CN103091300A - TNT (Trinitrotoluene) detection method based on surface-enhanced resonance Raman scattering - Google Patents
TNT (Trinitrotoluene) detection method based on surface-enhanced resonance Raman scattering Download PDFInfo
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- CN103091300A CN103091300A CN2013100329673A CN201310032967A CN103091300A CN 103091300 A CN103091300 A CN 103091300A CN 2013100329673 A CN2013100329673 A CN 2013100329673A CN 201310032967 A CN201310032967 A CN 201310032967A CN 103091300 A CN103091300 A CN 103091300A
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- 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
Abstract
The invention provides a TNT (Trinitrotoluene) detection method based on surface-enhanced resonance Raman scattering (SERRS), belonging to the field of detection of analytical chemistry. The TNT detection method comprises the following steps of: 1, synthesizing a silver nano particle to be used as an SERRS substrate; 2, carrying out sulfonation and sensibilization on TNT; and 3, carrying out SERRS selectivity detection on the TNT. The TNT detection method based on the SERRS has the characteristics of simple preparation, strong universality and functionalization, and is capable of realizing selectivity detection on trace TNT.
Description
Technical field
The present invention relates to a kind of analytical chemistry detection method, what be specifically related to is that a kind of surface enhanced resonance raman spectra is to the selectivity detection method of TNT.
Background technology
1974, the researchists such as Fleischman find, the Raman scattering luminous energy that is adsorbed on the Pyridine Molecules of coarse silver electrode surface is strengthened significantly, namely be adsorbed on the molecule of roughened metal surface, its Raman scattering light intensity can be far longer than the generally Raman scattering light intensity of this molecule, Surface enhanced raman spectroscopy that Here it is (SERS) phenomenon.In addition, the researchist also finds, when the absorption spectra peak that excites light wavelength and the molecule that is excited overlaps, the intensity of its raman scattering spectrum will be further enhanced, and this phenomenon is called as serrs (SERRS).Mechanism for SERRS, people generally believe it is the result of surface plasma body resonant vibration, namely when illumination is mapped to nanoparticle surface, the dipole concussion of electric charge can occur, plasma be excited and with the field coupled of light wave, and then the huge local electromagnetic field of resonance generation occurs, thereby its Raman scattering signal is strengthened greatly.Usually, the average raman scattering cross section of molecule amasss and is about 10
-30cm
2, than the average emission cross section of general fluorescence molecule (approximately 10
-16cm
2) low 14 orders of magnitude, can not realize monomolecular detection.But, along with SERS and SERRS phenomenon be it is found that in succession, just greatly improved the raman scattering cross section (approximately 10 of molecule
14Doubly), make monomolecular Surface enhanced raman spectroscopy detect and become possibility.
Traditional TNT analyzing detecting method comprises: vapor-phase chromatography, high performance liquid chromatography, mass spectrophotometry, x-ray imaging and metal detector etc.Although in these methods, some has certain high sensitivity,, their are serious relies on heavy, expensive analytical instrument, sometimes also needs well-trained technician to carry out complicated sample pretreatment, can not realize to TNT simply, detect fast.Nowadays, people have higher requirement to the selectivity detection of low concentration TNT.Due to TNT visibility region do not have chromophore and can not effectively be adsorbed on gold or silver etc. precious metal surface, in reality detects, just need to carry out chemical modification to TNT, such as TNT is carried out sulfonation, TNT after modification can obtain and the metal surface between stronger interaction, more be conducive to the detection of target molecule.In addition, in order to improve the sensitivity that quality testing to be measured is surveyed, can use specific enhanced sensitivity reagent to carry out enhanced sensitivity to determinand, its enhanced sensitivity principle is mainly by forming a kind of high order complex, increase the net sectional area of colour developing molecule, thereby improved the sensitivity that determinand is identified.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, and a kind of simple, sensitive TNT analyzing detecting method based on surface enhanced resonance raman spectra is provided.
In order to solve the problems of the technologies described above, the present invention is achieved by the following technical programs.
