CN110243802A - Based on C60Method for detecting imidacloprid by proportional Raman enhancement and ultrasensitivity - Google Patents
Based on C60Method for detecting imidacloprid by proportional Raman enhancement and ultrasensitivity Download PDFInfo
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- CN110243802A CN110243802A CN201910491470.5A CN201910491470A CN110243802A CN 110243802 A CN110243802 A CN 110243802A CN 201910491470 A CN201910491470 A CN 201910491470A CN 110243802 A CN110243802 A CN 110243802A
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- YWTYJOPNNQFBPC-UHFFFAOYSA-N imidacloprid Chemical compound [O-][N+](=O)\N=C1/NCCN1CC1=CC=C(Cl)N=C1 YWTYJOPNNQFBPC-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000005906 Imidacloprid Substances 0.000 title claims abstract description 77
- 229940056881 imidacloprid Drugs 0.000 title claims abstract description 77
- 238000001069 Raman spectroscopy Methods 0.000 title claims abstract description 35
- 238000001514 detection method Methods 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 claims description 37
- 238000000479 surface-enhanced Raman spectrum Methods 0.000 claims description 20
- 239000012086 standard solution Substances 0.000 claims description 19
- 230000035945 sensitivity Effects 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 13
- 230000002708 enhancing effect Effects 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002604 ultrasonography Methods 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002086 nanomaterial Substances 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 claims description 2
- 238000001237 Raman spectrum Methods 0.000 abstract description 10
- 239000000575 pesticide Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000011896 sensitive detection Methods 0.000 abstract 1
- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical compound Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 description 55
- 239000011259 mixed solution Substances 0.000 description 10
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 8
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 8
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 description 4
- LCCNCVORNKJIRZ-UHFFFAOYSA-N parathion Chemical compound CCOP(=S)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 LCCNCVORNKJIRZ-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WCXDHFDTOYPNIE-RIYZIHGNSA-N (E)-acetamiprid Chemical compound N#C/N=C(\C)N(C)CC1=CC=C(Cl)N=C1 WCXDHFDTOYPNIE-RIYZIHGNSA-N 0.000 description 3
- 239000005875 Acetamiprid Substances 0.000 description 3
- 239000005562 Glyphosate Substances 0.000 description 3
- 206010020751 Hypersensitivity Diseases 0.000 description 3
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 3
- 229940097068 glyphosate Drugs 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012490 blank solution Substances 0.000 description 2
- -1 chlopyrifos Chemical compound 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- MTXSIJUGVMTTMU-JTQLQIEISA-N (S)-anabasine Chemical compound N1CCCC[C@H]1C1=CC=CN=C1 MTXSIJUGVMTTMU-JTQLQIEISA-N 0.000 description 1
- 241001600407 Aphis <genus> Species 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 206010047700 Vomiting Diseases 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- OIPILFWXSMYKGL-UHFFFAOYSA-N acetylcholine Chemical compound CC(=O)OCC[N+](C)(C)C OIPILFWXSMYKGL-UHFFFAOYSA-N 0.000 description 1
- 229960004373 acetylcholine Drugs 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 229930014345 anabasine Natural products 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000036471 bradycardia Effects 0.000 description 1
- 208000006218 bradycardia Diseases 0.000 description 1
- 230000002612 cardiopulmonary effect Effects 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000008673 vomiting Effects 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/38—Diluting, dispersing or mixing samples
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
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- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses a method based on C60A method for detecting imidacloprid by proportional Raman enhancement and ultrasensitivity. Through C60Mixed with R6G in proper concentration ratio, only C is shown by Raman detection60Adding imidacloprid solution to be detected properly and carrying out Raman detection, C60The main characteristic peak of (A) disappears, and the intensity of the R6G peak increases with the increase of the imidacloprid concentration. Therefore, the concentration of imidacloprid can be measured by the correlation of the change of the Raman spectrum peak intensity of R6G, and the lowest detection limit can reach 10‑9The mol/L realizes the ultra-sensitive detection of imidacloprid. The invention has the advantages that the novel Raman detection method has the effect of ultra-sensitively detecting imidacloprid, can be applied to detecting target compounds without Raman signals or with weak Raman signals, and develops a novel idea for further researching the Raman spectrum technology to detect pesticides.
Description
Technical field
The invention belongs to Raman spectrum analysis detection technique fields, and in particular to one kind is based on C60The enhancing of ratio Raman
The method of super sensitivity detection imidacloprid.
