CN1295345C - NDA nano network braided carbon electrode and its preparation method - Google Patents
NDA nano network braided carbon electrode and its preparation method Download PDFInfo
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- CN1295345C CN1295345C CNB031321496A CN03132149A CN1295345C CN 1295345 C CN1295345 C CN 1295345C CN B031321496 A CNB031321496 A CN B031321496A CN 03132149 A CN03132149 A CN 03132149A CN 1295345 C CN1295345 C CN 1295345C
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Abstract
The present invention relates to a DNA nanometer network braiding carbon electrode and a preparation method thereof, which is characterized in that a carbon basis electrode is put in a DNA solution having the concentration of 1 mu g/ml to 5 mg/ml; staggered overlapped DNA with molecule chains fully stretched is deposited on the surface of a carbon-based electrode under the 1.5 to 2.2V exerted electrode potential corresponding to a 50 mmol/L NaCl-Ag/AgCl reference electrode; meshes and screen wires assembled and braided by itself is a three-dimensional net-shaped structure with nanometer scale; the DNA is connected with the basis electrode by electric conducting chemical bonds; the effective surface area of the electrode is increased by 100 to 1000 times, the sensitivity of a voltampere response is enhanced by 50 to 600 times, and the dimension of the electrode is not obviously increased; a high-performance DNA electrochemical sensor is used in a solution at 100 DEG C, and the pH value of the solution is from 3 to 12. The present invention can be used for micro-electrochemical probes, new energy storage electrodes and release control electrodes of new medicines.
Description
Technical field:
The invention belongs to electroanalytical chemistry, biosensor technology field, particularly relate to DNA self-assembled nanometer Network Weaving carbon dioxide process carbon electrode and preparation method thereof.
Background technology:
" biological chemistry (on) " (China's higher education press, 1990, p329) point out, thymus nucleic acid (DNA) is to be the spirrillum long-chain heteropolymer molecule of skeleton with phosphoric acid-pentose, contain gland and look sidelong at purine (A), bird is looked sidelong at purine (G), cytosine(Cyt) (C), four bases of thymus pyrimidine (T), and by the genetic information of these four alkali yl codings record living species, DNA be on the earth except that RNA viruses all life common genophores, addressable structure with a kind of nanoscale, therefore, store in information, nanometer biotechnology, aspects such as biological chemistry sensing have broad application prospects.For example U.S. Pat 5,591, and 578; US5,705,348; US5,780,234; US5,770,369; US6,238,870 all on the DNA chain grappling donor-receiver right, this donor-receiver injects electronics and receives electronics, the directed flow of electronics on the guiding dna molecular plaing a part respectively.But aforesaid method need adopt special chemically modified means, and certain metal complex of the specific position grappling on DNA is as giving body group or acceptor groups.In fact, without polishing just can directly absorption of dna molecular is assembled on the electrode surface, but so immobilized effect is unsatisfactory, and the electrochemical sensor current sensitivity of made is lower.Existing as U.S.'s " electroanalysis " (Electroanalysis, 1992,4:929-932) report that can use active coupling reagent catalytic dna to set up covalent linkage with electrode is connected, but used DNA only limits to contain the specific single stranded DNA of G base and/or C base, therefore limitation is arranged; Holland's " biosensor and biological electronics " (Biosensors﹠amp is arranged recently; Bioelectronics, 2003,18:555-564) report stretches double chain DNA molecule with two-dimensional electrophoresis and is connected method between the diverging electrodes of gold or aluminium, but requires the distance of interdigital of diverging electrodes quite little, only several microns are not suitable for operating on conventional electrodes.U.S.'s " Langmuir " (Langmuir, 2003,19:3830-3839) also reported the absorption assembling of dna molecular on the regular pyrolytic graphite of height, but DNA makes dna molecular stable inadequately a little less than the adsorption on the pyrolytic graphite.
Summary of the invention:
The invention provides a kind of DNA nanometer network braiding carbon dioxide process carbon electrode and preparation method thereof, directly carrying out the covalent linkage conduction with 3 of DNA ' end and electrode is connected, can make the electrode effective surface area increase to 100～1000 times of base carbon electrode, a volt-ampere response sensitivity increases to 50～600 times.
