CN108645835A - Gold nanoparticle SERS active-substrate of highly branchedization and preparation method thereof - Google Patents
Gold nanoparticle SERS active-substrate of highly branchedization and preparation method thereof Download PDFInfo
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Abstract
The invention discloses gold nanoparticle SERS active-substrates of a kind of highly branchedization and preparation method thereof.Pattern and the controllable HBGNPs of optical property is made by adjusting the amount of reaction condition and reactant in the gold nanoparticle for restoring gold chloride one-step synthesis highly branchedization using Dopamine hydrochloride as reducing agent first；Then HBGNPs is coupled on the burnishing surface of silicon chip of amination processing, be prepared HBGNPs uniformly, the surface-enhanced Raman scattering activity substrate of dense arrangement；In preparation process, need to make silicon chip surface activate with the concentrated sulfuric acid, dioxygen water mixed liquid first；The silicon chip of activation is vertically disposed in the progress modified cleaning-drying in surface in 3 TSL 8330 ethanol solutions later；It keeps the polishing of amination silicon chip to immerse HBGNPs solution up, HBGNPs is made to deposit and by Electrostatic Absorption to silicon chip surface.The preparation method of above-mentioned SERS active-substrate is simple for process, of low cost, yield is high, SERS active-substrate performance obtained significantly, homogeneity and reproducibility it is preferable.
Description
Technical field
The invention belongs to field of material technology, it is related to synthesis and its SERS active-substrate and its structure side of a kind of HBGNPs
Method.
Background technology
Raman spectrum is a kind of lossless spectral technique, the feature with fingerprint recognition, can obtain substance in molecular level
Structural information.And when signaling molecule is adsorbed onto the rough surface of nanoscale, Raman signal often at the enhancing of multiple, this
Kind phenomenon is referred to as Surface enhanced Raman scattering（Hereinafter referred to as SERS）.SERS, which has, to be stablized, is not easy to be quenched, not by water and biology
The features such as sample autofluorescence interferes], obtained extensively in various aspects such as chemistry, physics, biotic environment monitoring, public safeties
Application.And the premise that SERS signal obtains is to prepare the SERS substrates with enough enhancement effects, which, which should have, is easy to
The features such as preparation, stable, homogeneity and favorable reproducibility.
In order to obtain the sufficiently strong nano materials of SERS, scientific research personnel has carried out continuous trial, wherein gold and silver
Because preferable chemical stability and SERS effects are widely used, especially gold nanoparticle has stable, nontoxic and is easily-synthesized
The characteristics of.With the increasingly maturation of nano material preparation technology, the gold nanoparticle with different-shape is synthesized, including
Nanometer rods, dendritic nanoparticles and nano flower etc..However, the study found that relative to other nano materials, there are sharp edges
With the gold nanoparticle of highly branchedization at branch angle（highly branched gold nanoparticles, HBGNPs）It is right
The change of local dielectric environment is extremely sensitive, and " hot spot " (Hot of the sharp protrusion on its surface or coupling regime
Spots the intensity of peripheral electromagnetic field) is significantly enhanced, and then shows excellent SERS effects.And the racemosus reported at present
The gold nanoparticle at angle（Include the gold nanoparticle etc. of Jenner's popped rice, gold nano star, highly branchedization）Synthetic method it is main
There are two types of：Seed mediated method and one-step synthesis.Seed mediated growth method step is complicated at present, required time is long, required of high cost, because
And constrain its development.Relative to seed mediated method, one-step synthesis has easy, efficient and relative clean advantage,
But this method simultaneously there is also be easy to be influenced by external condition, the size of particle and pattern disadvantage more rambunctious.Therefore
The simple and quick synthesis for realizing HBGNPs, is still a challenging job.
Ideal SERS active-substrate should also have homogeneity and reproduction other than possessing sufficiently strong SERS effects
Property it is good, easily prepared and storage, it is easy to use the features such as, this be the key that determine its can be applied in biomolecule detection because
Element.Currently, the assemble method of SERS active-substrate is mainly following several（1）Noble metal nano particles solution is directly dropped in into base
On piece self-assembling formation SERS active-substrate.（2）The surface that noble metal nano particles or substrate are modified using chemical method, in electrostatic
The SERS active-substrate of noble metal nano particles array structure is prepared under force effect.（3）Utilize physical etchings or chemical deposition etc.
