CN103257063B - A kind of water body polycyclic aromatic hydrocarbon detection reagent and application thereof - Google Patents
A kind of water body polycyclic aromatic hydrocarbon detection reagent and application thereof Download PDFInfo
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Abstract
The invention discloses a kind of water body polycyclic aromatic hydrocarbon detection reagent, described detection reagent is made up of reagent A and reagent B, and described reagent A is graphene/nanometer noble metal composite aqueous solution; Described reagent B is surfactant solution.The invention also discloses a kind of application of water body polycyclic aromatic hydrocarbon detection reagent, comprise the following steps: first reagent B is scattered in palycyclic aromatic solution; In above-mentioned mixed liquor, add reagent A again, mix; Finally get appropriate mixed solution and carry out Raman detection, obtain the SERS collection of illustrative plates of palycyclic aromatic.The invention provides a kind of water body polycyclic aromatic hydrocarbon detection reagent and application thereof, can detect the palycyclic aromatic in water body fast, easy to detect, data redundancy is good, can realize single component or the multi-analyte immunoassay of palycyclic aromatic.
Description
Technical field
The present invention relates to technical field of organic pollutant detection, particularly relate to a kind of water body polycyclic aromatic hydrocarbon detection reagent and application thereof.
Background technology
Palycyclic aromatic is the organic compound of two or more aromatic rings of class composition, has very strong carcinogenic, teratogenesis, mutagenesis bio-toxicity.Although the absolute content of palycyclic aromatic in water is very low, the harm of palycyclic aromatic has disguised and paroxysmal feature, once there is major pollution incident, will produce catastrophic effect and even can continue to endanger several generations.Therefore countries in the world have formulated environmental legislation about PAHs and standard in succession, and are listed in environmental monitoring project.Mainly liquid chromatography is comprised to the traditional analysis detection method of palycyclic aromatic, mass spectrum etc., these detection means reliable results, be widely used, but also there is many problems in some aspects in these methods, such as detect consuming time, particularly complicated sample pretreatment process (extraction, concentrates, and is separated) needs the time of technical professional's at substantial to complete.And along with people are to public safety and health in recent years, the pay attention to day by day of environmental protection, also more and more harsher to the requirement of palycyclic aromatic detection means performance, traditional detection means are not competent gradually.Therefore, exploitation one has fast, detection means is extremely urgent reliably.
Surface enhanced raman spectroscopy (SERS) is a kind of surface optics effect, when molecular adsorption is on the surface of nanoscale noble metal, due to Electromagnetic enhancement effect and Chemical enhancement effect, its Raman signal intensity can improve 5-6 the order of magnitude, even can realize Single Molecule Detection (enhancer 1014-1015) under given conditions.Therefore SERS technology is expected to detect for the trace of multiring aromatic hydrocarbon substance and ultratrace.
Publication number is that the Chinese patent of CN102608093A discloses a kind of palycyclic aromatic detection method, and the method is by the Fe of mercaptan modified
3o
4Ag magnetic nanoparticle as surface reinforced Raman active substrate, for enrichment and the detection of palycyclic aromatic.The method is simple to operate, but substrate preparation technology is more complicated, and the dispersiveness of substrate in water is not ideal enough.
Graphene be a kind of by carbon atom with sp
2hybrid orbital composition hexangle type is the flat film of honeycomb lattice, has unique physics, chemical property, presents wide application prospect in fields such as material, electronics, biologies.Graphene/nanometer noble metal composite, has high-specific surface area, adsorbable and enrichment different kinds of molecules, and merges the Chemical enhancement effect of Graphene and the strong electromagnetic humidification of nano-noble metal, has high SERS active.Owing to lacking polar functional group in palycyclic aromatic molecule, need modify graphene/nanometer noble metal composite surface, by finishing coat enrichment palycyclic aromatic molecule, good SERS signal could be obtained, but alkyl chain modify after graphene/nanometer noble metal composite hydrophobicity increase, in aqueous, these factors limit the application of graphene/nanometer noble metal composite in water body polycyclic aromatic hydrocarbon detects to very difficult stable dispersion.
Summary of the invention
The invention provides a kind of water body polycyclic aromatic hydrocarbon detection reagent and application thereof, can detect the palycyclic aromatic in water body fast, easy to detect, data redundancy is good, can realize single component or the multi-analyte immunoassay of palycyclic aromatic.
