CN104101630B - Method for preparing nano-porous structure based on nano-particle self-assembly and application thereof - Google Patents
Method for preparing nano-porous structure based on nano-particle self-assembly and application thereof Download PDFInfo
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Landscapes
- Apparatus Associated With Microorganisms And Enzymes (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention relates to a method for preparing a nano-porous structure based on nano-particle self-assembly. Particularly, a capillary tube serves as a support body, and relying on the support body, nano-particles are self-assembled at the pointed end of the capillary tube through a cross-linking agent to form the nano-porous structure. The method for preparing the nano-porous structure is simple and low in cost, has the advantages that the nano aperture is adjustable in size, is convenient to move and position, and has an extensive application range.
Description
Technical field
The invention belongs to nano-pore technical field, be a kind of using mono-dispersed nano particle by being self-assembly of nanometer
The method of loose structure and its application.
Background technology
There is various nano-pores and nanochannel, they are to connect internal and outside and carry out material in organism
Approach with energy exchange.Inspired by ion channel on cell membrane, had been developed that multiple artificial nano pore system, such as egg
White nano-pore and solid nano hole etc..The preparation in artificial nano hole not only promote Novel Biosensor receive flow control apparatus, point
The fast development of the aspects such as sub- filter plant, Single Molecule Detection, and greatly accelerate entering of third generation dna sequencing research
Step.The nano-scale device of structure includes biological nano hole (passage) at present, and solid nano hole (passage) is mutually tied with two classes
The hybridized nanometer hole (passage) closed, solid nano hole will be better than biological nano hole in terms of chemistry, machinery, heat endurance.Mesh
The front main thought preparing solid nano hole is to make the thick free standing structure film of 30～500nm with conventional micro-processing technology in advance, then
Directly in free standing structure film, prepare nano-pore using electron beam or ion beam, conventional micro-processing technology includes electron beam carve, from
Beamlet etches, wet etching etc..But these preparation methods have Preparation equipment costliness, preparation condition harshness, preparation at present
The problems such as technical requirements height, aperture poor controllability, preparation are complicated less than process during aperture below 10 nanometers loaded down with trivial details.
Therefore, still await proposing a kind of preparation method of improved nano-porous structure.
Content of the invention
The first object of the present invention is to provide a kind of " from bottom to top " to receive using the preparation of mono-dispersed nano particles self assemble
The method of meter Duo Kong, the method overcomes and prepares required expensive equipment existing for solid nano hole, condition technical requirements at present
The problems such as high, small-bore is difficult to preparation.
The present invention is mainly achieved through the following technical solutions:
A kind of method preparing nano-porous structure based on nano-particles self assemble, using capillary as supporter, is propping up
Under the support of support body, nano-particle is self-assembled into nanoporous knot by the crosslinking agent being placed in capillary at the tip of capillary
Structure.
Specifically, the method preparing nano-porous structure based on nano-particles self assemble of the present invention, is to hand over
Connection agent is placed in capillary, and by its tip immersion solution containing nano-particle, crosslinking agent is from most advanced and sophisticated diffusion and nanoparticle
Son contact and key and, through continuous self assembly, eventually form the loose structure of neat appearance.
Wherein, described supporter is capillary glass tube, quartz capillary, stainless steel capillary, Red-copper Capillary Tube, polytetrafluoro
Ethene capillary or plastic capillary, preferably capillary glass tube and quartz capillary.
Capillary glass tube and quartz capillary preparation method are simple, and preparation condition is ripe, easily operate, and controllability is preferable,
Stainless steel capillary and Red-copper Capillary Tube are prepared into nanoscale capillary condition and require harsh, more difficult, the polytetrafluoroethylene (PTFE) of preparation
Capillary and plastic capillary, because itself having hydrophobic property, are suitably used in nonaqueous phase environment.
Above-mentioned capillary form is circle, but is not limited to circle, can be square, triangle etc.；Can wrap in capillary
Containing drainage tube, but it is not limited to the capillary that must have flow tube.Additionally, capillary is nanoscale only at tip, its afterbody is grand
See size, total length is several millimeters to more than ten centimetres.Capillary be prepared as prior art, the present invention does not especially limit to this
Fixed.
Wherein, the most advanced and sophisticated aperture of described supporter in 50nm～10 m, preferably aperture in 100～500nm, in this aperture model
In enclosing, the micron gold goal that supporter is assembled into, shape is regular, and rectifying effect is obvious after gold nano grain self assembly.
