CN109459481A - A kind of method of modifying in bionic nano duct and bionic nano duct and its application - Google Patents
A kind of method of modifying in bionic nano duct and bionic nano duct and its application Download PDFInfo
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- CN109459481A CN109459481A CN201811311824.5A CN201811311824A CN109459481A CN 109459481 A CN109459481 A CN 109459481A CN 201811311824 A CN201811311824 A CN 201811311824A CN 109459481 A CN109459481 A CN 109459481A
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Abstract
The present invention provides a kind of method of modifying in bionic nano duct, comprising the following steps: the substrate with bionic nano duct is placed between effectiveness type polyelectrolyte solution and pairing polyelectrolyte solution；Under electric field induction, effectiveness type polyelectrolyte and pairing polyelectrolyte are acted on by electrical coupling in bionic nano duct and realize self assembly；Wherein, effectiveness type polyelectrolyte and pairing polyelectrolyte have opposite charge.The method of modifying has widened the range of choice of effectiveness type polyelectrolyte significantly, can modify and the electrically charged identical effectiveness type polyelectrolyte of institute in duct.And have the advantages that modification time-consuming is short, response works well, modification is reversible, bionic nano duct is reusable.The present invention also provides a kind of bionic nano hole as made from above-mentioned method of modifying and its preparing the application received and flowed in device.
Description
Technical field
The present invention relates to bionic nano duct, the particularly a kind of method of modifying in bionic nano duct and preparation
Bionic nano duct and its application.
Background technique
There is various nano pores in the organism of nature, play respectively for movable be normally carried out of life
From unique effect.It is a kind of asymmetric mass transfer duct with excellent performance such as protein channel, complicated peptide link
Structure makes it possess excellent selectivity and responsiveness.The structure and function of scientist organism in nature has carried out depth
After the research and understanding of level, it is intended to utilize the complex arts pair such as nanotechnology, molecular biology, surface chemistry and Statistical Physics
The structure of life entity and the intelligent bionic research of progress, to realize the purpose for imitating the nano pore in life entity.People
Work nano pore is bionical to design and developing because of the controllability that its shape and surface chemistry form as a kind of stable duct
Nano pore provides good research platform, therefore how nano pore to be modified to the bionic nano hole with bionic function
Road just becomes one of the emphasis of research.
Currently, the method for modifying in bionic nano duct mainly has surface carboxyl groups activation method and polyelectrolyte absorption method.Surface
Activated carboxylic method mainly uses 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride (EDC) and N- hydroxysuccinimidyl
Acid imide (NHSS) by the activated carboxylic on nano pore inner wall, the response molecule with amino by specificly-response unit with
Carboxyl, which reacts, to be formed covalent bond and modifies to nano pore inner wall, and then realizes bionical response function.Surface carboxyl groups activation method,
In modification due to the charged group that is utilized on the inner wall of bionic nano duct so as to cause in duct in non-responsive state
Under electric current be decreased obviously so that nano pore flux decline；And surface carboxyl groups activation method is a kind of irreversible modification,
Bionic nano hole is difficult to reuse；In addition, the modification overlong time of surface carboxyl groups activation method, preparation efficiency are low.And poly- electrolysis
Matter absorption method is mainly to utilize main chain real with the electrostatic interaction between the polyelectrolyte and electronegative inner surfaces of pores of positive electricity
It now modifies, is generally adopted by the mode that bionic nano duct is directly soaked into polyelectrolyte solution.Polyelectrolyte is inhaled
Attached method, the charge that polyelectrolyte is had must be with the opposite charges of inner surfaces of pores, because of bionic nano duct institute at present
It is electrically charged generally to be negative electricity, therefore can not just lead to by the response unit that aobvious elecrtonegativity generates electrochemical environment variation in duct
Cross polyelectrolyte modification method modify to nano pore, this just greatly limits the range of choice of polyelectrolyte, cause it is many at
Ripe response model and response molecule can not be all modified by polyelectrolyte absorption method to duct inner wall.Accordingly, it is desirable to provide one
The method of modifying in the bionical duct of kind, to make up the deficiency of surface carboxyl groups activation method and polyelectrolyte modification method.