The preparation method of DNA nanometer network of the present invention braiding carbon dioxide process carbon electrode is characterized in that: with carbon material basic electrode in the dna solution of suitably preparation, applying under the electropotential, DNA is carried out electrochemical deposition;
The dna solution of described suitable preparation comprises that with pure water or the pH scope that contains 0～100mmol/L NaCl be 5.0～8.0 Tutofusin tris buffered soln (Tris), hac buffer or phosphate buffer solution as the concentration of the solvent dna solution at 1 μ g/ml～5mg/ml;
The described electropotential that applies is the DC stabilization current potential with respect to 50mmol/L NaCl-Ag/AgCl reference electrode that applies at electrode surface, and scope is at 1.5～2.2V.
Can also carry out alkaline purification or thermal treatment to the electrode of above-mentioned prepared acquisition.
Described alkaline purification is to soak 5～10 minutes in the NaOH of pH12～14 solution, removes adsorbed molecules, and the hydrolytically unstable chemistry is built, with the chemical property of stabilized electrodes.
Described thermal treatment is to soak 3～5 minutes in 80～100 ℃ of hot water, allows the dna molecular sex change of electrode surface, so that electrode is suitable for working in hot solution.
DNA nanometer network braiding carbon dioxide process carbon electrode of the present invention by method for preparing, it is characterized in that depositing on carbon material basic electrode surface that the molecule chain fully trails, crisscross, the mutual folded DNA that connects, the mesh that self-assembly is woven into, netting twine are the tridimensional network of nanoscale;
Described carbon material basic electrode comprises carbon fiber electrode, glassy carbon electrode, Graphite Electrodes, high regular pyrolytic graphite electrode or carbon nanomaterial electrode.
Described DNA comprises the DNA that purifies in the biology, the DNA of synthetic, and passes through the DNA that thermally denature is unwind.
DNA nanometer network braiding carbon dioxide process carbon electrode of the present invention, owing under the electropotential that accurately applies, carry out electrochemical deposition, make its DNA settling self-assembly braiding form nanometer network, with 3 of DNA ' end with carbon-based electrode between set up the good covalent linkage of firm electroconductibility and be connected, make the electrode effective surface area increase 100～1000 times, but significantly do not increase electrode size; Not hydrolysis comes off in the strong alkali solution of pH12～14, becomes high performance electrochemical sensor.Because 3 of dna molecular ' end can interact with carbon electrodes and be combined into key, so can be used for preparing the DNA of nanometer network braiding carbon dioxide process carbon electrode of the present invention, comprise the DNA that purifies in the biology, the DNA of synthetic, and the DNA that unwinds of process thermally denature.
Compared with prior art, DNA nanometer network braiding carbon dioxide process carbon electrode of the present invention has following advantage:
The present invention is owing to carry out the electrochemical deposition of DNA nanometer network braiding carbon dioxide process carbon electrode under the electropotential that accurately applies, realized that dna molecular connects and assembling in the firm conduction of electrode surface, this is the self-assembled modified mode of a kind of new DNA, directly carrying out the covalent linkage conduction with 3 of DNA ' end and electrode is connected, do not need grappling electron donor(ED) or acceptor groups on DNA in advance, also not by being adsorbed on the electrode surface deposition, more do not need active coupling reagent, both can on conventional electrodes, operate, also can on small or ultra micro small electrode, operate; Since in the DNA braid dna molecular chain intersect, overlapping and interconnect, be woven into nanometer network in the self-assembly of support carbon electrodes, and with carbon-based electrode between have good being connected of firm electroconductibility, make the electrode effective surface area increase 100～1000 times, can be used as a kind of novel energy or medicine storage electrode; Owing to have good being connected of firm electroconductibility between DNA braid and carbon-based electrode, make the volt-ampere response sensitivity of electrode improve 50～600 times, can be used for the research and the monitoring of lower concentration, small number of molecules.Because DNA nanometer network of the present invention braiding electrode, be mesh, netting twine three-dimensional structure at nanoscale, can not cause the obvious increase of electrode apparent size; DNA braiding electrode of the present invention is become by dna molecular self-assembly under the CONTROLLED POTENTIAL effect, and manufacturing conditions is controlled easily, does not need the nano-manipulation technology, promotes the use of easily.DNA braiding electrode of the present invention is if handle through highly basic, and then the pH performance is better, can use in the medium of pH3～12 wide regions; If through boiling water thermal treatment, then thermostability is better, can use in 100 ℃ of following hot solution.Electrode of the present invention is a kind of high performance electrochemical sensor.Because nanometer network braiding carbon dioxide process carbon electrode of the present invention can use the DNA that purifies in the biology, the DNA of synthetic, and through the DNA that thermally denature is unwind, has enriched the type of DNA electrochemical sensor.
