CN103293108A - A one-dimensional arrangement hotspot structure of gold nanoballs and applications thereof - Google Patents

A one-dimensional arrangement hotspot structure of gold nanoballs and applications thereof Download PDF

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CN103293108A
CN103293108A CN2013102547916A CN201310254791A CN103293108A CN 103293108 A CN103293108 A CN 103293108A CN 2013102547916 A CN2013102547916 A CN 2013102547916A CN 201310254791 A CN201310254791 A CN 201310254791A CN 103293108 A CN103293108 A CN 103293108A
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gold nano
nano ball
gold
dispersion liquid
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CN103293108B (en
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王荣瑶
王鹏
丁腾
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Beijing Institute of Technology BIT
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Abstract

The invention provides a one-dimensional arrangement hotspot structure of gold nanoballs and applications thereof, belonging to the field of surface plasmon micro/nanostructures. The one-dimensional arrangement hotspot structure of gold nanoballs is obtained by centrifugating a gold nanoball dispersion liquid twice, adjusting a CTAB content, and adding linker molecules. By using the one-dimensional arrangement hotspot structure of gold nanoballs, circular dichroism signals of molecules in hot spots can be observed in visible light range, and linker molecules of different enantiomers can be detected in about one minute, with a detectable concentration of the linker molecules is in micromole, and the one-dimensional arrangement hotspot structure of gold nanoballs has Raman enhancement effect on molecules in hot spots. According to the invention, the one-dimensional arrangement hotspot structure of gold nanoballs is quick in detecting speed, high in sensitivity, simple in operation, and non-toxic and harmless.

Description

A kind of gold nano ball one dimension is arranged hotspot architecture and application thereof
Technical field
The invention provides a kind of gold nano ball one dimension and arrange hotspot architecture and application thereof, belong to surface plasma little/the micro-nano structure field.
Background technology
In recent years, ripe day by day along with artificial synthetic metal nanoparticle investigation of materials, the various optical sensors that develop based on the surface phasmon photonics of metal nanoparticle uniqueness play a significant role at biomedical sector.Under the resonance excitation of light, the free electron collective oscillation of gold nano grain, be local surface plasma resonance (Localized Surface Plasmon Resonance, LSPR), make hot spot region at particle aggregate, for example the nano-scale gap place of particle-particle obtains electromagnetism and strengthens up to 10 11Magnitude.Local electric field enhancement effect based on this surface phasmon claims hot spot-effect again.People have developed the kinds of surface enhanced spectrum with extensive use, strengthen fluorescence spectrum etc. as Surface enhanced raman spectroscopy spectrum and surface.Recently, exploitation is the another challenge research focus in this field based on the surface phasmon circular dichroism chirality spectral probe of local electric field enhancement effect.With other noble metal nano particles (as silver, copper etc.) compare, gold nano grain has good stable in coenocorrelation, biocompatibility, biological safety, this makes gold nano grain in medical treatment, biomolecule is surveyed, aspects such as medical diagnosis on disease show great application prospect, research and development field at the surface phasmon photonics material is subjected to extensive concern (X.H.Huang, S.Neretina and M.A.El-Sayed, Gold Nanorods:From Synthesis and Properties to Biological and Biomedical Applications, Adv.Mater.2009,21,4880-4910; Huanjun Chen, Lei Shao, Qian Liand Jianfang Wang.Gold nanorods and their plasmonic properties.Chem.Soc.Rev., 2013,42,2679.).
