CN103364392B - A kind of analyzing detecting method of surface-enhanced Raman of benzo (a) pyrene - Google Patents
A kind of analyzing detecting method of surface-enhanced Raman of benzo (a) pyrene Download PDFInfo
- Publication number
- CN103364392B CN103364392B CN201310167201.6A CN201310167201A CN103364392B CN 103364392 B CN103364392 B CN 103364392B CN 201310167201 A CN201310167201 A CN 201310167201A CN 103364392 B CN103364392 B CN 103364392B
- Authority
- CN
- China
- Prior art keywords
- benzo
- pyrene
- nanometer particle
- mercaptan
- golden nanometer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 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 141
- 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 70
- 238000001069 Raman spectroscopy Methods 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 73
- 239000000758 substrate Substances 0.000 claims abstract description 63
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 36
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052737 gold Inorganic materials 0.000 claims abstract description 22
- 239000010931 gold Substances 0.000 claims abstract description 22
- 239000002105 nanoparticle Substances 0.000 claims abstract description 17
- 238000012113 quantitative test Methods 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 9
- 238000004458 analytical method Methods 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 10
- 238000001338 self-assembly Methods 0.000 claims description 10
- 239000002356 single layer Substances 0.000 claims description 9
- -1 n-dodecyl Chemical group 0.000 claims description 8
- 239000001509 sodium citrate Substances 0.000 claims description 7
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 7
- 230000005284 excitation Effects 0.000 claims description 5
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000010410 layer Substances 0.000 claims description 4
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000002474 experimental method Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000011088 calibration curve Methods 0.000 claims 1
- 239000012453 solvate Substances 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 13
- 230000002209 hydrophobic effect Effects 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 238000004611 spectroscopical analysis Methods 0.000 description 67
- 239000000243 solution Substances 0.000 description 42
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 12
- 239000010408 film Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 6
- 241000282693 Cercopithecidae Species 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 125000005605 benzo group Chemical group 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000012901 Milli-Q water Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000004375 physisorption Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 241000208125 Nicotiana Species 0.000 description 2
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000011280 coal tar Substances 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000001310 location test Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- SLGBZMMZGDRARJ-UHFFFAOYSA-N triphenylene Chemical compound C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 2
- 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
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical class COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 238000005251 capillar electrophoresis Methods 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000012921 fluorescence analysis Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- 239000003547 immunosorbent Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- BBNQQADTFFCFGB-UHFFFAOYSA-N purpurin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC(O)=C3C(=O)C2=C1 BBNQQADTFFCFGB-UHFFFAOYSA-N 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 230000000391 smoking effect Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004454 trace mineral analysis Methods 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000002460 vibrational spectroscopy Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses a kind of analyzing detecting method of surface-enhanced Raman of benzo (a) pyrene.The present invention is first at solution middle synthesis golden nanometer particle mutually, golden nanometer particle is modified by mercaptan, nano particle can be self-assembled into large-area golden nanometer particle film at gas/liquid interface, be transferred to silicon chip, as SERS substrate, the hydrophobic carbon end of the chain of mercaptan can catch benzo (a) pyrene molecule, makes it in the effective range in the magnetic field of the plasma resonance of golden nanometer particle, thus carries out benzo (a) pyrene surface-enhanced Raman analysis detection.Because the gold nanometer particle grain size of synthesis is evenly distributed, regular, orderly at the nano particle structure of the individual layer of liquid-gas interface assembling, the quantitative test of benzo (a) pyrene can be realized as SERS substrate.The method feature is that substrate preparation is simple, and sample analysis time is short, utilize portable Raman also can realize on-line checkingi, and substrate also can reuse.
Description
Technical field
The present invention relates to the detection of surface-enhanced Raman, especially relate to a kind ofly utilize liquid-gas interface self assembly to prepare large area, regular SERS substrate carries out quantitative test detection to benzo (a) pyrene.
Background technology
Benzo (a) pyrene is a kind of condensed-nuclei aromatics, is present in 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 charcoal roast food.Because this kind of material has fat-soluble feature, simultaneously almost cannot natural degradation, once to air, water, the physical environments such as soil pollute, pole low content also can accumulate to adverse concentration, directly or after being taken in by human body by food chain, by 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---talks [J] from benzo (a) pyrene. tobacco science and technology, 1998, (5): 33 ~ 34. Wang Zhengangs. engine hygiene [M]. People's Health Publisher, the refined qin of 2000. 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 current existing detection benzo (a) pyrene mainly contains: fluorescence analysis, liquid chromatography, gas chromatography-mass spectrum, Capillary Electrophoresis, euzymelinked immunosorbent assay (ELISA) etc.Wherein, generally, measuring accuracy is high, is suitable for standardization for HPLC method and the application of GC-MS method, but often needs to carry out complicated sample preparation, and just can enter instrument and detect, detect length consuming time, instrument itself and maintenance expense are very expensive.Meanwhile, due to the diluting effect of carrier, also relatively reduce sensitivity, be not suitable for the large batch of detection of testing agency of basic unit.
