CN211880316U - Biocompatible micro-nano motor and preparation device thereof - Google Patents
Biocompatible micro-nano motor and preparation device thereof Download PDFInfo
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- CN211880316U CN211880316U CN201922328311.1U CN201922328311U CN211880316U CN 211880316 U CN211880316 U CN 211880316U CN 201922328311 U CN201922328311 U CN 201922328311U CN 211880316 U CN211880316 U CN 211880316U
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- 238000002360 preparation method Methods 0.000 title abstract description 19
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims abstract description 19
- 238000005234 chemical deposition Methods 0.000 claims abstract description 17
- 230000033001 locomotion Effects 0.000 claims description 26
- 229920006289 polycarbonate film Polymers 0.000 claims description 7
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 15
- 238000004070 electrodeposition Methods 0.000 abstract description 12
- 238000000151 deposition Methods 0.000 abstract description 9
- 230000008021 deposition Effects 0.000 abstract description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052748 manganese Inorganic materials 0.000 abstract description 8
- 239000011572 manganese Substances 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
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- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000009304 pastoral farming Methods 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 229940109850 royal jelly Drugs 0.000 description 1
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Abstract
The utility model discloses a little nano motor of biocompatible type and preparation facilities thereof belongs to nanometer technical field, combines together ultrasonic field and electrochemical deposition, through the propagation of ultrasonic vibration in liquid, reduces the local ion concentration of deposition area for the manganese content greatly reduced of the little nano motor who prepares reduces the damage to the human body, has certain biocompatibility. The micro-nano motor takes a polyethylene dioxythiophene (PEDOT) layer as a supporting outer layer, a Fe layer as an intermediate layer and MnO2The layer is a three-layer hollow tubular structure of an inner layer; the preparation device comprises: output terminal of signal generatorThe output end of the power amplifier is connected with the ultrasonic auxiliary chemical deposition platform, the ultrasonic auxiliary chemical deposition platform is connected with the electrochemical workstation, and the electrochemical workstation is connected with the computer.
Description
Technical Field
The utility model belongs to the technical field of the nanometer, concretely relates to little nano-motor of biocompatible type and preparation facilities thereof.
Background
With the development of nanoscience and nanotechnology, self-driven micro/nanomachines that convert local chemical fuels or external energy into nanoscale motion have become powerful tools in the fields of active drug delivery, environmental remediation, biological diagnostics, cellular operations, and the like. Methods for synthesizing the nanomotor include an electrodeposition method, a physical vapor deposition, a grazing angle deposition, a crimping method, a 3D laser direct writing method, and the like. Over the last two decades, significant efforts have been made to develop simple and low cost strategies. To date, the three classical modes of electrodeposition (i.e. potentiodynamic, potentiostatic, and galvanostatic) are widely used to fabricate micro/nanomachines to achieve rigid, flexible, tubular and helical micro/nanostructures. The manganese dioxide-based micro-nano motor is a novel micro-nano motor developed in recent years, and has the advantages of rich yield, low cost, high biocompatibility and the like compared with noble metal platinum.
MnO preparation around electrodeposition is currently being performed2Micro-nano motors have been developed for many studies. For example, the use of a mixture of sodium sulfate and manganese acetate as an electrolyte for the electrolytic deposition of manganese dioxide by Royal jelly et al, resulted in a smooth inner layer of dense manganese dioxide PEDOT/MnO2A micron motor. Mixing sodium sulfate, manganese acetate and citric acid, adjusting pH of the solution to alkaline, and using the solution as manganese dioxide electrolyte to obtain tubular PEDOT/MnO with rough and porous inner layer2A micron motor. Manganese dioxide is prepared by Sunhong flag et al in graphene tube inner layer by constant potential deposition to obtain erGo/MnO2The tubular nano motor can move at a speed of more than 700 [ mu ] m/s at the fastest speed.