Bibliographical information is arranged recently, the hot spot-effect that forms based on the assembly of the bar-shaped particulate of gold nano, be created in circular dichroism (CD) signal of set plasmon resonance frequency, can be used for surveying with distinguish solution in different body (the Zhening Zhu that singly reflect of biomolecule, Wenjing Liu, Zhengtao Li, Bing Han, Yunlong Zhou, Yan Gao, and Zhiyong Tang.Manipulation of Collective Optical Activity in One-Dimensional Plasmonic Assembly, ACS Nano2012,6:2326 – 2332), but the observation of this surface phasmon circular dichroism (CD) response only limits to have the linear assembly of the gold nanorods of anisotropic structure.In fact, because the gold nano ball structurally is isotropy, the assembling of gold nano ball mostly is unordered, make and also in the assembly of gold nano ball, do not observe surface phasmon circular dichroism (CD) phenomenon (Zhening Zhu so far, Wenjing Liu, Zhengtao Li, Bing Han, Yunlong Zhou, Yan Gao, and Zhiyong Tang.Manipulation of Collective Optical Activity in One-Dimensional Plasmonic Assembly, ACS Nano2012,6:2326 – 2332; I-Im S.Lim, Derrick Mott, Mark H.Engelhard, Yi Pan, Shalini Kamodia, Jin Luo, Peter N.Njoki, Shuiqin Zhou, Lichang Wang, and Chuan Jian Zhong, Interparticle Chiral Recognition of Enantiomers:ANanoparticle-Based Regulation Strategy, Anal.Chem.2009,81,689 – 698; Manabendra Chandra, Anne-Marie Dowgiallo, and Kenneth L.Knappenberger, Jr., Magnetic Dipolar Interactions in Solid Gold Nanosphere Dimers, JACS2012,134,4477-4480).
Summary of the invention
The purpose of this invention is to provide a kind of one dimension based on the gold nano ball and arrange hotspot architecture, the yardstick of described gold nano ball one dimension hotspot architecture is a few to tens of nanometers, can be by the electromagnetism enhancement effect, as seen the circular dichroism that is in the hot spot region molecule (CD) spectral response signal is transferred to from the ultraviolet spectrum district at common place/the infrared region spectral region survey.Can also detect in this hotspot architecture simultaneously, the molecule that is positioned at the hot spot region has the surface-enhanced Raman fingerprint signal.
For achieving the above object, technical scheme of the present invention is as follows:
A kind of gold nano ball one dimension is arranged hotspot architecture, prepares by the following method:
Step 1, preparative centrifugation gold nano ball dispersion liquid once
Prepare gold nano ball dispersion liquid stoste by seed mediated growth method, centrifugal precipitation and the supernatant liquid of obtaining wherein is precipitated as the gold nano ball that the surface is wrapped in cetyl trimethyl ammonium bromide (CTAB); After taking out supernatant liquid, in precipitation, add water, obtain centrifugal gold nano ball dispersion liquid once; The volume of preferred described centrifugal gold nano ball dispersion liquid once: the volume=1:1 of gold nano ball dispersion liquid stoste.
By seed mediated growth method, the process for preparing gold nano ball dispersion liquid stoste is as follows in the preferred steps one:
1. gold is planted and is prepared
Get CTAB solution, add gold chloride (HAuCl under the stirring condition 4) aqueous solution after, add sodium borohydride (NaBH 4) solution, stir 3min, obtain gold and plant standby;
Wherein, the amount of substance of CTAB during gold is planted: the amount of substance of gold chloride: the amount of substance=750:2.48:6 of sodium borohydride;
2. growth-promoting media preparation
Get CTAB solution, add gold chloride (HAuCl 4) aqueous solution, silver nitrate aqueous solution, sulfuric acid and aqueous ascorbic acid, obtain growth-promoting media;
Wherein, the amount of substance of CTAB in the growth-promoting media: the amount of substance of gold chloride: the amount of substance=10000:50.64:1 of silver nitrate;
The amount of substance of CTAB in the growth-promoting media: the amount of substance of sulfuric acid: the amount of substance of ascorbic acid=10 3: 10 2: 5.5;
3. the preparation of gold nano ball (AuNSs) dispersion liquid
Get the gold kind of step 1 preparation, join in the growth-promoting media of step 2 preparation, at 30 ℃ of 12~15h that grow down, obtain gold nano ball dispersion liquid stoste;
Wherein, the amount of substance of CTAB in the gold kind of the step 1 of getting preparation: amount of substance=7.5 * 10 of CTAB in the growth-promoting media of step 2 preparation -2: 1;
The centrifugal twice gold nano ball dispersion liquid that step 2, preparation are optimized
Get the centrifugal gold nano ball dispersion liquid once that step 1 prepares, centrifugal again, obtain precipitation and supernatant liquid; Wherein be precipitated as the gold nano ball that the surface is wrapped in CTAB; After taking out supernatant liquid, in precipitation, add water, obtain the gold nano ball dispersion liquid of centrifugal secondary; The volume of the gold nano ball dispersion liquid of preferred described centrifugal secondary: the volume=1.5:1 of centrifugal gold nano ball dispersion liquid once.