Background technique
Imidacloprid (Imidacloprid) is a kind of interior suction, efficient residual period long agricultural excellent anabasine insecticide,
Mainly act on insect nicotinic acetylcholine enzyme acceptor, be widely used in it is anti-eliminate aphis, blade face and the medium pest of soil.But pyrrole
Worm quinoline can also make one to generate snoozed, palpitaition, vomiting, and serious person leads to bradycardia and cardiopulmonary all standing, and has serious toxicity
Side effect, therefore the imidacloprid quickly tested and analyzed in water body has a very big significance.
Surface enhanced Raman scattering (Surface enhancement of Raman scattering, SERS) has inspection
Degree of testing the speed is fast, detection time is short, water interference is small, does not need the advantages that carrying out complex process to sample, before having wide development
Scape.Cao Xiaolin et al. synthesizes nanogold particle colloidal sol, detects imidacloprid (Chinese using Surface enhanced Raman spectroscopy technology
Journal of Analysis Laboratory, 2017,09:1007), but this method only directly enhances script molecule
Detection, detection limit lower, only 0.025mg/L.And Liu Cuiling et al. is real using Raman spectroscopy combination QuEChERS technology
Now to the detection of imidacloprid (Infrared and Laser Engineering, 2017,11:284) but this method detected
Journey is complex, and is also to detect to the directly enhancing of script molecule, and detection limit only has 0.148mg/kg, does not have hypersensitive
Detection.
Summary of the invention
The object of the invention is that, provide a kind of based on C to solve the above-mentioned problems60Ratio Raman enhances hypersensitive
The method for detecting imidacloprid, complicated to solve existing Raman spectroscopy detection imidacloprid process, detection limits lower technology and lacks
It falls into.
The present invention through the following technical solutions to achieve the above objectives:
One kind being based on C60The method of ratio Raman enhancing super sensitivity detection imidacloprid, comprising the following steps:
(1) by C60It is mixed with the double report molecules of R6G (rhodamine 6G), obtains mixed system；
(2) the imidacloprid standard solution for configuring series of concentrations gradient, is separately added into the mixed system of step (1), mixes
After be added dropwise in SERS substrate, carry out SERS detection after dry, SERS spectra figure obtained, according to SERS spectra figure R6G characteristic peak
Intensity with imidacloprid concentration increase and enhance correlation, construct standard curve；
(3) sample to be tested is added in the mixed system of step (1), is added dropwise after mixing in SERS substrate, drying is laggard
Row SERS detection, obtains SERS spectra figure, by the intensity of R6G characteristic peak known to SERS spectra figure, according to standard curve, calculate to
Imidacloprid concentration in sample.
It is further preferred that in the step (1), by C60After first being mixed respectively with solvent with the bis- report molecules of R6G, then press
Ratio mixes, and step includes: to prepare C60Concentration is 2 × 10-5-8×10-5The 5-10mL standard solution and R6G concentration of mol/L is 2
×10-7-8×10-7The two, is then mutually mixed by the 5-10mL standard solution of mol/L.
It is further preferred that C60Solvent be deionized water, the solvent of R6G is ethyl alcohol.
It is further preferred that the molar range of the imidacloprid in mixed system is added 10 in the step (2)-6Mol is arrived
5×10-12Between mol.
It is further preferred that the solvent of imidacloprid is ethyl alcohol.
It is further preferred that C60, R6G and/or imidacloprid solution mixing operation be all to be carried out under ultrasound condition.
It is further preferred that the sample dripping quantity in SERS substrate is 5 μ L in the step (2) or (3).
It is further preferred that SERS substrate is noble metal nano structure SERS substrate in the step (2), but it is not limited to this
A little substrates.
The principle of the present invention are as follows: by double report molecule debita spissitudo mixed systems, appropriate mole of amount pyrrole to be measured is added
After worm quinoline solution, one of A report Molecular Raman spectrum peak is quenched, and another B report molecule SERS peak intensity is with imidacloprid
Concentration increases and increases, to report the dense of the Raman spectral peaks Strength Changes relativity determination imidacloprid solution of molecule by B
Degree.And the Raman spectrum peak intensity and being positively correlated property of imidacloprid concentration of B report molecule are relied on, molecule is reported by measurement B
The enhancing of Raman ratio realizes the hypersensitive SERS detection to imidacloprid；
In C60In R6G mixed system, imidacloprid solution is added, so that imidacloprid and C60In conjunction with leading to C60Peak is quenched,
To making R6G start to occupy silver nanoparticle substrate site, gradually show the peak R6G, by SERS enhance R6G peak intensity to
Super sensitivity detection imidacloprid.