Method of the present invention, wherein said nano-particle is metal nanoparticle or non pinetallic nano particle, preferably
For other metals such as gold, silver, copper, nickel and the non pinetallic nano particle such as cupric oxide, silica, titanium dioxide.
More preferably golden nanometer particle, Nano silver grain or metal oxide nanoparticles.
Described nano particle diameter is in 3～100nm, preferably 5～50nm.
Nano-particle of the present invention provides that (i.e. self assembly is that capillary tip is immersed nano-particle as a solution
Complete in solution), its concentration is 0.125mg/ml～2.2mg/ml.
The nm of gold of different-grain diameter can form various sizes of nano-pore, in technical solutions according to the invention, institute's shape
The nano-pore becoming can be adjusted in 0.5-15nm, preferably 8nm.
Method of the present invention, wherein said crosslinking agent need to meet contact with nano-particle after can key and, and through company
Continuous self assembly eventually forms the loose structure of neat appearance, and the various known crosslinking agent meeting above-mentioned requirements may be used to
The present invention.Wherein, preferably described crosslinking agent be two ends respectively the dna containing one of sulfydryl, amino, carboxyl, azido, polypeptide or
Organic compound.
Or described crosslinking agent is the two ends dna chain containing sulfydryl, amino, carboxyl or azido, polypeptide or organise simultaneously
Compound.
Further, crosslinking agent of the present invention is preferably dimercaptan, and described dimercaptan does not limit to
For two ends, the dna(such as 3 ' end containing sulfydryl and 5 ' ends connect sulfydryl), can be other molecules that dimercapto is contained at two ends, example
As the polypeptide of sulfydryl, polymer etc. are contained in two ends.
Further, described crosslinking agent is not limited to biomolecule chain and the polymer chain of dimercapto, can be containing
The alkane chain of dimercapto, such as 1,3 dimercaptopropanes, 1,6 ethanthiols, 1,9 nonyl two mercaptan, 1,12 lauryl mercaptans etc..
Further, crosslinking agent is not restricted to include thiol group, can be to carry to link different nanometers
The dna with amino, two ends carry carboxylic respectively respectively for other compounds of particle group such as Diaminoalkane, dicarboxyl alkane, two ends
The dna of base, two ends respectively the polypeptide with amino, both sides respectively the polypeptide with amino, two ends respectively the dna with azido group, two
The end polypeptide with azido, two ends alkane with azido etc. respectively respectively.
Additionally, crosslinking agent of the present invention is not restricted to include two identical reactive groups, can be such as one end
Carry the dna molecule of amino with the sulfydryl other end.
Method of the present invention, most preferably described crosslinking agent is 3 ' ends and 5 ' ends connect the dna of sulfydryls, 1,3 the third two sulphur
Alcohol, 1,6 ethanthiols, 1,9 nonyl two mercaptan or 1,12 lauryl mercaptans, the assembling effect of such crosslinking agent is optimal.
The self assembling process time of the present invention is two hours, but is not limited to two hours, can be from one minute
To twenty four hours, different modification time, obtained nano-porous structure diameter is different.
The second object of the present invention is to protect the nano-porous structure being prepared by said method, described nanoporous
Structure uniform pore diameter, about 0.5-15nm, concrete structure is as shown in figure 1, as the assembling a diameter of 8nm of gold size, crosslinking agent is 1,9
During nonyl two mercaptan, the loose structure aperture that self assembly is formed is about 1.5nm.
Present invention also offers nano-porous structure the answering in chemical analysis and bioanalysis of above-mentioned self assembly preparation
With described chemical analysis includes the detection of simple metal ion, the detection of polymer, organic molecule detection.Bioanalysis
Including some ad hoc structure proteinoid, the dna of particular sequence or to external world environment change such as ph, salinity, temperature spy
The dna of different response.
It is true that the nano-porous structure that described self assembling process is formed, can there is the application of each side.Application one:
The detection of simple ion.Nanotube is the most advanced and sophisticated single hole for 100nm before assembling, and by electrochemical measurement i-v curve, single hole does not have
There is rectifying effect, after being completed, nanotube is most advanced and sophisticated to be loose structure, and pore size is several nanometers, due to aperture
Reduce rapidly, surveyed electrochemistry i-v signal occurs rectifying effect.When the ion with electric charge passes through many nano-pores, due to
The change of electric charge, rectifying effect can change.So the purpose of detection simple ion can be reached.Application two: bio-identification
The detection of process.If the property changing crosslinking agent during the nano-porous structure of assembling is (as the electrically charged change of crosslinking agent institute, length
Or species changes), the i-v signal of electrochemical measurement also can change.If crosslinking agent is the specific dna sequence of dimercapto
Row, then can identify specific dna, protein, or the other materials that other and dna have an effect by specific dna sequence.
