CN113155808B - Nanometer single hole based on capillary tip and preparation method and application thereof - Google Patents

Nanometer single hole based on capillary tip and preparation method and application thereof Download PDF

Info

Publication number
CN113155808B
CN113155808B CN202110324834.8A CN202110324834A CN113155808B CN 113155808 B CN113155808 B CN 113155808B CN 202110324834 A CN202110324834 A CN 202110324834A CN 113155808 B CN113155808 B CN 113155808B
Authority
CN
China
Prior art keywords
capillary
nano
tip
precursor
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110324834.8A
Other languages
Chinese (zh)
Other versions
CN113155808A (en
Inventor
王康
周鹃
吉丽娜
夏兴华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanjing University
Original Assignee
Nanjing University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanjing University filed Critical Nanjing University
Priority to CN202110324834.8A priority Critical patent/CN113155808B/en
Publication of CN113155808A publication Critical patent/CN113155808A/en
Application granted granted Critical
Publication of CN113155808B publication Critical patent/CN113155808B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65—Raman scattering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416—Systems
    • G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Abstract

The invention relates to a nano single hole based on a capillary tip, a preparation method and application thereof, wherein a deposition layer is arranged on the inner side wall of the capillary tip, the deposition layer extends out of a hollow conical structure to the outside of the capillary, and the nano single hole is positioned at the tip of the conical structure. The nano single-hole preparation method is simple, low in cost, small in single-hole size and controllable in structure, and can be used as an electrochemical device and combined with Raman spectrum. The bias voltage is applied to the two ends of the nanotube, so that the detection of the single molecules with smaller size by dynamic Raman is realized, the detection of the single protein molecules based on current and Raman spectrum is realized, and a novel method is provided for DNA sequencing and protein sequencing.

