CN103950891A - Preparing method of high conductivity chain-shaped photoelectric nanometer bridge - Google Patents
Preparing method of high conductivity chain-shaped photoelectric nanometer bridge Download PDFInfo
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- CN103950891A CN103950891A CN201410215277.6A CN201410215277A CN103950891A CN 103950891 A CN103950891 A CN 103950891A CN 201410215277 A CN201410215277 A CN 201410215277A CN 103950891 A CN103950891 A CN 103950891A
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Abstract
The invention provides a preparing method of a high conductivity chain-shaped photoelectric nanometer bridge and belongs to the technical field of material chemistry. The end surface regional functional technology of gold nanorods is used, the surface modification of oligonucleotide is realized to the designated region of the gold nanorods, and the chain-shaped structure of the nanorods is formed by means of the bionic identifying nature of the oligonucleotide; the nanometer photoelectric nanometer bridge of the nanorods is realized by regulating the conditions of the position of electrodes, the electric potential, the buffering medium and the like, so that two unconnected conductors can be powered on, a nanometer electric wire is obtained, and the conducting efficiency is effectively improved.
Description
Technical field
The preparation method who the present invention relates to a kind of chain photoelectric nano bridge of high conductivity, belongs to material chemistry technical field.
Background technology
Nano material refers to that three dimensions yardstick has the material of one dimension in nanometer scale at least.Nano material is the material of new generation between cluster and macroscopic material.Because the size of nano material has approached the relevant wavelength of de Broglie wavelength, superconduction of electronics and the Bohr radius of exciton, electronics is limited to a space that volume is very small, electron wave function is restricted, add that it has the special effects on large surface, thereby have quantum size effect, skin effect, small-size effect and macro quanta tunnel effect etc., therefore nano material demonstrates the character of novel optics, electricity, magnetics and the chemical aspect different from conventional body phase material.Will on the basis of single nano material character, there is new optics, electricity, magnetics and catalytic property in the assembling of nano material, (as: sensor, catalyst, Magnetized Material and optical material etc.) have potential using value in a lot of fields, therefore, the research of nanoparticle assembly becomes and becomes increasingly active.
Since nineteen nineties, nanometer assembling superstructure is through a large amount of scientific research personnel's unremitting effort,, there has been the sign that is tending towards ripe the preparation aspect such as appearance, particularly zero dimension and one dimension assembling superstructure that has had at present a large amount of successfully preparation modes and various assembling superstructure.But how utilizing numerous collaborative optical, electrical and magnetic property that these package assemblies are brought is the difficult challenge that current scientific research personnel faces.Recently, the preparation based on the nano level devices such as inorganic nano material, biomolecule material and bionic material and biology sensor is paid close attention to by numerous scientific research personnel.At present existing a small amount of nano-device is employed, but the specific region that how these nanometer assembling superstructures is integrated into macroscopical device accurately remains the tool hang-up of pendulum in face of scientific and technical personnel.
Summary of the invention
The preparation method who the object of this invention is to provide a kind of chain photoelectric nano bridge of high conductivity, has built dynamical nanometer electric wire.
Technical scheme of the present invention, a kind of preparation method of chain photoelectric nano bridge of high conductivity, it utilizes the gold nanorods of end region functionalization to build gold nano chain, forms nano chain photoelectric nano bridge, and has characterized the electric conductivity of nano chain photoelectric nano bridge.
Main implementation step of the present invention is: (1) gold nanorods synthetic; (2) gold nanorods end region functionalization; (3) formation of gold nano chain; (4) preparation of nano chain photoelectric nano bridge; (5) sign of the electric conductivity of nano chain photoelectric nano bridge.
