CN113155808A - Nano single hole based on capillary tip and preparation method and application thereof - Google Patents
Nano single hole based on capillary tip and preparation method and application thereof Download PDFInfo
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- VYXSBFYARXAAKO-UHFFFAOYSA-N ethyl 2-[3-(ethylamino)-6-ethylimino-2,7-dimethylxanthen-9-yl]benzoate;hydron;chloride Chemical compound [Cl-].C1=2C=C(C)C(NCC)=CC=2OC2=CC(=[NH+]CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a nano single hole based on a capillary tip and a preparation method and application thereof. The preparation method of the nanometer single hole is simple, low in cost, small in single hole size and controllable in structure, and can be used as an electrochemical device for being combined with Raman spectroscopy. Bias voltage is applied to two ends of the nanotube, so that the detection of single molecules with smaller size by dynamic Raman is realized, the detection of single protein molecules based on current and Raman spectrum is realized, and a new method is provided for DNA sequencing and protein sequencing.
Description
Technical Field
The invention belongs to the technical field of nanopores, and particularly relates to a nanopore 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 monomolecular electrochemical detection technology is developed rapidly on the detection of monomolecular behaviors, but the molecular structure information is difficult to be accurately judged directly through an electric signal of ion flow characteristics generated when molecules or ions pass through the nanopore. Ion current blocking events are also difficult to capture by the instrument, especially in the case of very small molecular sizes.
Disclosure of Invention
Aiming at the problems, the invention provides a nanometer single hole based on the tip of a capillary, the aperture of the nanometer single hole is controllable and can reach below 10nm, and the rear end of the capillary is in a macroscopic size, so that the nanometer single hole can be conveniently combined 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 strong 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 the single-molecule through hole can be realized, and structural information such as molecular orientation, oxidation-reduction state and the like can be further provided.
In order to achieve the purpose, the invention adopts the following technical scheme:
a nanometer single hole based on a capillary tip is provided with a deposition layer on the inner side wall of the capillary tip, a hollow conical structure extends out of the deposition layer, the nanometer single hole is located at the tip of the conical structure, and preferably, the diameter of the single hole is less than 150 nm.
Preferably, the tapered structure is a metal, and more preferably, the tapered structure is gold, silver, copper, or platinum. The tapered structure and the deposition layer may be of 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 is a quartz or glass capillary, the tail part is in macroscopic size, and the section is circular or polygonal, preferably circular. A draft tube may be included in the capillary tube. The total length of the capillary tube is 1-15 cm, preferably 2-10 cm. 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 tube is 20-200 nm, and the preferable diameter is 60 nm.
Preferably, the length of the tapered structure is 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 the capillary tip having the deposition layer on the inner side wall, then immersing the capillary tip into a second solution of the precursor, and then applying a voltage to the inside and outside of the capillary tip, wherein the precursor obtains electrons to grow on the capillary tip to form the tapered structure, and the nano single hole is located at the tip of the tapered structure. The precursor is an ion or a compound which can be reduced to obtain a target material. The first solution of the precursor and the second solution of the precursor may have different concentrations or the same concentration.
Preferably, the precursor is metal ions, preferably gold ions, silver ion solution, copper ions or platinum ions.
Preferably, the concentration of the first solution of the precursor or the second solution of the precursor is 5 to 200mM, most preferably 100 mM.
Preferably, the method for applying the voltage comprises the following steps: one electrode is inserted into the solution inside and outside the capillary tip, and then a voltage is applied between the two electrodes by linear sweep voltammetry or constant voltage amperometry. The current drop characteristic (linear sweep voltammetry) or the sharp decrease in current (constant voltage current-time method) can be stopped.
Preferably, the sweep range of the linear sweep voltammetry is 0 to-5V, the most preferred sweep range is 0 to-1.5V, and the sweep rate is 2 to 200mV/s, the most preferred sweep rate is 5 mV/s.
Preferably, the voltage range of the constant-voltage current-time method is-0.1V to-5V, most preferably the voltage is-1V, the voltage application time range is 1800s or less, and most preferably the time is 300 s.
And taking the deposition layer on the inner side wall of the tip of the capillary tube and the electrode inserted into the capillary tube as a bipolar electrode, and carrying out electrochemical reduction on the precursor at the tip of the deposition layer to grow a conical structure. In the electrochemical reduction, after the characteristic current drop or the current sharp reduction appears, the electrochemical reduction is stopped, and the nano single hole with more uniform and smaller aperture can be obtained at the tip of the capillary.