Regulate the CTAB content in the gold nano ball dispersion liquid of centrifugal secondary, make the Zeta potential of dispersion liquid at 24.0 ± 0.7mV~46.2 ± 1.7mV, the centrifugal twice gold nano ball dispersion liquid that is optimized.
Step 3, preparation gold nano ball one dimension are arranged hotspot architecture
In the centrifugal twice gold nano ball dispersion liquid of optimizing, add the connection molecule, connect the end group that molecule one end contains sulfhydrylation, can form the Au-S key with the gold nano ball by chemical exchange reaction, the other end contains the group that can form ionic link or hydrogen bond in solution.Make the concentration that connects molecule in dispersion liquid, be micromole's magnitude or mM magnitude, connect molecule and be in the hot spot region, obtain gold nano ball one dimension and arrange hotspot architecture.
Described gold nano ball one dimension is arranged hotspot architecture and be can be used for surveying the composition that singly reflects the body molecule, not only can survey the connection molecule that is positioned at the hot spot region, also detectable other molecule that enters the hot spot region.For example, by Raman spectrum analysis, can obtain to be positioned at the Raman fingerprint characteristic of hot spot region molecule.By the circular dichroism spectral analysis, can obtain to be positioned at the chirality optical signature of hot spot region molecule.
Beneficial effect
1. gold nano ball one dimension provided by the invention is arranged hotspot architecture, can be by the electromagnetism enhancement effect, as seen the circular dichroism that is in the hot spot region molecule (CD) chirality spectral response signal is transferred to from the ultraviolet spectrum district at common place/the infrared region spectral region survey.
2. gold nano ball one dimension provided by the invention is arranged hotspot architecture, can also detect the surface-enhanced Raman fingerprint signal that is positioned at the hot spot region molecule.
3. of the present inventionly arrange hotspot architecture by gold nano ball one dimension, be applicable to that the mirror image list of surveying and distinguish chiral molecules reflects body, detectable molecular conecentration from several micromoles to the mM magnitude.Detection method economy, quick, highly sensitive, simultaneously easy and simple to handle, nontoxic.
Description of drawings
Fig. 1 arranges the sem photograph of hotspot architecture for the gold nano ball one dimension that embodiment 1 is prepared;
What Fig. 2 prepared for embodiment 1 arranges in the hotspot architecture at gold nano ball one dimension, is positioned at the circular dichroism spectrogram of hot spot region molecule;
The gold nano ball one dimension that Fig. 3 prepares for embodiment 2 is arranged the sem photograph of hotspot architecture;
What Fig. 4 prepared for embodiment 2 arranges in the hotspot architecture at gold nano ball one dimension, is positioned at the circular dichroism spectrogram of hot spot region molecule;
The gold nano ball one dimension that Fig. 5 prepares for embodiment 3 is arranged the sem photograph of hotspot architecture;
What Fig. 6 prepared for embodiment 3 arranges in the hotspot architecture at gold nano ball one dimension, is positioned at the circular dichroism spectrogram of hot spot region molecule.
What Fig. 7 prepared for embodiment 4 arranges in the hotspot architecture at gold nano ball one dimension, is positioned at the Raman spectrogram of hot spot region molecule.
Embodiment
Describe the present invention in detail below by specific embodiment: in embodiment 1~4, by the uv-visible absorption spectra instrument, detect gold nano ball concentration and free CTAB concentration in the gold nano ball dispersion liquid, and gold nano ball one dimension is arranged the gold nano ball concentration in the hotspot architecture; Measure the Zeta potential of the centrifugal twice gold nano ball of different CTAB concentration by the potentiometric analysis of laser particle diameter; By scanning electron microscope, obtain pattern and structure that described gold nano ball one dimension is arranged hotspot architecture; By the circular dichroism spectrometer, detect the spectral signature that gold nano ball one dimension is arranged the hot spot region molecule of hotspot architecture.By Raman spectrometer, measure the Raman spectrum of the molecule that is positioned at the hot spot region.CTAB is available from Avanti company; Halfcystine and 1,4-BDT(1,4-phenyl two mercaptan) available from Shanghai Sigma reagent company.