The features such as it is narrow that Surface enhanced raman spectroscopy (SERS) has emission band, and contain much information, spectrum stability is high, the different characteristic Raman scattering signal of material tool, its maximum enhancer can reach 10
14-10
15, there is the advantage such as high sensitivity, high-resolution in trace detection and be widely used.But benzo (a) pyrene and precious metal-based basal surface does not have interactional functional group, utilizes SERS means to detect, target molecule must be made near SERS substrate surface by the suction-operated of physics or chemistry if want.Bibliographical information mainly adopts gold or Nano silver grain by chemical modification or physisorption can catch benzo (a) pyrene with the interactional molecule of palycyclic aromatic, make it in the effective range in magnetic field of the plasma resonance of gold or Nano silver grain, thus carry out SERS detection.These molecules being used for catching benzo (a) pyrene are broadly divided into three classes.The first kind is supermolecule chemical bonding by sulfydryl key on gold or Nano silver grain with cavity structure, as calixarenes (GuerriniL, Garcia-RamosJV, DomingoC, etal.SensingPolycyclicAromaticHydrocarbonswithDithiocarb amate-FunctionalizedAgNanoparticlesbySurface-EnhancedRam anScattering [J] .AnalyticalChemistry, 2009, 81:953 ~ 960.), cyclodextrin (XieYF, WangX, HanXX, etal.Sensingofpolycyclicaromatichydrocarbonswithcyclodex trininclusioncomplexesonsilvernanoparticlesbySurface-Enh ancedRamanScattering [J] .TheAnalyst, 2010, 135:1389 ~ 1394.) or (purpurine two kation can form void structure (GuerriniL after assembling by nitrogen-atoms or sulphur atom between gold or silver nano-grain to make molecular self-assembling, Garcia-RamosJV, DomingoC, etal.BuildingHighlySelectiveHotSpotsinAgNanoparticlesUsi ngBifunctionalViologensApplicationtotheSERSDetectionofPA Hs [J] .TheJournalofPhysicalChemistryC, 2008, 112:7527 ~ 7530.) form the supermolecule of certain cavity structure, utilize the hydrophobic environment of its cavity to catch benzo (a) pyrene in such as palycyclic aromatic, benzophenanthrene, triphenylene, benzene is swooned, anthracene, the non-polar molecules such as pyrene.Equations of The Second Kind can form the interactional molecule of π-π as metallic single-wall carbon nano-tube (LeytonP with benzo (a) pyrene system palycyclic aromatic molecule by physisorption on gold or Nano silver grain, Gomez-JeriaJS, Sanchez-CortesS, etal.Carbonnanotubebundlesasmolecularassembliesforthedet ectionofpolycyclicaromatichydrocarbons [J] .JournalofPhysicalChemistryB, 2006, 110:6470 ~ 6474.), humic acid (LeytonP, CordovaI, Lizama-VergaraPA, etal.Humicacidsasmolecularassemblersinthesurface-enhance dRamanscatteringdetectionofpolycyclicaromatichydrocarbon s [J] .VibrationalSpectroscopy, 2008, 46:77 ~ 81.).Physisorption is fixed on gold or Nano silver grain by filtering after mainly directly dripping molecular solution.3rd class is self assembly one deck molecule on gold, silver nano particle, forms ad hoc structure or environment, absorbing multiring aromatic hydrocarbon molecule.In copper substrate, such as assemble the two-dimensional array of the nanosphere particle of silicon dioxide, after vacuum evaporation silver, silverskin surface has ball bumps structure, certain herbaceous plants with big flowers mercaptan Iy self-assembled layer hydrophobic environment can be utilized can to play pre-concentration effect (JonesCL to palycyclic aromatic molecule after modifying certain herbaceous plants with big flowers mercaptan, BantzKC, HaynesCL.Partitionlayer-modifiedsubstratesforreversibles urface-enhancedRamanscatteringdetectionofpolycyclicaroma tichydrocarbons [J] .AnalyticalandBioanalyticalChemistry, 2009, 394:303 ~ 311.).But due to the nanosphere particle diameter comparatively large (500nm) of silicon dioxide, then plate the thick silverskin of 200nm, the radius-of-curvature comparatively large (for 450nm) of silver nanoparticle shell, SERS strengthens effect and can relatively weaken.Meanwhile, silverskin is unstable in atmosphere, is easily oxidized, and silver-plated itself also need uses large-scale vacuum coater.
