CN107639228A - 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 PDF

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CN107639228A
CN107639228A CN201710786022.9A CN201710786022A CN107639228A CN 107639228 A CN107639228 A CN 107639228A CN 201710786022 A CN201710786022 A CN 201710786022A CN 107639228 A CN107639228 A CN 107639228A
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gallium
indium
nanometer rods
tin alloy
preparation
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CN107639228B (en
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贺强
李泽生
郭斌
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Harbin Institute of Technology
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Harbin Institute of Technology
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Abstract

The invention provides a kind of preparation method of gallium-indium-tin alloy nanometer rods and its application as nano-motor, belong to preparation and the actuation techniques field of micro-nano motor.The present invention corresponds to 20mL decentralized media according to 1g liquid metals and fed intake, and decentralized medium is the mixture of deionized water, methanol and ethanol;Instrument is crushed using probe type ultrasonic and carries out ultrasonication, and ultrasonic power control is 3~6h in 800~1000W, time, during which pays attention to dispersant of the supplement because of ultrasonic cavitation loss;After ultrasound terminates, the disperse system of acquisition is stood into 12h, makes its abundant aging;Disperse system after aging is centrifuged into 3min under the conditions of 750*G, takes supernatant, the liquid metal nanometer rods of preparation are included in supernatant;After liquid metal nanometer rods are prepared, under the electric field action that enzymatic reaction is formed, controllable aggregation can be carried out in disperse system, obtains the micro-nano motor of the enzyme chemotactic of the group behavior with patterning.