Summary of the invention
The present invention first is designed to provide a kind of method of modifying in bionic nano duct, which is to pass through electricity
Effectiveness type polyelectrolyte and pairing polyelectrolyte of the field induction with opposite charges generate electrical coupling effect inside duct and realize
Self assembly, and complete the modification to bionic nano duct.This method of modifying has widened the range of choice of polyelectrolyte, institute significantly
There is polyelectrolyte that can modify by the self assembly between the polyelectrolyte of another oppositely charged to duct inner wall,
Including the polyelectrolyte with duct inner wall belt identical charges；And after modifying, the electric current of duct inner wall not will be greatly reduced, can be with
Realize good response effect.
Second object of the present invention is to provide a kind of bionic nano duct being prepared by above-mentioned method of modifying.
Third object of the present invention is that providing the bionic nano duct being prepared through above-mentioned method of modifying is preparing
The application received in terms of flowing device.
First goal of the invention to realize the present invention, the method for modifying in bionic nano duct provided by the invention, including
Following steps:
Substrate with bionic nano duct is placed between effectiveness type polyelectrolyte solution and pairing polyelectrolyte solution；
Wherein, the inner surface in the bionic nano duct has charge；Effectiveness type polyelectrolyte and pairing polyelectrolyte have opposite
Charge；
Under electric field induction, the effectiveness type polyelectrolyte and the pairing polyelectrolyte pass through in bionic nano duct
Self assembly is realized in electrical coupling effect, and completes the modification to bionic nano duct.
Preferably, the bionic nano duct is both ends aperture asymmetric bionic nano duct not of uniform size.
Preferably, the small one end in the asymmetric bionic nano duct aperture is towards effectiveness type polyelectrolyte solution side,
The big one end direction pairing polyelectrolyte solution side in the asymmetric bionic nano duct aperture.
Preferably, the base material with bionic nano duct includes polyethylene terephthalate, polyamides Asia
Amine, polycarbonate.
Further, the method for modifying in the bionic nano duct further includes the step that bionic nano duct is formed on the substrate
Suddenly；
Preferably, the method that the step of forming bionic nano duct on the substrate uses includes track etching method, mould
Plate method, ibl or electron beam lithography.
Preferably, the aperture in the bionic nano duct is 5nm-800nm；
Preferably, when the bionic nano duct is asymmetric bionic nano duct, the asymmetric bionic nano hole
The macropore stomidium diameter in road is 300nm-800nm.
Preferably, when the bionic nano duct is asymmetric bionic nano duct, the asymmetric bionic nano hole
The macropore stomidium diameter in road is 300nm-800nm, small aperture 5nm-80nm.
Preferably, the effectiveness type polyelectrolyte includes synthesis polyelectrolyte, the synthesis polyelectrolyte of chemical modification, biology
Macromolecular polyelectrolyte；The pairing polyelectrolyte includes that synthesis polyelectrolyte, the synthesis polyelectrolyte of chemical modification, biology are big
Molecule polyelectrolyte.
Preferably, the effectiveness type polyelectrolyte is selected from diallyl dimethyl ammoniumchloride or repairs through p-aminophenyl boric acid
One of Sodium Polyacrylate of decorations, the pairing polyelectrolyte are selected from kayexalate, polyallylamine hydrochloride, single-stranded
One of DNA molecular；
Preferably, when the effectiveness type polyelectrolyte is diallyl dimethyl ammoniumchloride, the poly- electrolysis of pairing
Matter is kayexalate or single strand dna；
Preferably, described to match when the effectiveness type polyelectrolyte is the Sodium Polyacrylate through p-aminophenyl boric acid modified
It is polyallylamine hydrochloride to polyelectrolyte.
Preferably, the mass concentration of the effectiveness type polyelectrolyte solution is 0.01%-10%, the pairing polyelectrolyte
The mass concentration of solution is 0.01%-10%；
Preferably, the mass concentration ratio of the effectiveness type polyelectrolyte solution and the pairing polyelectrolyte solution is 1:
0.5-2。
Second object of the present invention, be to provide it is a kind of obtained according to above-mentioned bionic nano duct method of modifying it is bionical
Nano pore.
The third object of the present invention is that provide the bionic nano duct being prepared through above-mentioned method of modifying receives in preparation
Flow the application in terms of device.