Description of drawings:
Fig. 1 is that the natural double-stranded calf thymus DNA modified electrode of carbon fiber plate is at 5mmol/L pH7.1 Tris-HCl+50mmol/L NaCl+0.3m mol/L Co (phen)
3 3+Cyclic voltammogram in the solution.
Fig. 2 is Co on the carbon fiber plate basic electrode (phen)
3 3+Cyclic voltammogram.
Fig. 3 is Co (phen) on the carbon fiber plate strand calf thymus DNA modified electrode
3 3+Cyclic voltammogram.
Fig. 4 is the natural double-stranded calf thymus DNA modified electrode of carbon fiber plate, and Co (phen) after 3 minutes is handled in boiling through 10mmol/L Tris buffered soln
3 3+Cyclic voltammogram.
Fig. 5 is the natural double-stranded calf thymus DNA modified electrode of carbon fiber plate, with 10 minutes front and back of 0.2mol/L NaOH solution soaking Co (phen)
3 3+Cyclic voltammetry curve figure.
Fig. 6 is that the atomic force microscope downward view is the immobilized pattern photo of the nanometer network weave diagram of natural double-stranded calf thymus DNA on the regular pyrolytic graphite electrode of height of 1 μ m * 1 μ m.
Fig. 7 is the differentiated pulse voltammogram that the natural double-stranded calf thymus DNA modified electrode of carbon fiber plate is measured DOPAMINE CONTENT IN RABBIT in the solution.
Fig. 8 is the differentiated pulse voltammogram of Dopamine HCL on the used carbon fiber plate basic electrode of the present invention.
Embodiment:
Embodiment 1: carbon fiber plate double-stranded DNA modified electrode
The natural double-stranded calf thymus DNA for preparing is dissolved in Tutofusin tris pH7 buffered soln (Tris) solution that contains 50mmol/L NaCl, insert 6 micron diameter carbon fiber plate electrodes, apply 1.5～2.2V took out with respect to the current potential maintenance of 50mmol/L NaCl-Ag/AgCl in 30 minutes, rinse well with redistilled water, place air to dry naturally.
This electrode is inserted 5mmol/L pH7.1 Tris-HCl+50mmol/L NaCl+0.3mmol/L Co (phen)
3 3+In the solution, under 50mV/s, survey the cyclic voltammetric characteristic, obtain accompanying drawing 1; Basic carbon fiber plate electrode is inserted in the above-mentioned identical solution, under 50mV/s, survey the cyclic voltammetric characteristic, obtain accompanying drawing 2.
Cycle charging electric current (1) and Co (phen) with this electrode in the accompanying drawing 1
3 3+The cycle charging electric current (3) and the Co (phen) of basic carbon fiber plate electrode in reduction peak height (2) and the accompanying drawing 2
3 3+Reduction peak height (4) is compared as can be known, and the carbon fiber plate double-stranded DNA modified electrode of present embodiment preparation has improved 500 times than basic carbon fiber plate electrode charging current, and reduction peak has improved 200 times.
Be Co (phen)
3 3+The differentiated pulse volt-ampere (DPV) of reduction process compares, and the DPV peak current of the carbon fiber plate double-stranded DNA modified electrode of present embodiment preparation has improved 600 times than basic electrode.