Description

Nanometer single hole based on capillary tip and preparation method and application thereof
Technical Field
The invention belongs to the technical field of nanopores, and particularly relates to a nano single pore based on a capillary tip, and a preparation method and application thereof.
Background
The nanopore analysis technology has extremely important application in single molecule detection, and is expected to be applied to DNA sequencing and protein sequencing. The nanopore single-molecule electrochemical detection technology develops rapidly on single-molecule behavior detection, but it is difficult to accurately judge molecular structure information directly through ion flow characteristic electric signals generated when molecules or ions pass through nanopores. Ion current blocking events are also difficult to capture by instruments, especially in the case of small molecular sizes.
Disclosure of Invention
Aiming at the problems, the invention provides a nano single hole based on a capillary tip, the aperture of the nano single hole is controllable and can reach below 10nm, and the rear end of the capillary is of a macroscopic size, so that the nano single hole is convenient to combine with various mechanical and electronic devices. When the nanopore is a plasma nanopore formed by certain metals, analyte molecules pass through the plasma nanopore under the drive of a directional electric field, and a molecular dynamic spectrum with a stronger signal can be generated due to the surface plasma enhancement effect, so that more accurate molecular structure information is actually reflected. Through the dynamic surface enhanced Raman detection, the detection of single-molecule via holes can be realized, and structural information such as molecular orientation, redox state and the like can be further provided.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a nano single hole based on a capillary tip, wherein a deposition layer is arranged on the inner side wall of the capillary tip, the deposition layer extends out of a hollow conical structure towards the outside of the capillary, the nano single hole is positioned at the tip of the conical structure, and preferably, the aperture of the single hole is less than 150 nm.
Preferably, the tapered structure is metal, more preferably, the tapered structure is gold, silver, copper or platinum. The taper structure and the deposition layer may be the same or different materials.
Preferably, the material of the deposition layer is metal, and the preferred metal is gold, silver, copper or platinum.
The capillary tube is a quartz or glass capillary tube, the tail part is in macroscopic size, and the cross section is round or polygonal, preferably round. The capillary tube may contain a drain tube therein. The total length of the capillary is 1 to 15cm, preferably 2 to 10cm. The preparation of the capillary is prior art, and the present invention is not particularly limited thereto.
The diameter of the tip of the capillary is 20-200 nm, preferably 60nm.
Preferably, the tapered structure has a length of 500nm or less.
The invention also provides a preparation method of the nano single hole based on the capillary tip, which comprises the following steps:
injecting a first solution of a precursor into a capillary tip with a deposition layer on the inner side wall, immersing the capillary tip into a second solution of the precursor, and then applying voltage to the inner side and the outer side of the capillary tip, wherein electrons are obtained by the precursor to grow at the capillary tip to form the conical structure, and the nano single hole is positioned at the tip of the conical structure. The precursor is an ion or a compound capable of being reduced to obtain a target material. The concentration of the first solution of the precursor and the second solution of the precursor may be different or the same.
Preferably, the precursor is a metal ion, preferably a gold ion, a silver ion solution, a copper ion or a platinum ion.
Preferably, the concentration of the first solution of the precursor or the second solution of the precursor is 5 to 200mM, most preferably 100mM.
Preferably, the method for applying the voltage is as follows: one electrode is inserted into each of the inner and outer solutions of the capillary tip, and then a voltage is applied between the two electrodes by linear sweep voltammetry or constant voltage current-time method. The current drop (linear sweep voltammetry) or the sharp current decrease (constant voltage current-time method) of the characteristic can be stopped.
Preferably, the linear sweep voltammetry has a sweep range of 0 to-5V, most preferably 0 to-1.5V, and a sweep rate of 2 to 200mV/s, most preferably 5mV/s.
Preferably, the constant voltage current-time method has a voltage range of-0.1V to-5V, most preferably-1V, and a voltage application time range of 1800s or less, most preferably 300s.
And (3) taking a deposited layer arranged on the inner side wall of the tip end of the capillary and an electrode inserted into the capillary as a bipolar electrode, and carrying out electrochemical reduction on a precursor at the tip end of the deposited layer to grow a conical structure. In electrochemical reduction, after characteristic current drop or abrupt current reduction occurs, the electrochemical reduction is terminated, and then a relatively uniform nano single hole with smaller aperture can be obtained at the tip of the capillary.
The capillary tips with deposited layers on the inner sidewall are made by chemical reduction or other prior art techniques. The chemical reduction method comprises the following steps:
and injecting the solution of the precursor into the capillary tip as a deposition solution, and then immersing the capillary tip into a reducing agent solution. The precursor, the material of the corresponding deposited layer and the corresponding reducing agent are of the prior art, for example, chloroauric acid is used as the precursor of gold, and absolute ethanol solution of sodium borohydride is used for reduction.
Preferably, the concentration of the precursor in the chemical reduction method is 5 to 200mM, most preferably 100mM, and the concentration of the reducing agent is 1 to 10mM, most preferably 5mM.
Preferably, the reaction time of the chemical reduction method is 1 to 10min, and most preferably, the reaction time is 0.5 to 2min.
A third object of the present invention is to provide the use of the above described capillary tip based nano-single well in chemical or biological analysis, in particular in raman detection. The nanometer single hole has stronger Raman enhancement effect.
The nano single hole prepared by the invention is mainly used as an electrochemical device for combined use with Raman spectrum to detect single molecule via hole signals. Thus comprising two parts:
the electrochemical analysis steps are as follows: two metal wires made of the same material are respectively used as a working electrode and a counter electrode, the working electrode is inserted into a capillary tube filled with electrolyte and then used, the counter electrode is directly inserted into external electrolyte, the I-V curve of the counter electrode is tested by a linear sweep voltammetry, constant voltage is applied by a time-current method when single-molecule via holes are detected electrochemically, a current signal is amplified by using a current amplifier (Axiopatch 200B can be adopted), and a current is converted into data by using a converter (Digidata 1550B A/D can be adopted). And in the course of use in conjunction with raman spectroscopy, a constant potential is applied by time-current methods.
Raman spectrometry method: the laser with 633nm intensity was irradiated using a positive confocal raman microscope at a laser intensity of 6mW (power 100%). In order to measure only the signal of the tip metal nanopore, it is necessary to ensure that the metal is deposited only within 3 microns of the capillary tip.
The nano single hole based on the capillary tip has good application value in the field of single molecule Raman.
Application one: under the control of constant voltage, low concentration of the analyte (rhodamine 6G,10 -9 M) small molecules are oriented to pass through the metal nano holes, can be recorded by dynamic Raman spectrum and can be captured by rhodamine 6G single-componentDifferent molecular orientation information at the time of sub-vias.
And (2) application II: the via hole for detecting the hemoglobin single-molecule can detect different protein redox states when the hemoglobin single-molecule via hole is in use.
According to the technical scheme and the result, the nano single hole based on the capillary tip is innovatively prepared, and the electrochemical and the Raman are combined, so that the dynamic Raman detection of the single-molecule via hole under the drive of voltage is successfully realized. The advantages are simple, cheap and easily available raw materials, mild condition, stable structure and repeated use. And the rear end of the capillary tube is of a macroscopic size, so that the capillary tube is convenient to combine with various mechanical and electronic equipment, and has great potential application value.
Description of the drawings:
FIG. 1 is a schematic diagram of the method for preparing nano-single pores in example 1.
FIG. 2 is a schematic diagram of a method for preparing a deposited layer by chemical reduction in example 1.
FIG. 3 is an I-V graph of the applied voltage in example 1.
FIG. 4 is an electron micrograph of the capillary tip and its chemical reduction, electrochemical reduction, of example 1. Wherein a is the unreacted capillary tip; b is a side view of the chemically reduced capillary tip; c is a direct view of the electrochemically reduced capillary; d is a side view of the inside of the capillary tip after electrochemical reduction and after cutting with a focused ion beam.
FIG. 5 shows the I-V curve (A), electrochemical impedance (B), power spectral density (C), and Raman enhancement effect (D) of example 1 before and after the generation of the tapered structure and single hole.
FIG. 6 is a schematic diagram of an apparatus for combining electrochemistry with Raman in example 1.
FIG. 7 is a schematic diagram of the drive 10 at-1V voltage -3 M and 10 -9 M rhodamine 6G passes through the characteristic Raman spectrum of the conical gold nanometer single hole.
FIG. 8 is a schematic diagram of the drive 10 at-0.3V -9 M hemoglobin (solution 1M LiNO 3 PBS at ph 7.2) through a characteristic raman spectrum of gold nano-pores.
FIG. 9 is 10 -5 M and 10 -9 M hemoglobin molecule (1M LiNO solution 3 PBS at ph 7.2).
Detailed Description
The technical scheme of the present invention is further described below with reference to examples and drawings, but should not be construed as limiting the present invention:
example 1
The invention relates to a method for preparing nanometer single holes, which comprises the following steps:
(1) Preparing a capillary tip: the apparatus used was a SUTTER company P-2000 pull needle apparatus, the capillary tube was a SUTTER company quartz capillary tube (QF: 100-70-10, OD:1.00mm, ID:0.70 mm), and the total length was 10cm. The parameters were set to heat=750, filevent=3, variability=40, delay=175, pull=190.
The capillary tip diameter prepared under the above conditions using this specification of capillary was 60nm, as shown in FIG. 4A. The total length of the capillary tube is 2cm, and the rear end is of macroscopic size.
(2) Preparing a deposition layer by a chemical reduction method: 100mM chloroauric acid solution was injected into the capillary, and the tip of the capillary was immersed in 5mM NaBH at room temperature (25.+ -. 1 ℃ C.) 4 And (3) carrying out chemical reduction in a pure ethanol solution, reacting for 1-2 min, and depositing a conical gold deposition layer inside the tip of the capillary.
(3) Preparing nano single holes: 100mM chloroauric acid solution is injected into a capillary, then the tip of the capillary is immersed in the 100mM chloroauric acid solution, a gold electrode immersed in the chloroauric acid solution is inserted into the inside and the outside of the capillary respectively to serve as a working electrode and a counter electrode, and the working electrode and the counter electrode are directly applied with voltage of 0 to-1.5V by linear sweep voltammetry at a sweeping speed of 5mV/s (CHI-830B,CH Instrument Ins is used as an instrument). The gold deposition layer formed by chemical reduction is used as a bipolar electrode, electrochemical reduction is stopped after the characteristic current is reduced, an I-V curve chart is shown in figure 3, and the uniform Shan Kongjin with smaller aperture is finally obtained by reduction at the tip. The characterization of the nanopores for the capillary tips during the process is shown in FIG. 4. Wherein the length of the tapered structure is below 500 nm. The pore diameter of the single pore is about 13 nm.
(4) And (5) testing performance.
Electrochemical and Raman tests were performed on the prepared NaNO-single pores, FIG. 4A is a sample of 1M NaNO 3 And generating an I-V curve graph before and after generating the gold nano single holes with the conical structures in the solution. At high salt concentration, the generated product shows obvious ion rectification phenomenon. FIG. 4B is an electrochemical impedance spectrum of gold nano-pores with a conical structure before and after generation. In the low frequency region, the impedance increases after the generation of the nanopores, indicating the formation of small apertures. FIG. 4C is a graph of power spectral density before and after generation of a gold nano-pore with a tapered structure. Although the noise of the generated nano single hole is increased, compared with other existing solid nano holes, the nano hole has lower power spectrum density in high-frequency measurement, shows smaller noise and has good application foundation in electrochemical detection. Fig. 4D is a graph of raman enhancement effects before and after generation of a tapered structure gold nanopore. Rhodamine 6G is used as a Raman signal molecule to calculate a Raman enhancement factor, the nano single hole generated by gold shows excellent Raman enhancement effect, and the Raman enhancement factor reaches 1.1 multiplied by 10 8 。