Beneficial effects of the present invention are as follows:
The present invention provides a kind of method of modifying in bionic nano hole, and this method is mainly by electric field induction with opposite
The effectiveness type polyelectrolyte and pairing polyelectrolyte of charge generate electrical coupling effect in bionic nano duct and realize self assembly, and
Complete the modification to bionic nano duct.The method of modifying has widened the range of choice of effectiveness type polyelectrolyte significantly, as long as logical
Cross the suitable pairing polyelectrolyte of selection, so that it may effectiveness type polyelectrolyte is modified to duct inner wall, including with institute in duct
Electrically charged identical effectiveness type polyelectrolyte；Secondly, the electric current in bionical duct, which will not generate, to be decreased obviously, effectively after modification
Guarantee the realization of response effect；And section the time required to modification, it may be implemented in 20min；In addition, the modification is reversible
, the recycling in bionic nano duct can be realized by going modification.
Detailed description of the invention
Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing.
Fig. 1, which is shown, modifies schematic device used by bionic nano duct in embodiment 2.
Fig. 2 shows the duct interior change schematic diagrames of bionic nano duct modification modification front and back in embodiment 2.
Fig. 3 shows the VA characteristic curve in the bionic nano duct being prepared in embodiment 1.
Fig. 4 shows the VA characteristic curve in the bionic nano duct modified in embodiment 2.
Fig. 5 shows the VA characteristic curve in the bionic nano duct for going modification to obtain in embodiment 5.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with attached in the embodiment of the present invention
Figure, is clearly and completely described technical solution of the present invention, it is clear that described embodiment is a part of the invention
Embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making wound
Every other embodiment obtained under the premise of the property made is worked, shall fall within the protection scope of the present invention.
First aspect present invention provides a kind of method of modifying in bionic nano duct, and the method for modifying includes following step
It is rapid:
Substrate with bionic nano duct is placed between effectiveness type polyelectrolyte solution and pairing polyelectrolyte solution；
Wherein, the inner surface in the bionic nano duct has charge；Effectiveness type polyelectrolyte and pairing polyelectrolyte have opposite
Charge；
Under electric field induction, the effectiveness type polyelectrolyte and pairing polyelectrolyte are handed in bionic nano duct by electricity
Self assembly is realized in connection effect, and completes the modification to bionic nano duct.
It illustrates, no matter effectiveness type polyelectrolyte of the present invention refers to those skilled in the art for which kind of
Purpose selection is wanted to be modified to the polyelectrolyte inside bionic nano duct；Effectiveness type polyelectrolyte can be to have and imitate
The polyelectrolyte of raw response signal, the Sodium Polyacrylate such as through p-aminophenyl boric acid modified are also possible to have change is bionical to receive
The polyelectrolyte of charge species in metre hole road, the present invention to the concrete type of effectiveness type polyelectrolyte and effect with no restriction, i.e.,
As long as those skilled in the art have motivation to be modified to bionical duct inner wall, all within protection scope of the present invention.?
It in modification, needs to guarantee inside the modification to duct enough within a short period of time of effectiveness type polyelectrolyte, play corresponding
Effect.Pairing polyelectrolyte of the present invention, refer to effectiveness type polyelectrolyte with opposite charges can be with effectiveness
Electrical coupling effect occurs for type polyelectrolyte, and effectiveness type polyelectrolyte is helped to pass through the self-assembled modified poly- electricity to inside nano pore
Xie Zhi.
In the present invention, as long as effectiveness type polyelectrolyte and pairing polyelectrolyte have opposite charge, other conditions are not
It is restricted, i.e. effectiveness type polyelectrolyte and pairing polyelectrolyte can externally show opposite charging property just all in guarantor of the invention
Within the scope of shield.
In the present invention, induction effectiveness type polyelectrolyte and pairing polyelectrolyte are spread into nano pore respectively
Its electrode of electric field is identical as two kinds of polyelectrolyte institute's charged species respectively.It is negative electricity that even effectiveness type polyelectrolyte institute is electrically charged
Lotus, then the electrode for being added in effectiveness type polyelectrolyte solution end is exactly cathode, pairing polyelectrolyte positively charged at this time be exactly
It is spread under the action of electric field into nano pore, and then generation self assembly is acted on by electrical coupling with effectiveness type polyelectrolyte and is repaired
Decorations realize the charge regulation in duct and response sex modification to duct inner wall.
