CN103364392A - Analysis and detection method of surface enhanced Raman of benzo (a) pyrene - Google Patents
Analysis and detection method of surface enhanced Raman of benzo (a) pyrene Download PDFInfo
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- CN103364392A CN103364392A CN2013101672016A CN201310167201A CN103364392A CN 103364392 A CN103364392 A CN 103364392A CN 2013101672016 A CN2013101672016 A CN 2013101672016A CN 201310167201 A CN201310167201 A CN 201310167201A CN 103364392 A CN103364392 A CN 103364392A
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- benzo
- pyrene
- mercaptan
- enhanced raman
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- FMMWHPNWAFZXNH-UHFFFAOYSA-N Benz[a]pyrene Chemical compound C1=C2C3=CC=CC=C3C=C(C=C3)C2=C2C3=CC=CC2=C1 FMMWHPNWAFZXNH-UHFFFAOYSA-N 0.000 title claims abstract description 142
- TXVHTIQJNYSSKO-UHFFFAOYSA-N BeP Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC4=CC=C1C2=C34 TXVHTIQJNYSSKO-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000001069 Raman spectroscopy Methods 0.000 title claims abstract description 42
- 238000001514 detection method Methods 0.000 title abstract description 18
- 238000004458 analytical method Methods 0.000 title abstract 3
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- 239000010703 silicon Substances 0.000 claims abstract description 9
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- 238000001338 self-assembly Methods 0.000 claims description 12
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- OQUFOZNPBIIJTN-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;sodium Chemical compound [Na].OC(=O)CC(O)(C(O)=O)CC(O)=O OQUFOZNPBIIJTN-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses an analysis and detection method of surface enhanced Raman of benzo (a) pyrene. The method comprises the following steps that: firstly, gold nanoparticles are synthesized in a solution phase, are decorated by thiol and automatically assemble to form a large-area gold nanoparticle film in a gas/liquid interface, the large-area gold nanoparticle film is transferred to a silicon wafer to serve as an SERS (Surface Enhanced Raman Scattering) substrate, and the hydrophobic carbon chain end of the thiol can capture benzo (a) pyrene molecules to locate the benzo (a) pyrene molecules in the effective range of a plasma resonance magnetic field of the gold nanoparticles so as to analyze and detect the surface enhanced Raman of the benzo (a) pyrene. The particle diameters of the synthesized gold nanoparticles are uniformly distributed, the structure of a single layer of nanoparticles assembled in the gas/liquid interface is regular and orderly, and the nanoparticles can realize quantitative analysis on the benzo (a) pyrene if being taken as the SERS substrate. The method is simple in substrate preparation, short in sample analysis time and capable of realizing on-line detection through portable Raman, and the substrate can be reused.
Description
Technical field
The present invention relates to the detection of surface-enhanced Raman, especially relate to a kind ofly utilize the liquid-gas interface self assembly to prepare large tracts of land, regular SERS substrate is carried out quantitative test to benzo (a) pyrene and is detected.
Background technology
Benzo (a) pyrene is a kind of condensed-nuclei aromatics, be present in the coal tar, and coal tar is found in the cigarette that automobile exhaust gas (especially diesel motor), tobacco and combustion of wood produce, and in the charcoal roast food.Because this class material has fat-soluble characteristics; simultaneously almost can't natural degradation; in case to air; water; the physical environments such as soil pollute; utmost point low content also can accumulate to harmful concentration; after being taken in by human body directly or by food chain; can pass through skin; respiratory tract; the approach such as alimentary canal bring out skin; the cancer such as lung and alimentary canal (Jia Tao. the hazard ratio smoking of environmental pollution is much bigger---talk [J] from benzo (a) pyrene. tobacco science and technology; 1998; (5): 33～34. Wang Zhengangs. engine hygiene [M]. the People's Health Publisher; 2000. the refined qin of Liu; Wang Peng. palycyclic aromatic and carcinogenicity [J]. environmental protection; 1995, (9): 42～45.).Therefore the trace analysis of benzo (a) pyrene detects significant.The method of present existing detection benzo (a) pyrene mainly contains: fluorescence analysis, liquid chromatography, gas chromatography-mass spectrum, Capillary Electrophoresis, euzymelinked immunosorbent assay (ELISA) etc.Wherein, HPLC method and GC-MS method are used general, and measuring accuracy is high, is suitable for standardization, but often need to carry out complicated sample preparation, just can enter instrument and detect, and detect length consuming time, and instrument itself and maintenance expense are very expensive.Simultaneously because the diluting effect of carrier, also relative reduce sensitivity, be not suitable for the large batch of detection of testing agency of basic unit.