Method prepares the SERS active-substrate of noble metal nano particles array structure.First method is easy to operate, but prepare
The noble metal nano particles on SERS active-substrate surface are unevenly distributed, and cause signal stabilization poor.Prepared by second method
SERS active-substrate has homogeneity and reproducibility, but the spacing between nano-particle is larger, therefore the SERS enhancing effects of substrate
Fruit is than relatively limited.SERS active-substrate prepared by the third method can obtain very strong SERS signal, and stability and again
Renaturation is good, but complex manufacturing technology, and cost is higher.Compared with other materials, silicon nano material shows many excellent performances,
Such as surface modification, large specific surface area, preferable biocompatibility, therefore it has been used for electronics industry and field of biology.
There is certain defect in the SERS active-substrate reported at present, cannot be satisfied easy to operate, inexpensive, sensitivity, homogeneity and
The requirement of repeatability.
Invention content
The object of the present invention is to provide gold nanoparticle SERS active-substrates of a kind of highly branchedization and preparation method thereof.
Realizing the object of the invention technical solution is：
A kind of gold nanoparticle SERS active-substrate of hyperbranchedization of the present invention, including：Silicon chip substrate, in the silicon
Chip base on piece covers positively charged amino layer, and HBGNPs layers are adsorbed on the positively charged amino layer.
Further, HBGNPs layers by the silicon chip substrate for covering positively charged amino layer by being immersed in HBGNPs
In solution, make HBGNPs deposit and be coupled to positively charged amino layer surface to obtain.Wherein HBGNPs solution is by 50 mM chlorine
Auric acid（HAuCl4）53 mM Dopamine hydrochloride solution are added in solution after being mixed with water after, it is made after 30 min of heating reaction.
A kind of preparation method of the gold nanoparticle SERS active-substrate of highly branchedization of the present invention, step are：
（1）By 50mM HAuCl4After mixing with water, 53mM Dopamine hydrochloride solution is added in stirring to solution, under 40 ~ 80 °C
HBGNPs solution is made in 20 ~ 40 min of heating reaction, wherein HAuCl4The volume of solution, water and Dopamine hydrochloride solution three
Than being 0.1 ~ 0.6:10:0.4~3；
（2）Silicon chip substrate is subjected to surface hydroxylation processing, obtains hydroxylated silicon chip substrate；
（3）After hydroxylated silicon chip substrate is carried out surface amination processing, keeps amination surface upward, be placed in HBGNPs
24 h or more in solution makes HBGNPs deposit and is coupled to amination surface, takes out the silicon chip substrate of modification HBGNPs, and use is ultrapure
It is dry after water cleaning.
Further, step（1）In, HAuCl4The volume ratio preferably 0.4 of solution, water and Dopamine hydrochloride solution three:
10:2。
Further, step（1）In, heat reaction time preferred 30min.
Further, step（1）In, preferably 60 °C of heating temperature.
Further, step（1）In, it is 7 by clean silicon chip substrate merging volume ratio:3 concentrated sulfuric acid and hydrogen peroxide is mixed
It closes in solution, 1 h is placed under 80 ± 5 °C of water bath conditions, makes the hydroxyl of silicon chip surface（-OH）Increase, is finally filled with ultra-pure water
Divide and the hydroxylated silicon chip substrate is made after rinsing silicon chip substrate surface.
Further, step（2）In, hydroxylated silicon chip substrate is immersed into 0.1%3- aminopropyl trimethoxy silicon vertically
In alkane-ethanol solution, 12 h are placed under confined conditions, make its surface amination, are dried up with nitrogen after ultrapure water is used in combination, and are made
Obtain the amidized silicon chip substrate.
Further, step（3）In, drying temperature is not higher than 80 °C.