According to some specific embodiments, in the present invention, used bionic nano duct is inner surface with electricity
The both ends aperture of lotus asymmetric bionic nano duct not of uniform size.
According to some preferred embodiments, the small one end in the asymmetric bionic nano duct aperture is poly- towards effectiveness type
Electrolyte solution side, the big one end direction pairing polyelectrolyte solution side in the asymmetric bionic nano duct aperture.
The pore size at nano pore both ends is inconsistent, under the action of electric double layer effect, the electricity of big nose end and small bore end
Chemical environment can generate certain difference.Simultaneously because the inner surface in asymmetric duct has charge, therefore, it is located at duct both ends
Polyelectrolyte under the action of electric field and inner surfaces of pores charge, asymmetric distribution is realized inside duct, have phase
Charge neutrality will not occur in duct and react to form macromolecular so that blocking duct inner wall for the polyelectrolyte of counter charges, but logical
It crosses electrical coupling to act in mutual self assembly to nano pore wall, completes the modification in bionic nano duct.It will be asymmetric imitative
The small one end in raw nano pore aperture is conducive to effectiveness type polyelectrolyte after modification towards effectiveness type polyelectrolyte solution side
Duct in occupy an leading position.
The present invention be directed to nano pore flux after the modification time of existing surface carboxyl groups activation method length, modification to decline, imitative
Raw duct is difficult to response unit in the problem of reusing and polyelectrolyte absorption method and selects restricted disadvantage, and provides
It is a kind of using have different charges polyelectrolyte, electric field induction under from the both ends in bionical hole enter inside duct realize from
It assembles and modifies to the bionic nano duct method of modifying of duct inner wall, this method is while overcoming prior art disadvantage, also
The advantages of comprehensive two kinds of different technologies.
The present invention has widened the range of choice of effectiveness type polyelectrolyte significantly, the method for modifying provided according to the present invention, only
To pass through the suitable pairing polyelectrolyte of selection, so that it may effectiveness type polyelectrolyte is modified to duct inner wall, including with duct
The interior electrically charged identical effectiveness type polyelectrolyte of institute.Therefore method of modifying provided by the invention is overcoming polyelectrolyte absorption method only
Can selection in duct electrically charged this disadvantage of opposite polyelectrolyte while, can also will be mature in activated carboxylic method
It responds molecule and response unit system is used into method of modifying provided by the invention.
In addition, method of modifying of the invention is by effectiveness type polyelectrolyte and pairing polyelectrolyte with opposite charges
Between electrical coupling effect realize self assembling process, it is faster compared with the covalent bond modification in activated carboxylic method.
It in the present invention, is to be interacted between polyelectrolyte by electrical coupling in bionic nano duct, therefore it will not
There is the case where a large amount of charged groups disappear in nano pore, so bionic nano duct is after modification, corresponding effect can be with
It is effectively guaranteed.
In the present invention, make since method of modifying provided by the invention is mainly based upon the electrical coupling between polyelectrolyte
With, therefore there is invertibity, by the immersion of saturated salt solution, destroy polyelectrolyte and inner surfaces of pores and polyelectrolyte phase
Charge effect between mutually, and then under the action of high electric-field intensity, polyelectrolyte can diffuse to except nano pore, be gone
Modification, it is available to go to modify later bionic nano duct, and then realize the recycling in bionic nano duct.
According to some specific embodiments, the base material with bionic nano duct includes poly terephthalic acid
Glycol ester, polyimides, polycarbonate.
According to some specific embodiments, the method for modifying in the bionic nano duct further comprises in substrate
The step of forming bionic nano duct；
According to some preferred embodiments, the method packet that the step of formation bionic nano duct uses on the substrate
Include track etching method, template, ibl or electron beam lithography.
According to some specific embodiments, the aperture in the bionic nano duct is 5-800nm；For example, described bionical
The aperture of nano pore can also be but be not limited to 10-750nm, 20-700nm, 30-650nm, 40-600nm, 50-550nm,
60-500nm, 70-450nm, 80-400nm, 90-350nm or 100-300nm etc..
According to some specific embodiments, in the present invention, the macropore stomidium diameter in the asymmetric bionic nano duct
For 300nm-800nm.
According to some preferred embodiments, in the present invention, the macropore stomidium diameter in the asymmetric bionic nano duct
For 300nm-800nm, small bore end aperture is 5nm-80nm.