Application three: Raman enhanced spectrum analysis.The different length of crosslinking agent can adjust the distance between nano-particle, works as nano-particle
The distance between when being in suitable size, during illumination, due to Electromagnetic enhancement effect, then the Raman letter going out shown by crosslinking agent
Number can been significantly enhanced.
Using technique scheme, present invention advantage specific as follows: 1, material therefor is simple, is easy to get, inexpensively；2nd, raw material
Process technology is ripe, reproducible；3rd, prepare nanoporous method simple, mild condition；4th, nanoporous entirety pattern size
Controlled, nano-porous structure aperture is controlled；5th, this nano-porous structure applicability is extensive；6th, capillary rear end is macro-size,
Conveniently be combined with machinery, electronic equipment, realize the positioning in three dimensions.
Brief description:
Fig. 1, the preparation method course schematic diagram of the nano-porous structure of the present invention；
Wherein 1 is that nano-glass capillary 2 is (golden for nano-porous structure for golden nanometer particle 4 for 1,9 nonyl two mercaptan 3
Ball)；
Electron microscope after Fig. 2, the processing of nano-glass capillary；
Fig. 3, the monodisperse nanoparticle electron microscope of synthesis；
Fig. 4, the electron microscope of nano-porous structure by being self-assembly of；
In Fig. 5, solution, simulation self-assembly forms loose structure electron microscope；
Fig. 6, electrochemical testing device structural representation；Wherein, 5: beaker；6: electrolyte solution；7: capillary glass tube；8:
Platinum filament, 9: platinum filament；
Fig. 7, electrochemistry i-v curve map；Dotted line represents the surveyed electric current in single glass nano hole；Solid line represents nano-porous structure
Surveyed electric current；
Fig. 8, Raman enhanced spectrum figure comparison diagram.
Specific embodiment
With reference to embodiment, technical scheme is described further, but should not be construed as to the present invention's
Limit:
Embodiment 1
Fig. 1 is the formation schematic diagram of nano-porous structure of the present invention.As shown in figure 1, nano-particles self assemble preparation nanometer
The method (technology) of loose structure, including the nano-glass capillary 1 as supporter, with the lower energy of 1,9 nonyl, two mercaptan 2 effect
The golden nanometer particle 3 of enough self assemblies.1,9 nonyl two mercaptan 2 is added to the tip of nano-glass capillary 1, then by most advanced and sophisticated leaching
Enter in monodispersed solution of gold nanoparticles (can be prepared by embodiment 7), due to diffusion, 1,9 nonyl two mercaptan with
Golden nanometer particle 3 contacts, the thiol group at two thiol molecule two ends respectively with two golden nanometer particle 3 keys and, pass through this
The continuous self assembly of sample, eventually forms the nano-porous structure 4(gold goal of a neat appearance), aperture by Nanoparticle Size and
Cross-linker molecules are adjusted jointly.
Fig. 2 is the electron microscope of single nano-glass capillary, from figure 2 it can be seen that nano-glass capillary tip hole
Internal diameter size is about 100nm.
Fig. 3 is the electron microscope of monodispersed golden nanometer particle, as can be seen from the figure nano-particle good dispersion, particle chi
Very little uniform, diameter is about 8nm.
Fig. 4 is the electron microscope by the nano-porous structure being self-assembly of, and as can be seen from Figure 4 assembly is in ball
Shape, diameter is about a few micrometers.
Embodiment 2
Supporter used is capillary glass tube in embodiment 1, changes supporter for quartzy capillary in example 2
Pipe, other conditions are constant, by the nano-porous structure (gold goal) being self-assembly of a few micrometers of gold size nano-particle.
Embodiment 3
GOLD FROM PLATING SOLUTION nano-particle and 1,9 nonyl two mercaptan self assembly.By solution of gold nanoparticles and 1,9 nonyl two thiol solution
Mixing, then by two mercaptan interconnections, this assembling process is to simulate golden nanometer particle and two mercaptan in glass to golden nanometer particle
Capillary tip carries out the process of self assembly.