It is narrow that Surface enhanced raman spectroscopy (SERS) has emission band, contains much information, and spectrum stability is high, the different characteristics such as the characteristic Raman scattering signal of material tool, and its maximum enhancer can reach 10
14-10
15, aspect trace detection, have the advantages such as high sensitivity, high-resolution and be widely used.But benzo (a) pyrene and precious metal-based basal surface does not have an interactional functional group, if want to utilize the SERS means to detect, must make target molecule near the SERS substrate surface by the suction-operated of physics or chemistry.Mainly be to adopt at gold or Nano silver grain can catch benzo (a) pyrene with the interactional molecule of palycyclic aromatic on by chemical modification or physisorption on the bibliographical information, make it in the effective range in the magnetic field of the plasma resonance of gold or Nano silver grain, detect thereby carry out SERS.These molecules that are used for catching benzo (a) pyrene are broadly divided into three classes.The first kind is that chemical bonding has the supermolecule of cavity structure by the sulfydryl key on gold or Nano silver grain, such as calixarenes (Guerrini L, Garcia-Ramos J V, Domingo C, et al.Sensing Polycyclic Aromatic Hydrocarbons with Dithiocarbamate-Functionalized Ag Nanoparticles by Surface-Enhanced Raman Scattering[J] .Analytical Chemistry, 2009,81:953～960.), cyclodextrin (Xie Y F, Wang X, Han X X, et al.Sensing of polycyclic aromatic hydrocarbons with cyclodextrin inclusion complexes on silver nanoparticles by Surface-Enhanced Raman Scattering[J] .The Analyst, 2010,135:1389～1394.) or make molecular self-assembling (purpurine two kations can form void structure (Guerrini L after the assembling by nitrogen-atoms or sulphur atom between gold or the silver nano-grain, Garcia-Ramos J V, Domingo C, et al.Building Highly Selective Hot Spots in Ag Nanoparticles Using Bifunctional Viologens Application to the SERS Detection of PAHs[J] .The Journal of Physical Chemistry C, 2008,112:7527～7530.) supermolecule of the certain cavity structure of formation utilizes the hydrophobic environment of its cavity to catch such as the benzo in the palycyclic aromatic (a) pyrene, benzophenanthrene, triphenylene, benzene is dizzy, anthracene, the non-polar molecules such as pyrene.Equations of The Second Kind is can be that the palycyclic aromatic molecule forms the interactional molecule of π-π such as metallic single-wall carbon nano-tube (Leyton P at gold or Nano silver grain with benzo (a) pyrene by physisorption, Gomez-Jeria J S, Sanchez-Cortes S, et al.Carbon nanotube bundles as molecular assemblies for the detection of polycyclic aromatic hydrocarbons[J] .Journal of Physical Chemistry B, 2006,110:6470～6474.), humic acid (Leyton P, Cordova I, Lizama-Vergara P A, et al.Humic acids as molecular assemblers in the surface-enhanced Raman scattering detection of polycyclic aromatic hydrocarbons [J] .Vibrational Spectroscopy, 2008,46:77～81.).Physisorption mainly is to be fixed on gold or the Nano silver grain by filtering after directly dripping molecular solution.The 3rd class is self assembly one deck molecule on the gold, silver nano particle, forms ad hoc structure or environment, the absorbing multiring aromatic hydrocarbon molecule.For example assemble the two-dimensional array of the nanosphere particle of silicon dioxide in the copper substrate, behind the vacuum evaporation silver, the silverskin surface has the ball bumps structure, can utilize certain herbaceous plants with big flowers mercaptan self assembly layer hydrophobic environment to play pre-concentration effect (Jones C L to the palycyclic aromatic molecule after modifying certain herbaceous plants with big flowers mercaptan, Bantz K C, Haynes C L.Partition layer-modified substrates for reversible surface-enhanced Raman scattering detection of polycyclic aromatic hydrocarbons [J] .Analytical and Bioanalytical Chemistry, 2009,394:303～311.).But because the nanosphere particle diameter of silicon dioxide large (500nm) plates the thick silverskin of 200nm again, the radius-of-curvature of silver nanoparticle shell is large (be 450nm), and SERS enhancing effect can weaken relatively.Simultaneously, silverskin is unstable in air, and oxidation easily occurs, and silver-platedly itself also need use large-scale vacuum coater.