According to some preferred embodiments, for example, the macropore stomidium diameter in the bionic nano duct can also be but not
It is limited to 350-750nm, 400-700nm, 450-650nm or 500-600nm etc.；The small bore end aperture can also be but be not limited to
8-75nm, 10-70nm, 13-65nm, 16-60nm, 19-55nm, 22-50nm or 25-45nm etc..
According to some specific embodiments, the effectiveness type polyelectrolyte and pairing polyelectrolyte include synthesizing poly- electricity
Xie Zhi, synthesis polyelectrolyte, the large biological molecule polyelectrolyte that upper functional unit is modified as desired by chemical mode.
According to some preferred embodiments, the effectiveness type polyelectrolyte is selected from diallyldimethylammonium chloride or warp
One of the Sodium Polyacrylate of p-aminophenyl boric acid modified, the pairing polyelectrolyte are selected from kayexalate, poly- third
One of enamine hydrochloride, single strand dna.
According to some preferred embodiments, when the effectiveness type polyelectrolyte is diallyl dimethyl ammoniumchloride
When, the pairing polyelectrolyte is kayexalate or single strand dna；
According to some preferred embodiments, when the effectiveness type polyelectrolyte is poly- third through p-aminophenyl boric acid modified
When olefin(e) acid sodium, the pairing polyelectrolyte is polyallylamine hydrochloride.
According to some specific embodiments, the mass concentration of the effectiveness type polyelectrolyte solution is 0.01%-10%,
The mass concentration of the pairing polyelectrolyte solution is 0.01%-10%.
According to some preferred embodiments, for example, the mass concentration of the effectiveness type polyelectrolyte solution can also be
But be not limited to 0.02%-9%, 0.03%-8%, 0.04%-7%, 0.05%-6%, 0.06%-5% or 1%-4% etc..
According to some preferred embodiments, for example, the mass concentration of the pairing polyelectrolyte solution can also be but
It is not limited to 0.02%-9%, 0.03%-8%, 0.04%-7%, 0.05%-6%, 0.06%-5% or 1%-4% etc..
According to some preferred embodiments, the effectiveness type polyelectrolyte solution and the pairing polyelectrolyte solution
Mass concentration ratio is 1:0.5-2.
According to some specific embodiments, the induction effectiveness type polyelectrolyte and pairing polyelectrolyte diffuse to bionical
Electric field inside nano pore is generated by the 1V voltage being added on electrode plate.
Second aspect of the present invention provide a kind of method of modifying using above-mentioned bionic nano duct be prepared it is bionical
Nano pore.
Third aspect present invention, which provides the bionic nano duct being prepared through above-mentioned method of modifying and receives in preparation, flows device
Application in terms of part.
Hereafter the present invention will be further detailed by way of example, but protection scope of the present invention is unlimited
In these embodiments.
Embodiment 1
Prepare asymmetric bionic nano duct
To polyimides (PI) film of heavy ion bombardment, the method etched using track prepares asymmetrical nanometer
Duct, wherein used etching liquid is the NaClO solution that available chlorine content is 14%, preventing liquid is the solution of 1M KI, 60
At DEG C, 3.5h is etched, after being cleaned with deionized water, it is the PI in the asymmetric bionic nano duct of 300nm that obtaining, which has large aperture,
Film.
Using Ag/AgCl electrode, test -2.0V~2.0V measures its volt-ampere by interval of 0.2V in 0.1M KCl solution
Characteristic curve, it is 28 that electric current when with -2.0V and 2.0V, which calculates commutating ratio, and VA characteristic curve is as shown in Figure 3.
Embodiment 2
Modify asymmetric bionic nano duct
As shown in Figure 1, it is 5% that the PI film with asymmetrical nano pore prepared by embodiment 1, which is placed in mass concentration,
Diallyl dimethyl ammoniumchloride (PDMC) solution and mass concentration be 7% poly- kayexalate (PSS) solution
Between, wherein the small bore end that PI film is set is towards PDMC solution side, and big nose end is towards PSS solution side.Apply 1V electricity using Pt electrode
Pressure, wherein the platinum electrode in PSS solution is cathode, and the platinum electrode in PDMC solution is anode, after applying electric field 400s, by PI film
It takes out, is then cleaned with deionized water, obtain the PI film with the bionic nano duct after modification.
