example.And the specific features of description, structure, material or feature can be with suitable mode combinations in any one or more embodiment or example.
Although illustrated and described embodiments of the invention, those having ordinary skill in the art will appreciate that: in the situation that not departing from principle of the present invention and aim, can carry out multiple variation, modification, replacement and modification to these embodiment, scope of the present invention is limited by claim and equivalent thereof.
Claims (4)
1. in gold electrode surfaces, form a method for self assembly molecule film, it is characterized in that, comprising:
DNA solution, the first thiol solution and SPB solution are mixed, to obtain the mixed liquor that contains DNA and mercaptan;
The mixed liquor that contains DNA and mercaptan described in described gold electrode is placed in, to form elementary self assembly molecule film in described gold electrode surfaces; And
The gold electrode that surface is formed to elementary self assembly molecule film is placed in the second thiol solution, to form self assembly molecule film in described gold electrode surfaces,
Wherein,
Described DNA solution is the TE solution of DNA, the ethanolic solution that described the first thiol solution is MCH,
In described DNA solution, the concentration of DNA is 20 micro-rubbing, and in described the first thiol solution, the concentration of MCH is that 1 milli rubs,
Described SPB solution contains:
The volume ratio of described SPB solution, DNA solution and the first thiol solution is 94:5:1,
Described the second thiol solution contains:
Rub 10 milliliters of MCH of 10 millis
10 milliliters of ethanol
Deionized water complements to 100 milliliters,
The gold electrode that described surface is formed to elementary self assembly molecule film is placed in the second thiol solution 2 hours.
2. method according to claim 1, is characterized in that, before the mixed liquor that contains DNA and mercaptan described in described gold electrode is placed in, by mechanical buffing and electrochemical polish at least one, polishing is carried out in the surface of described gold electrode.
3. method according to claim 1, is characterized in that, the mixed liquor 16-20 hour that contains DNA and mercaptan described in described gold electrode is placed in.
4. a gold electrode, is characterized in that, described gold electrode surfaces is formed with self assembly molecule film, and described self assembly molecule film is to form according to the method described in claim 1-3 any one.
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