Summary of the invention
The analyzing detecting method of the surface-enhanced Raman of described benzo (a) pyrene may further comprise the steps:
1) synthetic golden nanometer particle:
In solution phase, reduce gold chloride with sodium citrate and prepare golden nanometer particle colloidal sol.Concentration by the control reactant, can prepare the uniform golden nanometer particle colloidal sol of particle diameter at temperature of reaction and reaction time.
2) mercaptan is modified golden nanometer particle and is self-assembled into the SERS active substrate in liquid-gas interface:
After aurosol concentrated, washs, add an amount of mercaptan, make golden nanometer particle modified monolayer mercaptan, can self assembly layer of gold nanoparticulate thin films at liquid-gas interface, be transferred on the silicon chip dryly, can make the SERS active substrate.
3) drip benzo (a) pyrene solution at the SERS active substrate, after it is natural drying, carry out the SERS quantitative test at Raman spectrometer and detect.
In step 1), described synthetic golden nanometer particle is spherical or oval golden nanometer particle, and particle diameter can be 40-100nm.The concentration of gold chloride is 0.1-0.3mmol/L, the concentration 30-40mmol/L of sodium citrate, and volume ratio is 100-230.Reaction conditions: refluxing under magnetic agitation is heated to boiling, and then rapid adding citric acid sodium continues reflux heating 30-50min, naturally cools to room temperature after making its complete reaction.Experimental phenomena: solution begins first to be black, then by the faint yellow brownish red that gradually becomes.
In step 2) in, described concentrated be that solution of gold nanoparticles stoste 26-32ml synthetic in the step 1) is concentrated into approximately 1ml.Centrifugal condition is that the control rotating speed is 4000-10000r/min, centrifugation time 5-30min.
In step 2) in, described mercaptan can be selected from positive hexyl mercaptan, positive ten mercaptan or positive lauryl mercaptan etc., and its concentration can be 1-5mmol/L, and it adds volume 150-300 μ L.
In step 2) in, described liquid-gas interface refers to the interface of air and aurosol joint, the surface of ie in solution.
In step 2) in, described SERS active substrate is the single layer of gold nanoparticulate thin films that the golden nanometer particle film is self-assembled at liquid-gas interface after mercaptan is modified.
In step 2) in, described golden nanometer particle modified monolayer mercaptan refers to can obtain the strongest surface-enhanced Raman signal under other experiment condition permanence condition.
Wherein, single layer of gold nano particle SERS substrate, the volume of concentrated golden nanometer particle and the volume ratio of mercaptan are 1:0.1-0.4.Like this, can obtain single layer structure.And more preferably, when the volume of concentrated golden nanometer particle and the volume ratio of mercaptan are 1:0.2, the strongest characteristic peak 1386cm-1 intensity of benzo (a) pyrene can reach maximal value.
In step 2) in, described SERS active substrate is that drying can make the SERS active substrate.