Concrete steps are:
(1) gold nanorods is synthetic
Be about 3.0 gold nanorods according to the synthetic draw ratio of the method for patent " a kind of preparation method of the self-assembled material with surface reinforced Raman active " (patent No.: ZL 201010605799.9).Simple step is as follows:
1. crystal seed is synthetic: the three hydration tetra chlorauric acids of getting the pre-configured 2g/L of 0.1mL at 28.0 DEG C join in the softex kw solution of 0.2M of 1mL, and now, solution colour is by the colourless yellowish-brown that becomes.Then to the 0.01M sodium borohydride solution that adds the new preparation of 0.12mL in above-mentioned mixed system, rapid stirring 2 min.Solution colour becomes light brown from yellowish-brown.The water-bath of above-mentioned synthetic crystal seed being put into 28.0 DEG C leaves standstill reaction 30 min, make not participate in completely the synthetic sodium borohydride approach exhaustion of crystal seed, (the one, the gold ion of complete reaction and being consumed not in the further reduction system of sodium borohydride, the 2nd, in standing course of reaction, sodium borohydride further reduces because hydrolysis causes its content), the crystal seed of preparation will carry out next step reaction in 4h after synthetic.
2. gold nanorods growth course: after crystal seed has synthesized, carry out the growth of gold nanorods.After the three hydration tetra chlorauric acids of the 2g/L of 5mL join in the softex kw of 5mL 0.2M, add the ultra-pure water of 4 mL, mix.The 0.01M liquor argenti nitratis ophthalmicus of 0.125mL joins in above-mentioned mixed system, mixes, and subsequently the 0.1M ascorbic acid solution of 65 μ L is added to above-mentioned system solution, and vigorous stirring is reacted 2 min at 28.0 DEG C, and solution is become colourless by brown.Finally, add the seed-solution of 0.05mL softly to stir and evenly mix 20s.The color of 28.0 DEG C of reactions solution after 2 hours is drabon look.Synthetic gold nanorods solution is through centrifugal 10 min of 10000r/min, abandon supernatant, adopt the softex kw solution of 0.005M that precipitation is heavily disperseed, clean once, the most at last gold nanorods Solution Dispersion with initial isopyknic solution in, room temperature leaves standstill preserves, to carry out next step sign and experiment demand.
(2) gold nanorods end region functionalization
The preparation (being abbreviated as AuNR-DNA1) of gold nanorods-few DNA 1: utilize the synthetic gold nanorods of seeded growth method 10 μ L, add the DNA1 of the sulfydryl modification of the 1mM of 5 μ L, jolting reaction 8h, the centrifugal 15min of 7500r/min, abandon supernatant, washing once, with the softex kw Solution Dispersion NR-DNA1 compound of the 0.005M of 10 μ L, 4 DEG C of preservations, stand-by;
The preparation (being abbreviated as AuNR-DNA2) of gold nanorods-few DNA 2: utilize the synthetic gold nanorods of seeded growth method 10 μ L, add the DNA 2 of the sulfydryl modification of the 1mM of 5 μ L, jolting reaction 8h, the centrifugal 15min of 7500r/min, abandon supernatant, washing once, with the softex kw Solution Dispersion AuNR-DNA2 compound of the 0.005M of 10 μ L, 4 DEG C of preservations, stand-by.
DNA 1, sequence, as shown in SEQ ID NO.1, is specially: 5 '-SH-AAAAAAAACC CCCCCC-3 '; DNA 2, sequence, as shown in SEQ ID NO.2, is specially: 5 '-SH-GGGGGGGGTT TTTTTT-3 '.
(3) preparation of gold nano chain
Get the AuNR-DNA1 of the above-mentioned preparation of 5 μ L and the AuNR-DNA2 of the above-mentioned preparation of 5 μ L mixes, after incubated at room 12h, by oligonucleotide DNA 1 and the DNA 2 assembling superstructure of the specific bionical identification formation gold nano chain of the gold nanorods of regional function respectively, conditions such as the ionic strength, pH value, reaction time by regulation and control hybridization buffer and then realize the control of controlled, the ordered structure of gold nano chain, make gold nano chain solution.
(4) preparation of the photoelectric nano bridge of nano chain
Prepare by classical optical lithography in advance taking silicon as substrate, taking two thin gold bars as positive and negative electrode, centre is in the host material of groove, when the gold nano chain solution of above-mentioned preparation is added dropwise in this groove, longer nano chain structure wherein is just spontaneously connected to two, edge above gold bar, form the photoelectric nano bridge of nano chain, by controlling the path of positive and negative electrode, on the reaction conditions such as buffer medium and then control gold bar, form the photoelectric nano bridge of single nano chain, realize the preparation of the photoelectric nano bridge of nano chain.