Summary of the invention
The analyzing detecting method of the surface-enhanced Raman of described benzo (a) pyrene comprises the following steps:
1) golden nanometer particle is synthesized:
With sodium citrate solution mutually in reduction gold chloride prepare golden nanometer particle colloidal sol.By controlling the concentration of reactant, temperature of reaction and reaction time, the golden nanometer particle colloidal sol of uniform particle sizes can be prepared.
2) mercaptan is modified golden nanometer particle and is self-assembled into SERS active-substrate in liquid-gas interface:
After aurosol being carried out concentrate, washing, add appropriate mercaptan, make golden nanometer particle modified monolayer mercaptan, can self assembly one deck golden nanometer particle film at liquid-gas interface, be transferred on silicon chip dry, can SERS active-substrate be obtained.
3) in SERS active-substrate, drip benzo (a) pyrene solution, after its natural drying, on Raman spectrometer, carry out SERS quantitative test detection.
In step 1), the golden nanometer particle of described synthesis is spherical or oval golden nanometer particle, and particle diameter can be 40-100nm.The concentration of gold chloride is the concentration 30-40mmol/L of 0.1-0.3mmol/L, sodium citrate, and volume ratio is 100-230.Reaction conditions: reflux heating is to boiling under magnetic stirring, then rapid adding citric acid sodium, continues reflux heating 30-50min, naturally cools to room temperature after making its complete reaction.Experimental phenomena: solution first starts, for black, then to gradually become brownish red by faint yellow.
In step 2) in, described concentrated be by synthesize in step 1) solution of gold nanoparticles stoste 26-32ml be concentrated into about 1ml.Centrifugal condition is 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 n-dodecyl mereaptan 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 golden nanometer particle film is self-assembled into after mercaptan is modified on liquid-gas interface.
In step 2) in, described golden nanometer particle modified monolayer mercaptan refers under other experiment condition permanence condition, can obtain the strongest surface-enhanced Raman signals.
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, single layer structure can be obtained.And more preferably, when the concentrated volume of 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 obtain 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 analysis detects, and is with three of benzo (a) the pyrene powder of solid stronger peak 1240cm
-1, 1345cm
-1, 1386cm
-1for characteristic peak, carry out qualitative analysis benzo (a) pyrene and whether exist.
In step 3), described quantitative test detects, with the logarithm value of concentration for horizontal ordinate, with the intensity of any one characteristic peak above-mentioned for ordinate, and production standard curve.The range of linearity of quantitative test is 10nmol/L-10000nmol/L, linearly dependent coefficient (R
2) can more than 0.99 be reached, the recovery is between 90%-104%, and detectability can be low to moderate 1nmol/L.
The present invention synthesizes golden nanometer particle first in the solution, mercaptan is utilized to modify golden nanometer particle, nano particle can be self-assembled into large area, regular golden nanometer particle film at liquid-gas interface, be transferred to silicon chip, as SERS active-substrate, after dripping benzo (a) pyrene, utilize n-dodecyl mereaptan Iy self-assembled layer hydrophobic environment can adsorb benzo (a) pyrene, the quantitative test realizing the surface-enhanced Raman of benzo (a) pyrene detects.
The present invention is at solution middle synthesis golden nanometer particle mutually, mercaptan is utilized to modify golden nanometer particle, because the hydrophobic effect of the carbochain of mercaptan self assembly can form regular single layer of gold nanoparticulate thin films at liquid-gas interface, be transferred to silicon chip, as SERS active-substrate, the hydrophobic effect of the carbochain of mercaptan can catch nonpolar benzo (a) pyrene molecule, under the Electromagnetic enhancement effect of golden nanometer particle, can carry out SERS analyze detection to benzo (a) pyrene.Because the gold nanometer particle grain size of synthesis is even, it can the orderly nano particle structure of the regular individual layer of large area self assembly at liquid-gas interface, and this uniform substrate can realize quantitative test to benzo (a) pyrene.And this substrate preparation is simple, having can reusing.
The present invention proposes a kind of analyzing detecting method of surface-enhanced Raman of benzo (a) pyrene, utilize the golden nanometer particle that mercaptan is modified, the hydrophobic end of the chain of mercaptan not only can be utilized to catch benzo (a) pyrene, and its hydrophobic end of the chain can be utilized to be self-assembled into large-area regular ordered structure at liquid-gas interface, as SERS substrate, quantitative test is carried out to benzo (a) pyrene.This substrate not only makes simply, but also can reuse.Have detected the SERS substrate of benzo (a) pyrene, after absolute ethyl alcohol is flushed, still can be used for detecting, reusable edible 3-6 circulation.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope diagram of the SERS active-substrate prepared in second step.
Fig. 2 is the SERS active-substrate Raman spectrogram and its detection 10 prepared in second step
-7the SERS spectrogram of mol/L benzo (a) pyrene solution and the Raman spectrogram of benzo (a) pyrene pressed powder.