The beneficial effects of the present invention are: the present invention provides one kind to be based on C60Ratio Raman enhances super sensitivity detection pyrrole worm
The method of quinoline provides a kind of new think of the method achieve to imidacloprid SERS super sensitivity detection for imidacloprid SERS detection
Think.This method can be applied to detect no Raman signal or the weaker target compound of Raman signal, and entire detection method
It is easy to operate.
Detailed description of the invention
Fig. 1 is based on C60The method route of ratio Raman enhancing super sensitivity detection imidacloprid；
Fig. 2 is the C of embodiment 160With the Raman detection spectrogram of R6G and various concentration imidacloprid mixed solution；
Fig. 3 (A) is C60It is isometric with imidacloprid, atrazine, Acetamiprid, glyphosate, chlopyrifos, parathion respectively with R6G
Mixed SERS spectra figure；
Fig. 3 (B) is the ratio of 3 the main feature peak intensities and blank mixed liquor of R6G under different pesticides；
Fig. 4 is the C of embodiment 360With the Raman detection spectrogram of R6G and various concentration imidacloprid solution.
Specific embodiment
The application is described in further detail with reference to the accompanying drawing, it is necessary to it is indicated herein to be, implement in detail below
Mode is served only for that the application is further detailed, and should not be understood as the limitation to the application protection scope, the field
Technical staff can make some nonessential modifications and adaptations to the application according to above-mentioned application content.
One kind being based on C60The method of ratio Raman enhancing super sensitivity detection imidacloprid, comprising the following steps:
(1) by C60It after first being mixed respectively with solvent with the bis- report molecules of R6G, then mixes in proportion, step includes: to prepare
C60Concentration is 2 × 10-5-8×10-5The 5-10mL standard solution and R6G concentration of mol/L is 2 × 10-7-8×10-7The 5- of mol/L
The two, is then mutually mixed by 10mL standard solution, obtains mixed system.
(2) the imidacloprid standard solution (such as 10 of series of concentrations gradient is configured-9, 10-8, 10-7, 10-6, 10-5, 10-4With 10- 3Mol/L series of concentrations), it is separately added into the mixed system of step (1), wherein the molar range that imidacloprid is added is 10-6mol
To 5 × 10-12Between mol；After being mixed under ultrasound condition, the mixed liquor of 5 μ L is drawn using liquid-transfering gun, is added in SERS substrate, do
SERS detection is carried out after dry, obtains SERS spectra figure.
The correlation for being increased and being enhanced with imidacloprid concentration according to the intensity of SERS spectra figure R6G characteristic peak constructs standard
Curve.
(3) 5 μ L samples to be tested are drawn, are added in the mixed system of step (1), is added dropwise after mixing in SERS substrate, is done
SERS detection is carried out after dry, obtains SERS spectra figure, by the intensity of R6G characteristic peak known to SERS spectra figure, according to standard curve,
Calculate imidacloprid concentration in sample to be tested.
Wherein, C60Solvent be deionized water, the solvent of R6G and imidacloprid is ethyl alcohol.
Embodiment 1
It present embodiments provides based on C60The method of ratio Raman enhancing super sensitivity detection imidacloprid, comprising the following steps:
(1)C60With the bis- report molecular ratios mixing of R6G: preparing C60Concentration is 4 × 10-5The 10mL standard solution of mol/L and
R6G concentration is 4 × 10-7The two, is then mutually mixed by the 10mL standard solution of mol/L, and ultrasound is uniformly mixed it.
(2)C60, R6G and the mixing of imidacloprid series concentration: prepare serial imidacloprid concentration (10-9, 10-8, 10-7, 10-6, 10-5, 10-4With 10-3Mol/L standard solution) takes out 5mL solution respectively and is added in above-mentioned (1) mixed solution, and ultrasonic vibration makes it
It is uniformly dispersed, 5uL then is added dropwise in SERS substrate with liquid-transfering gun respectively, carries out SERS detection after dry.