Embodiment 1
Step 1, preparative centrifugation gold nano ball dispersion liquid once
1. gold is planted and is prepared
Get the CTAB solution 7.5ml of 0.1mol/L, add 1.8ml water, adding concentration under the stirring condition is the gold chloride (HAuCl of 24.7mmol/L 4) aqueous solution 100.4 μ l after, add the sodium borohydride (NaBH of 0.01mol/L 4) solution 600 μ l, stir 3min, obtain gold and plant standby;
2. growth-promoting media preparation
Get the CTAB solution 100ml of 0.1mol/L, adding concentration is the gold chloride (HAuCl of 24.7mmol/L 4) aqueous solution 2.05ml, concentration is the silver nitrate aqueous solution 0.1ml of 0.01mol/L, concentration is the sulfuric acid 2ml of 0.5mol/L, concentration is the aqueous ascorbic acid 0.55ml of 0.1mol/L.
3. the preparation of gold nano ball dispersion liquid
The gold of getting step 1 preparation is planted 240 μ L and is joined in the growth-promoting media of step 2 preparation, at 30 ℃ of growth 12h down, obtains gold nano ball dispersion liquid stoste.Described gold nano ball stoste after centrifuging, is obtained precipitation and supernatant liquid, wherein be precipitated as the gold nano ball that the surface is wrapped in CTAB; Behind pipettor taking-up supernatant liquid, in precipitation, add 100ml water, obtain centrifugal gold nano ball dispersion liquid once.
The centrifugal twice gold nano ball dispersion liquid that step 2, preparation are optimized
Get the centrifugal gold nano ball dispersion liquid once of 1mL step 1 preparation.With described centrifugal gold nano ball dispersion liquid once centrifugal (under the 12000 commentaries on classics conditions centrifugal 5 minutes) again, obtain precipitation and supernatant liquid, wherein be precipitated as the gold nano ball that the surface is wrapped in CTAB; Behind pipettor taking-up supernatant liquid, precipitate part backfill 1.5mL deionized water (conductivity is 18.2M Ω), obtain the gold nano ball dispersion liquid of centrifugal secondary.By in the gold nano ball dispersion liquid of centrifugal secondary, adding the aqueous solution of CTAB, regulate the content of CTAB, recording Zeta potential is 30.3 ± 2.3mV, the centrifugal twice gold nano ball dispersion liquid that is optimized.
Step 3, preparation gold nano ball one dimension are arranged hotspot architecture
Get three parts of volumes and be 600 μ l, Zeta potential is the centrifugal twice gold nano ball dispersion liquid of the optimization of 30.3 ± 2.3mV, respectively called after a1, a2, a3.Wherein a3 is as blank, add L-in the a1 and singly reflect body halfcystine molecular solution, add D-in the a2 and singly reflect body halfcystine molecular solution, semicystinol concentration behind the adding halfcystine solution among a1, the a2 is 9 μ mol/L, gold nano ball wherein is combined with the halfcystine molecule, obtains gold nano ball one dimension and arranges hotspot architecture (AuNSs-Cys).
Fig. 1 is that embodiment 1 described gold nano ball one dimension is arranged the sem photograph of hotspot architecture, illustrates that the present invention has realized that arranging hotspot architecture by gold nano ball one dimension has formed the surface plasmons hotspot architecture.So-called focus refers to produce the local electric field of huge enhancing between adjacent two gold nano ball particles, make the gap between two particles become the hot spot region.
With the CD spectrometer to a3 and a1, a2 after adding halfcystine solution survey, the CD spectrum that obtains is as shown in Figure 2.Wherein horizontal ordinate is excitation wavelength, and unit is nanometer; Ordinate is the CD signal intensity, and unit is milliradian.Corresponding a1, a2, a3 distinguish called after A1, A2, A3 successively with spectral line;
Wherein, A3 is as blank, at the CD signal of visible/near-infrared band of wavelength 400~820nm close to 0; From A1, A2, can find out, as seen/near-infrared band produces the CD spectral response of mirror image, explanation can observe at gold nano ball one dimension in set plasmon resonance frequency (visible-range) and arrange in the hotspot architecture, be positioned at circular dichroism (CD) spectral signal of the molecule of hot spot region, and can reflect the body composition to halfcystine molecular chiral list and survey.
