CN108051493A - A kind of preparation method being used for from the polyaminoacid micro-nano motor driven - Google Patents
A kind of preparation method being used for from the polyaminoacid micro-nano motor driven Download PDFInfo
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- CN108051493A CN108051493A CN201711210007.6A CN201711210007A CN108051493A CN 108051493 A CN108051493 A CN 108051493A CN 201711210007 A CN201711210007 A CN 201711210007A CN 108051493 A CN108051493 A CN 108051493A
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- polyaminoacid
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- 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
- G01N27/417—Systems using cells, i.e. more than one cell and probes with solid electrolytes
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- 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
Abstract
The invention belongs to field of nanometer technology, specifically disclose a kind of preparation method being used for from the polyaminoacid micro-nano motor driven.This method includes the assembling of three-electrode cell, the preparation of polyaminoacid micro-nano mitron, the polyaminoacid/preparation of metal micro-nano pipe, the release of the micro-nano tubular motor of polyaminoacid；The micro-nano motor is simple with preparation method, Biocompatibility is good, the features such as biological degradability is high, it can be realized using the polyaminoacid micro-nano motor of the present invention in corresponding fuel solution from driving, expand micro-nano motor in the application space in the fields such as biomedicine, chemistry, environment.
Description
Technical field
The invention belongs to field of nanometer technology, and in particular to be used for a kind of from the polyaminoacid micro-nano motor driven
Preparation method.
Background technology
In recent years, with the fast development of nanometer technology, having from the artificial micro-nano motor of driving force becomes nanometer
The hot spot of scientific circles' research.In general, micro-nano motor is that chemical energy, luminous energy, electric energy etc. can be converted into movement by one kind
The micro-nano device of kinetic energy or driving force, characteristic size are generally several nanometers to several microns, and with light-weight, volume
Small, thrust output is big (characteristic size can export the thrust of about several Micro-Newtons in tens nanometers of nano-motor), low in energy consumption
Outstanding advantages of.At present, miniature artificial motor is divided mainly to have by driving mechanism：From electrophoresis, bubble promotes, self-diffusion and outside
It stimulates four kinds of (such as light, magnetic, ultrasonic wave).
At this stage, the key for building micro-nano motor is the design and preparation of basis material, wherein, polyaniline (PANI),
Polyglycolic acid fibre (PEDOT) and redox graphene are the existing structure most common matrixes of variety classes micro-nano motor
Material, they, which are respectively provided with good electric conductivity, can be conducive to the electropolymerization of interior catalyst type metal and metal oxide.But
First two belongs to high molecular polymer, and toxicity is big, and biological degradability is poor, and redox graphene is in the environment and organism
The shortcomings that interior toxicity and biological degradability is still uncertain, and three lacks there are surface functional group.Polyaminoacid
(PAA) it is that one kind has good biodegradability properties, biocompatibility and side chain functionalities (such as hydroxyl, carboxyl, sulfydryl and amino
Deng) physics and chemical characteristic high-molecular compound, have biodegradability, it is nontoxic, do not destroy ecological environment, test table
The bright degradation rate of 28 days of polyaminoacid in the environment is finally degraded to the water and carbon dioxide of no any toxicity up to 76%,
Therefore it has good biocompatibility, and the chemicals that alternative many pollutes the environment is described as " green " by people
Product.But traditional polyaminoacid synthetic method step is complicated, is also easy to produce toxic by-product, and due to the mechanical performance of itself
Difference limits its development.To sum up, explore and invent a kind of nontoxic, good biocompatibility, the strong poly- amino of biological degradability
Sour micro-nano motor preparation method is of great significance for the application for expanding artificial micro-nano motor.
The content of the invention
The purpose of the present invention is intended to overcome the deficiency of the prior art, and it is micro-nano to provide a kind of polyaminoacid for being used to drive certainly
The preparation method of motor expands the application space of artificial micro-nano motor.
