CN102320564A - Nanopore preparation method based on tungsten needle tip and thick-wall glass tube - Google Patents
Nanopore preparation method based on tungsten needle tip and thick-wall glass tube Download PDFInfo
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- CN102320564A CN102320564A CN201110257948A CN201110257948A CN102320564A CN 102320564 A CN102320564 A CN 102320564A CN 201110257948 A CN201110257948 A CN 201110257948A CN 201110257948 A CN201110257948 A CN 201110257948A CN 102320564 A CN102320564 A CN 102320564A
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Abstract
The invention discloses a nanopore preparation method based on a tungsten needle tip and a thick-wall glass tube, which relates to a glass tube nanopore. The method comprises the following steps of: preparing the tungsten needle tip; encapsulating the tungsten needle tip with the glass tube, and preparing a tungsten nano disk electrode; and etching the encapsulated tungsten needle tip to obtain the glass nanopore. A tungsten wire is cheap, and has the characteristics of high hardness, high melting point, small expansion coefficient and the like. Electrochemical etching preparation method for the tungsten needle tip is efficient, particularly, the coefficient of thermal expansion of the tungsten is much smaller than that of the glass, so that desired encapsulation result can be obtained just by using a normal thick-wall glass tube. Thick-wall and regular-size glass tubes are used for preparation of the nanopore, and the thick-wall and regular-size glass tubes are not easy to be broken off in the preparation process and have excellent operability, so that the preparation success rate is high, and research result of a subsequent bionic membrane is better. The prepared nanopore has a large end face, and the nanopore is suitable for construction of the subsequent bionic membrane, and is not easy to be damaged and has long service life. When the nanopore is used for the research on the bionic membrane, the leakage current is small, and the signal-to-noise ratio is high, so that the nanopore is suitable for the research on the aspects of biosensors, DNA sequencing, drug screening, channel protein functions and the like.
Description
Technical field
The present invention relates to a kind of glass tube nano-pore, especially relate to preparation method, belong to nano biological electrochemical sensing technical field based on the nano-pore of tungsten tip and heavy wall glass tube.
Background technology
The vital movement of organism mainly is that base unit carries out with the cell, and cell is kept apart through cell membrane and surrounding environment, is keeping metastable cell interior environment.Cell membrane mainly is arranged in bilayer (BLM) by lipid; And be inlaid with the protein of various functions; Bearing the mass exchange, energy exchange of cell and external environment and the effect of signal conduction ([1] Yang Fuyu. biomembrane (second edition) [M]. Beijing: Science Press, 2007.).Channel protein is the transmembrane protein that is present in cell membrane, and its (selectivity) to molecular is penetrating to play an important role to regulating the bodily fuctions, and the character of channel protein and the research of function are had important science and application value.
Artificial constructed phospholipid bilayer film and to introduce channel protein therein be popular approach ([2] Cornell, B.A., Braach-Maksvytis, the V.L.B. that makes up bionical film and the channel protein function is studied on the surface of solids or little, nano-pore; King, L.G., Osman, P.D.J.; Raguse, B., Wieczorek, L.; Pace, R.J., 1997.Nature 387 (6633), 580-583; [3] Hirano-Iwata, A., Aoto, K., Oshima, A., Taira, T., Yamaguchi, R.T., Kimura, Y., Niwano, M., 2009.Langmuir 26 (3), 1949-1952; [4] Sugihara, K., Voros, J., Zambelli, T., 2010.ACS Nano 4 (9), 5047-5054.).The phospholipid bilayer film that forms at the surface of solids is called support membrane, and its advantage is the good mechanical stability of film, is fit to be made into device, but environment is controlled not good enough; And the phospholipid bilayer film that forms on little, the nano-pore is called the suspension film, and its advantage is the environment of analog cell film well, help the research of channel protein, but the mechanical stability and the life-span of suspension film is neither like support membrane.The reduced bore can carry the suspension film stability and the life-span ([5] Goryll, M., Wilk, S., Laws; G.M., Thornton, T., Goodnick, S.; Saraniti, M., Tang, J.; Eisenberg, R.S., 2003.Superlattices and Microstructures 34 (3-6), 451-457; [6] Simon, A., Girard-Egrot, A., Sauter, F., Pudda, C., D ' Hahan, N.P., Blum, L., Chatelain, F., Fuchs, A.J., 2007.Colloid Interface Sci.308,337.).People such as White ([7] Zhang, B., Galusha, J., Shiozawa, P.G., Wang, G.L., Bergren, A.J., Jones, R.M., White, R.J., Ervin, E.N., Cauley, C.C., White, H.S., 2007.Anal.Chem.79 (13), 4778-4787; [8] White, R.J., Ervin, E.N., Yang; T., Chen, X., Daniel, S.; Cremer, P.S., White, H.S., 2007.J.Am.Chem.Soc.129 (38); 11766-11775.) having proposed to be template, to seal the method that the process of then removing the metal needle point again prepares the glass nano hole with the metal needle point through glass tube, the stability and the life-span of suspension film improve all greatly, have been successfully used to the research of single ion channel.Yet; The preparation in glass nano hole at present all adopts Au silk or Pt silk as template, not only when material expensive, needle point production costs, and need select the material of glass well; So that its thermal coefficient of expansion is greater than Au silk or Pt silk, it is still not fully up to expectations to be prepared into power.