A kind of TNT detection method based on surface enhanced resonance raman spectra, the method comprises the following steps:
(1) synthetic silver nano-grain: the liquor argenti nitratis ophthalmicus heating that is 100ml amount of substance concentration 1mM is back to boiling, then adding volume to it is that the 4ml massfraction is that the sodium citrate solution of 1 ﹪ boiled 1 hour altogether, obtain silver nano-grain, it is stand-by as the SERRS substrate;
(2) TNT is carried out sulfonation and enhanced sensitivity: the TNT aqueous solution that is 0.1mM to 1ml amount concentration is that 0.1M sulfonated reagent sodium sulfite solution mixes with 1ml amount concentration, to guarantee TNT by sulfonation fully, the chloro-hexadecane yl pyridines solution that is the TNT solution after sulfonation and 1ml amount concentration then 0.1M mixes and standing 10 minutes at least;
(3) TNT being carried out selectivity detects: get the mixed solution 10 μ ls of step (2) after standing, drip on the silicon chip of silver nano-grain as substrate that step (1) obtains uniformly, drying is placed under Raman spectrometer and detects, and can obtain the SERRS characteristic fingerprint signal of TNT.
The synthetic silver nano-grain diameter of described step (1) is 70～80nm.
The principles of science of the present invention is analyzed:
One, with silver nano-grain as the SERRS substrate, form fine and close orderly silver nano-grain top layer, have very strong enhancing effect and a SERRS active.
When two, the absorption spectra peak of the excitation wavelength of Raman spectrometer and the molecule that is excited overlaps, the dipole concussion of electric charge can occur, plasma be excited and with the field coupled of light wave, and then the huge local electromagnetic field of resonance generation occurs, thereby the Raman scattering signal of the molecule that is excited is strengthened greatly.Ultraviolet absorption spectrum peak (530nm) through the TNT of oversulfonate and enhanced sensitivity just overlaps with the excitation wavelength (532.06nm) of Raman spectrometer, effect due to surface plasma resonance, being formed very strong local electromagnetic field by the position of laser excitation, make detection signal greatly strengthen.
Three, TNT is carried out sulfonation and can improve its water wettability, itself and SERRS substrate are effectively adsorbed.TNT is carried out enhanced sensitivity can form a kind of high order complex, and then increased the net sectional area of colour developing molecule, improved the sensitivity that determinand is identified.
With respect to prior art, technique effect of the present invention is as follows:
(1) the TNT detection method of surface enhanced resonance raman spectra has solved the problem that conventional TNT detection method exists on simple, efficient, universality is strong.On this basis, we utilize the chloro-hexadecane yl pyridines to carry out enhanced sensitivity to TNT.This method is very simple, needs the experiment parameter of control seldom, only needs the ratio of the amount of substance of control reaction time and reactant.Only just can obtain best determinand mixed system by the concentration of controlling enhanced sensitivity reagent, thereby realize the selectivity of trace TNT is detected.
(2) in addition, this detection method material requested is simple, and the operating cycle is short, and cost is lower, and has very low detectability.
Description of drawings
Fig. 1 is a kind of technical scheme schematic diagram of the TNT detection method based on surface enhanced resonance raman spectra.
Fig. 2 is the SEM figure as the Morphologies of Silver Nanoparticles of SERRS substrate.
Fig. 3 is the ultraviolet spectrogram of products therefrom when TNT is carried out sulfonation and enhanced sensitivity.
Fig. 4 is to the testing result of aqueous solution under Raman spectrometer of TNT take silver nano-grain as substrate.
Embodiment
Below in conjunction with drawings and Examples in detail the present invention is described in detail, but the present invention is not limited to following embodiment.
As shown in Figure 1, a kind of technical scheme of the TNT detection method based on surface enhanced resonance raman spectra comprises the following steps: A: synthetic silver nano-grain is as the SERRS substrate; B: use sodium sulphite, chloro-hexadecane yl pyridines to carry out sulfonation and enhanced sensitivity to TNT; C: get the silicon chip surface at the bottom of a little B system solution drops in money base, drying is placed under Raman spectrometer and detects, and can obtain the SERRS characteristic fingerprint signal of TNT.
Embodiment
(1) preparation of silver nano-grain:
The present invention makes silver nano-grain by wet heating with sodium citrate reduction silver nitrate, and the size of its silver nano-grain can regulate and control by amount and the reaction time that adds reductive agent.At first we be volume that 100ml amount of substance concentration is that the liquor argenti nitratis ophthalmicus heating of 1mM is back to boiling, and then adding volume to it is that the 4ml massfraction is that the sodium citrate solution of 1 ﹪ boiled 1 hour altogether.As shown in Figure 2, the silver nano-grain of the resulting diameter of reaction about 70～80nm is stand-by as the SERRS substrate.
(2) TNT is carried out sulfonation and enhanced sensitivity:
The TNT aqueous solution that is 0.1mM to amount of substance concentration is mixed with sulfonated reagent sodium sulfite solution equal-volume (1ml), and the amount concentration of sulfonated reagent is 0.1M, to guarantee that TNT is by sulfonation fully.Then, the TNT solution after sulfonation is fully mixed with the chloro-hexadecane yl pyridines solution of 1ml 0.1M.Standing 10 minutes of whole solution system characterizes with ultraviolet-visible pectrophotometer.As shown in Figure 3, TNT and sodium sulphite generation addition reaction through chloro-hexadecane yl pyridines sensitization, generate red complex, at 466nm and 530nm place, ultraviolet absorption peak are arranged.
(3) TNT is carried out the selectivity detection of surface-enhanced resonance raman:
Get the mixed solution 10 μ ls of step (2) after standing, drip uniformly on the silicon chip of silver nano-grain as substrate that step (1) obtains, adopt the burnt Raman spectrometer of LabRAM HR800 copolymerization, the TNT aqueous solution is detected.The excitation wavelength of using is 532.06 nm, and excitation source is the He-Ne laser instrument.The surface-enhanced resonance raman spectrogram that gathers as shown in Figure 4,1365 cm wherein
-1The characteristic peak of position is the surface-enhanced resonance raman fingerprint peaks of TNT, and result shows that its SERRS signal is stronger.
The present invention is based on the weak point of conventional TNT detection method, on the conceptual foundation of existing surface enhanced resonance raman spectra (SERRS), use sodium sulphite to carry out sulfonation to TNT, utilize the chloro-hexadecane yl pyridines to carry out enhanced sensitivity to TNT, realized the selectivity of explosive TNT is detected.It is worth mentioning that, this novel detection method has reached the re-set target of trace detection TNT.
Claims (2)
1. the TNT detection method based on surface enhanced resonance raman spectra, is characterized in that, the method comprises the following steps:
(1) synthetic silver nano-grain: the liquor argenti nitratis ophthalmicus heating that is 100ml amount of substance concentration 1mM is back to boiling, then adding volume to it is that the 4ml massfraction is that the sodium citrate solution of 1 ﹪ boiled 1 hour altogether, obtain silver nano-grain, it is stand-by as the SERRS substrate;
(2) TNT is carried out sulfonation and enhanced sensitivity: the TNT aqueous solution that is 0.1mM to 1ml amount concentration is that 0.1M sulfonated reagent sodium sulfite solution mixes with 1ml amount concentration, to guarantee TNT by sulfonation fully, the chloro-hexadecane yl pyridines solution that is the TNT solution after sulfonation and 1ml amount concentration then 0.1M mixes and standing 10 minutes at least;
(3) TNT being carried out selectivity detects: get the mixed solution 10 μ ls of step (2) after standing, drip on the silicon chip of silver nano-grain as substrate that step (1) obtains uniformly, drying is placed under Raman spectrometer and detects, and can obtain the SERRS characteristic fingerprint signal of TNT.
2. a kind of TNT detection method based on surface enhanced resonance raman spectra as claimed in claim 1, is characterized in that, the synthetic silver nano-grain diameter of described step (1) is 70～80nm.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103411945A (en) * | 2013-06-24 | 2013-11-27 | 吉林大学 | Method for performing surface-enhanced Raman detection on phenolic and polycylic aromatic hydrocarbon compounds by generating azo molecule |
| CN105424678A (en) * | 2015-12-04 | 2016-03-23 | 山东大学 | Noble metal sol spray for in-situ detection of explosives through surface enhancing raman spectrum as well as preparation method and application thereof |
| CN105445251A (en) * | 2014-08-14 | 2016-03-30 | 杭州坚峰科技有限公司 | Spectral probe and preparation method and use thereof |
| CN105445252A (en) * | 2015-11-06 | 2016-03-30 | 合肥学院 | Dopamine detection method based on surface enhanced resonance Raman spectrum |
| CN109164085A (en) * | 2018-08-27 | 2019-01-08 | 嘉兴长维新材料科技有限公司 | A method of methamphetamine class drugs are detected based on Surface enhanced Raman scattering technology |
| CN110082340A (en) * | 2019-05-30 | 2019-08-02 | 合肥工业大学 | The flexible detection method that orderly micro-nano patterned films detect trace TNT |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102156117A (en) * | 2011-03-22 | 2011-08-17 | 中国科学院长春应用化学研究所 | Substrate for surface enhanced Raman scattering and preparation method thereof |
| CN102706853A (en) * | 2012-06-05 | 2012-10-03 | 湖南大学 | Raman reinforced substrate material, preparation and application methods thereof |
-
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- 2013-01-29 CN CN201310032967.3A patent/CN103091300B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102156117A (en) * | 2011-03-22 | 2011-08-17 | 中国科学院长春应用化学研究所 | Substrate for surface enhanced Raman scattering and preparation method thereof |
| CN102706853A (en) * | 2012-06-05 | 2012-10-03 | 湖南大学 | Raman reinforced substrate material, preparation and application methods thereof |
Non-Patent Citations (3)
| Title |
|---|
| 杨桂法等: "TNT- -CPC体系的显色反应及其应用", 《湖南大学学报》, 31 March 1990 (1990-03-31), pages 88 - 91 * |
| 袁伟恩: "银、阳离子表面活性剂和蛋白质纳米微粒体系的光谱特性研究及分析应用", 《中国优秀博硕士学位论文全文数据库 工程科技I辑》, 31 March 2005 (2005-03-31) * |
| 郭志男等: "基于三明治结构的SERS方法痕量检测TNT分子", 《光谱学与光谱分析》, 31 October 2012 (2012-10-31), pages 153 - 154 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103411945A (en) * | 2013-06-24 | 2013-11-27 | 吉林大学 | Method for performing surface-enhanced Raman detection on phenolic and polycylic aromatic hydrocarbon compounds by generating azo molecule |
| CN105445251A (en) * | 2014-08-14 | 2016-03-30 | 杭州坚峰科技有限公司 | Spectral probe and preparation method and use thereof |
| CN105445252A (en) * | 2015-11-06 | 2016-03-30 | 合肥学院 | Dopamine detection method based on surface enhanced resonance Raman spectrum |
| CN105424678A (en) * | 2015-12-04 | 2016-03-23 | 山东大学 | Noble metal sol spray for in-situ detection of explosives through surface enhancing raman spectrum as well as preparation method and application thereof |
| CN105424678B (en) * | 2015-12-04 | 2019-02-12 | 山东大学 | A kind of noble metal aerosol spray and the preparation method and application thereof applied to Surface enhanced Raman spectroscopy in situ detection explosive |
| CN109164085A (en) * | 2018-08-27 | 2019-01-08 | 嘉兴长维新材料科技有限公司 | A method of methamphetamine class drugs are detected based on Surface enhanced Raman scattering technology |
| CN110082340A (en) * | 2019-05-30 | 2019-08-02 | 合肥工业大学 | The flexible detection method that orderly micro-nano patterned films detect trace TNT |
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