CN103293108B - 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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CN103293108B
CN103293108B CN201310254791.6A CN201310254791A CN103293108B CN 103293108 B CN103293108 B CN 103293108B CN 201310254791 A CN201310254791 A CN 201310254791A CN 103293108 B CN103293108 B CN 103293108B
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gold
gold nanosphere
dimensional arrangement
dispersion liquid
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CN103293108A (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 nanosphere one dimensional arrangement hotspot architecture and application thereof
Technical field
The invention provides a kind of gold nanosphere one dimensional arrangement hotspot architecture and application thereof, belong to surface plasma micro-/micro-nano structure field.
Background technology
In recent years, ripe day by day along with the investigation of materials of Prof. Du Yucang metal nanoparticle, based on metal nanoparticle uniqueness surface phasmon photonics and the various optical sensors that develop play a significant role at biomedical sector.Under the resonance excitation of light, the free electron collective oscillation of gold nano grain, i.e. local surface plasma resonance (Localized Surface Plasmon Resonance, LSPR), make the hot spot region at particle aggregate, the nano-scale gap place of such as pellet-pellet, obtains Electromagnetic enhancement up to 10 11magnitude.Based on the local electric field enhancement effect of this surface phasmon, also known as hot spot-effect.People have developed the kinds of surface enhanced spectrum with extensive use, as Surface Enhanced Raman Scattering Spectrum and surface-enhanced fluorescence spectrum etc.Recently, the surface phasmon circular dichroism chirality spectral probe developed based on local electric field enhancement effect is the another challenge study hotspot in this field.With other noble metal nano particles (as silver, copper etc.) compare, gold nano grain has good stability in coenocorrelation, biocompatibility, biological safety, this makes gold nano grain in medical treatment, biomolecule detects, the aspects such as medical diagnosis on disease show huge application prospect, extensive concern (X.H.Huang is subject in the research and development field of surface phasmon photonics material, S.Neretina and M.A.El-Sayed, Gold Nanorods:From Synthesis and Properties toBiological and Biomedical Applications, Adv.Mater.2009, 21, 4880-4910, HuanjunChen, Lei Shao, Qian Liand Jianfang Wang.Gold nanorods and their plasmonicproperties.Chem.Soc.Rev., 2013,42,2679.).
There is bibliographical information recently, based on the hot spot-effect that the assembly of Gold nanorods is formed, produce circular dichroism (CD) signal in set plasmon resonance frequency, can be used for detecting with distinguish biomolecule in solution difference singly reflect body (Zhening Zhu, Wenjing Liu, Zhengtao Li, Bing Han, YunlongZhou, Yan Gao, and Zhiyong Tang.Manipulation of Collective Optical Activity inOne-Dimensional Plasmonic Assembly, ACS Nano2012, 6:2326 – 2332), but the observation that this surface phasmon circular dichroism (CD) responds is only limitted to have the linear assembly of the gold nanorods of anisotropic structure.In fact; because gold nanosphere is structurally isotropy; the assembling of gold nanosphere mostly is unordered; make also in the assembly of gold nanosphere, not observe surface phasmon circular dichroism (CD) phenomenon (Zhening Zhu so far; Wenjing Liu; Zhengtao Li; Bing Han; Yunlong Zhou; YanGao; and Zhiyong Tang.Manipulation of Collective Optical Activity inOne-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 ChiralRecognition 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 NanosphereDimers, JACS2012,134,4477-4480).
Summary of the invention
The object of this invention is to provide a kind of one dimensional arrangement hotspot architecture based on gold nanosphere, the yardstick of described gold nanosphere one dimension hotspot architecture is a few to tens of nanometers, by Electromagnetic enhancement effect, circular dichroism (CD) the spectral response signal being in hot spot region molecule transfer to as seen from the ultraviolet spectrum district at usual place/spectral region, infrared region detect.Can also detect in this hotspot architecture, the molecule being positioned at hot spot region has surface-enhanced Raman fingerprint signal simultaneously.
For achieving the above object, technical scheme of the present invention is as follows:
A kind of gold nanosphere one dimensional arrangement hotspot architecture, prepares by the following method:
Step one, preparative centrifugation gold nanosphere dispersion liquid once
Prepare gold nanosphere crude dispersion by seed mediated growth method, to be centrifugally precipitated and supernatant liquid, be wherein precipitated as the gold nanosphere that surface is wrapped in cetyl trimethyl ammonium bromide (CTAB); After taking out supernatant liquid, add water in precipitation, obtain centrifugal gold nanosphere dispersion liquid once; The volume of preferred described centrifugal gold nanosphere dispersion liquid once: the volume=1:1 of gold nanosphere crude dispersion.