Summary of the invention
The object of the invention is to the existing above-mentioned shortcoming of existing preparation glass nano hole technology, and a kind of preparation method of the nano-pore based on tungsten tip and heavy wall glass tube is provided.
The present invention includes following steps:
1) preparation tungsten tip;
2) glass tube is sealed tungsten tip, preparation tungsten nanometer plate electrode;
3) tungsten tip sealed of etching makes the glass nano hole.
In step 1), the concrete grammar of said preparation tungsten tip can adopt electrochemical etching method.
In step 2) in; The concrete grammar that said glass tube is sealed tungsten tip can be: greater than 0.1MPa, flame temperature is under 1000～1200 ℃ of conditions in vacuum, and the end that tungsten tip is sharp-pointed is encapsulated in the glass; Polish through the end face of machine glazed finish again the glass part that is encapsulated with tungsten tip; Until the tip of exposing tungsten tip, make tungsten nanometer plate electrode, the said length of exposing the tip of tungsten tip can be several to the hundreds of nanometer.
In step 3), the tungsten tip that said etching is sealed, the concrete grammar that makes the glass nano hole can be: through electrochemical etching entrapped tungsten tip in the tungsten nanometer plate electrode is removed, obtained the glass nano hole.
Preparation technology compares with the existing glass nano-pore, and the present invention has following outstanding advantage:
1) tungsten filament is not only cheap, and has that hardness is big, fusing point is high and characteristic such as the coefficient of expansion is little.In addition, the preparation of the electrochemical etching of tungsten tip is efficient, and especially therefore the thermal coefficient of expansion of tungsten adopts common heavy wall glass tube can obtain the effect of sealing satisfactory for result much smaller than glass.
2) the present invention utilizes the glass tube of heavy wall pipe stock size, and the preparation process is frangible not, and operability is good, and success rate is high, and the research effect of follow-up bionical film is good.
3) end face in the prepared glass nano hole of the present invention is big, not only is suitable for the structure of follow-up bionical film, be difficult for being damaged, and service life is longer.
4) when utilizing the prepared glass nano hole of the present invention to carry out the research of bionical film, have that leakage current is little, the signal to noise ratio advantages of higher, be applicable to the research of aspects such as bio-sensing, dna sequencing, drug screening, channel protein function.
5) the heavy wall glass tube is that the polishing of follow-up glass tube end face and the laying step of phospholipid bilayer film provide convenience.
Description of drawings
Fig. 1 prepares the sketch map in tungsten nanometer plate electrode and glass nano hole for the present invention.In Fig. 1, (A) be tungsten nanometer plate electrode, (B) be the glass nano hole; Mark 1 is represented glass tube, and 2 represent tungsten tip; d
1Represent the glass nano hole, d
2Represent glass tube internal diameter (d
2=2.5mm), h represents glass tube thickness (h=1.0mm).
Fig. 2 is for the glass nano hole of the present invention's preparation and upward make up the electrical conductive behavior that hangs the phospholipid bilayer film.In Fig. 2, abscissa is current potential Potential (V), and ordinate is electric current Current (pA); Curve 1 is the electrical conductive behavior in the glass nano hole of silylation modification, and the resistance in the PBS of 1.0M KCl (pH=7.4) buffer solution is 0.5M Ω; Curve 2 is electrical conductive behaviors of suspension phospholipid bilayer film, and resistance is 75.8G Ω.In Fig. 2, * 1/5000 represent silylation modification the current value in glass nano hole all divided by numerical value 5000, obtain curve 1.