Using Ag/AgCl electrode, test -2.0V~2.0V measures its volt-ampere by interval of 0.2V in 0.1M KCl solution
Characteristic curve, it is -191 that electric current when with -2.0V and 2.0V, which calculates commutating ratio, and VA characteristic curve is as shown in Figure 4.
Compare Fig. 3 and Fig. 4 it can be found that rectification in bionic nano duct inverts on PI film after modification.
Embodiment 3
Modify asymmetric bionic nano duct
Device refering to what is shown in Fig. 1, but effectiveness type polyelectrolyte solution and pairing polyelectrolyte solution change, specifically
For the PI film with asymmetrical nano pore for preparing embodiment 1 is placed in the polyallylamine hydrochloride that mass concentration is 2%
(PAAm) solution and mass concentration be between 3% Sodium Polyacrylate (PAANa-APBA) solution through p-aminophenyl boric acid modified,
Wherein, the big nose end that PI film is set is towards PAAm solution side, and small bore end is towards PAANa-APBA solution side.Apply 1V using Pt electrode
Voltage, wherein the platinum electrode in PAANa-APBA solution is cathode, and the platinum electrode in PAAm solution is anode, applies electric field 400s
Afterwards, PI film is taken out, is then cleaned with deionized water, obtain the PI film with the bionic nano duct after modification.
Using Ag/AgCl electrode, respectively in 0.1M NaNO3The 0.1M NaNO of solution and the KF containing 100nM3It is surveyed in solution
Examination -2.0V~2.0V surveys its VA characteristic curve by interval of 0.2V, compares curent change when its -2V, it can be observed that repairing
Duct after decorations generates great curent change compared with the duct before modification in the environment for having fluorine ion, and commutating ratio
Change also more obvious, the commutating ratio of nano pore specifically: be 6.8 (free-florides) and 8.1 (having fluorine) before modification, be 22 after modification
(free-floride) and 39 (having fluorine).
Using Ag/AgCl electrode, respectively in 0.1M NaNO3The 0.1M NaNO of solution and the glucose containing 100mM3In solution
Test -2.0V~2.0V surveys its VA characteristic curve by interval of 0.2V, compares its rectification variation, it can be observed that after modification
Duct compared with the duct before modification, more obvious rectification promotion is generated in the environment for having glucose, by 7 promoted to
24。
Embodiment 4
Modify asymmetric bionic nano duct
Device refering to what is shown in Fig. 1, but effectiveness type polyelectrolyte solution and pairing polyelectrolyte solution change, specifically
For the PI film with asymmetrical nano pore for preparing embodiment 1 is placed in the DNA single-stranded (5 '-that concentration is 10 μM
(NH2C6)-AAAAAA-3 ') solution and mass concentration between 0.05% diallyl dimethyl ammoniumchloride (PDMC) solution,
Wherein, the big nose end that PI film is set is towards the single-stranded solution side of DNA, and small bore end is towards PDMC solution side.Apply 1V electricity using Pt electrode
, wherein the platinum electrode in DNA solution is cathode, and the platinum electrode in PDMC solution is anode, after applying electric field 1200s, by PI
Film takes out, and is then cleaned with deionized water, obtains the PI film with the bionic nano duct after modification.
Using Ag/AgCl electrode, test -2.0V~2.0V measures volt-ampere spy by interval of 0.2V in 0.1M KCl solution
Linearity curve, the commutating ratio that electric current when with -2.0V and 2.0V calculates modification front and back is respectively 24 and -2, modifies the IV curve of front and back
It will be observed that rectification reversion, it was demonstrated that and large biological molecule polyelectrolyte (such as: single stranded DNA) it can be used as pairing polyelectrolyte
It is used to modify.
Embodiment 5
It goes to modify asymmetric bionic nano duct
By embodiment 2 modify after PI film be soaked into saturated sodium chloride solution, for 24 hours after, in saturated sodium chloride solution
The voltage for the use of platinum electrode application -8.8V~8.8V step-length being 1.1V, scans 300 circulations, then takes out PI film.
