CN103472049A - Organophosphorus detection method based on hollow-core fiber - Google Patents
Organophosphorus detection method based on hollow-core fiber Download PDFInfo
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- CN103472049A CN103472049A CN2013102569972A CN201310256997A CN103472049A CN 103472049 A CN103472049 A CN 103472049A CN 2013102569972 A CN2013102569972 A CN 2013102569972A CN 201310256997 A CN201310256997 A CN 201310256997A CN 103472049 A CN103472049 A CN 103472049A
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Abstract
The invention belongs to the field of analytical chemistry technology, and discloses an organophosphorus detection method based on a hollow-core fiber. The method comprises following steps: an organophosphorus sample solution is injected into the hollow-core fiber, wherein the inner wall of the hollow-core fiber is provided with nanoparticles; incidence of exciting light is performed through one end of the hollow-core fiber, and emergent light, which is enforced by total reflection of the inner wall of the hollow-core fiber and the nanoparticles, is detected by a Raman spectrum acquisition system at the other end so as to obtain a Raman spectrum; the Raman spectrum is analyzed, the kind of the organophosphorus sample is determined based on the change of Raman peak positions, and the concentration of the organophosphorus sample is determined based on the intensity of Raman peaks. Total reflection of light signals is realized by taking the hollow-core fiber as a surface enhanced Raman substrate in the detection of organophosphorus; light attenuation of light propagation process in the hollow- core fiber is relatively less, and is negligible, so that signal enhancement is more significant; the organophosphorus detection method is low in cost; and sample amount required by the organophosphorus detection method is precious little.
Description
Technical field
The present invention relates to technical field of analytical chemistry, particularly the organic phosphorus detection method based on hollow-core fiber.
Background technology
In recent years, food security faces great challenge, and people's health is on the hazard, thereby the micro substance of detection low concentration becomes the focus of research.Raman spectrum is compared other spectrum, and abundant molecular structure and molecular vibration information can be provided, thereby has become species analysis and material is differentiated strong instrument.But in practical process, because raman scattering cross section is 10
30the order of magnitude, be only the per mille of Rayleigh scattering, and be easy to be flooded by fluorescence background, thereby, limited its application in every field.If using the metal of multi-form roughening as substrate, Raman scattering intensity can improve 10
5～10
6doubly.In addition, this Surface enhanced raman spectroscopy is quench fluorescence effectively, and test substance is realized to pollution-free, not damaged, highly sensitive detection.
Surface enhanced raman spectroscopy (Surface Enhanced Raman Scattering, be called for short " SERS ") refers to when molecular adsorption arrives some metal Nano structure substrate surperficial, the phenomenon that the Raman signal of molecule significantly strengthens.1974, the people such as M.Fleischmann found the SERS phenomenon first, and their experiment shows to have obtained enhancing at the Raman spectrum of coarse silver electrode surface Pyridine Molecules.The compound that is adsorbed on the roughening metal surface is because the surperficial local plasmon excimer caused Electromagnetic enhancement that is excited is that physics strengthens, and the cluster on rough surface and adsorb active site that molecular composition Raman on it strengthens chemistry strengthen, the two effect makes the Raman scattering of determinand produce great enhancement effect, and its enhancer can reach 10
3～10
7, found that the metal that can produce SERS has a few metals such as Ag, Au, Cu and Pt, take the enhancement effect of Ag as best, the most commonly used.This technology has advantages of that selectivity is good and highly sensitive, and actual detectability can reach 10
-12the gram level.The surface that current more general viewpoint is the SERS activity often can produce the local electric field be enhanced, and is that the metal surface plasma resonance oscillations causes, this is called as physics and strengthens.And the absorption of molecule on metal often is accompanied by the variation that the transfer of electric charge causes molecular entergy level, or molecular adsorption also causing strengthening on the system point of special metal surface, and both of these case all is called as chemistry to be strengthened.Although also have in theory arguement.Yet utilize the research of SERS, but carry out in many-side.As the analysis of micro constitutent in used this technical research residual detection of the evaluation of intermediate product, metal and the thermal decomposition process of burn into catalysis, drugs, vegetable and fruit surface agricultural chemicals, ink marks etc.
