CN107639228B - The preparation method of gallium-indium-tin alloy nanometer rods and its application as nano-motor - Google Patents
The preparation method of gallium-indium-tin alloy nanometer rods and its application as nano-motor Download PDFInfo
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- CN107639228B CN107639228B CN201710786022.9A CN201710786022A CN107639228B CN 107639228 B CN107639228 B CN 107639228B CN 201710786022 A CN201710786022 A CN 201710786022A CN 107639228 B CN107639228 B CN 107639228B
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Abstract
The present invention provides a kind of preparation method of gallium-indium-tin alloy nanometer rods and its as the application of nano-motor, belong to preparation and the actuation techniques field of micro-nano motor.The present invention corresponds to 20mL decentralized medium according to 1g liquid metal and feeds intake, and decentralized medium is the mixture of deionized water, methanol and ethyl alcohol；Instrument is crushed using probe type ultrasonic and carries out ultrasonication, and in 800~1000W, the time is 3~6h for ultrasonic power control, during which pays attention to supplementing the dispersing agent because of ultrasonic cavitation loss；After ultrasound, the disperse system of acquisition is stood into 12h, makes its abundant aging；Disperse system after aging is centrifuged 3min under the conditions of 750*G, takes supernatant, includes the liquid metal nanometer rods of preparation in supernatant；It after liquid metal nanometer rods are prepared, under the electric field action that enzymatic reaction is formed, can controllably be assembled in disperse system, obtain the micro-nano motor with the enzyme chemotactic of patterned group behavior.
Description
Technical field
The present invention relates to a kind of preparation method of gallium-indium-tin alloy nanometer rods and its as the application of nano-motor, belong to gallium
The applied technical field of the preparation of indium stannum alloy nanometer rods as well as enzyme-electrophoresis driving nano-motor.
Background technique
As research hotspot in recent years, liquid metal receives the concern of a large amount of researchers.Wherein, gallium indium tin is closed
Golden (Galinstan) overcomes the defect that pure gallium can not be in a liquid state in the environment of chilling temperature, gallium-indium-tin alloy
Fusing point liquid can be kept under most of low temperature environments down to -19 DEG C, it is wider that this has gallium-indium-tin alloy
General application type and method, especially when reaching nanoscale, the physics of gallium-indium-tin alloy, chemical property may be shown
With the difference under block state, this has prompted new research direction for nano science.
Artificial micro-nano motor is one of the research hotspot of nano science in recent years, and liquid metal is as hot spot material, together
Sample can be applied in the research of micro-nano motor.The excellent of smaller nanoparticle can be prepared using physical dispersion under ultrasonic field
Point using the liquid metal nanometer rods of the lesser gallium-indium-tin alloy of ultrasonication preparation scale, and utilizes the surface of nanometer rods electricity
Lotus is moved and is assembled in the electric field for forming it under enzymatic reaction.This thinking will expand liquid metal and micro-nano motor
In the application prospect of biological medicine related fields.
Summary of the invention
The problem of the purpose of the present invention is to solve the propositions of above-mentioned background technique, and then a kind of gallium-indium-tin alloy is provided and is received
The preparation method of rice stick and its application as nano-motor.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of preparation method of gallium-indium-tin alloy nanometer rods, steps are as follows:
Feed intake Step 1: corresponding to 20mL decentralized medium according to 1g gallium-indium-tin alloy, decentralized medium be deionized water, methanol with
The mixture of ethyl alcohol；
Step 2: being crushed instrument using probe type ultrasonic carries out ultrasonication, ultrasonic power was controlled in 800~1000W, time
For 3~6h, during which pay attention to supplementing the dispersing agent because of ultrasonic cavitation loss, the dispersing agent that when supplement uses is opened with this step in principle
The dispersing agent proportion used when the beginning is identical；
Step 3: the disperse system of acquisition is stood 10~14h, makes its abundant aging after ultrasound；
Step 4: the disperse system after aging is centrifuged 2~4min under the conditions of 750*G, supernatant is taken, is wrapped in supernatant
Gallium-indium-tin alloy liquid metal nanometer rods containing preparation, the diameter of gallium-indium-tin alloy liquid metal nanometer rods is 50~200nm, long
Degree is 0.6~1.3 μm.
In step 1, the volume ratio of deionized water, methanol and ethyl alcohol is 7:1:2 in the decentralized medium.
In step 1, the volume ratio of deionized water, methanol and ethyl alcohol is 3:1:1 in the decentralized medium.
In step 2, the ultrasonic power control is in 800W, time 5h.
In step 2, the ultrasonic power control is in 900W, time 4h.
In step 2, the ultrasonic power control is in 800W, time 3h.