Due to the limitation of the difficulty of the existing preparation technology, the element composition and the surface morphology of the micro-nano motor prepared by the electrodeposition method at present are generally changed by adjusting the deposition charge quantity and the deposition elements, and the methods are usually realized from the chemical aspect, are not accurate in regulation and control of element components and cannot form unique surface morphology. At present, a technology for changing the element composition and the surface appearance of the micro-nano motor by combining the preparation process of the micro-nano motor with the action of an ultrasonic field does not exist. The ultrasonic field can realize the change of the local ion concentration of the deposition area, so that the element content and the structure are changed in the electrochemical deposition process. Therefore, the research of the ultrasonic-assisted electrochemical deposition preparation of the micro-nano motor has obvious practical significance and practical value.
Disclosure of Invention
The invention provides a biocompatible micro-nano motor and a preparation device thereof, wherein an ultrasonic field is combined with electrochemical deposition, and the local ion concentration of a deposition area is reduced through the propagation of ultrasonic vibration in liquid, so that the manganese content of the prepared micro-nano motor is greatly reduced, the damage to a human body is reduced, and the biocompatible micro-nano motor has certain biocompatibility.
In order to achieve the purpose, the invention adopts the following technical scheme:
a biocompatible micro-nano motor is of a three-layer hollow tubular structure, a polyethylene dioxythiophene (PEDOT) layer is a supporting outer layer, a Fe layer is an intermediate layer, and MnO is added2The layer is an inner layer.
The length of the micro-nano motor is 10-20 mu m, and the outer diameter of the micro-nano motor is 4-8 mu m; the motion mode of the micro-nano motor is circular motion, autorotation circular motion or motion formed by superposing the motions, and the circular motion is that the micro-nano motor per se moves around the circumference in a circumferential tangent mode; the autorotation circular motion is formed by the rotation of the micro-nano motor at a fixed point in a circular radius mode.
A preparation device of a biocompatible micro-nano motor comprises: the device comprises a signal generator 1, a power amplifier 2, an electrochemical workstation 3, an ultrasonic auxiliary chemical deposition platform 4 and a computer 5; the output end of the signal generator 1 is connected with the input end of the power amplifier 2, the output end of the power amplifier 2 is connected with the ultrasonic auxiliary type chemical deposition platform 4, the ultrasonic auxiliary type chemical deposition platform 4 is connected with the electrochemical workstation 3, and the electrochemical workstation 3 is connected with the computer 5.
In the device, the signal generator 1 is a signal generator capable of generating 50-1000 kHz sine waves, square waves and triangular waves; the power amplifier 2 is a high-frequency power amplifier, and the ultrasonic field frequency of the ultrasonic auxiliary chemical deposition platform 4 is 50-500 kHz; the ultrasonic auxiliary chemical deposition platform 4 comprises an electrolytic cell 6, an ultrasonic transducer 7, a bottom plate 8, a bottom supporting structure 9, a working electrode 10, an auxiliary electrode 11 and a reference electrode 12; the bottom of the electrolytic cell 6 is connected with the bottom plate 8 through bolts, and a sealing ring is added at the bottom of the electrolytic cell to prevent the electrolyte from leaking; the ultrasonic transducer 7 is fixedly connected to the lower surface of the bottom plate 8 through glue, and when the ultrasonic transducer works, external electric signals are converted into mechanical vibration by the ultrasonic transducer, and the vibration is transmitted to electrolyte through the bottom plate; the bottom supporting structure 9 is used as a supporting structure and is arranged below the bottom plate 8, so that the ultrasonic transducer 7 is in a suspended state and is prevented from contacting with the ultrasonic transducer 7, and the working electrode 10, the auxiliary electrode 11 and the reference electrode 12 are arranged in the electrolytic cell 6.
The working electrode 10 is a polycarbonate film subjected to Au sputtering treatment, the auxiliary electrode 11 is a platinum wire or a stainless steel sheet, and the reference electrode 12 is an Ag/AgCl electrode; the thickness of the Au layer on the working electrode 10 is 30-45 nm.