In step 3), the excitation source wavelength that described Surface enhanced raman spectroscopy detects is 400-800nm, and laser facula is 1-2um.
In step 3), described analyzing and testing is three stronger peak 1240cm of benzo (a) the pyrene powder with solid
-1, 1345cm
-1, 1386cm
-1Be characteristic peak, come qualitative analysis benzo (a) pyrene whether to exist.
In step 3), described quantitative test detects, take the logarithm value of concentration as horizontal ordinate, and take the intensity of above-mentioned any one characteristic peak as ordinate, the production standard curve.The range of linearity of quantitative test is 10nmol/L-10000nmol/L, linearly dependent coefficient (R
2) can reach more than 0.99, the recovery is between 90%-104%, and detectability can be low to moderate 1nmol/L.
The present invention is synthetic golden nanometer particle in solution at first, utilize mercaptan to modify golden nanometer particle, nano particle can be self-assembled into large tracts of land, regular golden nanometer particle film at liquid-gas interface, be transferred to silicon chip, as the SERS active substrate, after dripping benzo (a) pyrene, utilize positive lauryl mercaptan self assembly layer hydrophobic environment to adsorb benzo (a) pyrene, realize that the quantitative test of the surface-enhanced Raman of benzo (a) pyrene detects.
The present invention is synthetic golden nanometer particle in solution phase, utilize mercaptan to modify golden nanometer particle, because the hydrophobic effect of the carbochain of mercaptan can self assembly form regular single layer of gold nanoparticulate thin films at liquid-gas interface, be transferred to silicon chip, as the SERS active substrate, the hydrophobic effect of the carbochain of mercaptan can be caught nonpolar benzo (a) pyrene molecule, under the Electromagnetic enhancement effect of golden nanometer particle, can carry out the SERS analyzing and testing to benzo (a) pyrene.Because synthetic gold nanometer particle grain size is even, but it is at the orderly nano particle structure of the regular individual layer of liquid-gas interface large tracts of land self assembly, this uniform substrate can realize quantitative test to benzo (a) pyrene.And but this substrate prepares simply, has reusing.
The present invention proposes the analyzing detecting method of the surface-enhanced Raman of a kind of benzo (a) pyrene, the golden nanometer particle that utilizes mercaptan to modify, not only can utilize the hydrophobic end of the chain of mercaptan that benzo (a) pyrene is caught, and can utilize its hydrophobic end of the chain to be self-assembled into large-area regular ordered structure at liquid-gas interface, as the SERS substrate, benzo (a) pyrene is carried out quantitative test.This substrate is not only made simply, but also can reuse.Detected the SERS substrate of benzo (a) pyrene, after the absolute ethyl alcohol flushing, still can be used for detecting reusable edible 3-6 circulation.
Description of drawings
Fig. 1 is the scanning electron microscope diagram of the SERS active substrate for preparing in the second step.
Fig. 2 is SERS active substrate Raman spectrogram and its detection 10 for preparing in the second step
-7The Raman spectrogram of the SERS spectrogram of mol/L benzo (a) pyrene solution and benzo (a) pyrene pressed powder.
Fig. 3 is the SERS active substrate for preparing in the second step verifies that but it has the SERS spectrogram of reusing.
Fig. 4 is four kinds of SERS active substrates detections 10 of modifying the golden nanometer particle preparation in the second step with the mercaptan of different volumes
-6The SERS spectrogram of mol/L benzo (a) pyrene solution.
Fig. 5 is four kinds of SERS active substrates detections 10 of modifying the golden nanometer particle preparation in the second step with the mercaptan of different volumes
-6Mol/L benzo (a) pyrene solution result's bar chart.
Fig. 6 is the SERS active substrate for preparing in the second step detects benzo (a) the pyrene solution of variable concentrations in diverse location SERS spectrogram.
Fig. 7 is the SERS active substrate for preparing in the second step detects benzo (a) the pyrene solution of variable concentrations in diverse location typical curve.
Table 1 is the recovery of five kinds of different concentrations of benzo (a) pyrene.