Fig. 3 is used to make up the embodiment of the bionical film that contains α-HL channel protein for the glass nano hole of the present invention's preparation.In Fig. 3, abscissa is time T ime (Secs), and ordinate is electric current Current (pA); Fig. 3 has write down the telescopiny of two α-HL channel proteins, and when each channel protein embedded, its current value step was 30pA, and background current is merely several pA, and the visible signal to noise ratio of measuring is high.
The specific embodiment
Following examples will combine accompanying drawing that the present invention is further described.
Concrete steps based on the preparation method of the nano-pore of tungsten tip and heavy wall glass tube are following:
(1) preparation tungsten tip
At first, cut the tungsten filament that is about 2.5cm and stab straight with tweezers with pliers; Secondly, tungsten filament is cleaned, clean 5min with acetone, the excusing from death of second alcohol and water successively, remove the spot that the tungsten filament surface exists; Then, insert the tungsten filament after cleaning in the 0.75M KOH solution as working electrode, and be to electrode with graphite, the alternating voltage of employing 25V carries out electrochemical etching; At last, the needle point that etching is obtained cleans with acetone, second alcohol and water successively, removes remaining impurities on the needle point.
(2) glass tube is sealed tungsten tip
At first, the not etched ends of prepared tungsten tip is inserted in the minute hand tube, exposed the tungsten tip of etching.Secondly, tungsten tip is placed in the middle of the pipe of the terminal about 5mm of glass tube, seal the end of glass tube, try one's best tungsten tip near sealing end afterwards with butane flame heat packs.Once more, the exhaust tube of vavuum pump is connected on the glass tube openend, greater than 0.1MPa, flame temperature is 1000～1200 ℃ in vacuum, can see that glass shrinks contact and seals tungsten tip.
(3) polishing makes tungsten nanometer plate electrode
Use silicon carbide paper and abrasive paper for metallograph (2 at first, successively
#, 4
#, 6
#) be polished to the glass disk end face apart from the terminal about 3mm place of tungsten tip step by step and reach mirror-smooth; Then, on polishing cloth, use Al
2O
3Powder (3 μ m, 1 μ m, 0.3 μ m, 0.05 μ m) polishes step by step, and polishing cloth is with 0.02M KCl solution-wet, and utilizes homemade electricity to lead detector and the tungsten tip of glass encapsulating and the electricity between solution are led monitor.When electric derivative value was uprushed, exposed at expression metal needle point tip, stops polishing immediately, obtains tungsten nanometer plate electrode; At last, at 10mM Ru (NH
3)
6Cl
3In+1.0M KCl the solution tungsten nanometer plate electrode is carried out the cyclic voltammetry scan curve and characterize, the radius of estimation tungsten nanometer plate electrode.
(4) tungsten tip sealed of etching makes the glass nano hole
The glass tungsten nanometer plate electrode of preparation is placed etching liquid (H
3PO
4+ KCl+C
4H
6O
4+ H
2O
2) in, add that the 25V alternating voltage carries out etching, until etching away the tungsten tip that glass encapsulating is lived fully, obtain the glass nano hole.The sign of nano-pore radius can be an electrode with two Ag/AgCl in the PBS of 1.0M KCl (pH=7.4) buffer solution, carries out cyclic voltammetry scan and characterizes.
The tungsten nanometer plate electrode that makes is shown in Fig. 1 (A); Through electrochemical etching entrapped tungsten tip in the tungsten nanometer plate electrode is removed the glass nano hole that obtains shown in Fig. 1 (B).
Fig. 3 has write down two α-HL channel protein and has successively got into the channel current that the phospholipid bilayer film is produced, and its signal to noise ratio is high, and suitable function to channel protein, bio-sensing etc. are furtherd investigate.
Claims (5)
1. based on the preparation method of the nano-pore of tungsten tip and heavy wall glass tube, it is characterized in that may further comprise the steps:
1) preparation tungsten tip;
2) glass tube is sealed tungsten tip, preparation tungsten nanometer plate electrode;
3) tungsten tip sealed of etching makes the glass nano hole.
2. the preparation method of the nano-pore based on tungsten tip and heavy wall glass tube as claimed in claim 1 is characterized in that in step 1), and the concrete grammar of said preparation tungsten tip adopts electrochemical etching method.
3. the preparation method of the nano-pore based on tungsten tip and heavy wall glass tube as claimed in claim 1; It is characterized in that in step 2) in, the concrete grammar that said glass tube is sealed tungsten tip is: greater than 0.1MPa, flame temperature is under 1000～1200 ℃ of conditions in vacuum; The end that tungsten tip is sharp-pointed is encapsulated in the glass; Polish through the end face of machine glazed finish again,, make tungsten nanometer plate electrode until the tip of exposing tungsten tip to the glass part that is encapsulated with tungsten tip.