Compared with prior art, the present invention has the following advantages：
（1）HBGNPs synthetic methods provided by the present invention only need Dopamine hydrochloride as reducing agent, in 30 min or so
It is interior that HBGNPs synthesis can be completed.Raw material is cheap and easy to get, simple for process, without protectiveness environment etc., and controllability is good, only needs letter
The amount and reaction temperature of dullness section reactant, you can realize the regulation and control to product morphology, and safe and non-toxic, be suitable for follow-up SERS
The assembling of active substrate.
（2）SERS substrates preparation method of the present invention is simple, and operability is strong, does not need special instrument and equipment.
Experimental cost is low, and required reagent is common chemical reagent.
（3）SERS substrates prepared by the present invention have repeatability well, can realize prepare with scale.
（4）HBGNPs is deposited and is adsorbed onto on the silicon chip of amination processing by electrostatic interaction by the present invention, is greatly increased
Be adsorbed on the quantity of silicon wafer polishing face HBGNPs, can obtain HBGNPs uniformly, the self-assembled structures of dense arrangement.In addition,
Using the SERS effects that HBGNPs is excellent, by the combination of these technological innovations, the shortcomings that compensating for electrostatic self-assembled method.
（5）Material and the equal no cytotoxicity of reagent used in substrate preparation, can be used for biomolecule, cell, live body etc.
Detection.
Description of the drawings
Fig. 1 is the HBGNPs synthesized using the Dopamine hydrochloride solution of different volumes（A）SEM photograph（B）UV-Vis-
NIR light spectrogram and（C）To mercaptobenzoic acid（4-MBA）The Raman spectrogram of the HBGNPs of label；Wherein, curve a, b, c and d points
Not Dui Ying 0.4,0.8,2.0 and 3.0 mL Dopamine hydrochloride synthesis HBGNPs SEM photograph.
Fig. 2 is to use different volumes HAuCl4Solution synthesizes the SEM photograph of HBGNPs（A）, UV-Vis-NIR spectrograms
（B）And the Raman spectrogram of the HBGNPs of 4-MBA labels（C）；Wherein, curve a, b, c and d respectively correspond to 0.1,0.2,0.4 with
And 0.6 mL HAuCl4Solution synthesizes the SEM photograph of HBGNPs.
Fig. 3 is the UV-Vis-NIR spectrograms that HBGNPs is synthesized under differential responses temperature condition（A）With 4-MBA labels
The Raman spectrogram of HBGNPs（B）.
Fig. 4 is the SEM photograph of HBGNP（A）, TEM photos（B）, HRTEM photos and（C）Corresponding SAED figures（D）.
Fig. 5 is flow chart prepared by the SERS active-substrate based on HBGNPs.
Fig. 6 is the SEM photograph and photograph via bright field of HBGNPs substrates（A）, 4-MBA label SERS active-substrate SERS
Images（B）With the Raman spectrogram of 3 different SERS substrates of 4-MBA labels（C）.
Fig. 7 is the Raman spectrogram for the HBGNPs substrates that the 4-MBA of various concentration is marked（A）, the logarithm of 4-MBA concentration with
Raman spectrum is in 1080 cm-1Locate the matched curve between feature peak intensity（B）, the HBGNPs substrates of 4-MBA, 4-MBA label
Raman spectrum（C）.
Specific implementation mode
In order to deepen the understanding of the present invention, the present invention is further described below in conjunction with embodiment and attached drawing.
Instrument and equipment and test condition used in the present invention is as follows：
Field emission scanning electron microscope photo is that the S-4800II type Flied emission scanning electrons produced by Hitachi, Japan are shown
Micro mirror measures.
Transmission electron microscope photo is surveyed by the TECNAI10 type projection electron microscopes that Dutch PHILIPS Co. produces
.
Raman spectrum and SERS imagings are the Invia Reflex type laser capture microdissection Ramans produced by Reinshaw company of Britain
Spectrometer measures.Test condition is 785 nm of optical maser wavelength, and the time for exposure is 10 s, and laser intensity is 50 mW, 50 × object lens.
UV-Vis-NIR spectrum are the UV-3600 types ultraviolet-visible-near-infrared spectrophotometrics produced by Japanese Shimadzu Corporation
It measures.