Embodiment 2: carbon fiber plate single stranded DNA modified electrode
With the quenching after 100 ℃ of boiling water unwind of natural double-stranded calf thymus DNA, obtain single stranded DNA solution.With diameter is that 6 microns carbon fiber plate working electrode inserts in this single stranded DNA solution, applies 1.5～2.2V with respect to the current potential of 50mmol/LNaCl-Ag/AgCl and keep taking out after 30 minutes, and washing is clean, places Co (phen)
3 3+In the solution, under 50mV/s, survey the cyclic voltammetric characteristic, obtain accompanying drawing 3, and compare as seen with the cyclic voltammetric performance chart accompanying drawing 2 of basic carbon fiber plate electrode, the cycle charging electric current (5) of the carbon fiber plate single stranded DNA modified electrode of present embodiment preparation has improved 230 times than basic carbon fiber plate electrode, Co (phen)
3 3+Reduction peak height (6) has improved 154 times.
Be Co (phen)
3 3+The DPV of reduction process compares as can be known with the DPV of basic electrode, and the DPV peak current of the carbon fiber plate single stranded DNA modified electrode of present embodiment preparation increases 500 times than basic electrode.
Embodiment 3: the thermal treatment of carbon fiber plate double-stranded DNA modified electrode
With embodiment 1 prepared carbon fiber plate double-stranded DNA modified electrode, immerse Tris buffered soln boiling 3 minutes, to take out, washing is clean, places Co (phen)
3 3+In the solution, do cyclic voltammetry scan, the results are shown in accompanying drawing 4.
Cyclic voltammetry curve by the modified electrode before the cyclic voltammetry curve in the accompanying drawing 4 and the thermal treatment is compared, and as can be known: the cycle charging electric current (7) of thermal treatment rear electrode increases 1 times (be the equal of basic carbon fiber plate electrode 1000 times), Co (phen)
3 3+Reduction peak height (8) is reduced to 25% (still be equivalent to basic carbon fiber plate electrode 50 times).
Embodiment 4: the alkaline purification of carbon fiber plate double-stranded DNA modified electrode
The carbon fiber plate double-stranded DNA modified electrode that embodiment 1 is prepared inserts in the 0.2mol/L NaOH aqueous solution and soaked 10 minutes, takes out, and washing is clean, inserts Co (phen)
3 3+Do cyclic voltammetry scan in the solution, the results are shown in accompanying drawing 5.The cyclic voltammetry curve (9) of alkaline purification rear electrode is compared Co (phen) with the cyclic voltammetry curve (10) of the electrode that does not carry out alkaline purification
3 3+The height of reduction peak slightly reduce, the cycle charging electric current slightly increases, but not clearly.
Embodiment 5: the self-assembled nanometer Network Weaving of double-stranded calf thymus DNA on the regular pyrolytic graphite electrode of height
Calf thymus DNA is dissolved in the Tutofusin tris buffered soln (Tris) that contains 50mmol/L NaCl, immerse high regular pyrolytic graphite working electrode, apply 1.5～2.2V with respect to the electropotential of 50mmol/L NaCl-Ag/AgCl and keep taking out after 30 minutes, rinse well with redistilled water, place air to dry naturally, the immobilized pattern of visible DNA under atomic force microscope, its visual field be 1 μ m * 1 μ m photo as shown in Figure 6, visible molecule chain fully trails from photo, crisscross, the mesh that the folded mutually DNA that connects is self-assembled into, the netting twine degree is all at the three-dimensional network braiding structure of the nanoscale of 10nm～100nm.