Description

The preparation method of gallium-indium-tin alloy nanometer rods and its application as nano-motor
Technical field
The present invention relates to a kind of preparation method of gallium-indium-tin alloy nanometer rods and its application as nano-motor, belong to gallium The applied technical field of the nano-motor of the preparation of indium stannum alloy nanometer rods as well as enzyme-electrophoresis driving.
Background technology
As study hotspot in recent years, liquid metal receives the concern of a large amount of researchers.Wherein, gallium indium tin is closed Golden (Galinstan) overcomes pure gallium can not be in a liquid state in the environment of chilling temperature the defects of, gallium-indium-tin alloy Fusing point can as little as -19 DEG C, liquid can be kept under most of low temperature environments, it is wider that this allows gallium-indium-tin alloy to have 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 is that nano science has prompted new research direction.
Artificial micro-nano motor is one of study hotspot of nano science in recent years, and liquid metal is as focus material, together Sample can apply in the research of micro-nano motor.The excellent of smaller nano-particle can be prepared using physical dispersion under ultrasonic field Point, using the liquid metal nanometer rods of the less gallium-indium-tin alloy of ultrasonication preparation scale, and utilize the surface electricity of nanometer rods Lotus, make to move and assemble in the electric field that it forms under enzymatic reaction.This thinking will expand liquid metal and micro-nano motor In the application prospect of biological medicine association area.
The content of the invention
The invention aims to solve the problems, such as that above-mentioned background technology proposes, and then a kind of gallium-indium-tin alloy is provided and received The preparation method of rice rod and its application as nano-motor.
The purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of gallium-indium-tin alloy nanometer rods, step are as follows:
Fed intake Step 1: corresponding to 20mL decentralized media according to 1g gallium-indium-tin alloys, decentralized medium be deionized water, methanol with The mixture of ethanol;
Step 2: crushing instrument using probe type ultrasonic carries out ultrasonication, ultrasonic power was controlled in 800~1000W, time For 3~6h, dispersant of the supplement because of ultrasonic cavitation loss is during which paid attention to, the dispersant used during supplement is opened with this step in principle The dispersant proportioning used during the beginning is identical;
Step 3: after ultrasound terminates, the disperse system of acquisition is stood into 10~14h, makes its abundant aging;
Step 4: the disperse system after aging is centrifuged into 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, a diameter of 50~200nm of gallium-indium-tin alloy liquid metal nanometer rods are long Spend for 0.6~1.3 μm.
In step 1, the volume ratio of deionized water, methanol and ethanol is 7 in the decentralized medium:1:2.
In step 1, the volume ratio of deionized water, methanol and ethanol is 3 in the decentralized medium:1:1.
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 terminates, 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 ion gradient effect caused by enzymatic reaction, makes gallium-indium-tin alloy liquid metal nanometer rods to enzyme Promote the region clustering that reaction occurs, obtain the micro-nano motor of enzyme-electrophoresis driving of the group behavior with patterning.
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, produces cation in the region that enzymatic reaction occurs, i.e. positive charge, and positive charge forms electric-force gradient to external diffusion, Due to the effect of electrophoresis, gallium-indium-tin alloy nano-motor can move to the big region of positive charge density, will after a period of time Form the pattern around enzymatic reaction region.
The preparation method process of the present invention is simple to operation, and the liquid metal nano-motor of electrophoresis driving, which has, well may be used Aggregation is controlled, being combined with enzymatic reaction makes the Assembling Behavior have higher biocompatibility, has in biological medicine association area Have broad application prospects.
Brief description of the drawings
Fig. 1 is using the stereoscan photograph of the liquid metal nanometer rods of gallium metal preparation, 3 μm of scale.
Fig. 2 is using the transmission electron microscope photo of the liquid metal nanometer rods of gallium metal preparation, scale 500nm.
Fig. 3 is the contrast photo that gallium-indium-tin alloy nano-motor forms pattern in aggregation:Upper figure is photo before aggregation;Figure below For photo after aggregation, 50 μm of scale.
Embodiment
The present invention is described in further detail below:The present embodiment enters under premised on technical solution of the present invention 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 for deionized water, methanol and ethanol mixture, in the decentralized medium The volume ratio of deionized water, methanol and ethanol is 7:1:2, it is Ultrasonic Cell Disruptor to prepare instrument.
Gallium-indium-tin alloy and mixed dispersant are put into beaker according to the corresponding 20mL decentralized media of 1g liquid metals, 800W Ultrasonication 5h under power, after ultrasound terminates, 12h is stood, 750*G centrifugation 3min, takes supernatant to preserve.
0.6~1.0 μm of the nanorod length of preparation, diameter about 120nm.
Embodiment 2
The decentralized medium used in the present embodiment for deionized water, methanol and ethanol mixture, in the decentralized medium The volume ratio of deionized water, methanol and ethanol is 7:1:2, it is Ultrasonic Cell Disruptor to prepare instrument.
Gallium-indium-tin alloy and mixed dispersant are put into beaker according to the corresponding 20mL decentralized media of 1g liquid metals, 900W Ultrasonication 5h under power, after ultrasound terminates, 12h is stood, 750*G centrifugation 3min, takes supernatant to preserve.
0.8~1.2 μm of the nanorod length of preparation, diameter about 100nm.
Embodiment 3
The decentralized medium used in the present embodiment for deionized water, methanol and ethanol mixture, in the decentralized medium The volume ratio of deionized water, methanol and ethanol is 3:1:1, it is Ultrasonic Cell Disruptor to prepare instrument.
Gallium-indium-tin alloy and mixed dispersant are put into beaker according to the corresponding 20mL decentralized media of 1g liquid metals, 800W Ultrasonication 3h under power, after ultrasound terminates, 12h is stood, 750*G centrifugation 3min, takes supernatant to preserve.
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 ethanol, deionized water, methanol and second The volume ratio of alcohol is 3:1:1, it is Ultrasonic Cell Disruptor to prepare instrument.
Gallium-indium-tin alloy and mixed dispersant are put into beaker according to the corresponding 20mL decentralized media of 1g liquid metals, Ultrasonication 6h under 1000W power, after ultrasound terminates, 12h is stood, 750*G centrifugation 3min, takes supernatant to preserve.
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 SEM (FEI Quanta 200F, USA) and transmission electron microscope (Hitachi H- 7650, Japan) pattern of the gallium-indium-tin alloy nanometer rods prepared is characterized, it has been observed that the nanometer rods prepared are in generally cylinder Shape, it is observed that the curved surface pattern of side, each several part diameter basic one of single nanometer rods under ESEM secondary electron pattern Cause;The length of nanometer rods is 0.6~1.3 μm, a diameter of 50~200nm.
Embodiment 6
Controllable aggregation of the gallium-indium-tin alloy nano-motor under enzymatic reaction
, it is necessary to prepare the hydrogel fritter of limitation enzymatic conversion zone in the present embodiment, comprise the following steps that:
Step 1: configuration concentration is 5mg/mL sodium alginate soln, and glucose oxidase is adulterated wherein, doping is dense Spend for 1mg/mL;
Step 2: taking the solution 5mL prepared in step 1,5mol/L calcium chloride solution 0.2mL is added thereto, rapidly The solution is well mixed, and poured into the plastic culture dish of cleaning;
Step 3: standing, after calcium alginate hydrogel solidification, hydrogel is taken out, and is cut into 1mm*1mm squares, is soaked Bubble is standby in phosphate buffer.
, it is necessary to prepare dimethyl silicone polymer passage in the present embodiment, comprise the following steps that:
Step 1: dimethylsiloxane monomer/the crosslinker mixture for premixing and finishing is sprawled in clean slide surface, It is about 1mm to sprawl thickness degree, and 2h is crosslinked at 80 DEG C;
Step 2: after the completion of crosslinking, slide is taken out, 10mm*2mm is depicted in dimethyl silicone polymer with scalpel Groove, as channel standby.
The major experimental step of the present embodiment is as follows:
Step 1: gallium-indium-tin alloy nano-motor (gallium-indium-tin alloy liquid metal nanometer rods) is added 0.001mol/L's In glucose solution, the number concentration of mixing is about 105/mL;
Step 2: the mixture in step 1 is added in ready dimethyl silicone polymer passage, and leaned in passage 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 bonded on toothpick, is allowed to fixed and can be suspended in passage in liquid, contacts but do not contacted with channel bottom with liquid;
Received Step 3: observing using optical microscope system (Olympus CKX-41, Japan) and recording gallium-indium-tin alloy Meter Ma Da motion conditions, it has been observed that after adding the hydrogel fritter 120min containing enzyme, gallium-indium-tin alloy nano-motor occurs Obvious clustering phenomena.
The present embodiment demonstrates the controllable aggregation of the liquid metal nano-motor of electrophoresis driving, and being combined with enzymatic reaction makes The Assembling Behavior has higher biocompatibility, has a extensive future.
The foregoing is only a preferred embodiment of the present invention, these embodiments are all based on the present invention Different implementations under general idea, and protection scope of the present invention is not limited thereto, it is any to be familiar with the art Technical staff the invention discloses technical scope in, the change or replacement that can readily occur in, should all cover the present invention's Within protection domain.Therefore, protection scope of the present invention should be defined by the protection domain of claims.