By seed mediated growth method in preferred steps one, the process preparing gold nanosphere crude dispersion is as follows:
1. prepared by gold kind
Get CTAB solution, under stirring condition, add gold chloride (HAuCl 4) aqueous solution after, add sodium borohydride (NaBH 4) solution, stir 3min, obtain gold and plant for subsequent use;
Wherein, gold plant in the amount of substance of CTAB: 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 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 growth-promoting media: the amount of substance of sulfuric acid: amount of substance=10 of ascorbic acid 3: 10 2: 5.5;
3. the preparation of gold nanosphere (AuNSs) dispersion liquid
Get gold kind prepared by step 1, join in the growth-promoting media of step 2 preparation, at 30 DEG C, grow 12 ~ 15h, obtain gold nanosphere crude dispersion;
Wherein, get the amount of substance of CTAB in gold kind prepared by step 1: amount of substance=7.5 × 10 of CTAB in growth-promoting media prepared by step 2 -2: 1;
The gold nanosphere dispersion liquid of centrifugal twice that step 2, preparation are optimized
Get the centrifugal gold nanosphere dispersion liquid once that step one prepares, again centrifugal, be precipitated and supernatant liquid; Wherein be precipitated as the gold nanosphere that surface is wrapped in CTAB; After taking out supernatant liquid, in precipitation, add water, obtain the gold nanosphere dispersion liquid of centrifugal secondary; The volume of the gold nanosphere dispersion liquid of preferred described centrifugal secondary: the volume=1.5:1 of centrifugal gold nanosphere dispersion liquid once.
Regulate the CTAB content in the gold nanosphere dispersion liquid of centrifugal secondary, make the Zeta potential of dispersion liquid in 24.0 ± 0.7mV ~ 46.2 ± 1.7mV, the gold nanosphere dispersion liquid of centrifugal twice that is optimized.
Step 3, prepare gold nanosphere one dimensional arrangement hotspot architecture
Connection molecule is added in the gold nanosphere dispersion liquid of centrifugal twice optimized, connect the end group that sulfhydrylation is contained in molecule one end, can form Au-S key with gold nanosphere by chemical exchange reaction, the other end contains the group that can form ionic link or hydrogen bond in the solution.Make the concentration of connection molecule in dispersion liquid to be micromole's magnitude or mM magnitude, to connect molecule and be in hot spot region, obtain gold nanosphere one dimensional arrangement hotspot architecture.
Described gold nanosphere one dimensional arrangement hotspot architecture can be used for detecting the composition singly reflecting body molecule, not only can detect the connection molecule being positioned at hot spot region, also detectable other molecule entering hot spot region.Such as, by Raman spectrum analysis, the Raman fingerprint characteristic being positioned at hot spot region molecule can be obtained.Analyzed by circular dichroism, the chirality optical signature being positioned at hot spot region molecule can be obtained.
Beneficial effect
1. gold nanosphere one dimensional arrangement hotspot architecture provided by the invention, by Electromagnetic enhancement effect, circular dichroism (CD) the chirality spectral response signal being in hot spot region molecule transfer to as seen from the ultraviolet spectrum district at usual place/spectral region, infrared region detect.
2. gold nanosphere one dimensional arrangement hotspot architecture provided by the invention, can also detect the surface-enhanced Raman fingerprint signal being positioned at hot spot region molecule.
3. of the present invention by gold nanosphere one dimensional arrangement hotspot architecture, the mirror image list being applicable to detect and distinguish chiral molecules reflects body, and detectable molecular conecentration is from several micromole to mM magnitude.Detection method economy, quick, highly sensitive, simultaneously easy and simple to handle, nontoxic.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of gold nanosphere one dimensional arrangement hotspot architecture embodiment 1 prepared;
Fig. 2 be embodiment 1 prepare in gold nanosphere one dimensional arrangement hotspot architecture, be positioned at the circular dichroism figure of hot spot region molecule;
Fig. 3 is the scanning electron microscope (SEM) photograph of the gold nanosphere one dimensional arrangement hotspot architecture that embodiment 2 prepares;
Fig. 4 be embodiment 2 prepare in gold nanosphere one dimensional arrangement hotspot architecture, be positioned at the circular dichroism figure of hot spot region molecule;
Fig. 5 is the scanning electron microscope (SEM) photograph of the gold nanosphere one dimensional arrangement hotspot architecture that embodiment 3 prepares;
Fig. 6 be embodiment 3 prepare in gold nanosphere one dimensional arrangement hotspot architecture, be positioned at the circular dichroism figure of hot spot region molecule.