The purpose of the present invention can be achieved by the following technical measures：
A kind of preparation method being used for from the polyaminoacid micro-nano motor driven, carries out as follows：
The assembling of S1 three-electrode cells：Makrolon perforated membrane is taken, is the steady of 50~100nm by its face plating thickness
Then deposit category is connected to the lower section that working electrode is assembled in electrolytic cell with aluminium foil, using silver-silver chloride electrode as reference electricity
Pole, platinum electrode are to electrode, form three-electrode cell；
The preparation of S2 polyaminoacid micro-nano mitrons：Using phosphate buffer as solvent, amino acid solution is prepared, by the amino
Poly- ammonia is made using electrochemical polymerization method in electrolyte solution of the acid solution as three-electrode cell in makrolon perforated membrane
Base acid micro-nano mitron；
The preparation of S3 polyaminoacid/metal micro-nano pipe：Metal ion solution is added in into three-electrode cell, using electricity
The metal or metal oxide are filled into polyaminoacid micro-nano mitron by chemical deposition, and polyaminoacid/metal micro-nano is made
Mitron；
The release of the micro-nano tubular motor of S4 polyaminoacid：The polyaminoacid that removal step S3 is obtained/metal micro-nano pipe
In polycarbonate membrane to get.
The purpose of the present invention can be also achieved by the following technical measures：
Porous membrane aperture described in step S1 is 0.05~5 μm.
Stable metal described in step S1 is golden or platinum one kind.
The pH of phosphate buffer described in step S2 is 5.0~7.0.
The concentration of amino acid solution described in step S2 is 0.1~3mmol/L.
Electrochemical polymerization method described in step S2 is cyclic voltammetry, and scanning potential range is -1.0V~3.0V, is scanned
Speed is 50mV/s, 2 circle of scanning.
Metal ion solution and its concentration described in step S3 are chloroplatinic acid 0.5g/L~5.0g/L or silver nitrate 1.0g/
L~5.0g/L or potassium permanganate 0.3g/L~3.0g/L.
Electrochemical deposition method described in step S3 is galvanostatic method, and electric current is -2mA, time 10min.
The minimizing technology of polycarbonate membrane in polyaminoacid described in step S4/metal micro-nano pipe is：By poly- carbonic acid
Ester perforated membrane takes out from three-electrode cell, is polished with polishing powder, rinses well, dries, and is then dissolved in dichloromethane,
It stands, abandoning supernatant, repeats dichloromethane dissolving once, each two are washed with ethyl alcohol and deionized water after removal supernatant
It is secondary, it is finally dispersed in a small amount of deionized water, it is spare.
Compared with prior art, the present invention has the following advantages：The present invention is used for from the micro-nano horse of polyaminoacid driven
The matrix using the high polyaminoacid of good biocompatibility, biological degradability as micro-nano motor is put forward for the first time in the preparation method reached
Material, using green, simple template electropolymerization prepares polyaminoacid, and no any noxious material generates, in addition, utilizing its table
The characteristic of Mian Ge functional groups, it is contemplated that the delivery effect to drug, biological substance (such as antibody, DNA) etc. can be realized, applied to life
The fields such as object medicine, chemistry, environment measuring.
Description of the drawings
Fig. 1 is the scanning electron microscope being used for from the polyaminoacid micro-nano motor driven that the embodiment of the present invention 1 is prepared
Figure；
Fig. 2 is the transmission electron microscope being used for from the polyaminoacid micro-nano motor driven that the embodiment of the present invention 1 is prepared
Figure；
Fig. 3 be the embodiment of the present invention 1 be prepared be used for from drive polyaminoacid micro-nano motor in 4.5% peroxide
Change in hydrogen from driving motion diagram.
Specific embodiment
The specific embodiment of the present invention is described in detail below in conjunction with attached drawing.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explain the present invention, and wherein the species of amino acid and embodiment are not intended to limit this hair
It is bright.A kind of preparation method being used for from the polylysine micro-nano motor driven of embodiment 1
The preparation method carries out as follows：
The assembling of S1 three-electrode cells：The makrolon perforated membrane that aperture is 5 μm is taken, plating thickness is by its face
Then the platinum of 70nm is connected to the lower section that working electrode is assembled in electrolytic cell with aluminium foil, using silver-silver chloride electrode as reference electricity
Pole, platinum electrode are to electrode, form three-electrode cell；
The preparation of S2 polylysine micro-nano mitrons：Using the phosphate buffer of pH=6.0 as solvent, 2.0mmol/L is prepared
Lysine solution using the lysine solution as the electrolyte solution of three-electrode cell, uses cyclic voltammetry (scanning current potential
Scope is -1.0V~3.0V, sweep speed 50mV/s, and scanning 2 is enclosed) polylysine micro-nano is made in makrolon perforated membrane
Mitron；
The preparation of S3 polylysines/platinum micro-nano mitron：2.0g/L platinum acid chloride solutions are added in into three-electrode cell, are used
Platinum is filled into polyaminoacid micro-nano mitron by galvanostatic method (electric current is -2mA, time 10min), and polyaminoacid/platinum is made
Micro-nano mitron；
The release of the micro-nano tubular motor of S4 polyaminoacid：In the polylysine that removal step S3 is obtained/platinum micro-nano mitron
Polycarbonate membrane to get.