4. the preparation method of the nano-pore based on tungsten tip and heavy wall glass tube as claimed in claim 3 is characterized in that the said length of exposing the tip of tungsten tip is several to the hundreds of nanometer.
5. the preparation method of the nano-pore based on tungsten tip and heavy wall glass tube as claimed in claim 1; It is characterized in that in step 3); The tungsten tip that said etching is sealed; The concrete grammar that makes the glass nano hole is: through electrochemical etching entrapped tungsten tip in the tungsten nanometer plate electrode is removed, obtained the glass nano hole.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104671668A (en) * | 2014-12-30 | 2015-06-03 | 西北大学 | Preparation method of single micro/nano hole based on glass materials |
| CN107843632A (en) * | 2017-10-25 | 2018-03-27 | 三峡大学 | A kind of solid-state phosphate anion selection electrode based on tungsten filament, preparation method and application |
| CN113042119A (en) * | 2021-02-25 | 2021-06-29 | 厦门大学 | Annular nano-pore and preparation and test method thereof |
| CN115464511A (en) * | 2022-09-19 | 2022-12-13 | 厦门大学 | Device integrating multi-channel aperture detection and nanopore preparation and using method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1438655A (en) * | 2003-03-27 | 2003-08-27 | 上海交通大学 | Scanning-tunnel microscope needle-tip automatic controlled etching instrument |
| WO2005039743A2 (en) * | 2003-10-23 | 2005-05-06 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Nanoporous filter or support membrane and method for production therof |
| CN101437467A (en) * | 2004-08-13 | 2009-05-20 | 斯特根有限公司 | Medical devices having porous layers and methods for making the same |
| KR100948705B1 (en) * | 2007-07-13 | 2010-03-22 | 연세대학교 산학협력단 | Method And Appratus For Manufacturing Hyperfine Needle Electrode |
| US20110138551A1 (en) * | 2008-06-20 | 2011-06-16 | Braun Gmbh | Electric Toothbrush |
-
2011
- 2011-09-02 CN CN201110257948A patent/CN102320564A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1438655A (en) * | 2003-03-27 | 2003-08-27 | 上海交通大学 | Scanning-tunnel microscope needle-tip automatic controlled etching instrument |
| WO2005039743A2 (en) * | 2003-10-23 | 2005-05-06 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Nanoporous filter or support membrane and method for production therof |
| CN101437467A (en) * | 2004-08-13 | 2009-05-20 | 斯特根有限公司 | Medical devices having porous layers and methods for making the same |
| KR100948705B1 (en) * | 2007-07-13 | 2010-03-22 | 연세대학교 산학협력단 | Method And Appratus For Manufacturing Hyperfine Needle Electrode |
| US20110138551A1 (en) * | 2008-06-20 | 2011-06-16 | Braun Gmbh | Electric Toothbrush |
Non-Patent Citations (4)
| Title |
|---|
| BO ZHANG，ET AL.: "Bench-Top Method for Fabricating Glass-Sealed Nanodisk Electrodes, Glass Electrodes，and Glass Nanopore Membranes of Controlled Size", 《ANALYTICAL CHEMISTRY》 * |
| RYAN J.WHITE，ET AL.: "Single Ion-Channel Recordings Using Glass Nanopore Membranes", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| SHIN,JUN HO ET AL.: "Glass nanopore-based ion-selective electrodes", 《ANALYTICAL CHEMISTRY》 * |
| STEPHEN J.SOWERBY ET AL.: "Dynamically resizable nanometre-scale apertures for molecular sensing", 《SENSORS AND ACTUATORS B-CHEMICAL》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104671668A (en) * | 2014-12-30 | 2015-06-03 | 西北大学 | Preparation method of single micro/nano hole based on glass materials |
| CN107843632A (en) * | 2017-10-25 | 2018-03-27 | 三峡大学 | A kind of solid-state phosphate anion selection electrode based on tungsten filament, preparation method and application |
| CN113042119A (en) * | 2021-02-25 | 2021-06-29 | 厦门大学 | Annular nano-pore and preparation and test method thereof |
| CN115464511A (en) * | 2022-09-19 | 2022-12-13 | 厦门大学 | Device integrating multi-channel aperture detection and nanopore preparation and using method thereof |
| CN115464511B (en) * | 2022-09-19 | 2023-08-01 | 厦门大学 | Device integrating multi-channel aperture detection and nanopore preparation and application method thereof |
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Application publication date: 20120118 |