Fig. 7 be embodiment 4 prepare in gold nanosphere one dimensional arrangement hotspot architecture, be positioned at the Raman spectrogram of hot spot region molecule.
Embodiment
The present invention is described in detail: in embodiment 1 ~ 4 below by specific embodiment, by uv-visible absorption spectra instrument, detect the gold nanosphere concentration in gold nanosphere dispersion liquid and free CTAB concentration, and the gold nanosphere concentration in gold nanosphere one dimensional arrangement hotspot architecture; The Zeta potential of the gold nanosphere of centrifugal twice of different CTAB concentration is measured by laser particle potentiometric analysis; By scanning electron microscope, obtain pattern and the structure of described gold nanosphere one dimensional arrangement hotspot architecture; By circular dichroism instrument, detect the spectral signature of the hot spot region molecule of gold nanosphere one dimensional arrangement hotspot architecture.By Raman spectrometer, measure the Raman spectrum being positioned at the molecule of hot spot region.CTAB is purchased from Avanti company; Halfcystine and Isosorbide-5-Nitrae-BDT(1,4-phenyl two mercaptan) purchased from Shanghai Reagent Company of Sigma.
Embodiment 1
Step one, preparative centrifugation gold nanosphere dispersion liquid once
1. prepared by gold kind
Get the CTAB solution 7.5ml of 0.1mol/L, add 1.8ml water, under stirring condition, add the gold chloride (HAuCl that concentration is 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 for subsequent use;
2. growth-promoting media preparation
Get the CTAB solution 100ml of 0.1mol/L, add the gold chloride (HAuCl that concentration is 24.7mmol/L 4) aqueous solution 2.05ml, concentration is the silver nitrate aqueous solution 0.1ml of 0.01mol/L, and concentration is the sulfuric acid 2ml of 0.5mol/L, and concentration is the aqueous ascorbic acid 0.55ml of 0.1mol/L.
3. the preparation of gold nanosphere dispersion liquid
Get step 1 prepare gold plant 240 μ L join step 2 prepare growth-promoting media in, at 30 DEG C, grow 12h, obtain gold nanosphere crude dispersion.By described gold nanosphere stoste after centrifuging, be precipitated and supernatant liquid, be wherein precipitated as the gold nanosphere that surface is wrapped in CTAB; After taking out supernatant liquid with pipettor, in precipitation, add 100ml water, obtain centrifugal gold nanosphere dispersion liquid once.
The gold nanosphere dispersion liquid of centrifugal twice that step 2, preparation are optimized
Get the centrifugal gold nanosphere dispersion liquid once of 1mL step one preparation.By described centrifugal gold nanosphere dispersion liquid once again centrifugal (under 12000 turns of conditions centrifugal 5 minutes), be precipitated and supernatant liquid, be wherein precipitated as the gold nanosphere that surface is wrapped in CTAB; After taking out supernatant liquid with pipettor, sediment fraction backfill 1.5mL deionized water (conductivity is 18.2M Ω), obtains the gold nanosphere dispersion liquid of centrifugal secondary.By adding the aqueous solution of CTAB in the gold nanosphere dispersion liquid of centrifugal secondary, regulate the content of CTAB, recording Zeta potential is 30.3 ± 2.3mV, the gold nanosphere dispersion liquid of centrifugal twice that is optimized.
Step 3, prepare gold nanosphere one dimensional arrangement hotspot architecture
Get three parts of volumes and be 600 μ l, Zeta potential is the gold nanosphere dispersion liquid of centrifugal twice of the optimization of 30.3 ± 2.3mV, respectively called after a1, a2, a3.Wherein a3 is as blank, in a1, add that L-is mono-reflects body cysteine molecule solution, in a2, add that D-is mono-reflects body cysteine molecule solution, semicystinol concentration after adding cysteine solution in a1, a2 is 9 μm of ol/L, gold nanosphere is wherein combined with cysteine molecule, obtains gold nanosphere one dimensional arrangement hotspot architecture (AuNSs-Cys).