Embodiment
The present invention is further illustrated below by specific embodiment.
1) synthetic particle diameter is the golden nanometer particle of 55 ± 10nm:
Get the 200mL massfraction and be 0.01% aqueous solution of chloraurate in the 250mL round-bottomed flask, under magnetic agitation, reflux and be heated to boiling, then add rapidly the 1.4mL massfraction and be 1% sodium citrate aqueous solution, solution becomes black within half a minute, continue reflux heating 40min, solution is by the faint yellow brownish red that gradually becomes, and naturally cools to room temperature after making its complete reaction, can obtain the golden nanometer particle colloidal sol (referring to Fig. 1) that diameter is about 55 ± 10nm.
2) golden nanometer particle is self-assembled into the SERS active substrate:
Utilize the method for centrifuging with 1) in synthetic aurosol carry out concentration, and wash (centrifugal condition is 8000r/min, 10min) centrifugal 1 time with ultrapure water.Get the solution of gold nanoparticles of 1mL after concentrated in clean monkey, then the positive lauryl mercaptan-methanol solution with 200 μ L 1mmol/L is added drop-wise in the concentrated solution of gold nanoparticles, golden nanometer particle is at liquid-gas interface meeting self assembly one deck oiliness golden nanometer particle film, golden film is transferred on the clean silicon chip, and drying can make SERS active substrate (referring to Fig. 1).
3) on the XploRA Raman spectrometer, this SERS active substrate is detected, utilize simultaneously this substrate to detect 10
-7Mol/L benzo (a) pyrene solution.
Fig. 1 is the scanning electron microscope diagram of the SERS active substrate for preparing in the second step.In Fig. 1, scale is 200nm.As can be seen from the figure the golden nanometer particle on this SERS active substrate is arranged in extraordinary, large-area single layer structure.
Fig. 2 is the test result of embodiment 1.In Fig. 2, horizontal ordinate is Raman shift, and ordinate is raman scattering intensity.A is the SERS spectrogram of synthetic golden nanometer particle among the figure, and B is the SERS active substrate Raman spectrogram of preparation, and C detects 10 for the SERS active substrate of preparation
-7The SERS spectrogram of mol/L benzo (a) pyrene solution, D are the Raman spectrogram of benzo (a) pyrene pressed powder.This experimental result shows that this SERS active substrate is noiseless to the SERS detection of benzo (a) pyrene, and has successfully detected 10
-7Mol/L benzo (a) pyrene.
Embodiment 2
1) synthetic particle diameter is the golden nanometer particle of 55 ± 10nm:
Get the 200mL massfraction and be 0.01% aqueous solution of chloraurate in the 250mL round-bottomed flask, under magnetic agitation, reflux and be heated to boiling, then add rapidly the 1.4mL massfraction and be 1% sodium citrate aqueous solution, solution becomes black within half a minute, continue reflux heating 40min, solution is by the faint yellow brownish red that gradually becomes, and naturally cools to room temperature after making its complete reaction, can obtain the golden nanometer particle colloidal sol that diameter is about 55 ± 10nm.
2) golden nanometer particle is self-assembled into the SERS active substrate:
Utilize the method for centrifuging with 1) in synthetic aurosol carry out concentration, and wash (centrifugal condition is 8000r/min, 10min) centrifugal 1 time with ultrapure water.Get the solution of gold nanoparticles of 1mL after concentrated in clean monkey, then the positive lauryl mercaptan-methanol solution with 200 μ L 1mmol/L is added drop-wise in the concentrated solution of gold nanoparticles, golden nanometer particle is at liquid-gas interface meeting self assembly one deck oiliness golden nanometer particle film, golden film is transferred on the clean silicon chip, and drying can make the SERS active substrate.
3) with 25 μ L
10-
7Mol/L benzo (a) pyrene solution drips on this SERS active substrate, detects at the XploRA Raman spectrometer after natural drying under the room temperature.