The electrolytic cell 6 is a hollow cylindrical structure made of Polytetrafluoroethylene (PTFE), and has an outer diameter of 50mm, an inner diameter of 20mm and a height of 50 mm. The ultrasonic transducer 7 is a sandwich Langewen transducer, the working frequency is 50-500 kHz, and the working voltage is 50-100V. The bottom plate 8 is made of organic glass and has the size of 50 x 50 x 5 mm3。
Has the advantages that: the invention provides a biocompatible micro-nano motor and a preparation device thereof, wherein the preparation process of the micro-nano motor is combined with the action of an ultrasonic field, so that the element composition and the surface appearance of the micro-nano motor are changed; the ultrasonic field can realize the change of the local ion concentration of the deposition area, so that the element content and the structure are changed in the electrochemical deposition process. MnO2MnO as a hydrogen peroxide solution decomposition catalyst2The content is in direct proportion to the movement speed, the high manganese content is required to obtain the micro-nano motor moving at high speed, but the high manganese content means great harm to human bodies,after the preparation device is introduced into ultrasonic field assisted preparation, the movement speed of the micro-nano motor can reach 300-700 mu m/s, and compared with a nano motor with high manganese content, the speed is not reduced, while the content of manganese in the micro-nano motor prepared by the preparation device is reduced from 17.68% to 4.71% -11.33%, the damage to human bodies is small, and the preparation device has better biocompatibility.
Drawings
FIG. 1 is a schematic diagram of a three-layer structure of a micro-nano motor;
FIG. 2 is a schematic diagram of a micro-nano motor manufacturing apparatus;
FIG. 3 is a schematic structural diagram of an ultrasonic-assisted chemical deposition platform;
FIG. 4 is a scanning electron microscope image of the micro-nano motor;
FIG. 5 is a scanning electron microscope image of the micro-nano motor pipe orifice;
FIG. 6 is a diagram of a micro-nano motor moving around a circle;
FIG. 7 is a diagram of the autorotation circular motion trajectory of the micro-nano motor;
in the figure, 1 is a signal generator, 2 is a power amplifier, 3 is an electrochemical workstation, 4 is an ultrasonic auxiliary chemical deposition platform, 5 is a computer, 6 is an electrolytic cell, 7 is an ultrasonic transducer, 8 is a bottom plate, 9 is a bottom supporting structure, 10 is a working electrode, 11 is an auxiliary electrode, and 12 is a reference electrode.
Detailed Description
The invention is described in detail below with reference to the following figures and specific examples:
as shown in fig. 1 and 4, the biocompatible micro-nano motor is a three-layer hollow tubular structure, the polyethylene dioxythiophene (PEDOT) layer is a supporting outer layer, the Fe layer is an intermediate layer, and MnO is added2The layer is an inner layer.
The length of the micro-nano motor is 10-20 micrometers, the outer diameter of the micro-nano motor is 4-8 micrometers, the motion mode of the micro-nano motor is circular motion, autorotation circular motion or motion formed by superposition of the circular motion and the autorotation circular motion, as shown in figure 6, the circular motion is that the micro-nano motor moves around the circumference in a circular tangent mode; as shown in fig. 7, the rotation circular motion is formed by the micro-nano motor rotating at a fixed point in a circular radius manner.
As shown in fig. 2, a device for preparing a biocompatible micro-nano motor includes: the device comprises a signal generator 1, a power amplifier 2, an electrochemical workstation 3, an ultrasonic auxiliary chemical deposition platform 4 and a computer 5; the output end of the signal generator 1 is connected with the input end of the power amplifier 2, the output end of the power amplifier 2 is connected with the ultrasonic auxiliary type chemical deposition platform 4, the ultrasonic auxiliary type chemical deposition platform 4 is connected with the electrochemical workstation 3, and the electrochemical workstation 3 is connected with the computer 5.