The preparation method of the gold nanoparticle SERS active-substrate of highly branchedization of the present invention, including（1）With salt
Sour dopamine prepares HBGNPs as reducing agent, by one-step synthesis；（2）Amidized silicon chip is formed with positive charge
Silicon wafer polishing face；（3）The silicon wafer polishing of positive charge is placed in HBGNPs solution upwardly, 24 h is placed at normal temperatures, carries
The HBGNPs of negative electrical charge is deposited, and is coupled to silicon chip surface by electrostatic interaction, investigate SERS active-substrate homogeneity,
Repeatability and enhancing effect.
Its specific steps are：
（1）HBGNPs is prepared by one-step synthesis, 10mL ultra-pure waters are separately added into the beaker cleaned up, is quickly stirred
While sequentially add HAuCl4Solution（50 mM）With Dopamine hydrochloride solution（53 mM）, 30 min of heating reaction, you can system
Obtain HBGNPs.Change and Dopamine hydrochloride, HAuCl in reaction system is added4Volume and reaction temperature, study them to HBGNPs
The influence of pattern, optical property and SERS effects.
（2）Monocrystalline silicon piece is cut into the small square of the cm of 1 cm × 1.Then respectively with acetone, absolute ethyl alcohol, go from
Sub- water is cleaned by ultrasonic 3 times, and each scavenging period is 20 min, it is ensured that the cleaning of silicon chip.Above-mentioned clean silicon chip is placed in volume
Than being 7:In 3 98% concentrated sulfuric acid, 30% hydrogen peroxide mixed solution, 1 h is placed under 80 °C of water bath conditions, make silicon chip surface-
OH increases, and finally fully silicon chip surface is rinsed three times with ultra-pure water, to eliminate the absorption of foreign ion sulfate radical.
（3）The silicon chip that activated, end group is hydroxyl is immersed into 0.1%3- TSL 8330s-vertically
In ethanol solution, 12 h are placed under confined conditions, make the upper amino of silicon chip surface connection, and nitrogen is used after taking-up ultrapure water 3 times
Drying.It keeps silicon wafer polishing to be placed in 24 h in HBGNPs solution upwardly, so that HBGNPs is deposited and be coupled to silicon chip surface.It takes out
The silicon chip of HBGNPs modifications, is cleaned 3 times, 80 °C are dried for standby with ultra-pure water.
The preparation method of inexpensive, scale SERS active-substrate of the present invention, i.e., increased using deposition
Add Electrostatic Absorption to the quantity of silicon amide on piece HBGNPs, and the SERS effects for combining HBGNPs excellent make up Electrostatic Absorption side
The deficiency of method, forms that a kind of method is simple, high-performance SERS active-substrate of high sensitivity, favorable reproducibility.
The synthesis of the HBGNPs that pattern is good and SERS effects are strong of embodiment 1 a kind of and characterization
1. influence of the Dopamine hydrochloride to the pattern of HBGNPs, optical property and SERS effects
It is separately added into 10mL ultra-pure waters in the beaker that 4 clean up, quickly sequentially adds 0.4 mL's while stirring
HAuCl4Solution（50 mM）And different volumes（0.4、0.8、2.0、3.0 mL）Dopamine hydrochloride solution（53 mM）, it is heated to
60 °C, until reacting 30 min.Detect the pattern and UV-Vis-NIR spectrum of HBGNPs.At room temperature, 50 mL a concentration of 1 are prepared
×10-3The 4-MBA aqueous solutions of mol/L preserve under the conditions of 4 °C.By 50 μ L a concentration of 1 × 10-3The 4-MBA of mol/L is water-soluble
Liquid is added in the HBGNPs solution of 0.5 mL synthesis, is uniformly mixed.Mixed liquor is stood into 1 h, detects its Raman spectrum.