4) then wash gently this substrate for several times with absolute ethyl alcohol, again this SERS active substrate is detected after natural drying.
5) continue to drip 25 μ L 10 at this SERS active substrate
-7Mol/L benzo (a) pyrene solution detects it after natural drying again.
6) repetition 4), 5) twice.
Fig. 3 is the experimental result of embodiment 2.Horizontal ordinate is Raman shift in Fig. 3, and unit is cm
-1Ordinate is raman scattering intensity, and unit is cps.A is the Raman spectrogram of SERS active substrate among the figure, and B, D, F, H are for dripping 10
-7The SERS spectrogram of mol/L benzo (a) pyrene solution, C, E, G are the Raman spectrogram of SERS active substrate after the absolute ethyl alcohol flushing.Adopt spectral condition: excitation wavelength 785nm, 100 * object lens, power is 3.05mW approximately, and grating 1200T, aperture 300 μ m, slit 100 μ m, time shutter 20s, each spectrogram accumulate 5 times under the average mode.As can be seen from the figure, on the SERS active substrate after the absolute ethyl alcohol flushing at 1240cm
-1, 1345cm
-1And 1386cm
-1The characteristic peak (shown in C, E, G among the figure) of benzo (a) pyrene does not appear in the place; And ought again drip 10
-7During mol/L benzo (a) pyrene solution, on this SERS active substrate at 1240cm
-1, 1345cm
-1And 1386cm
-1The characteristic peak (shown in D, F, H among the figure) of benzo (a) pyrene has appearred again in the place, but the intensity at spectrum peak weakens to some extent with respect to the intensity of composing the peak among the B.But this result shows this SERS active substrate and has preferably reusing.
Embodiment 3
1) synthetic particle diameter is the golden nanometer particle of 55 ± 10nm:
Get the 200mL massfraction and be 0.01% aqueous solution of chloraurate in the 250mL round-bottomed flask, under magnetic agitation, reflux and be heated to boiling, then add rapidly the 1.4mL massfraction and be 1% sodium citrate aqueous solution, solution becomes black within half a minute, continue reflux heating 40min, solution is by the faint yellow brownish red that gradually becomes, and naturally cools to room temperature after making its complete reaction, can obtain the golden nanometer particle colloidal sol that diameter is about 55 ± 10nm.
2) golden nanometer particle is self-assembled into the SERS active substrate:
Utilize the method for centrifuging with 1) in synthetic aurosol carry out concentration, and wash (centrifugal condition is 8000r/min, 10min) centrifugal 1 time with ultrapure water.Respectively get the solution of gold nanoparticles of 1mL after concentrated in four clean monkeys, then the positive lauryl mercaptan-methanol solution with 100 μ L, 200 μ L, 300 μ L, 400 μ L1mmol/L is added drop-wise to respectively in above-mentioned four monkeys, golden nanometer particle is at liquid-gas interface meeting self assembly one deck oiliness golden nanometer particle film, golden film is transferred on the clean silicon chip, and drying can make four kinds of SERS active substrates.
3) on the XploRA Raman spectrometer, to the diverse location test 10 of above-mentioned four kinds of SERS active substrates
-6Mol/L benzo (a) pyrene solution.
Fig. 4 is the SERS spectrogram of the experimental result of embodiment 3, and Fig. 5 is the bar chart of embodiment 3 experimental results.
In Fig. 4, horizontal ordinate is Raman shift, and unit is cm
-1Ordinate is raman scattering intensity, and unit is cps.The positive lauryl mercaptan that A to D is followed successively by 100 μ L, 200 μ L, 300 μ L, 400 μ L1mmol/L among the figure is modified on the SERS active substrate of golden nanometer particle preparation and is detected 10
-6The SERS spectrogram of mol/L benzo (a) pyrene.Adopt spectral condition: excitation wavelength 785nm, 50 * object lens, power is 2.78mW approximately, and grating 1200T, aperture 300 μ m, slit 100 μ m, time shutter 10s, each spectrogram accumulate 5 times under the average mode.