Fig. 5 is gold size self assembly electron microscope in dimercapto solution, and as can be seen from Figure 5 gold size is in dimercapto solution
There occurs self assembly, about 1, the gap between nano-particle nanometer, compared with embodiment 1 gained loose structure, this technology
Scheme is the simulation process that assembled in capillary tip of embodiment 1, further illustrate in embodiment 1 golden nanometer particle with
The cross-linking process of 1,9 nonyl two mercaptan, defines many nano-pore structures after demonstrating self assembly from example, and nano aperture is about
For 1 nanometer.
Embodiment 4
The 100nm capillary glass tube that the present embodiment is assembled to tip is most advanced and sophisticated and tip is self-assembly of nanoporous
Structure (embodiment 1 gained loose structure) has carried out electro-chemical test respectively, and Fig. 6 is electrochemical testing device figure, and wherein, 5 are
Beaker, 6 is electrolyte solution, and 7 is the most advanced and sophisticated capillary glass tube modifying nano-porous structure (gold goal), and 8,9 is platinum filament, further
, described electrolyte solution 6 is tetrabutylammonium perchlorate's acetonitrile solution.
Concrete test process is: 1, beaker 5 is soaked 24 hours in chloroazotic acid, after cleaned up standby with secondary water, make
With front use acetonitrile solution rinse three times.
Prepare the acetonitrile solution of 0.15mol/l tetrabutylammonium perchlorate, load in the most advanced and sophisticated capillary glass tube 7 for 100nm
The electrolyte solution 2 of certain volume, puts into platinum filament 9 in capillary glass tube 7, and another platinum filament 8 is directly placed in beaker 1, with
Platinum filament 8 is working electrode, and platinum filament 9 is reference and auxiliary electrode, and setting starting voltage is+1v, and final voltage is -1v, scanning speed
Rate is 10 millivolts and per second carries out i-v curved measurement.
Fig. 7 is electrochemical data test chart, and wherein, dotted line represents capillary glass tube tip not to carry out modifying gold nano grain
Hole surveyed i-v curve；Solid lineRepresent capillary glass tube tip and carry out Gold nanoparticle and be self-assembly of the surveyed i-v of loose structure
Curve；Solid line and dotted line electric current are contrasted it can be seen that capillary glass tube tip gold size is self-assembly of i- after loose structure
V curve has certain rectifying effect, and before and after assembling, most advanced and sophisticated aperture is caused whole by the acute variation of nanometers up to a hundred to several nanometers
Stream effect.
Embodiment 5
The present embodiment carries out to pure nonane solution and capillary glass tube tip forming nano-porous structure (enforcement after self assembly
Example 1 gained loose structure-gold goal) carry out raman spectroscopy measurement respectively.The gold goal that capillary glass tube tip is self-assembly of is received
Rice loose structure in, be to be linked by dimercapto nonane between golden nanometer particle and golden nanometer particle, thus golden nanometer particle with
The distance between Gold nanoparticle is about 1.3 nanometers, when laser irradiates during gold goal, golden nanometer particle and golden nanometer particle
Between have very strong Electromagnetic enhancement effect, so dimercapto nonane has very strong raman characteristic peak.And for single
Pure nonane, then its Raman signal is weak a lot.
The design parameter of measurement Raman is: 633nm laser irradiates, and laser intensity used is 10%.
Fig. 8 is Raman signal institute mapping spectrum.Wherein, the Raman signal that solid line is surveyed by simple nonane, dotted line is Jenner
After rice corpuscles passes through the connection of 1,9 nonyl two mercaptan, self assembly is survey Raman gained spectrogram after nano-porous structure.
Embodiment 6
The most advanced and sophisticated preparation of capillary glass tube, instrument used draws pin instrument, glass capillary for sutter company of U.S. p-2000
Manage the borosiligate glass with filament for sutter company, o.d:1.0mm, i.d:0.58mm, total length
For 10cm.Arrange parameter is line 1:heat=350, fil=3, vel=30, del=200, pul=
Line 2:heat=340, fil=2, vel=27, del=160, pul=250
The a diameter of 100nm of capillary tip being prepared under these conditions with the capillary of this specification.
Or quartz capillary used is quarta glass, o.d:1.0mm, the i.d:0.70 mm of sutter company,
Total length is 7.5cm.Arrange parameter is
Line 1:heat=600, fil=3, vel=45, del=150, pul=60
Line 2:heat=650, fil=3, vel=50, del=140, pul=140
The capillary tip diameter prepared under these conditions with the capillary of this specification is about 60nm.