The capillary tip with the deposited layer on the inner sidewall is made by chemical reduction or other prior art. The chemical reduction method comprises the following steps:
and injecting a solution of the precursor into the capillary tip as a deposition solution, and then immersing the capillary tip into a reducing agent solution to obtain the nano-tube. The precursor, the corresponding deposition layer material and the corresponding reducing agent are the prior art, for example, chloroauric acid is used as the precursor of gold, and the gold is reduced by adopting an absolute ethyl alcohol solution of sodium borohydride.
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 5 mM.
Preferably, the reaction time of the chemical reduction method is 1-10 min, and the most preferred reaction time is 0.5-2 min.
The third purpose of the invention is to provide the application of the nano single hole based on the capillary tip in chemical analysis or biological analysis, especially in Raman detection. The nano single hole has stronger Raman enhancement effect.
The prepared nano single hole is mainly used as an electrochemical device to be combined with Raman spectrum to detect a single-molecule through hole signal. Thus comprising two parts:
the electrochemical analysis comprises the following steps: 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 filled with electrolyte and then used, the counter electrode is directly inserted into external electrolyte, an I-V curve of the capillary is tested by a linear sweep voltammetry method, constant voltage is applied by a time-current method when a monomolecular via hole is detected electrochemically, a current amplifier (Axopatch 200B can be adopted) is used for amplifying a current signal, and a converter (Digidata 1550B A/D can be adopted) is used for converting the current into data. And a constant potential is applied by a time-current method in the process of being used in conjunction with raman spectroscopy.
Raman spectrum measurement method: the laser intensity of the laser used was 6mW (power 100%) using an upright confocal Raman microscope with laser irradiation at 633 nm. To measure the signal only from the metal nanopore at the tip, it is necessary to ensure that the metal is only deposited within 3 microns of the capillary tip.
The nanometer single hole based on the capillary tip has good application value in the single molecule Raman field.
The application one is as follows: under the control of constant voltage, the object to be measured (rhodamine 6G, 10) with low concentration-9M) small molecules directionally penetrate through the metal nano-holes, can be recorded by dynamic Raman spectroscopy, and are captured to different molecular orientation information when the rhodamine 6G single-molecule through holes are formed.
The application II comprises the following steps: the different protein redox states can be detected when the hemoglobin single molecule is passed through the hole.
According to the technical scheme and the result, the nano single hole based on the capillary tip is innovatively prepared, electrochemistry and Raman are combined, and dynamic Raman detection of the single-molecule through hole under voltage driving is successfully realized. The method has the advantages of simple, cheap and easily-obtained raw materials, mild conditions, stable device structure and repeated use. And the rear end of the capillary tube is in a macroscopic size, so that the capillary tube can be conveniently combined with various mechanical and electronic devices, and has great potential application value.
Description of the drawings:
fig. 1 is a schematic diagram of a method for preparing a nano single pore in example 1.
Fig. 2 is a schematic view of a method for preparing a deposition layer by chemical reduction in example 1.
FIG. 3 is an I-V graph of applied voltage in example 1.
FIG. 4 is an electron micrograph of the tip of the capillary and its chemically and electrochemically reduced tip in example 1. Wherein a is an unreacted capillary tip; b is a side view of the capillary tip after chemical reduction; c is a direct view of the capillary after electrochemical reduction; d is a side view of the inside of the capillary tip after electrochemical reduction and cutting with a focused ion beam.
FIG. 5 shows the I-V curve (A), electrochemical impedance plot (B), power spectral density plot (C), and Raman enhancement effect plot (D) before and after the formation of the cone structure and the single hole in example 1.
FIG. 6 is a schematic view of an apparatus for combining electrochemistry with Raman in example 1.
FIG. 7 shows the drive 10 at-1V-3M and 10-9And the M rhodamine 6G passes through a characteristic Raman spectrogram of the conical gold nanometer single hole.
FIG. 8 shows the drive 10 at-0.3V-9M hemoglobin (solution is 1M LiNO)3PBS, ph 7.2) by a characteristic raman spectrum of gold nanoperforations.
FIG. 9 is 10-5M and 10-9M hemoglobin molecule (1M LiNO in solution)3PBS of ph 7.2) via hole current signal trace plot.
Detailed Description
The following description of the embodiments of the present invention is provided for further illustration with reference to the following examples and drawings, but should not be construed as limiting the present invention:
example 1
The method for preparing the nano single hole comprises the following steps:
(1) preparing a capillary tip: the apparatus used was a SUTTER P-2000 pin puller, the capillary being a SUTTER quartz capillary (QF:100-70-10, OD:1.00mm, ID:0.70mm) having a total length of 10 cm. The setting parameters are heat 750, parameter 3, location 40, delay 175 and pull 190.