Fig. 1 is the scanning electron microscope (SEM) photograph of the gold nanosphere one dimensional arrangement hotspot architecture described in embodiment 1, illustrates present invention achieves to define surface plasmons hotspot architecture by gold nanosphere one dimensional arrangement hotspot architecture.So-called focus, refers to the local electric field producing huge enhancing between adjacent two gold nanoshell particles, makes the gap between two particles become hot spot region.
With CD spectrometer to a3 with add a1, a2 after cysteine solution and detect, the CD spectrum obtained as shown in Figure 2.Wherein horizontal ordinate is excitation wavelength, and unit is nanometer; Ordinate is CD signal intensity, and unit is milliradian.Spectral line is distinguished called after A1, A2, A3 by corresponding a1, a2, a3 successively;
Wherein, A3 as blank, at the CD signal of the visible/near infrared wave band of wavelength 400 ~ 820nm close to 0; Can find out from A1, A2, the CD spectral response of mirror image is produced at visible/near infrared wave band, explanation can observe in gold nanosphere one dimensional arrangement hotspot architecture in set plasmon resonance frequency (visible-range), be positioned at circular dichroism (CD) spectral signal of the molecule of hot spot region, and Body components can be reflected to halfcystine molecular chiral list and detect.
Embodiment 2
Step one, preparative centrifugation gold nanosphere dispersion liquid once
Wherein, centrifugal gold nanosphere dispersion liquid is once prepare in embodiment 1.
The gold nanosphere dispersion liquid of centrifugal twice that step 2, preparation are optimized
Get the centrifugal gold nanosphere dispersion liquid once of 1mL step one preparation.By described centrifugal gold nanosphere dispersion liquid once again centrifugal (12000 turns, 5 minutes), be precipitated and supernatant liquid, be wherein precipitated as the gold nanosphere that surface is wrapped in CTAB; After taking out supernatant liquid with pipettor, sediment fraction backfill deionized water (18.2M Ω, 1.5mL) obtains the gold nanosphere dispersion liquid of centrifugal secondary.Regulate the content of CTAB in the gold nanosphere dispersion liquid of centrifugal secondary by the aqueous solution of CTAB, recording Zeta potential is 24.0 ± 0.7mV, the gold nanosphere dispersion liquid of centrifugal twice that is optimized.
Step 3, prepare gold nanosphere one dimensional arrangement hotspot architecture
Get two parts of volumes and be 600 μ l, Zeta potential is the gold nanosphere dispersion liquid of centrifugal twice of the optimization of 24.0 ± 0.7mV, called after b1, b2 respectively, in b1, add that L-is mono-reflects body cysteine molecule solution, in b2, add that D-is mono-reflects body cysteine molecule solution, after adding cysteine solution, in b1, b2, semicystinol concentration is 9 μm of ol/L, and gold nanosphere is wherein combined with cysteine molecule, obtains gold nanosphere one dimensional arrangement hotspot architecture (AuNSs-Cys).
Fig. 3 is the scanning electron microscope (SEM) photograph of the gold nanosphere one dimensional arrangement hotspot architecture described in embodiment 2, illustrates present invention achieves to define surface plasmons hotspot architecture by gold nanosphere one dimensional arrangement hotspot architecture.
Detect adding b1 and b2 after cysteine solution with CD spectrometer, the CD spectrum obtained as shown in Figure 4.Wherein horizontal ordinate is excitation wavelength, and unit is nanometer; Ordinate is CD signal intensity, and unit is milliradian, and spectral line is distinguished called after B1, B2 by corresponding b1, b2 successively;
Can find out from B1, B2, the CD spectral response of mirror image is produced at visible/near infrared wave band, explanation can observe in gold nanosphere one dimensional arrangement hotspot architecture in set plasmon resonance frequency (visible-range), be positioned at circular dichroism (CD) spectral signal of the molecule of hot spot region, and Body components can be reflected to halfcystine molecular chiral list and detect.
Embodiment 3
Step one, preparative centrifugation gold nanosphere dispersion liquid once
Wherein, centrifugal gold nanosphere dispersion liquid is once prepare in embodiment 1.
The gold nanosphere dispersion liquid of centrifugal twice that step 2, preparation are optimized
Get the centrifugal gold nanosphere dispersion liquid once of 1mL step one preparation.By described centrifugal gold nanosphere dispersion liquid once again centrifugal (12000 turns, 5 minutes), be precipitated and supernatant liquid, be wherein precipitated as the gold nanosphere that surface is wrapped in CTAB; After taking out supernatant liquid with pipettor, sediment fraction backfill deionized water (18.2M Ω, 1.5mL) obtains the gold nanosphere dispersion liquid of centrifugal secondary.Regulate the content of CTAB in the gold nanosphere dispersion liquid of centrifugal secondary by the aqueous solution of CTAB, recording Zeta potential is 46.2 ± 1.7mV, the gold nanosphere dispersion liquid of centrifugal twice that is optimized.