In the device, the signal generator 1 is a signal generator capable of generating 50-1000 kHz sine waves, square waves and triangular waves; the power amplifier 2 is a high-frequency power amplifier, and the ultrasonic field frequency is 50-500 kHz.
As shown in fig. 3, the ultrasonic-assisted chemical deposition platform 4 comprises an electrolytic cell 6, an ultrasonic transducer 7, a bottom plate 8, a bottom support structure 9, a working electrode 10, an auxiliary electrode 11 and a reference electrode 12; the bottom of the electrolytic cell 6 is connected with the bottom plate 8 through bolts, and a sealing ring is added at the bottom of the electrolytic cell to prevent the electrolyte from leaking; the ultrasonic transducer 7 is fixedly connected to the lower surface of the bottom plate 8 through glue, and when the ultrasonic transducer works, external electric signals are converted into mechanical vibration by the ultrasonic transducer, and the vibration is transmitted to electrolyte through the bottom plate; the bottom supporting structure 9 is used as a supporting structure and is arranged below the bottom plate 8, so that the ultrasonic transducer 7 is in a suspended state and is prevented from contacting with the ultrasonic transducer 7, and the working electrode 10, the auxiliary electrode 11 and the reference electrode 12 are arranged in the electrolytic cell 6.
The working electrode 10 is a polycarbonate film subjected to Au sputtering treatment, the auxiliary electrode 11 is a platinum wire or a stainless steel sheet, and the reference electrode 12 is an Ag/AgCl electrode; the thickness of the Au layer on the working electrode 10 is 30-45 nm.
The electrolytic cell 6 is a hollow cylindrical structure made of Polytetrafluoroethylene (PTFE), and has an outer diameter of 50mm, an inner diameter of 20mm and a height of 50 mm. The ultrasonic transducer 7 is a sandwich Langewen transducer, the working frequency is 50-500 kHz, and the working voltage is 50-100V. The bottom plate 8 is made of organic glass and has a size of 50 x 50 x 5 mm3。
Connecting the devices according to the structure, taking a polycarbonate film subjected to Au sputtering treatment as a working electrode, a platinum wire as an auxiliary electrode, an Ag/AgCl electrode as a reference electrode, adding an electrolyte of polyethylene dioxythiophene (PEDOT) into an electrolytic cell, and performing electrochemical deposition on an outer layer of the polyethylene dioxythiophene (PEDOT) support by using an electrochemical workstation; taking the polycarbonate film subjected to Au sputtering as a working electrode, a stainless steel sheet as an auxiliary electrode and an Ag/AgCl electrode as a reference electrode, and carrying out electrochemical deposition on a Fe intermediate layer on the basis of the prepared polyethylene dioxythiophene (PEDOT) support outer layer; then combining the action of an ultrasonic field, wherein the voltage of the ultrasonic field is 50-100V, the amplitude is 100-200 nm, the frequency is 50 kHz-70 kHz, the main vibration direction is Z direction, a polycarbonate film subjected to Au sputtering treatment is taken as a working electrode, a stainless steel sheet is taken as an auxiliary electrode, an Ag/AgCl electrode is taken as a reference electrode, the ultrasonic field is applied, and MnO is carried out on the basis that the outer layer and the Fe intermediate layer are supported by the obtained polyethylene dioxythiophene (PEDOT)2Electrochemical deposition of the inner layer; finally, the obtained outer layer containing polyethylene dioxythiophene (PEDOT), the Fe intermediate layer and MnO2And polishing, dissolving and centrifuging the polycarbonate film on the inner layer to obtain the hollow tubular micro-nano motor.
The manganese content in the micro-nano motor is reduced to 4.71% -11.33% from 17.68%, after an ultrasonic field auxiliary preparation device is introduced into the preparation device, the movement speed of the micro-nano motor can still reach 300-700 mu m/s, and compared with a nano motor with high manganese content, the movement speed is not reduced, but the damage to a human body is small, and the biological compatibility is better.