Fig. 3 be the SERS active-substrate prepared in second step verify that it has can the SERS spectrogram of reusing.
Fig. 4 detects 10 by four kinds of SERS active-substrate prepared by the mercaptan modification golden nanometer particle of different volumes in second step
-6the SERS spectrogram of mol/L benzo (a) pyrene solution.
Fig. 5 detects 10 by four kinds of SERS active-substrate prepared by the mercaptan modification golden nanometer particle of different volumes in second step
-6the bar chart of mol/L benzo (a) pyrene solution result.
Fig. 6 is the SERS active-substrate prepared in second step detects benzo (a) the pyrene solution of variable concentrations SERS spectrogram in diverse location.
Fig. 7 is the SERS active-substrate prepared in second step detects benzo (a) the pyrene solution of variable concentrations typical curve in diverse location.
Table 1 is the recovery of five kinds of different concentrations of benzo (a) pyrenes.
Embodiment
Below by specific embodiment, the present invention is further illustrated.
Embodiment 1
1) synthesizing particle diameter is the golden nanometer particle of 55 ± 10nm:
Getting 200mL massfraction is that the aqueous solution of chloraurate of 0.01% is in 250mL round-bottomed flask, reflux heating is to boiling under magnetic stirring, then the sodium citrate aqueous solution that 1.4mL massfraction is 1% is added rapidly, solution becomes black within half a minute, continue reflux heating 40min, solution gradually becomes brownish red by faint yellow, naturally cools to room temperature after making its complete reaction, can obtain the golden nanometer particle colloidal sol (see Fig. 1) that diameter is about 55 ± 10nm.
2) golden nanometer particle is self-assembled into SERS active-substrate:
Utilize the method for centrifuging by 1) in the aurosol of synthesis carry out concentration, and with milli-Q water centrifugal 1 time (centrifugal condition is 8000r/min, 10min).Get 1mL concentrate after solution of gold nanoparticles in clean monkey, then n-dodecyl mereaptan-the methanol solution of 200 μ L1mmol/L is added drop-wise in concentrated solution of gold nanoparticles, golden nanometer particle is at liquid-gas interface meeting self assembly one deck oiliness golden nanometer particle film, transferred to by golden film on clean silicon chip, drying can obtain SERS active-substrate (see Fig. 1).
3) on XploRA Raman spectrometer, this SERS active-substrate is detected, utilize this substrate to detect 10 simultaneously
-7mol/L benzo (a) pyrene solution.
Fig. 1 is the scanning electron microscope diagram of the SERS active-substrate prepared in second step.In FIG, scale is 200nm.As can be seen from the figure the golden nanometer particle in 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.In figure, A is the SERS spectrogram of the golden nanometer particle of synthesis, and B is the SERS active-substrate Raman spectrogram of preparation, and C is that the SERS active-substrate of preparation detects 10
-7the SERS spectrogram of mol/L benzo (a) pyrene solution, D is the Raman spectrogram of benzo (a) pyrene pressed powder.This experimental result shows that this SERS active-substrate detects noiseless to the SERS of benzo (a) pyrene, and successfully detected 10
-7mol/L benzo (a) pyrene.
Embodiment 2
1) synthesizing particle diameter is the golden nanometer particle of 55 ± 10nm:
Getting 200mL massfraction is that the aqueous solution of chloraurate of 0.01% is in 250mL round-bottomed flask, reflux heating is to boiling under magnetic stirring, then the sodium citrate aqueous solution that 1.4mL massfraction is 1% is added rapidly, solution becomes black within half a minute, continue reflux heating 40min, solution gradually becomes brownish red by faint yellow, 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 SERS active-substrate:
Utilize the method for centrifuging by 1) in the aurosol of synthesis carry out concentration, and with milli-Q water centrifugal 1 time (centrifugal condition is 8000r/min, 10min).Get 1mL concentrate after solution of gold nanoparticles in clean monkey, then n-dodecyl mereaptan-the methanol solution of 200 μ L1mmol/L is added drop-wise in concentrated solution of gold nanoparticles, golden nanometer particle is at liquid-gas interface meeting self assembly one deck oiliness golden nanometer particle film, transferred to by golden film on clean silicon chip, drying can obtain SERS active-substrate.
3) by 25 μ L
10-
7mol/L benzo (a) pyrene solution drips in this SERS active-substrate, detects under room temperature after natural drying on XploRA Raman spectrometer.
4) then rinse this substrate gently for several times with absolute ethyl alcohol, again this SERS active-substrate is detected after natural drying.
5) continue in this SERS active-substrate, drip 25 μ L10
-7mol/L benzo (a) pyrene solution, detects it after natural drying again.
6) repeat 4), 5) twice.