(5) nano chain and the sign of photoelectric nano bridge construction and the detection of performance
Employing accelerating potential is that the nano chain that ESEM, X-ray energy spectrometer, the dynamic laser light scattering experimental instrument of 200 keV builds gold nanorods self assembly characterizes, and successfully builds by known this kind of gold nano chain of above-mentioned characterization method;
Adopt the instruments such as SEM, X-ray energy spectrometer, ultraviolet-visual spectrometer and an atomic force electron microscope of transmitting to characterize the photoelectric nano bridge construction of preparation.
Adopt the magnitude of voltage that adds 40V above gold bar at adjacent two, by measuring the variation of two current values between gold bar, measure the electric conductivity of photoelectric nano bridge, known by measurement result, its electric conductivity excellence.
Beneficial effect of the present invention: the present invention utilizes the regional function technology of gold nanorods, realize the finishing that the specific region of gold nanorods has been realized to oligonucleotides, by the bionical recognition property of oligonucleotides, realize the formation of the structure of the chain of nanometer rods; By the position of regulation and control electrode, the condition such as size, buffer medium of electromotive force realizes the nano photoelectric nanometer bridge of nanometer rods, and then makes to realize energising between two conductors that are not connected, and obtains nanometer electric wire, effectively improves electrical efficiency.
Brief description of the drawings
The structural representation of the photoelectric nano bridge of the chain package assembly of Fig. 1 high conductivity.
The gold nanorods transmission electron microscope picture that Fig. 2 is free.
Detailed description of the invention
Embodiment 1
(1) gold nanorods is synthetic
Be about 3.0 gold nanorods according to the synthetic draw ratio of the method for patent " a kind of preparation method of the self-assembled material with surface reinforced Raman active " (patent No.: ZL 201010605799.9).Simple step is as follows:
1. crystal seed is synthetic: the three hydration tetra chlorauric acids of getting the pre-configured 2g/L of 0.1mL at 28.0 DEG C join in the softex kw solution of 0.2M of 1mL, and now, solution colour is by the colourless yellowish-brown that becomes.Then to the 0.01M sodium borohydride solution rapid stirring 2min that adds the new preparation of 0.12mL in above-mentioned mixed system.Solution colour becomes light brown from yellowish-brown.The water-bath of above-mentioned synthetic crystal seed being put into 28.0 DEG C leaves standstill reaction 30min, make not participate in completely the synthetic sodium borohydride approach exhaustion of crystal seed, (the one, the gold ion of complete reaction and being consumed not in the further reduction system of sodium borohydride, the 2nd, in standing course of reaction, sodium borohydride further reduces because hydrolysis causes its content), the crystal seed of preparation will carry out next step reaction in 4h after synthetic.
2. gold nanorods growth course: after crystal seed has synthesized, carry out the growth of gold nanorods.After the three hydration tetra chlorauric acids of the 2g/L of 5mL join in the softex kw of 5mL 0.2M, add the ultra-pure water of 4mL, mix.The 0.01M liquor argenti nitratis ophthalmicus of 0.125mL joins in above-mentioned mixed system, mixes, and subsequently the 0.1M ascorbic acid solution of 65 μ L is added to above-mentioned system solution, vigorous stirring reaction 2min at 28.0 DEG C, and solution is become colourless by brown.Finally, add the seed-solution of 0.05mL softly to stir and evenly mix 20s.After 28.0 DEG C of reaction 2h, the color of solution is drabon look.Synthetic gold nanorods solution is through 10000 rpms of centrifugal 10min, abandon supernatant, adopt the softex kw solution of 0.005 M that precipitation is heavily disperseed, clean once, the most at last gold nanorods Solution Dispersion with initial isopyknic solution in, room temperature leaves standstill preserves, to carry out next step sign and experiment demand.