Using Ag/AgCl electrode, test -2.0V~2.0V measures its volt-ampere by interval of 0.2V in 0.1M KCl solution
Characteristic curve, result are as shown in Figure 5.Comparison diagram 3 and Fig. 5 can be found that electric current of the nano pore in -2V in same number
Magnitude, it was demonstrated that nano pore may be reused.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
With to technical solution documented by foregoing embodiments, shape and aperture size such as to bionic nano hole, polyelectrolyte are molten
Liquid concentration etc. is modified；Or to part of technical characteristic, such as the material of the type of polyelectrolyte, bionic nano hole substrate
Etc. being equivalently replaced；And these are modified or replaceed, various embodiments of the present invention that it does not separate the essence of the corresponding technical solution
The spirit and scope of technical solution.
Claims (10)
1. a kind of method of modifying in bionic nano duct, which comprises the following steps:
Substrate with bionic nano duct is placed between effectiveness type polyelectrolyte solution and pairing polyelectrolyte solution；Its
In, the inner surface in the bionic nano duct has charge；Effectiveness type polyelectrolyte and pairing polyelectrolyte have opposite electricity
Lotus；
Under electric field induction, the effectiveness type polyelectrolyte and pairing polyelectrolyte are made in bionic nano duct by electrical coupling
With realizing self assembly, and complete modification to bionic nano duct.
2. the method for modifying in bionic nano duct according to claim 1, which is characterized in that the bionic nano duct is two
Stomidium diameter asymmetric bionic nano duct not of uniform size；Preferably, the asymmetric bionic nano duct aperture it is small one
End is electrolysed towards effectiveness type polyelectrolyte solution side, the big one end in the asymmetric bionic nano duct aperture towards pairing is poly-
Matter solution side.
3. the method for modifying in bionic nano duct according to claim 1, which is characterized in that described that there is bionic nano hole
The base material in road includes polyethylene terephthalate, polyimides, polycarbonate.
4. according to claim 1 or the method for modifying in the 3 bionic nano ducts, which is characterized in that the method for modifying is into one
Step includes the steps that bionic nano duct is formed on the substrate；Preferably, the step in bionic nano duct is formed on the substrate
Suddenly the method used includes track etching method, template, ibl or electron beam lithography.
5. the method for modifying in bionic nano duct according to claim 1, which is characterized in that the hole in the bionic nano duct
Diameter is 5nm-800nm；Preferably, described asymmetric bionical when the bionic nano duct is asymmetric bionic nano duct
The macropore stomidium diameter of nano pore is 300nm-800nm；Preferably, when the bionic nano duct is asymmetric bionic nano hole
When road, the macropore stomidium diameter in the asymmetric bionic nano duct is 300nm-800nm, and small bore end aperture is 5nm-80nm.
6. the method for modifying in bionic nano duct according to claim 1, which is characterized in that the effectiveness type polyelectrolyte packet
Include synthesis polyelectrolyte, the synthesis polyelectrolyte of chemical modification, large biological molecule polyelectrolyte；The pairing polyelectrolyte includes
Synthesis polyelectrolyte, the synthesis polyelectrolyte of chemical modification, large biological molecule polyelectrolyte.
7. the method for modifying in bionic nano duct according to claim 1, which is characterized in that the effectiveness type polyelectrolyte choosing
From one of diallyl dimethyl ammoniumchloride or the Sodium Polyacrylate through p-aminophenyl boric acid modified, the poly- electricity of pairing
It solves matter and is selected from one of kayexalate, polyallylamine hydrochloride, single strand dna；
Preferably, when the effectiveness type polyelectrolyte is diallyl dimethyl ammoniumchloride, the pairing polyelectrolyte is
Kayexalate or single strand dna；
Preferably, when the effectiveness type polyelectrolyte is the Sodium Polyacrylate through p-aminophenyl boric acid modified, the pairing is poly-
Electrolyte is polyallylamine hydrochloride.
8. the method for modifying in bionic nano duct according to claim 1, which is characterized in that the effectiveness type polyelectrolyte is molten
The mass concentration of liquid is 0.01%-10%, and the mass concentration of the pairing polyelectrolyte solution is 0.01%-10%；Preferably,
The mass concentration ratio of the effectiveness type polyelectrolyte solution and the pairing polyelectrolyte solution is 1:0.5-2.
9. a kind of bionic nano duct that the method for modifying in the bionic nano duct as described in claim 1-8 is prepared.
10. a kind of application of bionic nano duct as claimed in claim 9 in terms of stream device is received in preparation.
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