Embodiment 2
Step 1, preparative centrifugation gold nano ball dispersion liquid once
Wherein, centrifugal gold nano ball dispersion liquid once is to prepare among the embodiment 1.
The centrifugal twice gold nano ball dispersion liquid that step 2, preparation are optimized
Get the centrifugal gold nano ball dispersion liquid once of 1mL step 1 preparation.With described centrifugal gold nano ball dispersion liquid once centrifugal (12000 change, 5 minutes) again, obtain precipitation and supernatant liquid, wherein be precipitated as the gold nano ball that the surface is wrapped in CTAB; After taking out supernatant liquid with pipettor, (18.2M Ω 1.5mL) obtains the gold nano ball dispersion liquid of centrifugal secondary to precipitation part backfill deionized water.Regulate the content of CTAB in the gold nano ball dispersion liquid of centrifugal secondary with the aqueous solution of CTAB, recording Zeta potential is 24.0 ± 0.7mV, the centrifugal twice gold nano ball dispersion liquid that is optimized.
Step 3, preparation gold nano ball one dimension are arranged hotspot architecture
Get two parts of volumes and be 600 μ l, Zeta potential is the centrifugal twice gold nano ball dispersion liquid of the optimization of 24.0 ± 0.7mV, difference called after b1, b2, add L-in the b1 and singly reflect body halfcystine molecular solution, add D-in the b2 and singly reflect body halfcystine molecular solution, add behind the halfcystine solution that semicystinol concentration is 9 μ mol/L among b1, the b2, gold nano ball wherein is combined with the halfcystine molecule, obtains gold nano ball one dimension arrangement hotspot architecture (AuNSs-Cys).
Fig. 3 is that embodiment 2 described gold nano ball one dimensions are arranged the sem photograph of hotspot architecture, illustrates that the present invention has realized that arranging hotspot architecture by gold nano ball one dimension has formed the surface plasmons hotspot architecture.
With the CD spectrometer b1 and the b2 that adds behind the halfcystine solution surveyed, the CD spectrum that obtains as shown in Figure 4.Wherein horizontal ordinate is excitation wavelength, and unit is nanometer; Ordinate is the CD signal intensity, and unit is milliradian, and corresponding b1, b2 distinguish called after B1, B2 successively with spectral line;
From B1, B2, can find out, as seen/near-infrared band produces the CD spectral response of mirror image, explanation can observe at gold nano ball one dimension in set plasmon resonance frequency (visible-range) and arrange in the hotspot architecture, be positioned at circular dichroism (CD) spectral signal of the molecule of hot spot region, and can reflect the body composition to halfcystine molecular chiral list and survey.
Embodiment 3
Step 1, preparative centrifugation gold nano ball dispersion liquid once
Wherein, centrifugal gold nano ball dispersion liquid once is to prepare among the embodiment 1.
The centrifugal twice gold nano ball dispersion liquid that step 2, preparation are optimized
Get the centrifugal gold nano ball dispersion liquid once of 1mL step 1 preparation.With described centrifugal gold nano ball dispersion liquid once centrifugal (12000 change, 5 minutes) again, obtain precipitation and supernatant liquid, wherein be precipitated as the gold nano ball that the surface is wrapped in CTAB; After taking out supernatant liquid with pipettor, (18.2M Ω 1.5mL) obtains the gold nano ball dispersion liquid of centrifugal secondary to precipitation part backfill deionized water.Regulate the content of CTAB in the gold nano ball dispersion liquid of centrifugal secondary with the aqueous solution of CTAB, recording Zeta potential is 46.2 ± 1.7mV, the centrifugal twice gold nano ball dispersion liquid that is optimized.