Step 3, prepare gold nanosphere one dimensional arrangement hotspot architecture
Get three parts of volumes and be 600 μ l, Zeta potential is the gold nanosphere dispersion liquid of centrifugal twice of the optimization of 46.2 ± 1.7mV, called after c1, c2, c3 respectively, in c1, add that L-is mono-reflects body cysteine molecule solution, in c2, add that D-is mono-reflects body cysteine molecule solution, DL-cysteine molecular solution is added in c3, after adding cysteine solution, in c1, c2 and c3, semicystinol concentration is 9 μm of ol/L, gold nanosphere is wherein combined with cysteine molecule, obtains gold nanosphere one dimensional arrangement hotspot architecture (AuNSs-Cys).
Fig. 5 is the scanning electron microscope (SEM) photograph of the gold nanosphere one dimensional arrangement hotspot architecture that embodiment 3 prepares, and illustrates present invention achieves to define surface plasmons hotspot architecture by gold nanosphere one dimensional arrangement hotspot architecture.
Detecting adding c1, c2 and c3 after cysteine solution with CD spectrometer, obtaining CD spectrum as shown in Figure 6, wherein horizontal ordinate is excitation wavelength, and unit is nanometer; Ordinate is CD signal intensity, and unit is milliradian.Spectral line is distinguished called after C1, C2, C3 by corresponding c1, c2, c3 successively;
For C3, the halfcystine of racemization itself is without CD signal response, and at the visible/near infrared wave band of wavelength 400 ~ 820nm, CD signal is close to 0; Can find out from C1, C2, the circular dichroism response of mirror image is produced at visible/near infrared wave band, explanation can observe in gold nanosphere one dimensional arrangement hotspot architecture in set plasmon resonance frequency (visible-range), be positioned at circular dichroism (CD) spectral signal of hot spot region molecule, and Body components can be reflected to halfcystine molecular chiral list and detect.
Embodiment 4
Step one, preparative centrifugation gold nanosphere dispersion liquid once
Wherein, centrifugal gold nanosphere dispersion liquid is once prepare in embodiment 1.
The gold nanosphere dispersion liquid of centrifugal twice that step 2, preparation are optimized
Get the centrifugal gold nanosphere dispersion liquid once of 1mL step one preparation.By described centrifugal gold nanosphere dispersion liquid once again centrifugal (12000 turns, 5 minutes), be precipitated and supernatant liquid, be wherein precipitated as the gold nanosphere that surface is wrapped in CTAB; After taking out supernatant liquid with pipettor, sediment fraction backfill deionized water (18.2M Ω, 1.5mL) obtains the gold nanosphere dispersion liquid of centrifugal secondary.Regulate the content of CTAB in the gold nanosphere dispersion liquid of centrifugal secondary by the aqueous solution of CTAB, recording Zeta potential is 46.2 ± 1.7mV, the gold nanosphere dispersion liquid of centrifugal twice that is optimized.
Step 3, prepare gold nanosphere one dimensional arrangement hotspot architecture
Get the gold nanosphere dispersion liquid called after d1 that volume is centrifugal twice of the optimization of 600 μ l, and add 1,4-BDT molecular solution, add 1, after 4-BDT molecule, in d1, Isosorbide-5-Nitrae-BDT molecular conecentration is 9 μm of ol/L, gold nanosphere wherein and 1,4-BDT molecule combines, and obtains gold nanosphere one dimensional arrangement hotspot architecture.Separately get the Isosorbide-5-Nitrae-BDT molecular solution 600 μ l that concentration is 9 μm of ol/L, called after d2.
Respectively the d1 after adding Isosorbide-5-Nitrae-BDT molecule and simple Isosorbide-5-Nitrae-BDT molecular solution d2 is detected with Raman spectrometer, by spectral line successively called after D1, D2 respectively, obtain Raman spectrum as shown in Figure 7.Wherein horizontal ordinate is wave number, and unit is centimetre -1; Ordinate is Raman signal intensity.D1 is at wave-number range 400-600cm -1and 731cm -1there is the characteristic peak of Isosorbide-5-Nitrae-BDT molecule, illustrate in described gold nanosphere one dimensional arrangement hotspot architecture, the molecule being positioned at hot spot region can be detected there is surface-enhanced Raman fingerprint signal, the Raman identification of Isosorbide-5-Nitrae-BDT molecule can be carried out.