The capillary tip diameter prepared under the above conditions using this gauge capillary was 60nm, as shown in FIG. 4A. The total length of the capillary tube is 2cm, and the rear end of the capillary tube is in a macroscopic size.
(2) Chemical reduction method for preparing precipitateLaminating: a100 mM chloroauric acid solution was injected into the capillary and the capillary tip was immersed in 5mM NaBH at room temperature (25. + -. 1 ℃ C.)4And 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 tube.
(3) Preparing a nano single hole: 100mM chloroauric acid solution was injected into the capillary, then the tip of the capillary was immersed in 100mM chloroauric acid solution, and a gold electrode immersed in the chloroauric acid solution was inserted into each of the inside and outside of the tube as a working electrode and a counter electrode, respectively, which were directly applied with a voltage of 0 to-1.5V by linear sweep voltammetry at a sweep rate of 5mV/s (the Instrument used was CHI-830B, CH Instrument Ins). The gold deposition layer formed by chemical reduction is used as a bipolar electrode, electrochemical reduction is stopped after characteristic current drops, an I-V curve diagram is shown in figure 3, and finally single-hole gold with uniform pore diameter and small pore diameter is obtained by reduction at the tip. Characterization of the nanopore for the capillary tip in the process is shown in fig. 4. Wherein the length of the tapered structure is below 500 nm. The pore size of a single pore is about 13 nm.
(4) And (5) testing the performance.
Electrochemical and Raman tests were performed on the prepared nanopores, and FIG. 4A is a graph of 1M NaNO3I-V curve diagrams before and after the generation of the gold nanometer single hole with the conical structure in the solution. At high salt concentration, the ion rectification phenomenon is obvious after the generation. FIG. 4B is the electrochemical impedance spectrum before and after the generation of the gold nanometer single hole with the cone-shaped structure. In the low frequency region, the impedance increases after nanopore creation, indicating the formation of a small pore size. Fig. 4C is a power spectral density plot before and after the generation of a tapered structured gold nanopore. Although the generated noise of the nano single pore is increased, compared with other existing solid-state nano pores, the nano single pore has lower power spectral density in high-frequency measurement, shows lower noise and has a good application basis on electrochemical detection. Fig. 4D is a graph of raman enhancement effect before and after the formation of tapered gold nanopores. Rhodamine 6G is used as a Raman signal molecule for calculating a Raman enhancement factor, the gold-generated nano single hole shows excellent Raman enhancement effect, and the Raman enhancement factor reaches 1.1 multiplied by 108。
(5) electrochemical-Raman combination
The prepared gold nanometer single hole with the conical structure is applied to the combination of electrochemistry and Raman, and 10 is adopted-9M rhodamine 6G solution is as the determinand, and rhodamine 6G via hole is driven to the negative voltage, and the schematic diagram is shown in FIG. 5. When the concentration of the rhodamine 6G solution to be detected is 10-9And M, a characteristic Raman spectrogram generates a flickering signal, the signal can be obtained by calculation according to the concentration of the rhodamine 6G solution and the ion current of the via hole, and the number of molecules passing through the nanopore is less than one per second. As shown in fig. 6, 10-3Compared with the Raman spectrogram of a standard rhodamine 6G solution under the concentration of M, 10-9Characteristic peaks in a Raman spectrogram of the M rhodamine 6G solution are not uniform, and new peaks different from standard spectral peaks appear, wherein the new peaks are formed by different orientations of a single R6G molecule when passing through a gold nanopore, and single-molecule detection is verified in the next step, which indicates that the detected single-molecule rhodamine 6G is single-molecule.
Example 2
(1) By adjusting the parameters, a quartz capillary tube having a length of 10cm and a tip diameter of 20nm was produced.
(2) Preparing a deposition layer by a chemical reduction method: a200 mM chloroauric acid solution was injected into the capillary, and the capillary tip was immersed in a 100mM ascorbic acid solution at room temperature (25. + -. 1 ℃ C.) for chemical reduction, and reacted for 10min to deposit a tapered gold deposit on the inside of the capillary tip.
(3) Preparing a nano single hole: 200mM of silver nitrate solution is injected into the capillary, then the tip of the capillary is immersed into 5mM of silver nitrate solution, a platinum wire electrode is respectively inserted into the inside and the outside of the capillary and respectively used as a working electrode and a counter electrode, and the working electrode and the counter electrode are directly applied with voltage of-1V by a constant-voltage current-time method. The gold deposition layer formed by chemical reduction is used as a bipolar electrode, the electrochemical reduction is stopped after the current is sharply reduced (about 300s), and finally, the single-hole silver with more uniform 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 pore can also detect the raman characteristic peak of hemoglobin molecule under laser irradiation, and the displacement of partial peaks corresponds to different redox states of single hemoglobin via hole.