Step 3, preparation gold nano ball one dimension are arranged hotspot architecture
Get three parts of volumes and be 600 μ l, Zeta potential is the centrifugal twice gold nano ball dispersion liquid of the optimization of 46.2 ± 1.7mV, difference called after c1, c2, c3, add L-in the c1 and singly reflect body halfcystine molecular solution, add D-in the c2 and singly reflect body halfcystine molecular solution, in c3, add the DL-cysteine molecular solution, add behind the halfcystine solution that semicystinol concentration is 9 μ mol/L among c1, the c2 and c3, gold nano ball wherein is combined with the halfcystine molecule, obtains gold nano ball one dimension and arranges hotspot architecture (AuNSs-Cys).
The gold nano ball one dimension that Fig. 5 prepares for embodiment 3 is arranged the sem photograph of hotspot architecture, illustrates that the present invention has realized that arranging hotspot architecture by gold nano ball one dimension has formed the surface plasmons hotspot architecture.
With the CD spectrometer c1, c2 and the c3 that adds behind the halfcystine solution surveyed, obtain CD spectrum as shown in Figure 6, wherein horizontal ordinate is excitation wavelength, and unit is nanometer; Ordinate is the CD signal intensity, and unit is milliradian.Corresponding c1, c2, c3 distinguish called after C1, C2, C3 successively with spectral line;
For C3, the no CD signal response of the halfcystine of racemization itself, at visible/near-infrared band of wavelength 400~820nm, the CD signal is close to 0; From C1, C2, can find out, as seen/near-infrared band produces the circular dichroism spectral response of mirror image, explanation can observe at gold nano ball one dimension in set plasmon resonance frequency (visible-range) and arrange in the hotspot architecture, be positioned at circular dichroism (CD) spectral signal of hot spot region molecule, and can reflect the body composition to halfcystine molecular chiral list and survey.
Embodiment 4
Step 1, preparative centrifugation gold nano ball dispersion liquid once
Wherein, centrifugal gold nano ball dispersion liquid once is to prepare among the embodiment 1.
The centrifugal twice gold nano ball dispersion liquid that step 2, preparation are optimized
Get the centrifugal gold nano ball dispersion liquid once of 1mL step 1 preparation.With described centrifugal gold nano ball dispersion liquid once centrifugal (12000 change, 5 minutes) again, obtain precipitation and supernatant liquid, wherein be precipitated as the gold nano ball that the surface is wrapped in CTAB; After taking out supernatant liquid with pipettor, (18.2M Ω 1.5mL) obtains the gold nano ball dispersion liquid of centrifugal secondary to precipitation part backfill deionized water.Regulate the content of CTAB in the gold nano ball dispersion liquid of centrifugal secondary with the aqueous solution of CTAB, recording Zeta potential is 46.2 ± 1.7mV, the centrifugal twice gold nano ball dispersion liquid that is optimized.
Step 3, preparation gold nano ball one dimension are arranged hotspot architecture
Getting volume is the centrifugal twice gold nano ball dispersion liquid called after d1 of the optimization of 600 μ l, and add 1, the 4-BDT molecular solution, add 1, among the d1 1, the 4-BDT molecular conecentration is 9 μ mol/L, gold nano ball and 1 wherein behind the 4-BDT molecule, the combination of 4-BDT molecule obtains gold nano ball one dimension and arranges hotspot architecture.Other gets concentration is 1 of 9 μ mol/L, 4-BDT molecular solution 600 μ l, called after d2.
Respectively to adding d1 behind 1, the 4-BDT molecule and simple 1,4-BDT molecular solution d2 surveys with Raman spectrometer, and with spectral line called after D1 respectively successively, D2 obtains Raman spectrum as shown in Figure 7.Wherein horizontal ordinate is wave number, and unit is centimetre -1Ordinate is Raman signal intensity.D1 is at wave-number range 400-600cm -1And 731cm -1The characteristic peak that 1,4-BDT molecule occurs illustrates at described gold nano ball one dimension and arranges in the hotspot architecture, can detect the molecule that is positioned at the hot spot region and have the surface-enhanced Raman fingerprint signal, can carry out the Raman identification of 1,4-BDT molecule.
The present invention has obtained the support of state natural sciences fund, and fund number is 11174033,91127013.