In step 2, the ultrasonic power control is in 1000W, time 6h.
In step 3, after ultrasound, the disperse system of acquisition is stood into 12h.
3min is centrifuged under the conditions of 750*G in step 4, by the disperse system after aging.
Gallium-indium-tin alloy liquid metal nanometer rods as nano-motor application, by gallium-indium-tin alloy liquid metal nanometer rods
It is put into decentralized medium, under the effect of the ion gradient caused by enzymatic reaction, makes gallium-indium-tin alloy liquid metal nanometer rods to enzyme
Promote the region clustering that reaction occurs, obtains enzyme-electrophoresis driving micro-nano motor with patterned group behavior.
The motion principle of motor is in the present invention: the surface of gallium-indium-tin alloy liquid metal nanometer rods is negatively charged, utilizes
Enzymatic reaction generates cation, i.e. positive charge in the region that enzymatic reaction occurs, and positive charge forms electric-force gradient to external diffusion,
Due to the effect of electrophoresis, gallium-indium-tin alloy nano-motor can be mobile to the big region of positive charge density, will after a period of time
Form the pattern for surrounding enzymatic reaction region.
Preparation method process of the invention is simple to operation, and the liquid metal nano-motor of electrophoresis driving, which has, well may be used
Aggregation is controlled, makes the Assembling Behavior that there is higher biocompatibility in conjunction with enzymatic reaction, is had in biological medicine related fields
Have broad application prospects.
Detailed description of the invention
Fig. 1 is the stereoscan photograph of the liquid metal nanometer rods prepared using gallium metal, 3 μm of scale.
Fig. 2 is the transmission electron microscope photo of the liquid metal nanometer rods prepared using gallium metal, scale 500nm.
Fig. 3 is the comparison photo that gallium-indium-tin alloy nano-motor forms pattern in aggregation: upper figure is photo before assembling；The following figure
For aggregation after photo, 50 μm of scale.
Specific embodiment
The present invention is described in further detail below: the present embodiment under the premise of the technical scheme of the present invention into
Row is implemented, and gives detailed embodiment, but protection scope of the present invention is not limited to following embodiments.
Embodiment 1
The decentralized medium used in the present embodiment is the mixture of deionized water, methanol and ethyl alcohol, in the decentralized medium
The volume ratio of deionized water, methanol and ethyl alcohol is 7:1:2, and preparing instrument is Ultrasonic Cell Disruptor.
Gallium-indium-tin alloy and mixed dispersant are put into beaker according to the corresponding 20mL decentralized medium of 1g liquid metal, 800W
Ultrasonication 5h under power after ultrasonic, stands 12h, and 750*G is centrifuged 3min, supernatant is taken to save.
0.6~1.0 μm of the nanorod length of preparation, diameter about 120nm.
Embodiment 2
The decentralized medium used in the present embodiment is the mixture of deionized water, methanol and ethyl alcohol, in the decentralized medium
The volume ratio of deionized water, methanol and ethyl alcohol is 7:1:2, and preparing instrument is Ultrasonic Cell Disruptor.
Gallium-indium-tin alloy and mixed dispersant are put into beaker according to the corresponding 20mL decentralized medium of 1g liquid metal, 900W
Ultrasonication 5h under power after ultrasonic, stands 12h, and 750*G is centrifuged 3min, supernatant is taken to save.
0.8~1.2 μm of the nanorod length of preparation, diameter about 100nm.
Embodiment 3
The decentralized medium used in the present embodiment is the mixture of deionized water, methanol and ethyl alcohol, in the decentralized medium
The volume ratio of deionized water, methanol and ethyl alcohol is 3:1:1, and preparing instrument is Ultrasonic Cell Disruptor.
Gallium-indium-tin alloy and mixed dispersant are put into beaker according to the corresponding 20mL decentralized medium of 1g liquid metal, 800W
Ultrasonication 3h under power after ultrasonic, stands 12h, and 750*G is centrifuged 3min, supernatant is taken to save.
1~1.3 μm of the nanorod length of preparation, diameter about 130nm.
Embodiment 4
The decentralized medium used in this example is the mixture of deionized water, methanol and ethyl alcohol, deionized water, methanol and second
The volume ratio of alcohol is 3:1:1, and preparing instrument is Ultrasonic Cell Disruptor.
Gallium-indium-tin alloy and mixed dispersant are put into beaker according to the corresponding 20mL decentralized medium of 1g liquid metal,
Ultrasonication 6h under 1000W power after ultrasonic, stands 12h, and 750*G is centrifuged 3min, supernatant is taken to save.
0.6~0.9 μm of the nanorod length of preparation, diameter about 70nm.
Embodiment 5
The evaluation method and result of liquid metal nanorod structure.