Example 3
(1) By adjusting the parameters, a glass capillary tube 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 a nano single hole: 100mM chloroauric acid solution was injected into the capillary, and then the tip of the capillary was immersed in 20mM chloroauric acid solution, and a platinum wire electrode was inserted into the inside and outside of the tube as a working electrode and a counter electrode, respectively, which were directly applied with a voltage of 0 to-5V by linear sweep voltammetry at a sweep rate of 200mV/s (the apparatus used was CHI-830B, CH Instrument Ins). The silver deposition layer is used as a bipolar electrode, electrochemical reduction is stopped after characteristic current drops, and finally uniform single-hole gold is obtained through reduction at the tip. The pore size of a single pore is about 30 nm.
(4) The unimolecular hemoglobin passes through the single hole of the tapered gold nanometer: as shown in fig. 8, the ion current rises every time there is a single molecule of hemoglobin via.
Example 4
(1) By adjusting the parameters, a glass capillary tube 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 capillary tip was immersed in 5mM NaBH at room temperature (25. + -. 1 ℃ C.)4And 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 a nano single hole: 20mM of copper nitrate solution is injected into the capillary, then the tip of the capillary is immersed into 5mM of copper nitrate solution, a platinum wire electrode is respectively inserted into the inside and the outside of the capillary and is respectively used as a working electrode and a counter electrode, and the working electrode and the counter electrode are directly applied with voltage of-5V by a constant-voltage current-time method. The gold deposition layer is used as a bipolar electrode, electrochemical reduction is stopped after 1200s, and finally, more uniform single-hole copper is obtained through reduction at the tip. The pore size of a single pore is about 100 nm.
Example 5
(1) By adjusting the parameters, a quartz capillary tube having a length of 1cm and a tip diameter of 50nm was prepared.
(2) Preparing a deposition layer by a chemical reduction method: a5 mM chloroauric acid solution was injected into the capillary and the capillary tip was immersed in 5mM NaBH at room temperature (25. + -. 1 ℃ C.)4And 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 a nano single hole: 100mM chloroplatinic acid solution was injected into the capillary, and then the tip of the capillary was immersed in 10mM chloroplatinic acid solution, and a platinum wire electrode was inserted into the inside and outside of the tube as a working electrode and a counter electrode, respectively, which were directly applied with a voltage of 0 to-1.5V by linear sweep voltammetry at a sweep rate of 2mV/s (the apparatus used was CHI-830B, CH Instrument Ins.). The gold deposition layer formed by chemical reduction is used as a bipolar electrode, electrochemical reduction is stopped after characteristic current drops, and finally single-hole platinum with uniform pore diameter is obtained by reduction at the tip. The pore diameter of the single pore is about 10 nm.
Claims (10)
1. The nanometer single hole based on the capillary tip is characterized in that a deposition layer is arranged on the inner side wall of the capillary tip, a hollow conical structure extends out of the deposition layer, the nanometer single hole is located at the tip of the conical structure, and preferably, the aperture of the single hole is less than 150 nm.
2. The nanomonopore according to claim 1, characterized in that the material of the tapered structure or the deposited layer is a metal, preferably gold, silver, copper or platinum.
3. The nanomonopore according to claim 1, characterized in that the capillary tip has a diameter of 20 to 200nm, preferably a diameter of 60 nm.
4. The nanomonopore according to claim 1, characterized in that the length of the tapered structure is 500nm or less.
5. A method of preparing a nanomonopore according to any of claims 1 to 4, comprising the steps of:
injecting a first solution of a precursor into the capillary tip having the deposition layer on the inner side wall, then immersing the capillary tip into a second solution of the precursor, and then applying a voltage to the inside and outside of the capillary tip, wherein the precursor obtains electrons to grow on the capillary tip to form the tapered structure, and the nano single hole is located at the tip of the tapered structure.
6. The preparation method according to claim 5, wherein the precursor is a metal ion, preferably a gold ion, a silver ion solution, a copper ion or a platinum ion.
7. The method according to claim 5, wherein the concentration of the first solution of the precursor or the second solution of the precursor is 5 to 200mM, preferably 100 mM.
8. The method for preparing a composite material according to claim 5, wherein the voltage is applied by: one electrode is inserted into the solution inside and outside the capillary tip, and then a voltage is applied between the two electrodes by linear sweep voltammetry or constant voltage amperometry.
9. The manufacturing method of claim 5, wherein the capillary tip having the deposition layer on the inner sidewall is manufactured by a chemical reduction method.
10. Use of the nanomonopore according to any of claims 1 to 5 in chemical or biological analysis, preferably in raman detection.
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