(5) Electrochemical-raman combination
The prepared gold nanometer single hole with the conical structure adopts 10 in the application of combining electrochemistry and Raman -9 The M rhodamine 6G solution is used as an object to be detected, and the rhodamine 6G through hole is driven by negative voltage, and the schematic diagram is shown in fig. 5. When the concentration of rhodamine 6G solution to be detected is 10 -9 And M, a characteristic Raman spectrum shows a flickering signal, and the characteristic Raman spectrum is calculated according to the concentration of rhodamine 6G solution and the ion current of the via hole, wherein the number of molecules passing through the nanopore per second is less than one. As shown in FIG. 6, as well as 10 -3 Compared with a standard rhodamine 6G solution Raman spectrum under M concentration, 10 -9 The characteristic peaks in the Raman spectrum of the M rhodamine 6G solution are nonuniform, and a 'new peak' which is different from a standard spectrum peak appears, wherein the new peaks are formed by different orientations of single R6G molecules when passing through a gold nano-pore, and further single-molecule detection is verified, so that the single-molecule rhodamine 6G is detected.
Example 2
(1) By adjusting the parameters, a quartz capillary having a length of 10cm and a tip diameter of 20nm was produced.
(2) Preparing a deposition layer by a chemical reduction method: 200mM chloroauric acid solution was injected into the capillary, the capillary tip was immersed in 100mM ascorbic acid solution at room temperature (25.+ -. 1 ℃ C.) for chemical reduction, reaction was performed for 10min, and a cone-shaped gold deposition layer was deposited inside the capillary tip.
(3) Preparing nano single holes: 200mM silver nitrate solution is injected into a capillary, then the tip of the capillary is immersed into 5mM silver nitrate solution, a platinum wire electrode is inserted into the inside and the outside of the capillary respectively to serve as a working electrode and a counter electrode, and the working electrode and the counter electrode directly apply voltage-1V through a constant-voltage current-time method. The gold deposit formed by chemical reduction is used as a bipolar electrode, electrochemical reduction is stopped after the current drops sharply (about 300 s), and finally, single-hole silver with relatively uniform pore diameter and smaller pore diameter is obtained by reduction at the tip. The pore diameter of the single pore is about 8 nm.
(4) Detection of single molecule hemoglobin: as shown in fig. 7, the tapered silver nano single hole can also detect raman characteristic peaks of hemoglobin molecules under laser irradiation, and displacement of partial peaks corresponds to different redox states when single hemoglobin via hole is formed.
Example 3
(1) By adjusting the parameters, a glass capillary having a length of 15cm and a tip diameter of 200nm was produced.
(2) And depositing a silver layer on the inner wall of the tip of the capillary by adopting an electron beam evaporation technology.
(3) Preparing nano single holes: 100mM chloroauric acid solution is injected into a capillary, then the tip of the capillary is immersed in 20mM chloroauric acid solution, a platinum wire electrode is inserted into the inside and the outside of the capillary respectively to serve as a working electrode and a counter electrode, and the working electrode and the counter electrode are directly applied with voltage of 0 to-5V by a linear sweep voltammetry method, and the sweeping speed is 200mV/s (CHI-830B,CH Instrument Ins is used as an instrument). And the silver deposition layer is used as a bipolar electrode, electrochemical reduction is stopped after the characteristic current is reduced, and finally uniform single-hole gold is obtained through reduction at the tip. The pore diameter of the single pore is about 30nm.
(4) Single molecule hemoglobin over-cone gold nano single pore: as shown in fig. 8, the ion current increases every time there is a single molecule of hemoglobin via.
Example 4
(1) By adjusting the parameters, a glass capillary having a length of 5cm and a tip diameter of 100nm was produced.
(2) Preparing a deposition layer by a chemical reduction method: a5 mM chloroauric acid solution was injected into the capillary, and the tip of the capillary was immersed in 5mM NaBH at room temperature (25.+ -. 1 ℃ C.) 4 And (3) carrying out chemical reduction in a pure ethanol solution, reacting for 0.5min, and depositing a conical gold deposition layer inside the tip of the capillary.
(3) Preparing nano single holes: and (3) injecting 20mM copper nitrate solution into the capillary, immersing the tip of the capillary into 5mM copper nitrate solution, and inserting a platinum wire electrode into the inside and the outside of the capillary respectively to serve as a working electrode and a counter electrode, wherein the working electrode and the counter electrode directly apply voltage-5V through a constant-voltage current-time method. The gold deposition layer is used as a bipolar electrode, electrochemical reduction is stopped after 1200s, and finally uniform single-hole copper is obtained after reduction at the tip. The pore diameter of the single pore is about 100nm.
Example 5
(1) By adjusting the parameters, a quartz capillary having a length of 1cm and a tip diameter of 50nm was produced.
(2) Preparing a deposition layer by a chemical reduction method: a5 mM chloroauric acid solution was injected into the capillary, and the tip of the capillary was immersed in 5mM NaBH at room temperature (25.+ -. 1 ℃ C.) 4 And (3) carrying out chemical reduction in a pure ethanol solution, reacting for 0.5min, and depositing a conical gold deposition layer inside the tip of the capillary.
(3) Preparing nano single holes: 100mM chloroplatinic acid solution is injected into a capillary, then the tip of the capillary is immersed in 10mM chloroplatinic acid solution, a platinum wire electrode is inserted into the inside and the outside of the capillary respectively to serve as a working electrode and a counter electrode, and the working electrode and the counter electrode are directly applied with voltage of 0 to-1.5V by linear sweep voltammetry at a sweeping speed of 2mV/s (CHI-830B,CH Instrument Ins is used as an instrument). The gold deposition layer formed by chemical reduction is used as a bipolar electrode, electrochemical reduction is stopped after the characteristic current is reduced, and finally, a uniform single Kong Bo with smaller aperture is obtained by reduction at the tip. The pore diameter of the single pore is about 10 nm.