A kind of water body polycyclic aromatic hydrocarbon detection reagent, described detection reagent is made up of reagent A and reagent B, and described reagent A is graphene/nanometer noble metal composite aqueous solution; Described reagent B is surfactant solution.
The present invention carries out Chemical enhancement and Raman enhancing by reagent A graphene/nanometer noble metal composite aqueous solution to the solution containing palycyclic aromatic, and improve the dispersion of reagent A in palycyclic aromatic solution by reagent surfactant B solution, make palycyclic aromatic be adsorbed to the surface of reagent A uniformly, trace and the ultratrace detection of water body polycyclic aromatic hydrocarbon can be realized by Raman detection.
Preferably, described reagent A concentration is 0.5-5mg/ml, and in this concentration range, reagent A has dispersed and SERS activity preferably.
Preferably, the preparation of described reagent A comprises the following steps:
(1) graphene oxide solution, nano-noble metal salt solusion and deionized water are mixed obtain mixed liquor;
(2) mixed liquor is heated to 90 ~ 100 DEG C, adds reductive agent reaction;
(3) washing after reaction product cooling is separated and is dispersed in water, obtained reagent A.
Graphene oxide is the two-dimensional nanostructure of a kind of individual layer or few layer, after nano-noble metal is modified, carry out the reunion that reduction reaction can effectively prevent between graphene sheet layer again, meanwhile, noble metal nano particles on graphene sheet layer in certain state of aggregation.
Graphene can be reacted in the solution containing oxygenants such as the concentrated sulphuric acid, red fuming nitric acid (RFNA) or potassium permanganate, obtain described graphene oxide solution.
Preferably, the mass ratio of described graphene oxide solution and nano-noble metal salt solusion is 1: 1 ~ 1: 100, and under this ratio, the nano-noble metal concentration class of load on Graphene is better, has good SERS to strengthen effect.
Preferably, described reductive agent is citrate three sodium solution or glucose solution, and the concentration of reductive agent is 0.1% ~ 5%.Citrate three sodium solution or glucose solution are the more weak reductive agent of reductibility, nano-noble metal presoma reduction rate can be caused too fast if add strong reductant, formed and reunite, be unfavorable for that pattern controls, the addition of reductive agent is as the criterion with the abundant reduction realizing mixed liquor, the volume generally adding reductive agent is 5 ~ 40ml, and the grain diameter of the nano-noble metal obtained through reduction reaction is 10 ~ 100nm.
Preferably, the concentration of described reagent B is 0.5 ~ 10mg/ml, described reagent B is cetyl trimethyl ammonium bromide (CTAB) or tetradecyl trimethyl ammonium chloride (TTAC), this kind of cationic surfactant is selected to be because the compatibility of alkyl chain and palycyclic aromatic is better, can effective absorbing multiring aromatic hydrocarbon molecule, positively charged alkyl chain can be adsorbed on nano-noble metal surface simultaneously.
Present invention also offers a kind of application of above-mentioned water body polycyclic aromatic hydrocarbon detection reagent, comprise the following steps:
(1) reagent B is scattered in palycyclic aromatic solution;
(2) in above-mentioned mixed liquor, add reagent A, mix;
(3) get and carry out Raman detection through step (2) mixed solution in right amount, obtain the SERS collection of illustrative plates of palycyclic aromatic.
In palycyclic aromatic solution, add the absorption property that reagent B can improve palycyclic aromatic, after adding reagent A, palycyclic aromatic can be adsorbed to the surface of reagent A uniformly, then by Raman detection, can realize the Quick Measurement of palycyclic aromatic.
Preferably, after reagent B being scattered in palycyclic aromatic solution in step (1), the concentration of reagent B is 0.05 ~ 1.0mg/ml; Add after reagent A mixes in step (2), the volume fraction of reagent A is 5% ~ 30%.
Preferably, described palycyclic aromatic solution is one or more mixed liquors of perylene solution, pyrene solution, anthracene solution or fluorenes solution.The mixed liquor of detection method of the present invention to single palycyclic aromatic solution or multiple palycyclic aromatic all has good Detection results.