Fig. 3 is the experimental result of embodiment 2.Horizontal ordinate is Raman shift in figure 3, and unit is cm
-1; Ordinate is raman scattering intensity, and unit is cps.In figure, A is the Raman spectrogram of SERS active-substrate, and B, D, F, H are dropping 10
-7the SERS spectrogram of mol/L benzo (a) pyrene solution, C, E, G are the Raman spectrogram of SERS active-substrate after absolute ethyl alcohol rinses.Adopt spectral condition: excitation wavelength 785nm, 100 × object lens, power is about 3.05mW, grating 1200T, aperture 300 μm, slit 100 μm, time shutter 20s, and each spectrogram is accumulate 5 times under average mode.As can be seen from the figure, at 1240cm in the SERS active-substrate after absolute ethyl alcohol rinses
-1, 1345cm
-1and 1386cm
-1there is not the characteristic peak (as shown in C, E, G in figure) of benzo (a) pyrene in place; And again ought drip 10
-7during mol/L benzo (a) pyrene solution, at 1240cm in this SERS active-substrate
-1, 1345cm
-1and 1386cm
-1there is again the characteristic peak (as shown in D, F, H in figure) of benzo (a) pyrene in place, but the intensity at spectrum peak weakens to some extent relative to the intensity of composing peak in B.This result shows that this SERS active-substrate has preferably can reusing.
Embodiment 3
1) synthesizing particle diameter is the golden nanometer particle of 55 ± 10nm:
Getting 200mL massfraction is that the aqueous solution of chloraurate of 0.01% is in 250mL round-bottomed flask, reflux heating is to boiling under magnetic stirring, then the sodium citrate aqueous solution that 1.4mL massfraction is 1% is added rapidly, solution becomes black within half a minute, continue reflux heating 40min, solution gradually becomes brownish red by faint yellow, 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 SERS active-substrate:
Utilize the method for centrifuging by 1) in the aurosol of synthesis carry out concentration, and with milli-Q water centrifugal 1 time (centrifugal condition is 8000r/min, 10min).Respectively get 1mL concentrate after solution of gold nanoparticles in four clean monkeys, then n-dodecyl mereaptan-the methanol solution of 100 μ L, 200 μ L, 300 μ L, 400 μ L1mmol/L is added drop-wise in above-mentioned four monkeys respectively, golden nanometer particle is at liquid-gas interface meeting self assembly one deck oiliness golden nanometer particle film, transferred to by golden film on clean silicon chip, drying can obtain four kinds of SERS active-substrate.
3) on XploRA Raman spectrometer, to the diverse location test 10 of above-mentioned four kinds of SERS active-substrate
-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 result.
In the diagram, horizontal ordinate is Raman shift, and unit is cm
-1; Ordinate is raman scattering intensity, and unit is cps.In figure A to D be followed successively by 100 μ L, 200 μ L, 300 μ L, 400 μ L1mmol/L n-dodecyl mereaptan modify in the SERS active-substrate prepared of golden nanometer particle and detect 10
-6the SERS spectrogram of mol/L benzo (a) pyrene.Adopt spectral condition: excitation wavelength 785nm, 50 × object lens, power is about 2.78mW, grating 1200T, aperture 300 μm, slit 100 μm, time shutter 10s, and each spectrogram is accumulate 5 times under average mode.
In Figure 5, horizontal ordinate is the volume modifying golden nanometer particle mercaptan used, unit μ L; Ordinate is that benzo (a) pyrene is at 1386cm
-1sERS peak intensity values, unit is cps, and error bar represents standard deviation.Can find out from Fig. 4 and Fig. 5, the strongest characteristic peak 1386cm of benzo (a) pyrene
-1intensity can present along with the increase of the mercaptan volume modifying golden nanometer particle the trend first strengthening and reduce afterwards; When the mercaptan volume modifying golden nanometer particle is 200 μ L, the strongest characteristic peak 1386cm of benzo (a) pyrene
-1intensity can reach maximal value, and namely at this, to prepare the mercaptan optimum amount modifying golden nanometer particle in the method for SERS active-substrate be 200 μ L.
Embodiment 4
1) synthesizing particle diameter is the golden nanometer particle of 55 ± 10nm:
Getting 200mL massfraction is that the aqueous solution of chloraurate of 0.01% is in 250mL round-bottomed flask, reflux heating is to boiling under magnetic stirring, then the sodium citrate aqueous solution that 1.4mL massfraction is 1% is added rapidly, solution becomes black within half a minute, continue reflux heating 40min, solution gradually becomes brownish red by faint yellow, 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 SERS active-substrate:
Utilize the method for centrifuging by 1) in the aurosol of synthesis carry out concentration, and with milli-Q water centrifugal 1 time (centrifugal condition is 8000r/min, 10min).Get 1mL concentrate after solution of gold nanoparticles in clean monkey, then n-dodecyl mereaptan-the methanol solution of 200 μ L1mmol/L is added drop-wise in concentrated solution of gold nanoparticles, golden nanometer particle is at liquid-gas interface meeting self assembly one deck oiliness golden nanometer particle film, transferred to by golden film on clean silicon chip, drying can obtain SERS active-substrate.