Embodiment 6: carbon fiber plate double-stranded DNA modified electrode surface adsorption and electrochemical catalytic oxidation neurotransmitter dopamine
With embodiment 1 prepared carbon fiber plate double-stranded DNA modified electrode, immersion contains to be done differentiated pulse volt-ampere (DPV) and measures in the 5mmol/L pH7.1 Tris-HCl+50mmol/L NaCl solution of 0.5mmol/L Dopamine HCL, its pulse parameter: height 25mV, width 0.1s, sampling time 0.0167s, time of lag 0.2s, stride 8mV; Its differentiated pulse volt-ampere (DPV) curve as shown in Figure 7.As seen this Fig. 7 curve is compared with the DPV curve of base carbon disc electrode shown in Figure 8, and the DPV peak current (11) of Dopamine HCL electrochemical oxidation has improved 490 times than the DPV peak current (12) with the base carbon disc electrode.
Claims (4)
1, the preparation method of a kind of DNA nanometer network braiding carbon dioxide process carbon electrode is characterized in that: with carbon material basic electrode in the dna solution of suitably preparation, applying under the electropotential, DNA is carried out electrochemical deposition;
Described carbon material basic electrode comprises carbon fiber electrode, glassy carbon electrode, Graphite Electrodes, high regular pyrolytic graphite electrode or carbon nanomaterial electrode;
Described DNA comprises the DNA that purifies in the biology, the DNA of synthetic, and passes through the DNA that thermally denature is unwind;
The dna solution of described suitable preparation comprises that with pure water or the pH scope that contains 0～100mmol/L NaCl be 5.0～8.0 Tutofusin tris buffered soln (Tris), hac buffer or phosphate buffer solution as the concentration of the solvent dna solution at 1 μ g/ml～5mg/ml;
The described electropotential that applies is the DC stabilization current potential with respect to 50mmol/L NaCl-Ag/AgCl reference electrode that applies at electrode surface, and scope is at 1.5～2.2V.
2, the preparation method of DNA nanometer network as claimed in claim 1 braiding carbon dioxide process carbon electrode is characterized in that the electrode that is obtained soaked in the NaOH of pH12～14 solution and carried out alkaline purification in 5～10 minutes.
3, the preparation method of DNA nanometer network as claimed in claim 1 braiding carbon dioxide process carbon electrode is characterized in that the electrode that is obtained soaked in 80～100 ℃ of hot water and heat-treated in 3～5 minutes.
4, a kind of DNA nanometer network braiding carbon dioxide process carbon electrode by the preparation of claim 1 method, it is characterized in that depositing on carbon material basic electrode surface that the molecule chain fully trails, crisscross, the mutual folded DNA that connects, the mesh that self-assembly is woven into, netting twine are the tridimensional network of nanoscale;
Described carbon material basic electrode comprises carbon fiber electrode, glassy carbon electrode, Graphite Electrodes, high regular pyrolytic graphite electrode or carbon nanomaterial electrode;
Described DNA comprises the DNA that purifies in the biology, the DNA of synthetic, and passes through the DNA that thermally denature is unwind.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8613200B2 (en) | 2008-10-23 | 2013-12-24 | Bsst Llc | Heater-cooler with bithermal thermoelectric device |
| US9293680B2 (en) | 2011-06-06 | 2016-03-22 | Gentherm Incorporated | Cartridge-based thermoelectric systems |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101271079B (en) * | 2008-05-07 | 2010-12-08 | 天津大学 | Glass carbon electrode decorated by carbon nano tube-DNA complex and its production method and application |
| CN104391018B (en) * | 2014-10-22 | 2017-01-18 | 西北大学 | Three-dimensional DNA nano-structure, electrochemical biosensor as well as preparation methods and application thereof |
| CN105353020B (en) * | 2015-12-06 | 2017-12-01 | 北京工业大学 | The method that modifying DNA is combined with graphene |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010053522A1 (en) * | 2000-04-28 | 2001-12-20 | Fuji Photo Film Co., Ltd. | DNA chip and reactive electrode |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20010053522A1 (en) * | 2000-04-28 | 2001-12-20 | Fuji Photo Film Co., Ltd. | DNA chip and reactive electrode |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8613200B2 (en) | 2008-10-23 | 2013-12-24 | Bsst Llc | Heater-cooler with bithermal thermoelectric device |
| US9293680B2 (en) | 2011-06-06 | 2016-03-22 | Gentherm Incorporated | Cartridge-based thermoelectric systems |
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