C under the conditions of test cases 160With R6G and various concentration imidacloprid solution S ERS peak intensity effect, obtain such as Fig. 2 institute
The SERS spectra figure shown.In figure: a is C60The SERS spectra figure mixed in equal volume with the mixed solution of R6G with blank solution, b-h
It is C60With R6G respectively with imidacloprid concentration gradient 10-9, 10-8, 10-7, 10-6, 10-5, 10-4With 10-3The SERS light of mol/L mixing
Spectrogram.
, it is evident that working as C from Fig. 260SERS spectra only shows C after mixing with R6G with appropriate blank solution60Feature
Peak.And work as C60With R6G respectively at imidacloprid concentration gradient (10-9, 10-8, 10-7, 10-6, 10-5, 10-4With 10-3Mol/L it) mixes
Afterwards, SERS spectra figure C60Peak disappears, and the characteristic peak of R6G occurs, and R6G peak intensity increases with imidacloprid concentration and enhanced, and
Imidacloprid concentration is 10-9The characteristic peak of R6G can be clearly measured when mol/L, although the characteristic peak of the not high R6G of peak intensity is still
It is clear and legible.
The relevance for being increased and being enhanced with imidacloprid concentration based on above-mentioned R6G peak intensity draws R6G peak intensity and imidacloprid
The standard curve of concentration, the detection for imidacloprid concentration in subsequent sample to be tested.
Embodiment 2
To verify C60With the bis- report molecules of R6G to the selectivity of imidacloprid, present embodiments provide a kind of based on C60Ratio
The method that Raman enhancing detects different pesticide concentrations, comprising the following steps:
(1)C60With the bis- report molecular ratios mixing of R6G: preparing C60Concentration is 8 × 10-5The 5mL standard solution of mol/L and
R6G concentration is 8 × 10-7The two, is then mutually mixed by the 10mL standard solution of mol/L, and ultrasound is uniformly mixed it.
(2) compound concentration is 10-4(imidacloprid, atrazine, Acetamiprid, grass are sweet for the 5mL difference pesticide standard solution of mol/L
Then phosphine, chlopyrifos and parathion take 5mL difference the pesticide solution that C is respectively added respectively60With R6G mixed liquor, ultrasonic vibration fills it
Divide mixing, 5uL then is added dropwise in SERS substrate with liquid-transfering gun respectively, carries out SERS detection after dry.
Shown in SERS spectrogram such as Fig. 3 (A) (B) that the above results obtain, Fig. 3 (A) a-f is C60With R6G respectively with imidacloprid,
The SERS spectra figure that atrazine, Acetamiprid, glyphosate, chlopyrifos, parathion mix in equal volume, Fig. 3 (B) are under different pesticides
The ratio of 3 the main feature peak intensities and blank mixed liquor of R6G.From Fig. 3 (A) obviously it can be seen that pyrrole worm is added in spectral line a
The mixed solution Raman spectrum of quinoline shows C60Characteristic peak disappears, and the characteristic peak of R6G occurs；B. the mixed solution of atrazine is added
Raman spectrum shows C60Characteristic peak disappears, and the characteristic peak of R6G occurs, but raman scattering intensity is smaller than a；C and d. is that pyridine is added respectively
The mixed solution Raman spectrum of worm amidine and glyphosate, display only have C60Characteristic peak, the peak of no R6G；E. chlopyrifos is added
Mixed solution Raman spectrum shows C60Characteristic peak, but peak intensity is lower；F. the mixed solution Raman spectrum that parathion is added is aobvious
Show both without C60Characteristic peak does not have R6G characteristic peak yet.It obviously can be seen that 5 features of R6G when imidacloprid is added in Fig. 3 (B)
Peak all enhances 20 times or more, has been up to 28 times, has selectivity well.
Embodiment 3
It present embodiments provides a kind of based on C60The method that ratio Raman enhances super sensitivity detection imidacloprid, including following step
It is rapid:
(1)C60With the bis- report molecular ratios mixing of R6G: preparing C60Concentration is 8 × 10-5The 6mL standard solution of mol/L and
R6G concentration is 5 × 10-7The two, is then mutually mixed by the 10mL standard solution of mol/L, and ultrasound is uniformly mixed it.
(2)C60, R6G and the mixing of imidacloprid series concentration: prepare serial imidacloprid concentration (10-9, 10-8, 10-7, 10-6, 10-5, 10-4With 10-3M standard solution) takes out 5mL solution respectively and is added in above-mentioned (1) mixed solution, and ultrasonic vibration makes its dispersion
Uniformly, 5uL then is added dropwise in SERS substrate with liquid-transfering gun respectively, carries out SERS detection after dry.