3) on XploRA Raman spectrometer, to benzo (a) the pyrene solution of the diverse location test variable concentrations of SERS active-substrate.
Fig. 6 is the experimental result spectrogram of embodiment 3, and Fig. 7 is the fit standard curve map of embodiment 4 experimental result.
Horizontal ordinate is Raman shift in figure 6, and unit is cm
-1; Ordinate 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 dripping 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 about 2.78mW, grating 1200T, aperture 300 μm, slit 100 μm, time shutter 20s, and each spectrogram is accumulate 5 times under 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 the figure 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
-1sERS peak intensity values, unit is cps, and error bar represents standard deviation.In the figure 7, the range of linearity is 10nmol/L to 10000nmol/L, and fit standard curvilinear equation is y=119.88lg [C/nmolL
-1]-50.14, linearly dependent coefficient is R
2=0.9977, the detection calculating benzo (a) pyrene is limited to 1.29nmol/L(about 0.41 μ g/kg).This result shows to realize the quantitative detection to benzo (a) pyrene in this SERS active-substrate, and under the method, the detection of benzo (a) pyrene is limited to 1.29nmol/L(about 0.41 μ g/kg).In fact, this SERS active-substrate is utilized 1nmol/L benzo (a) pyrene can be detected, as shown in spectrogram B in Fig. 7.
With Fig. 7 standard curve for working curve, record five kinds of different concentrations of benzo (a) pyrene recovery results as shown in table 1.As shown in Table 1, the recovery of benzo (a) pyrene is between 89.93%-104.25%, and the typical curve of matching in key diagram 7 can line stabilization; Relative standard deviation (RSD) is between 2.34%-15.36%, and it can in range of receiving at the RSD that SERS detects.
Table 1 five kinds of different concentrations of benzo (a) pyrene recovery
Claims (8)
1. the analyzing detecting method of the surface-enhanced Raman of benzo (a) pyrene, comprises the following steps:
1) golden nanometer particle is synthesized:
With sodium citrate solution mutually in reduction gold chloride prepare golden nanometer particle colloidal sol;
2) golden nanometer particle is modified by mercaptan and is self-assembled into SERS active-substrate:
After being carried out by aurosol concentrating, washing, add appropriate mercaptan, described concentrated be by step 1) in synthesis solution of gold nanoparticles stoste 26-32ml be concentrated into 1ml; Centrifugal condition is control rotating speed is 4000-10000r/min, centrifugation time 5-30min; The concentrated volume of golden nanometer particle and the volume ratio of mercaptan are 1:0.1-0.4; Individual layer mercaptan in golden nanometer particle finishing, at liquid-gas interface self assembly one deck golden nanometer particle film, is transferred on silicon chip dry, can obtains SERS active-substrate;
3) the SERS quantitative test of benzo (a) pyrene detects
SERS active-substrate drips benzo (a) pyrene solution, after its natural drying, on Raman spectrometer, carries out SERS quantitative test.
2. the analyzing detecting method of the surface-enhanced Raman of benzo (a) pyrene as claimed in claim 1, it is characterized in that described golden nanometer particle is spherical or oval golden nanometer particle, particle diameter is 40-100nm.
3. the analysis of the surface-enhanced Raman of benzo (a) pyrene detects as claimed in claim 1, it is characterized in that the golden nanometer particle of described modified monolayer mercaptan is when other experiment condition is constant, the amount adding mercaptan makes its surface-enhanced Raman signals the strongest.
4. the analyzing detecting method of the surface-enhanced Raman of benzo (a) pyrene as claimed in claim 1, it is characterized in that the single layer of gold nano particle SERS substrate of modifying one deck mercaptan, the volume of concentrated golden nanometer particle and the volume ratio of mercaptan are 1:0.2.
5. the analyzing detecting method of the surface-enhanced Raman of benzo (a) pyrene as claimed in claim 1, it is characterized in that described mercaptan is selected from positive hexyl mercaptan, positive ten mercaptan or n-dodecyl mereaptan, its concentration is 1-5mmol/L.
6. the analyzing detecting method of the surface-enhanced Raman of benzo (a) pyrene as claimed in claim 1, is characterized in that described mercaptan is dissolved in methanol solvate and is mixed with the solution that concentration is 1-5mmol/L.
7. the analyzing detecting method of the surface-enhanced Raman of benzo (a) pyrene as claimed in claim 1, it is characterized in that the excitation source wavelength that described Surface enhanced raman spectroscopy detects is 400-800nm, laser facula is 1-2um.