In Fig. 5, horizontal ordinate is for modifying the volume of the used mercaptan of golden nanometer particle, the μ L of unit; Ordinate is that benzo (a) pyrene is at 1386cm
-1The SERS peak be worth by force, unit is cps, error bar represents standard deviation.Can find out the strongest characteristic peak 1386cm of benzo (a) pyrene from Fig. 4 and Fig. 5
-1Intensity can present along with the increase of the mercaptan volume of modifying golden nanometer particle and strengthen first the trend that reduces afterwards; When the mercaptan volume of modifying golden nanometer particle is 200 μ L, the strongest characteristic peak 1386cm of benzo (a) pyrene
-1Intensity can reach maximal value, and namely preparing the mercaptan optimum amount of modifying golden nanometer particle in the method for SERS active substrate at this is 200 μ L.
Embodiment 4
1) synthetic particle diameter is the golden nanometer particle of 55 ± 10nm:
Get the 200mL massfraction and be 0.01% aqueous solution of chloraurate in the 250mL round-bottomed flask, under magnetic agitation, reflux and be heated to boiling, then add rapidly the 1.4mL massfraction and be 1% sodium citrate aqueous solution, solution becomes black within half a minute, continue reflux heating 40min, solution is by the faint yellow brownish red that gradually becomes, and naturally cools to room temperature after making its complete reaction, can obtain the golden nanometer particle colloidal sol that diameter is about 55 ± 10nm.
2) golden nanometer particle is self-assembled into the SERS active substrate:
Utilize the method for centrifuging with 1) in synthetic aurosol carry out concentration, and wash (centrifugal condition is 8000r/min, 10min) centrifugal 1 time with ultrapure water.Get the solution of gold nanoparticles of 1mL after concentrated in clean monkey, then the positive lauryl mercaptan-methanol solution with 200 μ L 1mmol/L is added drop-wise in the concentrated solution of gold nanoparticles, golden nanometer particle is at liquid-gas interface meeting self assembly one deck oiliness golden nanometer particle film, golden film is transferred on the clean silicon chip, and drying can make the SERS active substrate.
3) on the XploRA Raman spectrometer, the diverse location of SERS active substrate is tested benzo (a) the pyrene solution of variable concentrations.
Fig. 6 is the experimental result spectrogram of embodiment 3, and Fig. 7 is the match canonical plotting of embodiment 4 experimental results.
Horizontal ordinate is Raman shift in Fig. 6, and unit is cm
-1Ordinate is raman scattering intensity, and unit is cps.A is the spectrogram of SERS active substrate, and B to I is followed successively by the SERS spectrogram of benzo (a) the pyrene solution that drips 1nmol/L, 10nmol/L, 50nmol/L, 100nmol/L, 500nmol/L, 1000nmol/L, 5000nmol/L, 10000nmol/L.Adopt spectral condition: excitation wavelength 785nm, 50 * object lens, power is 2.78mW approximately, and grating 1200T, aperture 300 μ m, slit 100 μ m, time shutter 20s, each spectrogram accumulate 5 times under the average mode.As we can see from the figure, the strongest characteristic peak 1386cm of benzo (a) pyrene
-1Intensity also strengthens along with the increase of concentration.
In Fig. 7, horizontal ordinate is the logarithm value of the concentration (nmol/L) of benzo (a) pyrene solution; Ordinate is that benzo (a) pyrene is at 1386cm
-1The SERS peak be worth by force, unit is cps, error bar represents standard deviation.In Fig. 7, the range of linearity is 10nmol/L to 10000nmol/L, and match typical curve equation is y=119.88 lg[C/nmol L
-1]-50.14, linearly dependent coefficient are R
2=0.9977, the detection that calculates benzo (a) pyrene is limited to approximately 0.41 μ g/kg of 1.29nmol/L().This result shows the quantitative detection that can realize benzo (a) pyrene on this SERS active substrate, the detection of benzo under the method (a) pyrene is limited to approximately 0.41 μ g/kg of 1.29nmol/L().In fact, utilize this SERS active substrate can detect 1nmol/L benzo (a) pyrene, shown in spectrogram B among Fig. 7.