Attached drawing 1A is the SEM photograph of the HBGNPs of the Dopamine hydrochloride synthesis of different volumes.As seen from the figure, when hydrochloric acid DOPA
When amine volume is 0.4 mL, product shape subcircular, also nm is differed grain size from 50 to 200, this is a kind of table that reducing agent lacks
It is existing.With the increase of Dopamine hydrochloride volume, the pattern that HBGNPs is made is gradually become the gold nano at racemosus angle by spherical structure
The length of structure, branch angle gradually increases, and the quantity at branch angle gradually increases.Attached drawing 1B is that the Dopamine hydrochloride of different volumes synthesizes
HBGNPs UV-Vis-NIR spectrograms.With the increase that Dopamine hydrochloride volume in reaction system is added, the LSPR of product
There is certain red shift in peak.Shown in attached drawing 1C, the HBGNPs synthesized using 2 mL Dopamine hydrochloride solution measures the signal of 4-MBA
It is maximum.
2. HAuCl4Influence to the pattern of HBGNPs, optical property and SERS effects
It is separately added into 10mL ultra-pure waters in the beaker that 4 clean up, quickly sequentially adds different volumes while stirring
（0.1、0.2、0.4、0.6 mL）HAuCl4Solution（50 mM）And 2.0 mL Dopamine hydrochloride solution（53 mM）, heating
To 60 °C, until reacting 30 min.Detect the pattern and UV-Vis-NIR spectrum of HBGNPs.At room temperature, 50 mL concentration are prepared
It is 1 × 10-3The 4-MBA aqueous solutions of mol/L preserve under the conditions of 4 °C.By 50 μ L a concentration of 1 × 10-3The 4-MBA of mol/L
Aqueous solution is added in the HBGNPs solution of 0.5 mL synthesis, is uniformly mixed.Its Raman spectrum is detected after mixed liquor is stood 1 h.
By attached drawing 2A it is found that with HAuCl4The increase of volume, be made HBGNPs grain size gradually increase, by 200 nm by
The branch angular length degree of cumulative greatly 600 nm, gold nanoparticle surface gradually increase, and the quantity at branch angle gradually increases.With reacting
HAuCl in system4There is certain red shift in the peaks LSPR of the increase of volume, product（Attached drawing 2B）.Shown in attached drawing 2C, work as HAuCl4
Volume settings be 0.4 mL when, the HBGNPs of synthesis shows strongest SERS effects.
3. influence of the reaction temperature to the optical property and SERS effects of HBGNPs
It is separately added into 10mL ultra-pure waters in the beaker that 4 clean up, quickly sequentially adds 0.4mL's while stirring
HAuCl4Solution（50 mM）And 2.0 mL Dopamine hydrochloride solution（53 mM）, in different temperatures（40、50、60、70、80
°C）Until 30 min of lower reaction.Detect the pattern and UV-Vis-NIR spectrum of HBGNPs.At room temperature, 50 mL a concentration of 1 are prepared
×10-3The 4-MBA aqueous solutions of mol/L preserve under the conditions of 4 °C.By 50 μ L a concentration of 1 × 10-3The 4-MBA of mol/L is water-soluble
Liquid is added in the HBGNPs solution of 0.5 mL synthesis, is uniformly mixed.Raman spectrum is detected after mixed liquor is stood 1 h.By attached drawing
Shown in 3A, as reaction temperature increases, the absorption peak strength of UV-Vis-NIR gradually increases, and the position at the peaks LSPR does not occur obviously
Variation.When temperature is less than 60 °C, with the raising of temperature, shown in attached drawing 3B, the Raman signal intensity of 4-MBA is measured
It gradually increases；And when temperature is higher than 60 °C, the Raman signal intensity for measuring 4-MBA gradually weakens.Therefore, in order to be had
The HBGNPs of sufficiently strong SERS effects, reaction temperature should be set as 60 °C.
4. in conclusion 2.0 mL Dopamine hydrochloride solution of selection（53 mM）、0.4 mLHAuCl4Solution（50 mM）And
Reaction temperature is 60 °C, for synthesizing HBGNPs of the present invention.The pattern and knot of HBGNPs are characterized by SEM and TEM
Structure, as shown in attached drawing 4A and 4B.About 400 nm of the grain size of HBGNPs, surface is containing there are many nanometer branch angles.These nanometer of branch angle makes
Obtaining on single nano-particle simultaneously there are multiple " hot spots ", conspicuousness to enhance SERS effects.Attached drawing 4C is the high score of HBGNPs
Distinguish transmission electron microscope photo（HRTEM）, the nanometer branch angle of nanoparticle surface is monocrystalline knot with consistent crystal lattice orientation
Structure.Clearly lattice fringe shows that product has good crystallinity and purity, the wherein nm corresponding As of spacing of lattice d=0.24 u's
(111) crystal face.Selective electron diffraction（SAED）The point diffraction to become clear in collection of illustrative plates also indicates that product is monocrystalline, the d values of diffraction spot
For 0.275 nm, 0.24 nm, 0.144 nm and 0.123 nm, correspond respectively to (311), (111), (220) and (220) of Au
The crystal face in face（Attached drawing 4D）.