8. the analyzing detecting method of the surface-enhanced Raman of benzo (a) pyrene as claimed in claim 1, is characterized in that, with calibration curve method to its quantitative test, making typical curve carry out quantitative test to it with the logarithm value of the intensity versus concentration of characteristic peak.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310167201.6A CN103364392B (en) | 2013-05-08 | 2013-05-08 | A kind of analyzing detecting method of surface-enhanced Raman of benzo (a) pyrene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310167201.6A CN103364392B (en) | 2013-05-08 | 2013-05-08 | A kind of analyzing detecting method of surface-enhanced Raman of benzo (a) pyrene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103364392A CN103364392A (en) | 2013-10-23 |
| CN103364392B true CN103364392B (en) | 2016-04-27 |
Family
ID=49366225
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310167201.6A Expired - Fee Related CN103364392B (en) | 2013-05-08 | 2013-05-08 | A kind of analyzing detecting method of surface-enhanced Raman of benzo (a) pyrene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103364392B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103774088B (en) * | 2014-02-13 | 2016-08-17 | 复旦大学 | A kind of SERS probe molecule is from collecting micro-pipe and its preparation method and application |
| CN103926234B (en) * | 2014-04-17 | 2016-11-23 | 福建出入境检验检疫局检验检疫技术中心 | A kind of monolayer nanometer gold surface reinforced Raman active substrate and preparation method thereof |
| CN103954606B (en) * | 2014-05-04 | 2016-06-01 | 北京化工大学 | A kind of based on nanometer ultrathin membrane of Au enhancing Raman spectrum and the application in dyestuff detects thereof |
| CN104089942A (en) * | 2014-07-14 | 2014-10-08 | 吉林大学 | Surface enhanced Raman substrate with super-hydrophobic property and application in polycyclic aromatic hydrocarbon detection |
| US9950079B2 (en) | 2015-09-03 | 2018-04-24 | International Business Machines Corporation | Functionalization of nanoparticles with polythioaminal thiol-containing polymers |
| CN105628674A (en) * | 2015-12-23 | 2016-06-01 | 山东大学 | In-situ microextraction and portable Raman spectrometer combined method for determining polycyclic aromatic hydrocarbon |
| CN107290324B (en) * | 2016-04-12 | 2020-09-08 | 中国人民解放军军事科学院军事医学研究院 | Application method for detecting hormone in food by combining SERS (surface enhanced Raman scattering) substrate |
| CN105973866B (en) * | 2016-05-05 | 2018-07-27 | 吉林大学 | A method of preparing low friction super hydrophobic surface using micro-and nano-particles coating enhances Raman substrate |
| CN108982421B (en) * | 2018-06-15 | 2021-12-17 | 集美大学 | Analysis and detection method of neomycin sulfate |
| CN109916879A (en) * | 2019-04-11 | 2019-06-21 | 重庆大学 | Material composition Raman spectra detection process based on the reunion enhancing of automatically controlled nano wire |
| CN110129754A (en) * | 2019-05-31 | 2019-08-16 | 苏州工业职业技术学院 | The preparation method and application of super-hydrophobic flower-shaped hierarchical structure Au@Ag nanometer sheet oldered array |
| CN110530839B (en) * | 2019-07-11 | 2021-11-30 | 宁波大学 | Preparation method of molybdenum disulfide/silver nano immune substrate material and repeatable immunodetection application thereof |
| EP3999834A1 (en) | 2019-07-15 | 2022-05-25 | Sicpa Holding SA | Method for manufacturing surface enhanced raman spectroscopy tags |
| CN114509421B (en) * | 2021-12-31 | 2024-04-09 | 电子科技大学 | Closely-connected ordered surface-enhanced Raman substrate and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006065762A3 (en) * | 2004-12-13 | 2007-02-08 | Univ South Carolina | Surface enhanced raman spectroscopy using shaped gold nanoparticles |
| US7989211B1 (en) * | 2006-09-27 | 2011-08-02 | Ut-Battelle, Llc | Functionalized gold surface-enhanced raman scattering substrate for rapid and ultra-sensitive detection of anionic species in the environment |
| CN102608093A (en) * | 2011-01-20 | 2012-07-25 | 中国科学院生态环境研究中心 | Detection method of polycyclic aromatic hydrocarbons (PAHs) |
| CN102706853A (en) * | 2012-06-05 | 2012-10-03 | 湖南大学 | Raman reinforced substrate material, preparation and application methods thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TR200802195A2 (en) * | 2008-04-01 | 2009-10-21 | Yed�Tepe �N�Vers�Tes� | Tissue differentiation method based on surface enriched raman scattering. |
-
2013
- 2013-05-08 CN CN201310167201.6A patent/CN103364392B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006065762A3 (en) * | 2004-12-13 | 2007-02-08 | Univ South Carolina | Surface enhanced raman spectroscopy using shaped gold nanoparticles |