Compared with prior art, Advantageous Effects of the present invention is:
(1) the present invention's trace detection of adopting reagent A and reagent B can realize palycyclic aromatic in water body, detection method is simple to operate, highly sensitive;
(2) the present invention effectively can improve the accumulation ability of graphene/nanometer noble metal composite to palycyclic aromatic in water, realizes super sensitivity detection.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the application of a kind of water body polycyclic aromatic hydrocarbon detection reagent of the present invention;
Fig. 2 is graphene/nanometer Ag compound obtained in embodiment 1 is reagent A, and CTAB is reagent B, detects 10
-4the SERS spectrum of M concentration pyrene solution;
Fig. 3 is graphene/nanometer Ag compound obtained in embodiment 2 is reagent A, and TTAC is reagent B, detects 10
-6the SERS spectrum of M Nong Du perylene solution;
Fig. 4 is graphene/nanometer Au compound obtained in embodiment 3 is reagent A, and CTAB is reagent B, detects 10
-4the SERS spectrum of M concentration pyrene solution;
Fig. 5 is graphene/nanometer Au & Ag compound obtained in embodiment 4 is reagent A, and TTAC is reagent B, detects 10
-5the SERS spectrum of M Nong Du perylene solution;
Fig. 6 is graphene/nanometer Ag compound obtained in embodiment 5 is reagent A, and CTAB is reagent B, detects 10
-4m concentration pyrene and 10
-5the SERS spectrum of M Nong Du perylene mixed solution;
Fig. 7 is graphene/nanometer Ag compound obtained in embodiment 6 is reagent A, and CTAB is reagent B, and detectable concentration is 10
-4the SERS spectrum of the pyrene of M, anthracene, fluorenes mixed solution.
Embodiment
Below by embodiment, the present invention is set forth further.
Embodiment 1
(1) 20ml10 is measured
-2the AgNO of M
3solution, 59ml deionized water, 1ml graphene oxide solution, mixes ultrasonic 15min under room temperature, is transferred in there-necked flask;
(2) above-mentioned solution is heated to 90 DEG C while stirring, adds 20ml1% citric acid three sodium solution fast, continue reaction 24h;
(3) after above-mentioned reactant being naturally cooled to room temperature, washing is separated, and obtained have good surface enhancing Ramam effect graphene/nanometer Ag compound;
(4) be again dispersed in water by the graphene/nanometer Ag compound that step (3) is obtained, concentration is 0.01M (content meter with silver), obtains reagent A;
(5) be that 2mg/ml reagent B (CTAB) mixes by the aqueous solution of pyrene and concentration, wherein after mixing, the concentration of pyrene is 10
-4the concentration of M, CTAB is 0.2mg/ml, then adds ultrasonic 30 minutes of 100 μ L reagent A mixing.By the above-mentioned solution of absorption 10 μ L during test sample preparation, drip and carry out Raman detection (excitation wavelength is 532nm) on the microslide through clean process, as shown in Figure 2, can be observed the characteristic peak of obvious pyrene.
Embodiment 2
(1) 20ml10 is measured
-2the AgNO of M
3solution, 59ml deionized water, 0.5ml graphene oxide solution, mixes ultrasonic 15min under room temperature, is transferred in there-necked flask;
Step (2)-(4) are identical with embodiment (1);
(aqueous solution of perylene and concentration are that the reagent B (TTAC) of 2mg/ml mixes by 5), and wherein the concentration of Hun He Hou perylene is 10
-6the concentration of M, TTAC is 0.4mg/ml, then adds ultrasonic 30 minutes of 100 μ L reagent A mixing.By the above-mentioned solution of absorption 10 μ L during test sample preparation, drip and carry out Raman detection (excitation wavelength is 532nm) on the microslide through clean process, as shown in Figure 3, can be observed the characteristic peak of bright aobvious perylene.
Embodiment 3
(1) 20ml10 is measured
-2the HAuCl of M
4solution, 59ml deionized water, 1ml graphene oxide solution, mixes ultrasonic 15min under room temperature, is transferred in there-necked flask;
(2) above-mentioned solution is heated to 100 DEG C while stirring, adds 20ml1% glucose solution fast, continue reaction 24h;
Step (3)-(5) are identical with embodiment (1), as shown in Figure 4, can be observed the characteristic peak of obvious pyrene.