Claims (10)

  1. A kind of 1. preparation method of gallium-indium-tin alloy nanometer rods, it is characterised in that
    Fed intake Step 1: corresponding to 20mL decentralized media according to 1g gallium-indium-tin alloys, decentralized medium is deionized water, methanol and ethanol Mixture;
    Step 2: crushing instrument using probe type ultrasonic carries out ultrasonication, ultrasonic power was controlled in 800~1000W, time 3 ~6h, during which pays attention to dispersant of the supplement because of ultrasonic cavitation loss, and the dispersant used during supplement starts with this step Dispersant proportioning it is identical;
    Step 3: after ultrasound terminates, the disperse system of acquisition is stood into 10~14h, makes its abundant aging;
    Step 4: the disperse system after aging is centrifuged into 2~4min under the conditions of 750*G, supernatant is taken, system is included in supernatant Standby gallium-indium-tin alloy liquid metal nanometer rods, a diameter of 50~200nm of gallium-indium-tin alloy liquid metal nanometer rods, length are 0.6~1.3 μm.
  2. 2. the preparation method of gallium-indium-tin alloy nanometer rods according to claim 1, it is characterised in that described in step 1 The volume ratio of deionized water, methanol and ethanol is 7 in decentralized medium:1:2.
  3. 3. the preparation method of gallium-indium-tin alloy nanometer rods according to claim 1, it is characterised in that described in step 1 The volume ratio of deionized water, methanol and ethanol is 3 in decentralized medium:1:1.
  4. 4. the preparation method of gallium-indium-tin alloy nanometer rods according to claim 1, it is characterised in that described in step 2 Ultrasonic power is controlled in 800W, time 5h.
  5. 5. the preparation method of gallium-indium-tin alloy nanometer rods according to claim 1, it is characterised in that described in step 2 Ultrasonic power is controlled in 900W, time 4h.
  6. 6. the preparation method of gallium-indium-tin alloy nanometer rods according to claim 1, it is characterised in that described in step 2 Ultrasonic power is controlled in 800W, time 3h.
  7. 7. the preparation method of gallium-indium-tin alloy nanometer rods according to claim 1, it is characterised in that described in step 2 Ultrasonic power is controlled in 1000W, time 6h.
  8. 8. the preparation method of gallium-indium-tin alloy nanometer rods according to claim 1, it is characterised in that in step 3, ultrasound After end, the disperse system of acquisition is stood into 12h.
  9. 9. the preparation method of gallium-indium-tin alloy nanometer rods according to claim 1, it is characterised in that in step 4, by always Disperse system after change centrifuges 3min under the conditions of 750*G.
  10. 10. the gallium-indium-tin alloy liquid metal nanometer rods prepared according to claim 1~9 any claim are as nano-motor Application, it is characterised in that gallium-indium-tin alloy liquid metal nanometer rods are put into decentralized medium, caused by enzymatic reaction from Under sub- gradient effect, the region clustering that makes gallium-indium-tin alloy liquid metal nanometer rods occur to enzymatic reaction, acquisition has pattern The micro-nano motor of the enzyme of the group behavior of change-electrophoresis driving.
CN201710786022.9A 2017-09-04 2017-09-04 The preparation method of gallium-indium-tin alloy nanometer rods and its application as nano-motor Active CN107639228B (en)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN110094314A (en) * 2019-04-22 2019-08-06 哈尔滨工业大学(深圳) A kind of preparation method of the spherical micro-nano motor using lye as fuel driven

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