(2) gold nanorods end region functionalization
The preparation (being abbreviated as AuNR-DNA1) of gold nanorods-few DNA 1: utilize the synthetic gold nanorods of seeded growth method 10 μ L, add the DNA 1 of the sulfydryl modification of the 1mM of 5 μ L, jolting reaction 8h, the centrifugal 15min of 7500r/min, abandon supernatant, washing once, with the softex kw Solution Dispersion AuNR-DNA1 compound of the 0.005M of 10 μ L, 4 DEG C of preservations, stand-by;
The preparation (being abbreviated as AuNR-DNA2) of gold nanorods-few DNA 2: utilize the synthetic gold nanorods of seeded growth method 10 μ L, add the DNA 2 of the sulfydryl modification of the 1mM of 5 μ L, jolting reaction 8h, the centrifugal 15min of 7500r/min, abandon supernatant, washing once, with the softex kw Solution Dispersion AuNR-DNA2 compound of the 0.005M of 10 μ L, 4 DEG C of preservations, stand-by.
DNA?1：5’-SH-AAAAAAAACC?CCCCCC-?3’，
DNA?2：5’-SH-GGGGGGGGTT?TTTTTT-3’，
(3) preparation of gold nano chain
Get the AuNR-DNA1 of the above-mentioned preparation of 5 μ L and the AuNR-DNA2 of the above-mentioned preparation of 5 μ L mixes, after incubated at room 12h, by oligonucleotide DNA 1 and DNA 2 respectively the specific bionical identification of the gold nanorods of regional functions form the assembling superstructure of gold nano chain, conditions such as ionic strength by regulation and control hybridization buffer, pH value, reaction time and then realize the control of controlled, the ordered structure of gold nano chain.
(4) preparation of the photoelectric nano bridge of nano chain
Prepare by classical optical lithography in advance taking silicon as substrate, taking two thin gold bars as positive and negative electrode, centre is in the special host material of groove, when the gold nano chain solution of above-mentioned preparation is added dropwise in this groove, longer nano chain structure wherein is just spontaneously connected to two, edge above gold bar, form the photoelectric nano bridge of nano chain, by controlling the path of positive and negative electrode, on the reaction conditions such as buffer medium and then control gold bar, form the photoelectric nano bridge of single nano chain, realize the preparation of the photoelectric nano bridge of nano chain.
(5) nano chain and the sign of photoelectric nano bridge construction and the detection of performance
Employing accelerating potential is that the nano chain that ESEM, X-ray energy spectrometer, the dynamic laser light scattering experimental instrument of 200 keV builds gold nanorods self assembly characterizes, and successfully builds by known this kind of gold nano chain of above-mentioned characterization method;
Adopt the instruments such as SEM, X-ray energy spectrometer, ultraviolet-visual spectrometer and an atomic force electron microscope of transmitting to characterize the photoelectric nano bridge construction of preparation.
Adopt at adjacent two and above gold bar, add the voltage of 40V to be, by the variation of the current value between measuring, measure its electric conductivity, known by measurement result, electric conductivity excellence.
Claims (3)
1. a preparation method for the chain photoelectric nano bridge of high conductivity, is characterized in that step is:
(1) gold nanorods end region functionalization:
A, gold nanorods-few DNA 1, be the preparation of AuNR-DNA1: utilize the synthetic gold nanorods of seeded growth method 10 μ L, add the DNA1 of the sulfydryl modification of the 1mM of 5 μ L, jolting reaction 8h, the centrifugal 15min of 7500r/min, abandons supernatant, and washing once, with the softex kw Solution Dispersion AuNR-DNA1 compound of the 0.005M of 10 μ L, 4 DEG C of preservations, stand-by;
B, gold nanorods-few DNA 2, be the preparation of AuNR-DNA2: utilize the synthetic gold nanorods of seeded growth method 10 μ L, add the DNA 2 of the sulfydryl modification of the 1mM of 5 μ L, jolting reaction 8h, the centrifugal 15min of 7500r/min, abandons supernatant, and washing once, with the softex kw Solution Dispersion AuNR-DNA2 compound of the 0.005M of 10 μ L, 4 DEG C of preservations, stand-by;
(2) preparation of gold nano chain: get AuNR-DNA2 prepared by AuNR-DNA1 prepared by 5 μ L steps (1) and 5 μ L and mix, after incubated at room 12h, by oligonucleotide DNA 1 and the DNA2 assembling superstructure of the specific bionical identification formation gold nano chain of the gold nanorods of regional function respectively, make gold nano chain solution;
(3) preparation of the photoelectric nano bridge of nano chain: prepare by classical optical lithography in advance taking silicon as substrate, taking two thin gold bars as positive and negative electrode, centre is in the host material of groove, gold nano chain solution prepared by step (2) is added dropwise in this groove, longer nano chain structure wherein is just spontaneously connected to two, edge above gold bar, form the photoelectric nano bridge of nano chain, by controlling the path of positive and negative electrode, on the reaction condition of buffer medium and then control gold bar, form the photoelectric nano bridge of single nano chain, realize the preparation of the photoelectric nano bridge of nano chain.