The above description is only a preferred embodiment of the present invention, and the purpose, technical solution and advantages of the present invention are further described in detail without limiting the invention, and any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. Biocompatible micro-scaleThe nano motor is characterized in that the micro-nano motor is of a three-layer hollow tubular structure, the polyethylene dioxythiophene layer is a supporting outer layer, the Fe layer is a middle layer, and MnO is added2The layer is an inner layer; the length of the micro-nano motor is 10-20 mu m, and the outer diameter of the micro-nano motor is 4-8 mu m; the motion mode of the micro-nano motor is the motion formed by encircling circular motion, autorotation circular motion or superposition of the motions.
2. A device for preparing a biocompatible micro-nano motor according to claim 1, comprising: the device comprises a signal generator (1), a power amplifier (2), an electrochemical workstation (3), an ultrasonic auxiliary chemical deposition platform (4) and a computer (5); the output end of the signal generator (1) is connected with the input end of the power amplifier (2), the output end of the power amplifier (2) is connected with the ultrasonic auxiliary chemical deposition platform (4), the ultrasonic auxiliary chemical deposition platform (4) is connected with the electrochemical workstation (3), and the electrochemical workstation (3) is connected with the computer (5).
3. The manufacturing device of the biocompatible micro-nano motor according to claim 2, wherein the signal generator (1) is a signal generator capable of generating 50-1000 kHz sine waves, square waves and triangular waves; the power amplifier (2) is a high-frequency power amplifier.
4. The apparatus for preparing biocompatible micro-nano motor according to claim 2, wherein the ultrasonic-assisted chemical deposition platform (4) comprises an electrolytic cell (6), an ultrasonic transducer (7), a bottom plate (8), a bottom support structure (9), a working electrode (10), an auxiliary electrode (11) and a reference electrode (12); the bottom of the electrolytic cell (6) is connected with the upper surface of the bottom plate (8), the ultrasonic transducer (7) is fixedly connected to the lower surface of the bottom plate (8), the bottom supporting structure (9) is placed below the bottom plate (8) as a supporting structure, the ultrasonic transducer (7) is in a suspended state and is prevented from contacting with the ultrasonic transducer (7), and the working electrode (10), the auxiliary electrode (11) and the reference electrode (12) are arranged in the electrolytic cell (6).
5. The manufacturing device of the biocompatible micro-nano motor according to claim 4, wherein the working electrode (10) is a polycarbonate film sputtered with a 30-45nm Au layer, the auxiliary electrode (11) is a platinum wire or a stainless steel sheet, and the reference electrode (12) is an Ag/AgCl electrode.
6. The apparatus for preparing biocompatible micro-nano motor according to claim 4, wherein a sealing ring is added at the bottom of the electrolytic cell (6).
7. The apparatus for preparing biocompatible micro-nano motor according to claim 4 or 6, wherein the electrolytic cell (6) is hollow cylindrical structure and made of polytetrafluoroethylene.
8. The apparatus for preparing biocompatible micro-nano motor according to claim 4, wherein the ultrasonic transducer (7) is a sandwich Lanjivin transducer, the working frequency is 50-500 kHz, and the working voltage is 50-100V; the bottom plate (8) is made of organic glass material and has the size of 50 x 50 x 5 mm3。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111082705A (en) * | 2019-12-23 | 2020-04-28 | 南京航空航天大学 | Biocompatible iron-manganese dioxide system micro-nano motor and preparation method thereof |
| CN113418971A (en) * | 2021-05-27 | 2021-09-21 | 南京航空航天大学 | Electrochemical sensor based on micro-nano ultrasonic robot |
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2019
- 2019-12-23 CN CN201922328311.1U patent/CN211880316U/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111082705A (en) * | 2019-12-23 | 2020-04-28 | 南京航空航天大学 | Biocompatible iron-manganese dioxide system micro-nano motor and preparation method thereof |
| CN113418971A (en) * | 2021-05-27 | 2021-09-21 | 南京航空航天大学 | Electrochemical sensor based on micro-nano ultrasonic robot |
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