Claims (15)

1. A nano single hole based on a capillary tip, which is characterized in that a deposition layer is arranged on the inner side wall of the capillary tip, the deposition layer extends out of a hollow conical structure towards the outside of the capillary, and the nano single hole is positioned at the tip of the conical structure; the taper structure or the deposition layer is made of metal.
2. The nano-single pore according to claim 1, wherein the pore diameter of the single pore is 150nm or less.
3. The nano-pore according to claim 1, wherein the tapered structure or the deposited layer is made of gold, silver, copper or platinum.
4. The nano-pore according to claim 1, wherein the capillary tip diameter is 20-200 nm.
5. The nano-pore according to claim 4, wherein the capillary tip diameter is 60nm.
6. The nano-pore according to claim 1, wherein the tapered structure has a length of 500nm or less.
7. The method for preparing the nano single hole according to any one of claims 1 to 6, which is characterized by comprising the following steps:
injecting a first solution of a precursor into a capillary tip with a deposition layer on the inner side wall, immersing the capillary tip into a second solution of the precursor, and then applying voltage to the inner side and the outer side of the capillary tip, wherein electrons are obtained by the precursor to grow at the capillary tip to form the conical structure, and the nano single hole is positioned at the tip of the conical structure.
8. The method of claim 7, wherein the precursor is a metal ion.
9. The method of claim 8, wherein the precursor is gold ion, silver ion solution, copper ion, or platinum ion.
10. The method according to claim 7, wherein the concentration of the first solution of the precursor or the second solution of the precursor is 5 to 200mm.
11. The method of claim 10, wherein the concentration of the first solution of the precursor or the second solution of the precursor is 100mM.
12. The method of claim 7, wherein the method of applying a voltage is: one electrode is inserted into each of the inner and outer solutions of the capillary tip, and then a voltage is applied between the two electrodes by linear sweep voltammetry or constant voltage current-time method.
13. The method of claim 7, wherein the capillary tips having a deposited layer on the inner sidewall are prepared by a chemical reduction process.
14. Use of a nano-single pore according to any one of claims 1-7 in chemical or biological analysis.
15. The use according to claim 14, characterized in that the use is in raman detection.
CN202110324834.8A 2021-03-26 2021-03-26 Nanometer single hole based on capillary tip and preparation method and application thereof Active CN113155808B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110324834.8A CN113155808B (en) 2021-03-26 2021-03-26 Nanometer single hole based on capillary tip and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110324834.8A CN113155808B (en) 2021-03-26 2021-03-26 Nanometer single hole based on capillary tip and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN113155808A CN113155808A (en) 2021-07-23
CN113155808B true CN113155808B (en) 2023-06-06