Use scanning electron microscope (FEI Quanta 200F, USA) and transmission electron microscope (Hitachi H-
7650, Japan) pattern of the gallium-indium-tin alloy nanometer rods of characterization preparation, it has been observed that the nanometer rods of preparation are generally in cylinder
Shape, the curved surface pattern of under scanning electron microscope secondary electron mode it is observed that side, each section diameter basic one of single nanometer rods
It causes；The length of nanometer rods is 0.6~1.3 μm, and diameter is 50~200nm.
Embodiment 6
Controllable aggregation of the gallium-indium-tin alloy nano-motor under enzymatic reaction
In the present embodiment, need to prepare the hydrogel fritter of limitation enzymatic conversion zone, the specific steps are as follows:
Step 1: configuration concentration is the sodium alginate soln of 5mg/mL, and glucose oxidase is adulterated wherein, adulterate dense
Degree is 1mg/mL；
Step 2: taking the solution 5mL prepared in step 1, the calcium chloride solution 0.2mL of 5mol/L is added thereto, rapidly
The solution is uniformly mixed, and is poured into clean plastic culture dish；
Step 3: standing, after calcium alginate hydrogel solidification, hydrogel is taken out, and be cut into 1mm*1mm square, soaked
It steeps spare in phosphate buffer.
In the present embodiment, need to prepare dimethyl silicone polymer channel, the specific steps are as follows:
Step 1: dimethylsiloxane monomer/crosslinker mixture that premix finishes is sprawled in clean slide surface,
Sprawling thickness degree is about 1mm, is crosslinked 2h at 80 DEG C；
Step 2: taking out glass slide after the completion of crosslinking, depicting 10mm*2mm in dimethyl silicone polymer with scalpel
Groove, as channel standby.
Steps are as follows for the major experimental of the present embodiment:
Step 1: gallium-indium-tin alloy nano-motor (gallium-indium-tin alloy liquid metal nanometer rods) are added 0.001mol/L's
In glucose solution, mixed number concentration is about 105/mL；
Step 2: the mixture in step 1 is added in ready dimethyl silicone polymer channel, and leaned in channel
The position of nearly side is put into the ready calcium alginate hydrogel fritter for being doped with glucose oxidase, and hydrogel is stopped with medical
Blood glue is sticked on toothpick, is allowed to fixed and can be suspended in channel in liquid, contact with liquid but not contact with the bottom of the channel；
It is received Step 3: observing and recording gallium-indium-tin alloy using optical microscope system (Olympus CKX-41, Japan)
The motion conditions of meter Ma Da, it has been observed that gallium-indium-tin alloy nano-motor occurs after the hydrogel fritter 120min containing enzyme is added
Apparent clustering phenomena.
The present embodiment demonstrates the controllable aggregation of the liquid metal nano-motor of electrophoresis driving, makes in conjunction with enzymatic reaction
The Assembling Behavior has higher biocompatibility, has a extensive future.
The foregoing is only a preferred embodiment of the present invention, these specific embodiments are all based on the present invention
Different implementations under general idea, and scope of protection of the present invention is not limited thereto, it is any to be familiar with the art
Technical staff in the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of, should all cover of the invention
Within protection scope.Therefore, the scope of protection of the invention shall be subject to the scope of protection specified in the patent claim.
Claims (9)
1. a kind of gallium-indium-tin alloy liquid metal nanometer rods exist as enzyme-electrophoresis driving nano-motor preparation method, feature
In,
Step 1: gallium-indium-tin alloy nano-motor is added in the glucose solution of 0.001mol/L, mixed number concentration is
105A/mL；
Step 2: the mixture in step 1 is added in ready dimethyl silicone polymer channel, and in channel close to one
The position of side is put into the ready calcium alginate hydrogel fritter for being doped with glucose oxidase, and hydrogel fritter is stopped with medical
Blood glue is sticked on toothpick, is allowed to fix and be suspended in channel in liquid, is contacted but do not contacted with the bottom of the channel with liquid；
Step 3: the motion conditions of gallium-indium-tin alloy nano-motor are observed and recorded using optical microscope system, it has been observed that
After addition is doped with the calcium alginate hydrogel fritter 120min of glucose oxidase, gallium-indium-tin alloy nano-motor occurs bright
Aobvious clustering phenomena；
In step 1, gallium-indium-tin alloy nano-motor the preparation method is as follows:
Step (1) corresponds to 20mL decentralized medium according to 1g gallium-indium-tin alloy and feeds intake, and decentralized medium is deionized water, methanol and second
The mixture of alcohol；