Take Fig. 7 Plays curve as working curve, record five kinds of different concentrations of benzo (a) pyrene recovery result as shown in table 1.As shown in Table 1, the recovery of benzo (a) pyrene is between 89.93%-104.25%, but the typical curve of match is line stabilization in the key diagram 7; Relative standard deviation (RSD) is between 2.34%-15.36%, but it is in the RSD range of receiving that SERS detects.
Five kinds of different concentrations of benzo of table 1 (a) pyrene recovery
Claims (10)
- Benzo (a) pyrene the analyzing detecting method of surface-enhanced Raman, may further comprise the steps:1) synthetic golden nanometer particle:In solution phase, reduce gold chloride with sodium citrate and prepare golden nanometer particle colloidal sol;2) golden nanometer particle is modified by mercaptan and is self-assembled into the SERS active substrate:After aurosol concentrated, washs, add an amount of mercaptan, individual layer mercaptan in the golden nanometer particle finishing at liquid-gas interface self assembly layer of gold nanoparticulate thin films, is transferred on the silicon chip dryly, can make the SERS active substrate;3) the SERS quantitative test of benzo (a) pyrene detectsDrip benzo (a) pyrene solution at the SERS active substrate, after it is natural drying, carry out the SERS quantitative test at Raman spectrometer.
- 2. the analyzing detecting method of the surface-enhanced Raman of benzo (a) pyrene as claimed in claim 1 is characterized in that described golden nanometer particle is spherical or oval golden nanometer particle, and particle diameter is 40-100nm.
- As claimed in claim 1 benzo (a) pyrene the analyzing and testing of surface-enhanced Raman, the golden nanometer particle that it is characterized in that described modified monolayer mercaptan is in the situation that other experiment condition is constant, and the amount that adds mercaptan can make its surface-enhanced Raman signal the strongest.
- 4. such as the analyzing detecting method of the surface-enhanced Raman of benzo (a) pyrene as described in the claim 1, it is characterized in that single layer of gold nano particle SERS substrate, the volume of concentrated golden nanometer particle and the volume ratio of mercaptan are 1:0.1-0.4.
- 5. such as the analyzing detecting method of the surface-enhanced Raman of benzo (a) pyrene as described in the claim 1, the single layer of gold nano particle SERS substrate that it is characterized in that modifying one deck mercaptan, the volume of concentrated golden nanometer particle and the volume ratio of mercaptan are 1:0.2.
- As claimed in claim 1 benzo (a) pyrene the analyzing detecting method of surface-enhanced Raman, it is characterized in that described concentrated be that solution of gold nanoparticles stoste 26-32ml synthetic in the step 1) is concentrated into 1ml; Centrifugal condition is that the control rotating speed is 4000-10000r/min, centrifugation time 5-30min.
- As claimed in claim 1 benzo (a) pyrene the analyzing detecting method of surface-enhanced Raman, it is characterized in that described mercaptan is selected from positive hexyl mercaptan, positive ten mercaptan or positive lauryl mercaptan, its concentration is 1-5mmol/L.
- As claimed in claim 1 benzo (a) pyrene the analyzing detecting method of surface-enhanced Raman, it is characterized in that described mercaptan is dissolved in to be mixed with the solution that concentration is 1-5mmol/L in the methanol solvate.
- As claimed in claim 1 benzo (a) pyrene the analyzing detecting method of surface-enhanced Raman, it is characterized in that the excitation source wavelength that described Surface enhanced raman spectroscopy detects is 400-800nm, laser facula is 1-2um.
- As claimed in claim 1 benzo (a) pyrene the analyzing detecting method of surface-enhanced Raman, it is characterized in that with calibration curve method its quantitative test is made typical curve with the intensity of characteristic peak to the logarithm value of concentration it is carried out quantitative test.
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