The minimizing technology of polycarbonate membrane in polyaminoacid described in step S4/metal micro-nano pipe is：By poly- carbonic acid
Ester perforated membrane takes out from three-electrode cell, is polished with polishing powder, rinses well, dries, and is then dissolved in dichloromethane,
It stands, abandoning supernatant, repeats dichloromethane dissolving once, each two are washed with ethyl alcohol and deionized water after removal supernatant
It is secondary, it is finally dispersed in a small amount of deionized water, it is spare.
A kind of preparation method being used for from the polyglycine micro-nano motor driven of embodiment 2
The preparation method carries out as follows：
The assembling of S1 three-electrode cells：The makrolon perforated membrane that aperture is 0.05 μm is taken, by its face plating thickness
For the gold of 50nm, the lower section that working electrode is assembled in electrolytic cell is then connected to aluminium foil, using silver-silver chloride electrode as reference
Electrode, platinum electrode are to electrode, form three-electrode cell；
The preparation of S2 polyglycine micro-nano mitrons：Using the phosphate buffer of pH=5.0 as solvent, 0.1mmol/L is prepared
Glycine solution using the glycine solution as the electrolyte solution of three-electrode cell, uses cyclic voltammetry (scanning current potential
Scope is -1.0V~3.0V, sweep speed 50mV/s, and scanning 2 is enclosed) polyglycine micro-nano is prepared in makrolon perforated membrane
Mitron；
The preparation of S3 polyglycines/silver micro-nano mitron：1.0g/L silver nitrate solutions are added in into three-electrode cell, are used
Silver is filled into polyglycine micro-nano mitron by galvanostatic method (electric current is -2mA, time 10min), and poly- sweet base acid/silver is made
Micro-nano mitron；
The release of the micro-nano tubular motor of S4 polyglycines：In poly- sweet base acid/silver-colored micro-nano mitron that step S3 is obtained
Polycarbonate membrane be removed to get.
Wherein, the minimizing technology of the polycarbonate membrane described in step S4 in poly- sweet base acid/silver-colored micro-nano mitron is：By poly- carbon
Acid esters perforated membrane takes out from three-electrode cell, is polished with polishing powder, rinses well, dries, then with molten in dichloromethane
Solution is stood, abandoning supernatant, is repeated dichloromethane dissolving once, is washed respectively with ethyl alcohol and deionized water after removing supernatant
Twice, finally it is dispersed in a small amount of deionized water, it is spare.
A kind of preparation method being used for from the polyalanine micro-nano motor driven of embodiment 3
The preparation method carries out as follows：
The assembling of S1 three-electrode cells：The makrolon perforated membrane that aperture is 0.2 μm is taken, plating thickness is by its face
Then the platinum of 100nm is connected to the lower section that working electrode is assembled in electrolytic cell with aluminium foil, using silver-silver chloride electrode as reference
Electrode, platinum electrode are to electrode, form three-electrode cell；
The preparation of S2 polyalanine micro-nano mitrons：Using the phosphate buffer of pH=7.0 as solvent, 3.0mmol/L is prepared
Alanine solution using the alanine solution as the electrolyte solution of three-electrode cell, uses cyclic voltammetry (scanning current potential
Scope is -1.0V~3.0V, sweep speed 50mV/s, and scanning 2 is enclosed) poly- acid propyl micro-nano is prepared in makrolon perforated membrane
Mitron；
The preparation of S3 polyalanines/manganese dioxide micro-nano mitron：0.5g/L potassium permanganate is added in into three-electrode cell
Solution uses galvanostatic method (electric current for -2mA, time 10min) that manganese dioxide is filled into poly- acid propyl micro-nano mitron,
Polyalanine/manganese dioxide micro-nano mitron is made；
The release of the micro-nano tubular motor of S4 polyalanines：Poly- acid propyl/manganese dioxide that step S3 is obtained is micro-nano
Polycarbonate membrane in pipe be removed to get.