Step (2) is crushed instrument using probe type ultrasonic and carries out ultrasonication, and ultrasonic power is controlled in 800~1000W, and the time is
3~6h, during which pays attention to supplementing the dispersing agent because of ultrasonic cavitation loss, and the dispersing agent that when supplement uses is started with this step
Dispersing agent proportion it is identical；
After step (3), ultrasound, the disperse system of acquisition is stood into 10~14h, makes its abundant aging；
Disperse system after aging is centrifuged 2~4min by step (4) under the conditions of 750*g, is taken supernatant, is included in supernatant
The gallium-indium-tin alloy liquid metal nanometer rods of preparation, the diameter of gallium-indium-tin alloy liquid metal nanometer rods are 50~200nm, length
It is 0.6~1.3 μm；Gallium-indium-tin alloy liquid metal nanometer rods are gallium-indium-tin alloy nano-motor；
In step 2, dimethyl silicone polymer channel the preparation method is as follows:
Step I sprawls dimethylsiloxane monomer/crosslinker mixture that premix finishes in clean slide surface, sprawls
Layer is crosslinked 2h at 80 DEG C with a thickness of 1mm；
After the completion of step II, crosslinking, glass slide is taken out, depicts the ditch of 10mm*2mm in dimethyl silicone polymer with scalpel
Slot, as channel standby；
In step 2, be doped with the calcium alginate hydrogel fritter of glucose oxidase the preparation method is as follows:
Step 1, configuration concentration are the sodium alginate soln of 5mg/mL, and adulterate glucose oxidase wherein, and doping concentration is
1mg/mL；
Step 2 takes the solution 5mL prepared in step 1, and the calcium chloride solution 0.2mL of 5mol/L is added thereto, rapidly that this is molten
Liquid is uniformly mixed, and is poured into clean plastic culture dish；
Step 3 is stood, and after calcium alginate hydrogel solidification, is taken out hydrogel, and be cut into 1mm*1mm square, is immersed in phosphorus
It is spare in phthalate buffer.
2. gallium-indium-tin alloy liquid metal nanometer rods according to claim 1 are as enzyme-electrophoresis driving nano-motor system
Preparation Method, which is characterized in that in step (1), the volume ratio of deionized water, methanol and ethyl alcohol is 7:1 in the decentralized medium:
2。
3. gallium-indium-tin alloy liquid metal nanometer rods according to claim 1 are as enzyme-electrophoresis driving nano-motor system
Preparation Method, which is characterized in that in step (1), the volume ratio of deionized water, methanol and ethyl alcohol is 3:1 in the decentralized medium:
1。
4. gallium-indium-tin alloy liquid metal nanometer rods according to claim 1 are as enzyme-electrophoresis driving nano-motor system
Preparation Method, which is characterized in that in step (2), the ultrasonic power control is in 800W, time 5h.
5. gallium-indium-tin alloy liquid metal nanometer rods according to claim 1 are as enzyme-electrophoresis driving nano-motor system
Preparation Method, which is characterized in that in step (2), the ultrasonic power control is in 900W, time 4h.
6. gallium-indium-tin alloy liquid metal nanometer rods according to claim 1 are as enzyme-electrophoresis driving nano-motor system
Preparation Method, which is characterized in that in step (2), the ultrasonic power control is in 800W, time 3h.
7. gallium-indium-tin alloy liquid metal nanometer rods according to claim 1 are as enzyme-electrophoresis driving nano-motor system
Preparation Method, which is characterized in that in step (2), the ultrasonic power control is in 1000W, time 6h.
8. gallium-indium-tin alloy liquid metal nanometer rods according to claim 1 are as enzyme-electrophoresis driving nano-motor system
Preparation Method, which is characterized in that in step (3), after ultrasound, the disperse system of acquisition is stood into 12h.
9. gallium-indium-tin alloy liquid metal nanometer rods according to claim 1 are as enzyme-electrophoresis driving nano-motor system
Preparation Method, which is characterized in that be centrifuged 3min under the conditions of 750*g in step (4), by the disperse system after aging.
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| US6933331B2 (en) * | 1998-05-22 | 2005-08-23 | Nanoproducts Corporation | Nanotechnology for drug delivery, contrast agents and biomedical implants |
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| JP2003293097A (en) * | 2002-04-03 | 2003-10-15 | Sumitomo Special Metals Co Ltd | Rapidly solidified alloy for nano-composite magnet, and its manufacturing method |
| WO2007001098A1 (en) * | 2005-06-25 | 2007-01-04 | Seoul Opto Device Co., Ltd. | Nanostructure having a nitride-based quantum well and light emitting diode employing the same |
| CN101165213A (en) * | 2007-08-08 | 2008-04-23 | 哈尔滨工业大学 | Method for preparing nano-stick array electrode capable of self-assembling after dispersing |
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