In sum, more than be preferred embodiment of the present invention only, be not for limiting protection scope of the present invention.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (6)

1. a gold nano ball one dimension is arranged hotspot architecture, it is characterized in that: described gold nano ball one dimension is arranged hotspot architecture and is prepared by the following method:
Step 1, preparative centrifugation gold nano ball dispersion liquid once
Prepare gold nano ball dispersion liquid stoste by seed mediated growth method, centrifugal precipitation and the supernatant liquid of obtaining behind the taking-up supernatant liquid, adds water in precipitation, obtain centrifugal gold nano ball dispersion liquid once;
The centrifugal twice gold nano ball dispersion liquid that step 2, preparation are optimized
Get the centrifugal gold nano ball dispersion liquid once that step 1 prepares, centrifugal again, obtain precipitation and supernatant liquid; Wherein be precipitated as the gold nano ball that the surface is wrapped in CTAB; After taking out supernatant liquid, in precipitation, add water, obtain the gold nano ball dispersion liquid of centrifugal secondary;
Regulate the CTAB content in the gold nano ball dispersion liquid of centrifugal secondary, make the Zeta potential of dispersion liquid at 24.0 ± 0.7mV~46.2 ± 1.7mV, the centrifugal twice gold nano ball dispersion liquid that is optimized;
Step 3, preparation gold nano ball one dimension are arranged hotspot architecture
In the centrifugal twice gold nano ball dispersion liquid of optimizing, add the connection molecule, make the concentration that connects molecule in dispersion liquid, be micromole's magnitude or mM magnitude, obtain gold nano ball one dimension and arrange hotspot architecture;
Described connection molecule one end contains the end group of sulfhydrylation, can form the Au-S key with the gold nano ball, and the other end contains the group that can form ionic link or hydrogen bond in solution.
2. a kind of gold nano ball one dimension according to claim 1 is arranged hotspot architecture, it is characterized in that: by seed mediated growth method, the process for preparing gold nano ball dispersion liquid stoste is as follows in the step 1:
1. gold is planted and is prepared
Get CTAB solution, after the aqueous solution of adding gold chloride, add sodium borohydride solution under the stirring condition, stir 3min, obtain gold and plant standby;
Wherein, the amount of substance of CTAB during gold is planted: the amount of substance of gold chloride: the amount of substance=750:2.48:6 of sodium borohydride;
2. growth-promoting media preparation
Get CTAB solution, add aqueous solution, silver nitrate aqueous solution, sulfuric acid and the aqueous ascorbic acid of gold chloride, obtain growth-promoting media;
Wherein, the amount of substance of CTAB in the growth-promoting media: the amount of substance of gold chloride: the amount of substance=10000:50.64:1 of silver nitrate;
The amount of substance of CTAB in the growth-promoting media: the amount of substance of sulfuric acid: the amount of substance of ascorbic acid=10 3: 10 2: 5.5;
3. the preparation of gold nano ball dispersion liquid
Get the gold kind of step 1 preparation, join in the growth-promoting media of step 2 preparation, at 30 ℃ of 12~15h that grow down, obtain gold nano ball dispersion liquid stoste;
Wherein, the amount of substance of CTAB in the gold kind of the step 1 of getting preparation: amount of substance=7.5 * 10 of CTAB in the growth-promoting media of step 2 preparation -2: 1.
3. a kind of gold nano ball one dimension according to claim 1 is arranged hotspot architecture, it is characterized in that: the volume of centrifugal gold nano ball dispersion liquid once described in the step 1: the volume=1:1 of gold nano ball dispersion liquid stoste.
4. a kind of gold nano ball one dimension according to claim 1 is arranged hotspot architecture, it is characterized in that: the volume of the gold nano ball dispersion liquid of centrifugal secondary described in the step 2: the volume=1.5:1 of centrifugal gold nano ball dispersion liquid once.
5. a kind of gold nano ball one dimension according to claim 1 is arranged hotspot architecture, it is characterized in that: connecting molecule described in the step 3 is halfcystine or 1,4-BDT.
6. arrange the application of hotspot architecture as each described a kind of gold nano ball one dimension of claim 1~5, it is characterized in that: described application is: arrange circular dichroism spectrum and/or the Raman spectrum of hotspot architecture by measuring gold nano ball one dimension, gold nano ball one dimension is arranged the composition of molecule in the hotspot architecture and surveyed.
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