Embodiment 7
The preparation of solution of gold nanoparticles: by the 30ml 30mm tetra chlorauric acid aqueous solution and 80ml 50mm tetra- n-Octyl Bromide
Change the mixing of ammonium toluene solution, stirring about 3min makes gold chloride be all transferred in toluene phase by aqueous phase, and color is by aqueous phase
Yellow becomes and turns to orange red in toluene phase, is rapidly added the sodium borohydride aqueous solution of 25ml 0.5m, color change is by orange red
Color gradually becomes shallower as white, then rapidly goes to deepen, is changed into atropurpureus, continues two hours of stirring.After the completion of use 0.1m sulphur
Once, 1m sodium carbonate liquor cleans twice, and pure water cleans 5 times for acid cleaning, is eventually adding anhydrous sodium sulfate absorption and exists slightly
Moisture, is transferred in memory, is placed in 4 DEG C of refrigerators and preserves.Gold nanoparticle solution concentration is 2.2mg/ml.
Using the method for the invention prepare many nano-pore structures simple and convenient it is easy to operation, success rate is high.Prepared by here
In method, the support without nanotube capillaries can not form ball shaped nano loose structure；Then can not without crosslinking agent
Form nano-porous structure；If first carrying out self assembly using 1,9 nonyl two mercaptan to gold nano grain in the solution places into handle
Glass tube is put in the solution assembling nor is formed the regular porous nanometer structure of this shape.
Claims (10)
1. a kind of based on nano-particles self assemble prepare nano-porous structure method it is characterised in that using capillary as
Support body, under the support of supporter, nano-particle is self-assembled at the tip of capillary by the crosslinking agent being placed in capillary
Nano-porous structure；
Wherein, the most advanced and sophisticated aperture of described supporter is in 50nm～10 m；Described crosslinking agent is 1,9 nonyl two mercaptan.
2. self assembly prepares the method for nano-porous structure it is characterised in that described supporter is glass according to claim 1
Glass capillary, quartz capillary, stainless steel capillary, Red-copper Capillary Tube, polytetrafluoroethylene capillary or plastic capillary.
3. self assembly according to claim 1 or claim 2 prepares the method for nano-porous structure it is characterised in that described supporter
Most advanced and sophisticated aperture is in 100-500nm.
4. self assembly prepares the method for nano-porous structure it is characterised in that described nano-particle is according to claim 1
Metal nanoparticle or non pinetallic nano particle.
5. self assembly according to claim 1 or 4 prepares the method for nano-porous structure it is characterised in that described nanoparticle
Son is golden nanometer particle, Nano silver grain or metal oxide nanoparticles.
6. self assembly according to claim 1 or 4 prepares the method for nano-porous structure it is characterised in that described nanoparticle
Seed footpath is in 3～100nm；Described nano-particle provides as a solution, and its concentration is 0.125g/ml～2.2g/ml.
7. self assembly prepares the method for nano-porous structure it is characterised in that described nanoparticle seed according to claim 6
Footpath is in 5～50nm.
8. self assembly prepares the method for nano-porous structure it is characterised in that described crosslinking agent is two according to claim 1
The end dna containing sulfydryl, polypeptide or organic compound respectively.
9. the nano-porous structure that the method for nano-porous structure is obtained is prepared in assembling described in any one of claim 1-8.
10. application in chemical analysis and bioanalysis for the nano-porous structure described in claim 9.
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| CN104597027B (en) * | 2015-01-09 | 2017-07-25 | 江南大学 | A kind of method based on Nano silver grain tetrahedron Raman Multiple detection |
| CN104807865B (en) * | 2015-05-08 | 2017-06-30 | 江苏省农业科学院 | It is applied to the preparation method of the electrochemical aptamer sensor of myoglobins detection |
| CN105110288B (en) * | 2015-08-27 | 2017-01-25 | 陕西科技大学 | Method for preparing patterned Ag nano-particles |
| CN105372320B (en) * | 2015-10-29 | 2019-05-31 | 南京大学 | Prepare the method and its application of nano pore |
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| CN106841157B (en) * | 2016-12-23 | 2019-12-17 | 南京大学 | method for preparing nano porous structure based on aqueous phase nanoparticle self-assembly and application thereof |
| CN108120709B (en) * | 2017-12-25 | 2020-09-18 | 合肥工业大学 | Capillary micro-droplet metal ball detection method for surface enhanced Raman spectroscopy |
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