The present invention obtains the support of state natural sciences fund, and fund number is 11174033,91127013.
In sum, these are only preferred embodiment of the present invention, be not intended to limit protection scope of the present invention.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (6)

1. a gold nanosphere one dimensional arrangement hotspot architecture, is characterized in that: described gold nanosphere one dimensional arrangement hotspot architecture prepares by the following method:
Step one, preparative centrifugation gold nanosphere dispersion liquid once
Prepare gold nanosphere crude dispersion by seed mediated growth method, to be centrifugally precipitated and supernatant liquid, after taking out supernatant liquid, add water in precipitation, obtain centrifugal gold nanosphere dispersion liquid once;
The gold nanosphere dispersion liquid of centrifugal twice that step 2, preparation are optimized
Get the centrifugal gold nanosphere dispersion liquid once that step one prepares, again centrifugal, be precipitated and supernatant liquid; Wherein be precipitated as the gold nanosphere that surface is wrapped in CTAB; After taking out supernatant liquid, in precipitation, add water, obtain the gold nanosphere dispersion liquid of centrifugal secondary;
Regulate the CTAB content in the gold nanosphere dispersion liquid of centrifugal secondary, make the Zeta potential of dispersion liquid in 24.0 ± 0.7mV ~ 46.2 ± 1.7mV, the gold nanosphere dispersion liquid of centrifugal twice that is optimized;
Step 3, prepare gold nanosphere one dimensional arrangement hotspot architecture
In the gold nanosphere dispersion liquid of centrifugal twice optimized, add connection molecule, make the concentration of connection molecule in dispersion liquid and be micromole's magnitude or mM magnitude, obtain gold nanosphere one dimensional arrangement hotspot architecture;
The end group of sulfhydrylation is contained in described connection molecule one end, and can form Au-S key with gold nanosphere, the other end contains the group that can form ionic link or hydrogen bond in the solution.
2. a kind of gold nanosphere one dimensional arrangement hotspot architecture according to claim 1, is characterized in that: by seed mediated growth method in step one, the process preparing gold nanosphere crude dispersion is as follows:
1. prepared by gold kind
Get CTAB solution, after adding the aqueous solution of gold chloride under stirring condition, add sodium borohydride solution, stir 3min, obtain gold and plant for subsequent use;
Wherein, gold plant in the amount of substance of CTAB: 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 the aqueous solution of gold chloride, silver nitrate aqueous solution, sulfuric acid and aqueous ascorbic acid, obtain growth-promoting media;
Wherein, the amount of substance of CTAB in 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 growth-promoting media: the amount of substance of sulfuric acid: amount of substance=10 of ascorbic acid 3: 10 2: 5.5;
3. the preparation of gold nanosphere dispersion liquid
Get gold kind prepared by step 1, join in the growth-promoting media of step 2 preparation, at 30 DEG C, grow 12 ~ 15h, obtain gold nanosphere crude dispersion;
Wherein, get the amount of substance of CTAB in gold kind prepared by step 1: amount of substance=7.5 × 10 of CTAB in growth-promoting media prepared by step 2 -2: 1.
3. a kind of gold nanosphere one dimensional arrangement hotspot architecture according to claim 1, is characterized in that: the volume of centrifugal gold nanosphere dispersion liquid once described in step one: the volume=1:1 of gold nanosphere crude dispersion.
4. a kind of gold nanosphere one dimensional arrangement hotspot architecture according to claim 1, is characterized in that: the volume of the gold nanosphere dispersion liquid of centrifugal secondary described in step 2: the volume=1.5:1 of centrifugal gold nanosphere dispersion liquid once.
5. a kind of gold nanosphere one dimensional arrangement hotspot architecture according to claim 1, is characterized in that: connecting molecule described in step 3 is halfcystine or Isosorbide-5-Nitrae-BDT.
6. the application of a kind of gold nanosphere one dimensional arrangement hotspot architecture as described in any one of Claims 1 to 5, it is characterized in that: described application is: by measuring circular dichroism and/or the Raman spectrum of gold nanosphere one dimensional arrangement hotspot architecture, the composition of gold nanosphere one dimensional arrangement hotspot architecture Middle molecule is detected.
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