2. the preparation method of the chain photoelectric nano bridge of high conductivity according to claim 1, it is characterized in that: in step (1), the sequence of DNA1 is 5 '-SH-AAAAAAAACC CCCCCC-3 ', and the sequence of DNA2 is 5 '-SH-GGGGGGGGTT TTTTTT-3 '.
3. the preparation method of the chain photoelectric nano bridge of high conductivity according to claim 1, is characterized in that step (2) and step (3) products obtained therefrom nano chain and the sign of photoelectric nano bridge construction and the detection of performance as follows:
Employing accelerating potential is that the nano chain that ESEM, X-ray energy spectrometer, the dynamic laser light scattering experimental instrument of 200 keV builds gold nanorods self assembly characterizes, and successfully builds by known this kind of gold nano chain of above-mentioned characterization method;
Adopt SEM, X-ray energy spectrometer, ultraviolet-visual spectrometer and an atomic force electron microscopy instrument for transmitting to characterize the photoelectric nano bridge construction of preparation;
Adopt the magnitude of voltage that adds 40V above gold bar at adjacent two, by measuring the variation of two current values between gold bar, measure the electric conductivity of photoelectric nano bridge, known by measurement result, its electric conductivity excellence.
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| CN104999071A (en) * | 2015-06-24 | 2015-10-28 | 深圳先进技术研究院 | Gold nanorod array and preparation method and application thereof |
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| CN102127541A (en) * | 2010-12-25 | 2011-07-20 | 江南大学 | Polymerase-chain-reaction-based gold nanorod controlled self-assembly method |
| CN102886528A (en) * | 2012-10-18 | 2013-01-23 | 江南大学 | Preparation method for gold nanorod self-assembly material with optical rotation characteristic based on polymerase chain reaction |
| US20130295563A1 (en) * | 2012-05-04 | 2013-11-07 | Snu R&Db Foundation | Nanoparticles in the shape of nanosnowman with a head part and a body part, a preparation method thereof and a detection method using the same |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2004020450A1 (en) * | 2002-08-30 | 2004-03-11 | Commonwealth Scientific And Industrial Research Organisation | Methods for the chemical and physical modification of nanotubes, methods for linking the nanotubes, methods for the directed positioning of nanotubes, and uses thereof |
| WO2006067276A1 (en) * | 2004-12-23 | 2006-06-29 | Nanolab Systems Oy | Utilization of nanowires in chemical and biological analysis |
| CN102127541A (en) * | 2010-12-25 | 2011-07-20 | 江南大学 | Polymerase-chain-reaction-based gold nanorod controlled self-assembly method |
| US20130295563A1 (en) * | 2012-05-04 | 2013-11-07 | Snu R&Db Foundation | Nanoparticles in the shape of nanosnowman with a head part and a body part, a preparation method thereof and a detection method using the same |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104999071A (en) * | 2015-06-24 | 2015-10-28 | 深圳先进技术研究院 | Gold nanorod array and preparation method and application thereof |
| CN104999071B (en) * | 2015-06-24 | 2017-04-05 | 深圳先进技术研究院 | A kind of gold nano stick array and its preparation method and application |
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Address after: 214016 Jiangsu city of Wuxi Province District Liangxi No. 898 South Road 7 layer beam Creek area of food science and Technology Park Patentee after: Jiangnan University Address before: Food College of Jiangnan University No. 1800 Li Lake Avenue 214122 in Jiangsu province Wuxi City Binhu District Patentee before: Jiangnan University |