Wherein, the minimizing technology of the polycarbonate membrane in polyalanine described in step S4/manganese dioxide micro-nano mitron is：
Makrolon perforated membrane from three-electrode cell is taken out, is polished with polishing powder, is rinsed well, is dried, then uses dichloromethane
It dissolves, stands, abandoning supernatant in alkane, repeat dichloromethane dissolving once, ethyl alcohol and deionized water are used after removing supernatant
Washing is each to be finally dispersed in a small amount of deionized water twice, spare.
A kind of preparation method being used for from the poly- leucine micro-nano motor driven of embodiment 4
Difference with embodiment 1 is, amino acid classes are different, lysine is replaced with leucine, the chlorine platinum in step S3
Acid solutions are 0.5g/L, other are the same as embodiment 1.
A kind of preparation method being used for from the polyphenylalanine micro-nano motor driven of embodiment 5
Difference with embodiment 1 is, amino acid classes are different, lysine is replaced with phenylalanine, the chlorine in step S3
Platinic acid solution concentration is 5.0g/L, other are the same as embodiment 1.
A kind of preparation method being used for from the poly- tryptophan micro-nano motor driven of embodiment 6
Difference with embodiment 2 is, amino acid classes are different, glycine is replaced with tryptophan, the nitric acid in step S3
Silver-colored solution concentration is 5.0g/L, other are the same as embodiment 2.
A kind of preparation method being used for from the poly- threonine micro-nano motor driven of embodiment 7
Difference with embodiment 3 is, amino acid classes are different, alanine is replaced with threonine, the Gao Meng in step S3
Sour potassium solution concentration is 3.0g/L, other are the same as embodiment 3.
A kind of preparation method being used for from the poly arginine micro-nano motor driven of embodiment 8
Difference with embodiment 3 is, amino acid classes are different, alanine is replaced with arginine, the Gao Meng in step S3
Sour potassium solution concentration is 0.3g/L, other are the same as embodiment 3.
1 scanning electron microscope of test example and transmission electron microscope characterization
Using made from embodiment 1-8 preparation methods be used for from drive polyaminoacid micro-nano motor, surface topography with
Structure is similar, tests by the way that 1 sample of embodiment is described, specifically as shown in Figs. 1-2.
From Fig. 1 and Fig. 2 as can be seen that using the polyaminoacid micro-nano being used for made from preparation method of the present invention from driving
Meter Ma Da configurations of surface are homogeneous, are the cylinder that diameter is about 5 μm, and surfacing is smooth.
The driving experiment of test example 2
It is molten in hydrogen peroxide from the polyaminoacid micro-nano motor driven using being used for made from embodiment 1-8 preparation methods
Motion conditions are similar in liquid, test by the way that 1 sample of embodiment is described, specific as shown in Figure 3.
Fig. 3 represents to be used for from the polylysine micro-nano motor driven with high-resolution Laser Scanning Confocal Microscope characterization embodiment 1
Release and the motion conditions from driving in 4.5% hydrogen peroxide, in the overall process of polylysine micro-nano motor movement
(0-30min) intercepts the movement of 3s, to characterize its motion conditions.
As shown in figure 3, movement locus is arc, movement velocity is 85 μm/s or so, has from driving force, can realize
Its movement in the solution.
Claims (9)
1. a kind of preparation method being used for from the polyaminoacid micro-nano motor driven, which is characterized in that carry out as follows：
The assembling of S1 three-electrode cells：Makrolon perforated membrane is taken, is that stablizing for 50~100nm is golden by its face plating thickness
Belong to, the lower section that working electrode is assembled in electrolytic cell is then connected to aluminium foil, using silver-silver chloride electrode as reference electrode, platinum
Silk electrode is to electrode, forms three-electrode cell；
The preparation of S2 polyaminoacid micro-nano mitrons：Using phosphate buffer as solvent, amino acid solution is prepared, the amino acid is molten
Polyaminoacid is made using electrochemical polymerization method in electrolyte solution of the liquid as three-electrode cell in makrolon perforated membrane
Micro-nano mitron；
The preparation of S3 polyaminoacid/metal micro-nano pipe：Metal ion solution is added in into three-electrode cell, using electrochemistry
The metal or metal oxide are filled into polyaminoacid micro-nano mitron by sedimentation, and polyaminoacid/metal micro-nano pipe is made；
The release of the micro-nano tubular motor of S4 polyaminoacid：In the polyaminoacid that removal step S3 is obtained/metal micro-nano pipe
Polycarbonate membrane to get.