Embodiment 4
(1) 10ml10 is measured respectively
-2the AgNO of M
3solution and HAuCl
4solution, 59ml deionized water, 1ml graphene oxide solution, mixes ultrasonic 15min under room temperature, is transferred in there-necked flask;
(2) above-mentioned solution is heated to 100 DEG C while stirring, adds 20ml1% citric acid three sodium solution fast, continue reaction 24h;
Step (3)-(4) are identical with embodiment (1);
(aqueous solution of perylene and concentration are that the reagent B (TTAC) of 2mg/ml mixes by 5), and wherein the concentration of Hun He Hou perylene is 10
-5the concentration of M, TTAC is 0.5mg/ml, then adds ultrasonic 30 minutes of 100 μ L reagent A mixing.By the above-mentioned solution of absorption 10 μ L during test sample preparation, drip and carry out Raman detection (excitation wavelength is 532nm) on the microslide through clean process, as shown in Figure 5, can be observed the characteristic peak of bright aobvious perylene.
Embodiment 5
Basic step is identical with embodiment 1, difference be target detection molecule be Bi with the potpourri of perylene, concentration is respectively 10
-4m and 10
-5m, as shown in Figure 6, the display of Raman spectrogram result can differentiate pyrene and perylene characteristic peak separately.
Embodiment 6
Basic step is identical with embodiment 1, and difference is that target detection molecule is the potpourri of pyrene, anthracene and fluorenes, and concentration is 10
-4m, as shown in Figure 7, the display of Raman spectrogram result can differentiate pyrene, anthracene and fluorenes characteristic peak separately.
Claims (8)
1. a water body polycyclic aromatic hydrocarbon detection reagent, is characterized in that, described detection reagent is made up of reagent A and reagent B, and described reagent A is graphene/nanometer noble metal composite aqueous solution; Described reagent B is surfactant solution, and described reagent B is cetyl trimethyl ammonium bromide or tetradecyl trimethyl ammonium chloride, and the concentration of reagent B is 0.5 ~ 10mg/ml.
2. water body polycyclic aromatic hydrocarbon detection reagent as claimed in claim 1, it is characterized in that, described reagent A concentration is 0.5-5mg/ml.
3. water body polycyclic aromatic hydrocarbon detection reagent as claimed in claim 2, it is characterized in that, the preparation of described reagent A comprises the following steps:
(1) graphene oxide solution, nano-noble metal salt solusion and deionized water are mixed obtain mixed liquor;
(2) mixed liquor is heated to 90 ~ 100 DEG C, adds reductive agent reaction;
(3) washing after reaction product cooling is separated and is dispersed in water, obtained reagent A.
4. water body polycyclic aromatic hydrocarbon detection reagent as claimed in claim 3, it is characterized in that, the mass ratio of described graphene oxide solution and nano-noble metal salt solusion is 1:1 ~ 1:100.
5. water body polycyclic aromatic hydrocarbon detection reagent as claimed in claim 3, it is characterized in that, described reductive agent is citrate three sodium solution or glucose solution, and the concentration of reductive agent is 0.1% ~ 5%.
6. an application for the water body polycyclic aromatic hydrocarbon detection reagent as described in as arbitrary in Claims 1 to 5, is characterized in that, comprise the following steps:
(1) reagent B is scattered in palycyclic aromatic solution;
(2) in above-mentioned mixed liquor, add reagent A, mix;
(3) get and carry out Raman detection through step (2) mixed solution in right amount, obtain the SERS collection of illustrative plates of palycyclic aromatic.
7. the application of water body polycyclic aromatic hydrocarbon detection reagent as claimed in claim 6, it is characterized in that, after reagent B being scattered in palycyclic aromatic solution in step (1), the concentration of reagent B is 0.05 ~ 1.0mg/ml; Add after reagent A mixes in step (2), the volume fraction of reagent A is 5% ~ 30%.
8. the application of water body polycyclic aromatic hydrocarbon detection reagent as claimed in claim 6, is characterized in that, described palycyclic aromatic solution is one or more mixed liquors of perylene solution, pyrene solution, anthracene solution or fluorenes solution.
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| selective molecular recognition of polycyclic aromatic hydrocarbons on calix arene-functionalized ag nanoparticles by surface-enchanced raman scattering;P.Leyton.etc;《J.Phys.Chem.B》;20041020;第108卷;17484-17490页 * |
| 表面增强拉曼光谱技术在多环芳烃检测中的应用;谢云飞等;《光谱学与光谱分析》;20110930;第31卷(第9期);2319-2323页 * |
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