Family

ID=76884959

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110324834.8A Active CN113155808B (en) 2021-03-26 2021-03-26 Nanometer single hole based on capillary tip and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN113155808B (en)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107356580A (en) * 2017-06-27 2017-11-17 南京大学 A kind of nanometer single hole based on dispersed nano lamella and its preparation method and application

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8168251B2 (en) * 2008-10-10 2012-05-01 The Board Of Trustees Of The Leland Stanford Junior University Method for producing tapered metallic nanowire tips on atomic force microscope cantilevers
US9255339B2 (en) * 2011-09-19 2016-02-09 Fei Company Localized, in-vacuum modification of small structures
CN108996461B (en) * 2018-06-21 2020-06-02 安徽师范大学 Glass nanopore with diameter less than 10nm, preparation method and application of glass nanopore in DNA detection
CN112114020A (en) * 2020-09-14 2020-12-22 安徽师范大学 Double-sensitive gold-modified DNA functionalized glass nanopore door control system, construction method and application

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107356580A (en) * 2017-06-27 2017-11-17 南京大学 A kind of nanometer single hole based on dispersed nano lamella and its preparation method and application

Also Published As

Publication number Publication date
CN113155808A (en) 2021-07-23

Similar Documents

Publication Publication Date Title
Bentley et al. Nanoscale electrochemical mapping
Wang et al. Miniaturized glucose sensors based on electrochemical codeposition of rhodium and glucose oxidase onto carbon-fiber electrodes
JP5467473B2 (en) Scanning electrochemical ion conductance microscope, its probe, and method of manufacturing the probe.
Zestos et al. Carbon nanospikes grown on metal wires as microelectrode sensors for dopamine
US9650720B2 (en) Method for surface-modifying neural electrode
EP1290431B1 (en) Method for producing a device for simultaneously carrying out an electrochemical and a topographical near-field microscopy
Defnet et al. Temporally-resolved ultrafast hydrogen adsorption and evolution on single platinum nanoparticles
CN103789807B (en) The nano-tube array that noble metal nano structural unit is constructed and preparation method and the application in organic molecule detects thereof
Noël et al. Fabrication, characterization, and chemical etching of Ag nanoelectrodes
Wang et al. Mesoporous CuO: Alternative enzyme-free glucose sensing structure with excellent kinetics of electrode process
Aydin et al. A facile method for fabricating carbon fiber-based gold ultramicroelectrodes with different shapes using flame etching and electrochemical deposition
CN110057897B (en) Carbon fiber electrode modified by electrophoretic deposition carbon nano tube and application thereof in detection of living ascorbic acid
CN109765209B (en) Preparation method and application of bifunctional expanded graphite/nanogold composite electrode
CN108483389B (en) Silver nano electrode and preparation method thereof
Qiao et al. Fabrication of nanoelectrodes for neurophysiology: cathodic electrophoretic paint insulation and focused ion beam milling
CN113155808B (en) Nanometer single hole based on capillary tip and preparation method and application thereof
CN113960133A (en) Boron-doped diamond microarray electrode loaded by metal nanosheet, preparation method thereof and application of boron-doped diamond microarray electrode in glucose sensor
Budai Carbon fiber-based microelectrodes and microbiosensors
US20200375509A1 (en) Diamond-containing electrodes for neurochemical detection
CN112525880A (en) Small-aperture nanopore device and preparation method and application thereof
Alimohammadi et al. A proposed implantable voltammetric carbon fiber–based microsensor for corticosteroid monitoring by cochlear implants
Hong-Na et al. Facile fabrication of gold functionalized nanopipette for nanoscale electrochemistry and surface enhanced Raman spectroscopy
Zarei et al. Stripping voltammetric determination of nicardipine using β-cyclodextrin incorporated carbon nanotube-modified glassy carbon electrode
Szunerits et al. Fabrication of a Sub‐Micrometer Electrode Array: Electrochemical Characterization and Mapping of an Electroactive Species by Confocal Raman Microspectroscopy
Bai et al. Fabrication of graphene coated carbon fiber microelectrode for highly sensitive detection application

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant