CN109752360A - The detection method of 2,4,6- trinitrotoluene - Google Patents
The detection method of 2,4,6- trinitrotoluene Download PDFInfo
- Publication number
- CN109752360A CN109752360A CN201711059128.5A CN201711059128A CN109752360A CN 109752360 A CN109752360 A CN 109752360A CN 201711059128 A CN201711059128 A CN 201711059128A CN 109752360 A CN109752360 A CN 109752360A
- Authority
- CN
- China
- Prior art keywords
- substrate
- tnt
- trinitrotoluene
- silver
- molecules
- 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.)
- Pending
Links
- SPSSULHKWOKEEL-UHFFFAOYSA-N 2,4,6-trinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O SPSSULHKWOKEEL-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000001514 detection method Methods 0.000 title claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 53
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims abstract description 34
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 26
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000004332 silver Substances 0.000 claims abstract description 22
- 229910052709 silver Inorganic materials 0.000 claims abstract description 22
- 238000001069 Raman spectroscopy Methods 0.000 claims abstract description 20
- WCDSVWRUXWCYFN-UHFFFAOYSA-N 4-aminobenzenethiol Chemical compound NC1=CC=C(S)C=C1 WCDSVWRUXWCYFN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 235000013878 L-cysteine Nutrition 0.000 claims abstract description 17
- 239000004201 L-cysteine Substances 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 17
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 229940106691 bisphenol a Drugs 0.000 claims abstract 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 22
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 17
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 14
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 14
- 238000006722 reduction reaction Methods 0.000 claims description 12
- 239000003638 chemical reducing agent Substances 0.000 claims description 11
- 238000010041 electrostatic spinning Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 239000002105 nanoparticle Substances 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 230000002950 deficient Effects 0.000 claims description 4
- 239000011888 foil Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000010408 film Substances 0.000 claims 2
- XSXWYGABGYBZRM-UHFFFAOYSA-N carbonic acid;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound OC(O)=O.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 XSXWYGABGYBZRM-UHFFFAOYSA-N 0.000 claims 1
- 239000010409 thin film Substances 0.000 claims 1
- 239000000015 trinitrotoluene Substances 0.000 abstract description 46
- 239000002131 composite material Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000010276 construction Methods 0.000 abstract 1
- 150000002148 esters Chemical class 0.000 abstract 1
- 229920000515 polycarbonate Polymers 0.000 description 12
- 239000004417 polycarbonate Substances 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000002121 nanofiber Substances 0.000 description 8
- 239000010944 silver (metal) Substances 0.000 description 8
- 238000009987 spinning Methods 0.000 description 8
- 239000000835 fiber Substances 0.000 description 7
- 239000003550 marker Substances 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000012279 sodium borohydride Substances 0.000 description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 description 6
- 230000009467 reduction Effects 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- PWKSKIMOESPYIA-UHFFFAOYSA-N 2-acetamido-3-sulfanylpropanoic acid Chemical compound CC(=O)NC(CS)C(O)=O PWKSKIMOESPYIA-UHFFFAOYSA-N 0.000 description 1
- 238000003841 Raman measurement Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000010946 fine silver Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- ONVGIJBNBDUBCM-UHFFFAOYSA-N silver;silver Chemical compound [Ag].[Ag+] ONVGIJBNBDUBCM-UHFFFAOYSA-N 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Landscapes
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses one kind 2,4, the detection method of 6- trinitrotoluene, poly- (bisphenol-A) carbonic ester film of doping Nano silver grain is set as surface enhanced Raman scattering substrate in substrate surface first, L-cysteine molecule is grafted on into substrate surface again, and TNT molecule can with the formation Mason sea of L-cysteine specificity write from memory compound, to realize identification and enrichment of the substrate to TNT；Finally, it will be grafted in above-mentioned composite substrate with the positive charge Nano silver grain for haling very much graceful active mark molecule 4- mercaptoaniline by TNT, it forms Ag-TNT-Ag composite construction and then generates more nanoscale gaps, it is in this characteristic of fixed proportion using TNT molecular amounts and the positive charge silver particles quantity with mark molecule of absorption, the Raman signal intensity by measuring mark molecule calculates TNT concentration in sample to be tested.For the present invention in the quantitative detection to TNT, accuracy is high, low in cost, has good specific recognition capability and surface-enhanced Raman effects.
Description
Technical Field
The invention belongs to the technical field of organic matter detection, and relates to a detection method of 2,4, 6-trinitrotoluene.
Background
As the explosive which is most widely used at present, 2,4, 6-trinitrotoluene (TNT) can generate a large amount of industrial wastewater containing TNT in the production and use processes, and has the characteristics of difficult degradation, high toxicity, complex components and the like. The TNT content in the wastewater is sensitively and accurately determined, the effective treatment of the TNT content is guaranteed, and many conventional methods such as chromatography, mass spectrometry and the like are used for determining the concentration of the TNT content to be lower than 10 at present-4There are major limitations to TNT wastewater detection below M.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a method for detecting 2,4, 6-trinitrotoluene.
The invention is realized by the following technical scheme:
a detection method of 2,4, 6-trinitrotoluene comprises the steps of firstly, arranging a silver nanoparticle-doped poly (bisphenol A) carbonate film on the surface of a substrate as a Surface Enhanced Raman Scattering (SERS) substrate, and grafting L-cysteine molecules by taking countless nano silver particles loaded on the film as reaction sites; then utilizing a Meisenheimer complex formed by the L-cysteine molecules and the TNT molecules to capture the TNT; and finally, adsorbing the positive charge silver nanoparticles with the labeled molecules of 4-mercaptoaniline onto electron-deficient aromatic rings of the TNT molecules through electrostatic adsorption, and calculating the concentration of the TNT in the sample to be detected by measuring the Raman signal intensity of the labeled molecules by utilizing the characteristic that the quantity of the TNT molecules and the quantity of the adsorbed positive charge silver particles with the labeled molecules are in a fixed ratio.
Further, the substrate is a glass substrate, a silicon substrate or an aluminum foil substrate.
Further, in the surface-enhanced Raman substrate, the mass ratio of the silver nanoparticles to the poly (bisphenol A) carbonate is 1: 1000-1: 39.4.
Further, the detection range of the TNT to be detected is 1 multiplied by 10-8M～ 1×10-12M, the detection limit under the triple signal-to-noise ratio is 2.05 multiplied by 10-13M。
Further, grafting of L-cysteine on the SERS substrate is realized by soaking the substrate in 1 mM L-cysteine aqueous solution for 10-12 h.
Furthermore, the capture of the 2,4, 6-trinitrotoluene (TNT) to be detected is realized by soaking the substrate grafted with the L-cysteine in a TNT sample to be detected for 20-24 h.
Further, the positive charge silver nano particles with the marker molecules of 4-mercaptoaniline are adsorbed to the electron-deficient aromatic ring of the TNT molecules through electrostatic adsorption, and the substrate for capturing the TNT molecules is soaked in the positive charge silver nano particle solution with the marker molecules of 4-mercaptoaniline for more than 12 hours.
Furthermore, the positive charge silver nano particle with the labeled molecule 4-mercaptoaniline is prepared by mixing and stirring a positive charge silver nano particle solution and a 4-mercaptoaniline solution for more than 10 hours in a dark place, and ensuring that the concentration of the mixed 4-mercaptoaniline is 1.0 multiplied by 10-4M, the obtained precipitate is obtained after centrifugal washing and redispersion, wherein, the concentration of the positive charge silver nano particle solution is 2.0 multiplied by 10-3And carrying out reduction reaction on the silver nitrate of the M and an excessive reducing agent to obtain the silver nitrate.
Further, the silver nanoparticle doped poly (bisphenol a) carbonate film SERS substrate is realized by the following steps:
(1) dissolving poly (bisphenol A) carbonate into an organic solvent according to a certain content, adding a certain content of silver nitrate, and performing electrostatic spinning on a substrate under the conditions of positive high pressure of 13.0-15.0 kv and negative high pressure of-1.5 kv;
(2) reducing the substrate subjected to electrostatic spinning in the step (1) by adopting a reducing agent to obtain the substrate,
wherein,
in the step (1), the content of poly (bisphenol A) carbonate in an organic solvent is 14 wt%, the content of silver nitrate in the organic solvent is 0.5 wt% -5 wt%, and the spinning temperature is 30-40 ℃; the electrostatic spinning time is 5min-10 min; the organic solvent adopts tetrahydrofuran and dimethylformamide according to the volume ratio of 6:4 in a mixed solvent; in the step (2), sodium borohydride is adopted as a reducing agent, the concentration of the reducing agent is 1 mM-100 mM, and the reduction time is 5s-10 min.
Compared with the prior art, the invention has the beneficial effects that:
(1) the polycarbonate/silver-silver composite surface enhanced Raman substrate has the advantages of low cost, high sensitivity and high accuracy. Meanwhile, the poly (bisphenol A) carbonate is used as a supporting material, the stable chemical structure and the excellent optical performance of the poly (bisphenol A) carbonate can ensure that the supported silver particles can realize maximum SERS enhancement, and meanwhile, the substrate material does not have any influence on the determination.
(2) The grain size of the silver nanoparticles can be adjusted through the reduction time, and the criss-cross spatial structure of the spinning fiber further increases the number of 'hot spots', so that the reinforcing effect is improved. And the substrate has a higher specific surface area, can provide more adsorption sites for molecules to be detected, cannot cause any interference on the determination, and has good repeatability and a controllable process.
(3) The introduction of the positive charge silver nanoparticles with the marker molecules can form an Ag-TNT-Ag composite structure with the TNT to be detected positioned in the middle with the original silver particles to strengthen SERS signals, and the quantity of the marker molecules and the quantity of the TNT form a fixed linear relation, so that the fixed linear relation is used as a basis for quantitatively detecting the TNT.
Drawings
FIG. 1 is a schematic diagram of the preparation of a polycarbonate/Ag-Ag composite surface enhanced Raman substrate.
FIG. 2 is a scanning electron micrograph (a. before reduction; b. after reduction) of the polycarbonate/Ag surface enhanced Raman substrate prepared in example 1 before and after in-situ chemical reduction.
FIG. 3 is a scanning electron microscope image of a composite substrate under different TNT concentration conditions. (a. no TNT; b.10)-11M TNT;c.10-9M TNT; d.10-7M TNT）。
FIG. 4 shows the concentration of TNT and the labeled molecule 4-mercaptoaniline at 1436 cm-1Standard curve of the intensity relationship of the raman peak.
Detailed Description
The present invention is further described with reference to the following specific examples and accompanying drawings, but should not be construed as limiting the scope of the invention. Any insubstantial modifications or adaptations of the invention from the foregoing disclosure by those skilled in the art are intended to be covered by the present invention.
According to the invention, a layer of silver nanoparticles with uniform particle size and dense arrangement is prepared on the surface of a substrate through electrostatic spinning of a silver nitrate-containing poly (bisphenol A) carbonate nanofiber membrane on the surface of the substrate and chemical reduction; then capturing 2,4, 6-trinitrotoluene (TNT) of an object to be detected by utilizing L-cysteine, and finally adsorbing the positive charge silver particles with the marker molecules 4-mercaptoaniline on the TNT by means of electrostatic interaction to form a polycarbonate/Ag-TNT-Ag composite structure. Because the quantity of the TNT molecules and the quantity of the adsorbed silver particles with the positive charges and the marker molecules are in a fixed ratio, the TNT concentration in the sample to be detected can be calculated by measuring the Raman signal intensity of the marker molecules. The substrate has good surface enhanced Raman effect and specific recognition capability on TNT, and can effectively measure the content of the TNT as low as 10-13Trace TNT molecules of the order of M.
Referring to fig. 1, silver nitrate-doped poly (bisphenol a) carbonate solution is subjected to an electrospinning technique to prepare nanofibers (step a), and a large amount of uniform and fine silver nanoparticles are generated on the surface of the nanofibers after reduction with sodium borohydride (step b). Due to the intricate three-dimensional structure of the spun fiber, sufficient nanogaps (i.e., raman "hot spots") are formed between the silver nanoparticles. Then taking the silver particles as reaction sites, grafting L-cysteine on the silver particles through soaking treatment, and then soaking the substrate in a TNT solution to be detected to enable the L-cysteine to react with the TNT so as to realize the specific adsorption of the substrate on TNT molecules (step d); and finally, adsorbing the positively charged silver particles with the markers on TNT molecules through electrostatic action, and finally forming an Ag-TNT-Ag composite structure on the spinning fibers (step c) for SERS measurement.
Example 1
The embodiment discloses a method for preparing a polycarbonate/silver composite surface enhanced Raman substrate by combining an electrostatic spinning technology and an in-situ chemical reduction technology, which specifically comprises the following steps:
(1) dissolving 14 wt% and 4.5 wt% of poly (bisphenol A) carbonate particles and silver nitrate in a mixed solvent of tetrahydrofuran and dimethylformamide (volume ratio is 6: 4) respectively according to mass fractions to prepare a polymer solution;
(2) fixing an aluminum foil on a receiving device of an electrostatic spinning machine, loading a polymer solution into an injector, placing the injector on a push injection table, adjusting the positive high pressure to be 15.0kv, the negative high pressure to be-1.5 kv, the push injection speed to be 0.5 ml/L, the experimental temperature to be 30 ℃, the humidity to be 20 percent and the spinning time to be 5min, and obtaining the polycarbonate nanofiber containing silver nitrate;
(3) placing the nano fiber obtained in the step (2) in 10 mM NaBH4And reacting in the solution for 25 s to obtain the polycarbonate/silver composite surface enhanced Raman substrate.
The scanning electron micrograph of the polycarbonate nanofiber containing silver nitrate prepared as described above is shown in fig. 2, and it can be seen that the surface of the spun fiber was relatively smooth before the fiber film was chemically reduced (fig. 2 a). After in-situ chemical reduction, silver nanoparticles with uniform particle size, density and regularity appear on the surface of the spinning membrane (fig. 2 b).
Example 2
The embodiment discloses a method for preparing a polycarbonate/Ag-Ag composite surface enhanced Raman substrate by combining electrostatic spinning, in-situ chemical reduction and chemical modification technologies (as shown in figure 1), which specifically comprises the following steps:
(1) dissolving 14 wt% and 2.3 wt% of poly (bisphenol A) carbonate particles and silver nitrate in a mixed solvent of tetrahydrofuran and dimethylformamide according to mass fraction (volume ratio is 6: 4) respectively to prepare a polymer solution;
(2) fixing an aluminum foil on a receiving device of an electrostatic spinning machine, loading a polymer solution into an injector, placing the injector on a push injection table, adjusting the positive high pressure to be 14.0kv, the negative high pressure to be-1.5 kv, the push injection speed to be 0.6 ml/L, the experimental temperature to be 40 ℃, the humidity to be 25 percent and the spinning time to be 10 min, and obtaining the polycarbonate nanofiber containing silver nitrate;
(3) and (3) placing the nano-fiber obtained in the step (2) in a 20 mM sodium borohydride solution for reaction for 10s to obtain the polycarbonate/Ag composite surface enhanced Raman substrate.
(4) 0.034 g of silver nitrate was added to 100 ml of 0.4M aqueous ammonia, and 0.018 g of cetyltrimethylammonium bromide was further added, and this solution was added dropwise to 100 ml of a mixed solution containing 0.03 g of sodium borohydride and 0.018 g of cetyltrimethylammonium bromide, and stirred for 4 hours in an ice-water bath. After the reaction is finished, heating the solution to remove residual ammonia water and decompose excessive sodium borohydride; then adding the labeled molecule 4-mercaptoaniline to make the concentration reach 1.0X 10-4M, stirring for 10 hours in a dark place, centrifuging for 10 minutes at 12000 rpm to remove redundant 4-mercaptoaniline molecules, and washing with high-purity water for three times.
(5) Immersing the polycarbonate/Ag composite substrate obtained in the step (3) in L-cysteine with the concentration of 1 mM for 10 hours to form an L-cysteine monomolecular layer on the surface of the substrate; after cleaning and drying, immersing the solution in TNT standard solution with known concentration for 24 hours, wherein TNT molecules in the solution can be specifically combined with L-cysteine to form a Messenleimer compound; and (3) finally, immersing the substrate in the 4-mercaptoaniline-marked positive charge silver particle solution obtained in the step (4) for 12 hours, cleaning and drying, and then carrying out Raman measurement, wherein the scanning electron microscope result is shown in figure 3, so that the positive charge silver nanoparticles adsorbed on the spinning fibers are gradually increased along with the increase of the concentration of TNT, aggregation occurs on the surfaces and joints of the spinning fibers, the appearance is rougher, and more nano-scale gaps (Raman' hot spots) are formed at the same time.
(6) Using the strongest 1436 cm in the Raman spectrum of the TNT standard samples with different concentrations obtained in the step (5)-1The intensity value of the Raman peak is vertical coordinate, the TNT concentration is horizontal coordinate, a standard curve is made, and a linear equation and a correlation coefficient are obtained (as shown in figure 4, the error bar is measured for 5 times).
(7) And (5) repeating the step, wherein the TNT solution with the known concentration is replaced by the TNT sample to be tested with the unknown concentration, and the SERS spectrogram shows 1436 cm-1Has a raman peak intensity of 7621.5. Substituting the standard equation into y =1871.3x +24445 to obtain the TNT water sample concentration to be measured as 1.023 x 10-9M。
Claims (10)
- The detection method of the 1.2,4, 6-trinitrotoluene is characterized in that firstly, a poly (bisphenol A) carbonate film doped with silver nanoparticles is arranged on the surface of a substrate and is used as a surface enhanced Raman scattering substrate, and L-cysteine molecules are grafted by taking nano silver particles loaded on the film as reaction sites; then capturing the 2,4, 6-trinitrotoluene by utilizing a Messemer compound formed by the L-cysteine molecule and the 2,4, 6-trinitrotoluene molecule to be detected; and finally, adsorbing the positive charge silver nano particles with the labeled molecules of 4-mercaptoaniline onto electron-deficient aromatic rings of the 2,4, 6-trinitrotoluene molecules through electrostatic adsorption, and calculating the concentration of the 2,4, 6-trinitrotoluene in the sample to be detected by measuring the Raman signal intensity of the labeled molecules by utilizing the characteristic that the number of the 2,4, 6-trinitrotoluene molecules and the number of the adsorbed positive charge silver particles with the labeled molecules are in a fixed ratio.
- 2. The method of claim 1, wherein the detection is quantitative for trace amounts of 2,4, 6-trinitrotoluene in water.
- 3. The detection method according to claim 1, wherein the substrate is a glass substrate, a silicon substrate, or an aluminum foil substrate.
- 4. The detection method according to claim 1, wherein the mass ratio of the silver nanoparticles to the poly (bisphenol-A) carbonate in the surface-enhanced Raman substrate is 1:1000 to 1: 39.4.
- 5. The detection method according to claim 1, wherein the detection range of 2,4, 6-trinitrotoluene to be detected is 1 x 10-8M～ 1×10-12M, the detection limit under the triple signal-to-noise ratio is 2.05 multiplied by 10-13M。
- 6. The detection method of claim 1, wherein grafting of the L-cysteine onto the surface-enhanced Raman scattering substrate is performed by soaking the substrate in a 1 mM L-cysteine aqueous solution for 10-12 h.
- 7. The detection method as claimed in claim 1, wherein the capture of the 2,4, 6-trinitrotoluene to be detected is realized by soaking the substrate grafted with L-cysteine in a 2,4, 6-trinitrotoluene sample to be detected for 20-24 h.
- 8. The detection method according to claim 1, wherein the adsorption of the positively charged silver nanoparticles bearing the labeled molecule 4-mercaptoaniline onto the electron-deficient aromatic rings of the 2,4, 6-trinitrotoluene molecules by electrostatic adsorption is achieved by immersing the substrate for capturing the 2,4, 6-trinitrotoluene molecules in a solution of the positively charged silver nanoparticles bearing the labeled molecule 4-mercaptoaniline for more than 12 hours.
- 9. The detection method of claim 7, wherein the positively charged silver nanoparticles with labeled molecule 4-mercaptoaniline are prepared by mixing and stirring a solution of positively charged silver nanoparticles and a solution of 4-mercaptoaniline in the dark for more than 10h while ensuring that the concentration of 4-mercaptoaniline after mixing is 1.0 x 10-4M, the obtained precipitate is obtained after centrifugal washing and redispersion, wherein, the concentration of the positive charge silver nano particle solution is 2.0 multiplied by 10-3And carrying out reduction reaction on the silver nitrate of the M and an excessive reducing agent to obtain the silver nitrate.
- 10. The detection method of claim 1, wherein the silver nanoparticle doped poly (bisphenol a) carbonate thin film SERS substrate is achieved by:(1) dissolving poly (bisphenol A) carbonate into an organic solvent according to a certain content, adding a certain content of silver nitrate, and performing electrostatic spinning on a substrate under the conditions of positive high pressure of 13.0-15.0 kv and negative high pressure of-1.5 kv;(2) and (2) reducing the substrate subjected to electrostatic spinning in the step (1) by using a reducing agent to obtain the substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711059128.5A CN109752360A (en) | 2017-11-01 | 2017-11-01 | The detection method of 2,4,6- trinitrotoluene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711059128.5A CN109752360A (en) | 2017-11-01 | 2017-11-01 | The detection method of 2,4,6- trinitrotoluene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109752360A true CN109752360A (en) | 2019-05-14 |
Family
ID=66397774
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711059128.5A Pending CN109752360A (en) | 2017-11-01 | 2017-11-01 | The detection method of 2,4,6- trinitrotoluene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109752360A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113125393A (en) * | 2019-12-31 | 2021-07-16 | Tcl集团股份有限公司 | Method for detecting 2,4, 6-trinitrotoluene |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102677212A (en) * | 2012-06-01 | 2012-09-19 | 苏州大学 | Surface-enhanced Raman scattering active substrate and preparation method thereof |
| CN102965101A (en) * | 2012-11-28 | 2013-03-13 | 苏州大学 | Material with surface-enhancement Raman scattering performance and catalytic activity, preparation method and application thereof |
| CN103344622A (en) * | 2013-05-09 | 2013-10-09 | 中国科学院合肥物质科学研究院 | Paper sensor used for detecting explosive residues in background environment and preparation method thereof |
| CN105548134A (en) * | 2015-12-04 | 2016-05-04 | 山东大学 | Wiping extraction-surface-enhanced Raman scattering film for on-site fast detection of explosive and its preparation method and use |
-
2017
- 2017-11-01 CN CN201711059128.5A patent/CN109752360A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102677212A (en) * | 2012-06-01 | 2012-09-19 | 苏州大学 | Surface-enhanced Raman scattering active substrate and preparation method thereof |
| CN102965101A (en) * | 2012-11-28 | 2013-03-13 | 苏州大学 | Material with surface-enhancement Raman scattering performance and catalytic activity, preparation method and application thereof |
| CN103344622A (en) * | 2013-05-09 | 2013-10-09 | 中国科学院合肥物质科学研究院 | Paper sensor used for detecting explosive residues in background environment and preparation method thereof |
| CN105548134A (en) * | 2015-12-04 | 2016-05-04 | 山东大学 | Wiping extraction-surface-enhanced Raman scattering film for on-site fast detection of explosive and its preparation method and use |
Non-Patent Citations (2)
| Title |
|---|
| GUO ZHINAN: "Ultrasensitive trace analysis for 2,4,6-trinitrotoluene using nano-dumbbell surface-enhanced Raman scattering hot spots", 《ANALYST》 * |
| MURUGESAN BALAMURUGAN, ET AL: "Three-Dimensional Surface-Enhance Raman Scattering Substrate Fabricated by Chemical Decoration of Silver Nanoparticles on Electrospun Polycarbonate Nanofibers", 《APPLIED SPECTROSCOPY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113125393A (en) * | 2019-12-31 | 2021-07-16 | Tcl集团股份有限公司 | Method for detecting 2,4, 6-trinitrotoluene |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | A molecularly imprinted polymer based on functionalized multiwalled carbon nanotubes for the electrochemical detection of parathion-methyl | |