2. the preparation method according to claim 1 being used for from the polyaminoacid micro-nano motor driven, which is characterized in that
Porous membrane aperture described in step S1 is 0.05~5 μm.
3. the preparation method according to claim 1 being used for from the polyaminoacid micro-nano motor driven, which is characterized in that
Stable metal described in step S1 is golden or platinum one kind.
4. the preparation method according to claim 1 being used for from the polyaminoacid micro-nano motor driven, which is characterized in that
The pH of phosphate buffer described in step S2 is 5.0~7.0.
5. the preparation method according to claim 1 being used for from the polyaminoacid micro-nano motor driven, which is characterized in that
The concentration of amino acid solution described in step S2 is 0.1~3mmol/L.
6. the preparation method according to claim 1 being used for from the polyaminoacid micro-nano motor driven, which is characterized in that
Electrochemical polymerization method described in step S2 is cyclic voltammetry, and scanning potential range is -1.0V~3.0V, and sweep speed is
50mV/s, 2 circle of scanning.
7. the preparation method according to claim 1 being used for from the polyaminoacid micro-nano motor driven, which is characterized in that
Metal ion solution and its concentration described in step S3 are chloroplatinic acid 0.5g/L~5.0g/L or silver nitrate 1.0g/L~5.0g/
L or potassium permanganate 0.3g/L~3.0g/L.
8. the preparation method according to claim 1 being used for from the polyaminoacid micro-nano motor driven, which is characterized in that
Electrochemical deposition method described in step S3 is galvanostatic method, and electric current is -2mA, time 10min.
9. the preparation method according to claim 1 being used for from the polyaminoacid micro-nano motor driven, which is characterized in that
The minimizing technology of polycarbonate membrane in polyaminoacid described in step S4/metal micro-nano pipe is：By makrolon perforated membrane
It takes out from three-electrode cell, is polished with polishing powder, rinsed well, dried, then dissolved in dichloromethane, stand, abandon
Supernatant is removed, repeats dichloromethane dissolving once, is washed respectively twice with ethyl alcohol and deionized water after removing supernatant, finally divided
It is dispersed in a small amount of deionized water, it is spare.
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Cited By (4)
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| CN108773831A (en) * | 2018-06-11 | 2018-11-09 | 南京师范大学 | L-arginine nano-particle and the degradable nano-motor and preparation method thereof that nitric oxide is power source |
| CN109187680A (en) * | 2018-08-01 | 2019-01-11 | 山西大学 | Based on copper ion modified cyclodextrin/poly arginine/carbon nanotube chiral sensor and preparation method thereof |
| CN113588966A (en) * | 2021-07-29 | 2021-11-02 | 陕西师范大学 | Preparation method and application of tubular western blotting zinc-based acid-driven magnetic micromotor |
| CN116930481A (en) * | 2023-09-12 | 2023-10-24 | 重庆医科大学绍兴柯桥医学检验技术研究中心 | Cross-molecule detection method for magnetic field driven micro-nano motor |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108773831A (en) * | 2018-06-11 | 2018-11-09 | 南京师范大学 | L-arginine nano-particle and the degradable nano-motor and preparation method thereof that nitric oxide is power source |
| CN108773831B (en) * | 2018-06-11 | 2019-07-02 | 南京师范大学 | L-arginine nanoparticle and nitric oxide are the degradable nano-motor and preparation method thereof of power source |
| CN109187680A (en) * | 2018-08-01 | 2019-01-11 | 山西大学 | Based on copper ion modified cyclodextrin/poly arginine/carbon nanotube chiral sensor and preparation method thereof |
| CN109187680B (en) * | 2018-08-01 | 2020-08-04 | 山西大学 | Chiral sensor based on copper ion modified cyclodextrin/polyarginine/carbon nano tube and preparation method thereof |
| CN113588966A (en) * | 2021-07-29 | 2021-11-02 | 陕西师范大学 | Preparation method and application of tubular western blotting zinc-based acid-driven magnetic micromotor |
| CN113588966B (en) * | 2021-07-29 | 2023-09-05 | 陕西师范大学 | Preparation method and application of tubular western blotting zinc-based acid driven magnetic micro motor |
| CN116930481A (en) * | 2023-09-12 | 2023-10-24 | 重庆医科大学绍兴柯桥医学检验技术研究中心 | Cross-molecule detection method for magnetic field driven micro-nano motor |
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Application publication date: 20180518 |