| US7989211B1 (en) * | 2006-09-27 | 2011-08-02 | Ut-Battelle, Llc | Functionalized gold surface-enhanced raman scattering substrate for rapid and ultra-sensitive detection of anionic species in the environment |
| CN102608093A (en) * | 2011-01-20 | 2012-07-25 | 中国科学院生态环境研究中心 | Detection method of polycyclic aromatic hydrocarbons (PAHs) |
| CN102706853A (en) * | 2012-06-05 | 2012-10-03 | 湖南大学 | Raman reinforced substrate material, preparation and application methods thereof |
Non-Patent Citations (2)
| Title |
|---|
| 利用新型核壳纳米粒子作为SERS基底检测苯并芘;肖海波;《中国知网硕士学位论文全文数据库工程科技Ⅰ辑》;20130215;第42-51页 * |
| 气/液界面自组装金纳米粒子薄膜作为SERS基底检测三聚氰胺;肖海波等;《光谱学与光谱分析》;20120831;第32卷(第8期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103364392A (en) | 2013-10-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103364392B (en) | A kind of analyzing detecting method of surface-enhanced Raman of benzo (a) pyrene | |
| Ma et al. | Intrinsic Raman signal of polymer matrix induced quantitative multiphase SERS analysis based on stretched PDMS film with anchored Ag nanoparticles/Au nanowires | |
| Ghasemi et al. | A colorimetric sensor array for detection and discrimination of biothiols based on aggregation of gold nanoparticles | |
| Liu et al. | A review: Research progress of SERS-based sensors for agricultural applications | |
| Wei et al. | A colorimetric sensor for determination of cysteine by carboxymethyl cellulose-functionalized gold nanoparticles | |
| Rawat et al. | Visual detection of arginine, histidine and lysine using quercetin-functionalized gold nanoparticles | |
| CN103398998B (en) | A kind of Raman microprobe for mercury ion detecting and preparation method thereof | |
| Zhang et al. | Identification of volatile biomarkers of gastric cancer cells and ultrasensitive electrochemical detection based on sensing interface of Au-Ag alloy coated MWCNTs | |
| Zhao et al. | On-site monitoring of thiram via aggregation-induced emission enhancement of gold nanoclusters based on electronic-eye platform | |
| Hussain et al. | Synthesis of bimetallic core-shelled nanoparticles modified by 2-mercaptoethanol as SERS substrates for detecting ferbam and thiabendazole in apple puree | |
| Durán et al. | β-Cyclodextrin coated CdSe/ZnS quantum dots for vanillin sensoring in food samples | |
| Sutariya et al. | A simple and rapid creatinine sensing via DLS selectivity, using calix [4] arene thiol functionalized gold nanoparticles | |
| Liu et al. | A novel fluorescent probe for ascorbic acid based on seed-mediated growth of silver nanoparticles quenching of carbon dots fluorescence | |
| Mohammadi et al. | Colorimetric detection of biothiols based on aggregation of chitosan-stabilized silver nanoparticles | |
| Liu et al. | Ultrasensitive and facile detection of multiple trace antibiotics with magnetic nanoparticles and core-shell nanostar SERS nanotags | |
| Moreno et al. | Nanostructured hybrid surface enhancement Raman scattering substrate for the rapid determination of sulfapyridine in milk samples | |
| Jia et al. | Synthesis and application of colloidal beta-cyclodextrin-decorated silver nanoparticles for rapid determination of malachite green in environmental water using surface-enhanced Raman spectroscopy | |
| TW201445125A (en) | Method for manufacturing and using a test paper and chemical composition thereof | |
| Zhang et al. | Gap controlled self-assembly Au@ Ag@ Au NPs for SERS assay of thiram | |
| Liu et al. | Titanium dioxide-coated core-shell silica microspheres-based solid-phase extraction combined with sheathless capillary electrophoresis-mass spectrometry for analysis of glyphosate, glufosinate and their metabolites in baby foods | |
| Bazrafshan et al. | Determination of lamotrigine by fluorescence quenching of N-doped graphene quantum dots after its solid-phase extraction using magnetic graphene oxide | |
| Şaylan et al. | Nickel hydroxide nanoflower–based dispersive solid-phase extraction of copper from water matrix | |
| Feng et al. | Green synthesis and characterization of gold nanoparticles and their application for the rapid detection of glycyrrhizin with immunochromatographic strips | |
| Cai et al. | Bimetallic copper-cerium nanoclusters: Assembly-induced aggregation into nanowire network and cysteine-triggered strong red fluorescence turn-on for highly sensitive and selective cysteine sensing | |
| Feng et al. | Molecularly imprinted core-shell Au nanoparticles for 2, 4-dichlorophenoxyacetic acid detection in milk using surface-enhanced Raman spectroscopy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160427 |