A kind of 2 enhancing effect of embodiment is good, method is simple, of low cost, the reproducible SERS based on HBGNPs lives
The preparation of property substrate and structural characterization, step：
1. 10 mL ultra-pure waters are added in the beaker cleaned up, the HAuCl of 0.4 mL is quickly added while stirring4Solution
（50 mM）And the Dopamine hydrochloride solution of 2.0mL（53 mM）, 60 °C are heated to, until reacting 30 min, that is, has synthesized shape
The HBGNPs that looks are good and SERS effects are strong.
2. monocrystalline silicon piece to be cut into the small square of the cm of 1 cm × 1.Then respectively with acetone, absolute ethyl alcohol, go from
Sub- water is cleaned by ultrasonic 3 times, and each scavenging period is 20 min, it is ensured that the cleaning of silicon chip is finally dried up with nitrogen for use.It will cleaning
Clean silicon chip is placed on volume ratio 7:3 98% concentrated sulfuric acid, 30% hydrogen peroxide mixed solution, 1 h of water-bath under the conditions of 80 °C,
So that-the OH of silicon chip surface is increased, finally fully rinse silicon chip surface three times with ultra-pure water, to eliminate the suction of foreign ion sulfate radical
It is attached.
3. the silicon chip that activated end group is hydroxyl is immersed vertically in 0.1%APTES- ethanol solutions, closed item
12 h are placed under part, make the upper amino of silicon chip surface connection, are dried up with nitrogen after taking-up ultrapure water 3 times.Keep silicon wafer polishing
It is positioned over 24 h in HBGNPs solution upwardly, makes HBGNPs depositions and Electrostatic Absorption is to silicon chip surface.Take out HBGNPs modifications
Silicon chip, cleaned 3 times, dried under the conditions of 80 °C, you can obtain SERS active-substrate of the present invention with ultra-pure water.
The preparation flow figure of SERS active-substrate is shown in attached drawing 5.
4. attached drawing 6A is the stereoscan photograph of SERS substrates, as seen from the figure, basic in the HBGNPs grain sizes of substrate surface
Unanimously, it and is evenly distributed, is fine and close.
The homogeneity and stability of the gold nanoparticle SERS active-substrate of 3 highly branchedization of embodiment
1. preparing HBGNPs substrates with embodiment 2.
2. the homogeneity of pair SERS substrates is evaluated.Using 4-MBA as Raman signal molecule to SERS active-substrate
Homogeneity is evaluated.The substrate for taking 1 embodiment 2 to prepare immerses concentration 1 × 10-4In the 4-MBA solution of M, after standing 2 h
Taking-up is dried.The 4-MBA dried the substrates marked are placed on Raman spectrometer, according to 4-MBA in 1080 cm-1The feature at place
Peak carries out SERS imagings to substrate, and selected region in laser scanning substrate is divided into 50 mm, the time for exposure between point and point
For 10s.Attached drawing 6B is the SERS imagings of the substrate of 4-MBA labels, and as figure shows, the substrate is in 1080 cm-1Signal at characteristic peak
It is more uniform, there is good homogeneity.
3. the repeatability of pair SERS substrates is evaluated.3 different substrates are taken to immerse a concentration of 1 × 10 respectively-4M's
In 4-MBA solution, is taken out after standing 2 h, dry to be placed on and measure their SERS spectra on Raman spectrometer.Attached drawing 6C is not
1 × 10 is measured with HBGNPs substrates-4The SERS spectra of M 4-MBA.The intensity no significant difference of these spectrum, illustrates HBGNPs
Substrate has good repeatability.