| Liu et al. | Electrochemical DNA biosensor based on microspheres of cuprous oxide and nano-chitosan for Hg (II) detection | |
| CN102706858B (en) | Selective detection method for TNT (trinitrotoluene) by enhanced Raman spectrometry of functionalized shell isolated nanoparticles | |
| Wang et al. | A reusable nanofibrous film chemosensor for highly selective and sensitive optical signaling of Cu 2+ in aqueous media | |
| Ardalani et al. | A new generation of highly sensitive potentiometric sensors based on ion imprinted polymeric nanoparticles/multiwall carbon nanotubes/polyaniline/graphite electrode for sub-nanomolar detection of lead (II) ions | |
| Szultka et al. | Development of novel molecularly imprinted solid-phase microextraction fibers and their application for the determination of antibiotic drugs in biological samples by SPME-LC/MS n | |
| Liang et al. | Composites of polyaniline nanofibers and molecularly imprinted polymers for recognition of nitroaromatic compounds | |
| Wang et al. | A selective voltammetric method for detecting dopamine at quercetin modified electrode incorporating graphene | |
| Asad et al. | Orange peel derived C‐dots decorated CuO nanorods for the selective monitoring of dopamine from deboned chicken | |
| Xu et al. | Construction of a novel electrochemical sensor based on molecularly imprinted polymers for the selective determination of chlorpyrifos in real samples | |
| Wang et al. | Boronic acid based imprinted electrochemical sensor for rutin recognition and detection | |
| He et al. | Nickel/nitrogen-doped carbon nanocomposites: Synthesis and electrochemical sensor for determination of p-nitrophenol in local environment | |
| CN110907425B (en) | Surface molecular imprinting SERS sensor based on core-shell structure poly-dopamine coated nano-gold particles and preparation and application thereof | |
| CN113125522B (en) | Polydopamine-modification-based tin dioxide nano composite gas-sensitive material and preparation method and application thereof | |
| Gao et al. | Determination of Perfluorooctanesulfonic acid in water by polydopamine molecularly imprinted/Gold nanoparticles sensor | |
| Zhang et al. | Synthesis of Ag nanoparticle doped MnO2/GO nanocomposites at a gas/liquid interface and its application in H2O2 detection | |
| CN106365159A (en) | Silver nanoparticle-carbon nanotube embedded graphene oxide composite film, and preparation method and application thereof | |
| Najarzadekan et al. | Transparent polycaprolactam electrospun nanofibers doped with 1, 10-phenanthroline optical sensor for colorimetric determination of iron (II) and vitamin C | |
| CN111793855A (en) | Precious metal nanoparticle composite SERS fiber and preparation method and application thereof | |
| CN109752360A (en) | The detection method of 2,4,6- trinitrotoluene | |
| Salama et al. | Disposable gold nanoparticle functionalized and bare screen-printed electrodes for potentiometric determination of trazodone hydrochloride in pure form and pharmaceutical preparations | |
| Yang et al. | High sensitivity and reproducibility of a bismuth/poly (bromocresol purple) film modified glassy carbon electrode for determination of trace amount of cadmium by differential pulse anodic stripping voltammetry | |
| Zhang et al. | Preparation of molecularly imprinted electrochemical sensor for detection of vincristine based on reduced graphene oxide/gold nanoparticle composite film | |
| Liu et al. | Highly efficient detection of Cd (Ⅱ) ions in water by graphitic carbon nitride and tin dioxide nanoparticles modified glassy carbon electrode | |
| Yang et al. | An ion imprinted electrochemical sensor based on flower‐like gold nanoparticles for the detection of trace arsenic (III) ions in water and food samples |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190514 |