C under the conditions of test cases 360, R6G and various concentration imidacloprid solution S ERS peak intensity effect.
Test condition: serial imidacloprid concentration (10 is prepared-8, 10-7, 10-6, 10-5With 10-4Mol/L standard solution) point
It Qu Chu not the above-mentioned C of 5mL solution addition60In R6G mixed solution, ultrasonic vibration makes it be uniformly dispersed, and then uses liquid-transfering gun respectively
5uL is added dropwise in SERS substrate, carries out SERS detection after dry.
The SERS spectrogram that the above results obtain is as shown in figure 4, a-e is C60With R6G respectively with imidacloprid concentration gradient 10-8,
10-7, 10-6, 10-5With 10-4The SERS spectra figure of mol/L mixing, it is evident that working as C from Fig. 460With R6G respectively at imidacloprid
Concentration gradient (10-8, 10-7, 10-6, 10-5With 10-4Mol/L after) mixing, SERS spectra figure C60Peak disappears, and the feature of R6G occurs
Peak, and the peak intensity of R6G increases with imidacloprid concentration and is enhanced, and has good correlation.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.
Claims (8)
1. one kind is based on C60The method of ratio Raman enhancing super sensitivity detection imidacloprid, which comprises the following steps:
(1) by C60It is mixed with the bis- report molecules of R6G, obtains mixed system；
(2) the imidacloprid standard solution for configuring series of concentrations gradient, is separately added into the mixed system of step (1), drips after mixing
It is added in SERS substrate, carries out SERS detection after dry, SERS spectra figure is obtained, according to the strong of SERS spectra figure R6G characteristic peak
Degree is increased with imidacloprid concentration and the correlation of enhancing, constructs standard curve；
(3) sample to be tested is added in the mixed system of step (1), is added dropwise after mixing in SERS substrate, is carried out after dry
SERS detection, obtains SERS spectra figure, and the intensity of R6G characteristic peak known to SERS spectra figure calculates to be measured according to standard curve
Imidacloprid concentration in sample.
2. according to claim 1 a kind of based on C60The method that ratio Raman enhances super sensitivity detection imidacloprid, feature
It is, in the step (1), by C60After first being mixed respectively with solvent with the bis- report molecules of R6G, then mix in proportion, step packet
It includes: preparing C60Concentration is 2 × 10-5-8×10-5The 5-10mL standard solution and R6G concentration of mol/L is 2 × 10-7-8×10- 7The two, is then mutually mixed by the 5-10mL standard solution of mol/L.
3. according to claim 1 a kind of based on C60The method that ratio Raman enhances super sensitivity detection imidacloprid, feature
It is, C60Solvent be deionized water, the solvent of R6G is ethyl alcohol.
4. according to claim 1 a kind of based on C60The method that ratio Raman enhances super sensitivity detection imidacloprid, feature
It is, in the step (2), the molar range of the imidacloprid in mixed system is added 10-6Mol to 5 × 10-12Between mol.
5. according to claim 1 a kind of based on C60The method that ratio Raman enhances super sensitivity detection imidacloprid, feature
It is, the solvent of imidacloprid is ethyl alcohol.
6. according to claim 1 a kind of based on C60The method that ratio Raman enhances super sensitivity detection imidacloprid, feature
It is, C60, R6G and/or imidacloprid solution mixing operation be all to be carried out under ultrasound condition.
7. according to claim 1 a kind of based on C60The method that ratio Raman enhances super sensitivity detection imidacloprid, feature
It is, in the step (2) or (3), the sample dripping quantity in SERS substrate is 5 μ L.
8. according to claim 1 a kind of based on C60The method that ratio Raman enhances super sensitivity detection imidacloprid, feature
It is, SERS substrate is noble metal nano structure SERS substrate in the step (2).
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| CN201910491470.5A CN110243802B (en) | 2019-06-06 | 2019-06-06 | Based on C60Method for detecting imidacloprid by proportional Raman enhancement and ultrasensitivity |
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| CN201910491470.5A CN110243802B (en) | 2019-06-06 | 2019-06-06 | Based on C60Method for detecting imidacloprid by proportional Raman enhancement and ultrasensitivity |
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| CN110243802B CN110243802B (en) | 2021-07-06 |
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