The SERS performances of the gold nanoparticle SERS active-substrate of 4 highly branchedization of embodiment
1. preparing HBGNPs substrates with embodiment 2.
2. substrate is to the measurement of 4-MBA Monitoring lower-cuts.5 substrates are taken to be soaked respectively into a concentration of 1 × 10-6, 1 × 10-7, 1
×10-8, 1 × 10-9, 1 × 10-10In the 4-MBA solution of M, is taken out after standing 2 h, dry to be placed on Raman spectrometer and measure
Their SERS spectra.Its Raman spectrum is shown in that the lowest detection limit of attached drawing 7A, HBGNPs substrate is 1 × 10-10 M.In order to more
Intuitively show the relationship for the HBGNPs substrate Raman signal intensities that Raman signal molecule 4-MBA concentration is marked with it, the two is right
The point answered is made and is fitted（Attached drawing 7B）：I = 15965logC+138355（C is the concentration of 4-MBA, and I is corresponding Raman light
Spectrum is in 1080 cm-1The intensity at place, fit indices R2=94.93%）.Substrate of the present invention to 4-MBA Monitoring lower-cuts be 1 ×
10-10 M。
3. substrate is to the analysis enhancement factor of 4-MBA（AEF）Calculating（Attached drawing 7C）.In the feelings for being not suitable for any substrate
Under condition, a concentration of C is measuredRS4-MBA Raman spectrum, C in the present embodimentRSIt is 1 × 10-2 M, by 1080 cm of this spectrum-1Place
Peak intensity be labeled as IRS, select C in step 2SERSA spectrum, C in the present embodimentSERSIt is 1 × 10-9M, by this spectrum
1080 cm-1The peak intensity at place is labeled as ISERS, according to formula
AEF=7 × 10 are calculated7, illustrate that HBGNPs substrate enhancing effects are preferable, there is good application in biological detection
Foreground.
Claims (10)
1. the gold nanoparticle SERS active-substrate of highly branchedization, which is characterized in that including：Silicon chip substrate, in the silicon chip
Positively charged amino layer is set on substrate, HBGNPs layers are adsorbed on the positively charged amino layer.
2. SERS active-substrate as described in claim 1, which is characterized in that the HBGNPs layers are positively charged by that will be arranged
The silicon chip substrate of amino layer be immersed in HBGNPs solution, make HBGNPs deposit and be coupled to positively charged amino layer surface to obtain
It arrives.
3. SERS active-substrate as claimed in claim 2, which is characterized in that HBGNPs solution is by 50 mM HAuCl4Solution
After 53 mM Dopamine hydrochloride solution are added after being mixed with water, it is made after 20 ~ 40 min of heating reaction under 40 ~ 80 °C, wherein
HAuCl4The volume ratio of solution, water and Dopamine hydrochloride solution three is 0.1 ~ 0.6:10:0.4~3.
4. a kind of preparation method of the gold nanoparticle SERS active-substrate of highly branchedization, which is characterized in that including walking as follows
Suddenly：
（1）By 50mM HAuCl4After mixing with water, 53mM Dopamine hydrochloride solution is added in stirring to solution, under 40 ~ 80 °C
HBGNPs solution is made in 20 ~ 40 min of heating reaction, wherein HAuCl4The volume of solution, water and Dopamine hydrochloride solution three
Than being 0.1 ~ 0.6:10:0.4~3；
（2）Silicon chip substrate is subjected to surface hydroxylation processing, obtains hydroxylated silicon chip substrate；
（3）After hydroxylated silicon chip substrate is carried out surface amination processing, keeps amination surface upward, be placed in HBGNPs
24 h or more in solution makes HBGNPs deposit and is coupled to amination surface, takes out the silicon chip substrate of modification HBGNPs, and use is ultrapure
It is dry after water cleaning.
5. method as claimed in claim 4, which is characterized in that step（1）In, HAuCl4Solution, water and Dopamine hydrochloride solution
The volume ratio of three is 0.4:10:2.
6. method as claimed in claim 4, which is characterized in that step（1）In, the heating reaction time is 30min.
7. method as claimed in claim 4, which is characterized in that step（1）In, heating temperature is 60 °C.
8. method as claimed in claim 4, which is characterized in that step（1）In, it is by clean silicon chip substrate merging volume ratio
7:In 3 concentrated sulfuric acid and hydrogen peroxide mixed solution, 1 h is placed under 80 ± 5 °C of water bath conditions, makes the hydroxyl of silicon chip surface（-
OH）Increase, the hydroxylated silicon chip substrate is made after silicon chip substrate surface is finally fully rinsed with ultra-pure water.
9. method as claimed in claim 4, which is characterized in that step（2）In, hydroxylated silicon chip substrate is immersed vertically
In 0.1%3- TSL 8330s-ethanol solution, 12 h are placed under confined conditions, are made its surface amination, are used in combination
It is dried up with nitrogen after ultrapure water, the amidized silicon chip substrate is made.
10. method as claimed in claim 4, which is characterized in that step（3）In, drying temperature is not higher than 80 °C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110879221A (en) * | 2019-11-06 | 2020-03-13 | 广州供电局有限公司 | Silicon-based silver nano surface enhanced substrate and preparation method thereof |
| CN113109319A (en) * | 2021-05-18 | 2021-07-13 | 济南大学 | Preparation of three-dimensional structure molecularly imprinted Raman sensor and application of sensor in probenazole detection |
| CN113203726A (en) * | 2021-05-11 | 2021-08-03 | 江苏大学 | Preparation method of surface-enhanced Raman substrate for rapidly detecting fluorene in haze particles |
| CN113588625A (en) * | 2021-08-16 | 2021-11-02 | 广西电网有限责任公司电力科学研究院 | Preparation method of solid-phase SERS nano-substrate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101676711A (en) * | 2008-09-21 | 2010-03-24 | 西北师范大学 | Substrate with surface-enhanced Raman scattering activity and preparation method thereof |
| CN102253027A (en) * | 2011-05-09 | 2011-11-23 | 东南大学 | Surface-enhanced Raman scattering active substrate based on star-shaped gold nanoparticles and preparation method thereof |
| CN102590173A (en) * | 2012-01-19 | 2012-07-18 | 东南大学 | Preparation method for graphene-based surface enhanced Raman scattering probe |
| CN105499602A (en) * | 2015-12-21 | 2016-04-20 | 上海交通大学 | Method for preparing SERS substrate compounded with gold nanoparticles based on reduction method |
-
2018
- 2018-04-24 CN CN201810371385.0A patent/CN108645835A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101676711A (en) * | 2008-09-21 | 2010-03-24 | 西北师范大学 | Substrate with surface-enhanced Raman scattering activity and preparation method thereof |
| CN102253027A (en) * | 2011-05-09 | 2011-11-23 | 东南大学 | Surface-enhanced Raman scattering active substrate based on star-shaped gold nanoparticles and preparation method thereof |
| CN102590173A (en) * | 2012-01-19 | 2012-07-18 | 东南大学 | Preparation method for graphene-based surface enhanced Raman scattering probe |
| CN105499602A (en) * | 2015-12-21 | 2016-04-20 | 上海交通大学 | Method for preparing SERS substrate compounded with gold nanoparticles based on reduction method |
Non-Patent Citations (1)
| Title |
|---|
| 杜雨晴等: "《三维结构金纳米花的快速可控合成及其分析应用研究》", 《分析测试学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110879221A (en) * | 2019-11-06 | 2020-03-13 | 广州供电局有限公司 | Silicon-based silver nano surface enhanced substrate and preparation method thereof |
| CN113203726A (en) * | 2021-05-11 | 2021-08-03 | 江苏大学 | Preparation method of surface-enhanced Raman substrate for rapidly detecting fluorene in haze particles |
| CN113109319A (en) * | 2021-05-18 | 2021-07-13 | 济南大学 | Preparation of three-dimensional structure molecularly imprinted Raman sensor and application of sensor in probenazole detection |
| CN113588625A (en) * | 2021-08-16 | 2021-11-02 | 广西电网有限责任公司电力科学研究院 | Preparation method of solid-phase SERS nano-substrate |
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