After the SERS effect is found, the various SERS substrates that have Raman to strengthen effect constantly are produced out, there is superpower Raman and strengthen effect, the easy SERS substrate be easy to get is the focus of research always, in recent years, the various continuous studied personnel of SERS substrate with different-shape structure make, but the preparation process complexity of these SERS substrates, the equipment needed thereby costliness, and can't reuse, can cause the waste of energy resources, thereby make the chemical substance analysis of using Surface enhanced raman spectroscopy to carry out the signal enhancing mostly only rest on laboratory stage, can't promote in actual applications.
Summary of the invention
The object of the present invention is to provide a kind of organic phosphorus detection method based on hollow-core fiber, make in the detection of organophosphorus and using hollow-core fiber as surface enhanced Raman substrate, can realize the total reflection of light signal, and light signal is propagated in hollow-core fiber, decay very little, almost can ignore, thereby better signal humidification is arranged, and it is with low cost, required sample size is few.
For solving the problems of the technologies described above, embodiments of the present invention provide a kind of organic phosphorus detection method based on hollow-core fiber, comprise following steps:
S1., one hollow-core fiber is provided; Wherein, there is nano particle on described hollow-core fiber inwall;
S2. inject the organophosphorus sample liquid in described hollow-core fiber;
S3. exciting light is from described hollow-core fiber one end incident, adopts the emergent light of Raman spectrum acquisition system after the other end of described hollow-core fiber detects the enhancing of inwall total reflection by described hollow-core fiber and nano particle, the acquisition Raman spectrum; Wherein, described Raman spectrum comprises Raman shift and raman scattering intensity;
S4. described Raman spectrum is carried out to spectrum analysis, according to the variation of Raman peak position, determine the kind of organophosphorus; According to Raman peaks intensity, determine the concentration of organophosphorus.
Embodiment of the present invention in terms of existing technologies, have on inwall in the hollow-core fiber of nano particle and inject the organophosphorus sample liquid, by by exciting light from hollow-core fiber one end incident, adopt the emergent light of Raman spectrum acquisition system after the other end of hollow-core fiber detects the enhancing of inwall total reflection by hollow-core fiber and nano particle, obtain Raman spectrum, Raman spectrum is carried out to spectrum analysis, according to the variation of Raman peak position, determine the kind of organophosphorus; According to Raman peaks intensity, determine the concentration of organophosphorus.Make in the detection of organophosphorus and using hollow-core fiber as surface enhanced Raman substrate, can realize the total reflection of light signal, and, light signal is propagated in hollow-core fiber, decay very little, almost can ignore, thereby better signal humidification is arranged, and it is with low cost, required sample size is few.
By following steps, prepared by the hollow-core fiber that in addition, has nano particle on described inwall:
Adopt chemical plating process at hollow-core fiber inwall metal cladding;
The described hollow-core fiber that has plated metal level is carried out to high temperature rapid thermal annealing, on described hollow-core fiber inwall, form nano particle.
Adopt high temperature rapid thermal annealing technique, be easy to form nano particle on the hollow-core fiber inwall, make the manufacturing process of SERS substrate simple, with low cost.
In addition, the diameter of described hollow-core fiber is 2 millimeters, and the diameter of described nano particle is less than or equal to 200 nanometers.Further make sample size required in organophosphorus detects few.
In addition, in described step S2, comprise following steps:
An end punching at described hollow-core fiber;
Described organophosphorus sample liquid is injected in hollow-core fiber from described hole.
Inject the organophosphorus sample liquid by the end punching at hollow-core fiber, make the method for processing sample very simple, easy operating, and be conducive to real-time detection fast.
In addition, in described step S4, comprise following sub-step:
Described Raman spectrum is converted into digital signal by described ccd detector;
By PC, described digital signal is carried out to spectrum analysis.
Realize spectrum analysis by PC, realize automatic analysis, further be conducive to real-time detection fast.
The accompanying drawing explanation
Fig. 1 is the process flow diagram according to the organic phosphorus detection method based on hollow-core fiber of a better embodiment of the present invention;
Fig. 2 is the schematic diagram that exciting light is vertically squeezed into hollow-core fiber;
Fig. 3 is that exciting light is squeezed into the schematic diagram of hollow-core fiber with the incident angle of presetting.
Embodiment
For making the purpose, technical solutions and advantages of the present invention clearer, below in conjunction with accompanying drawing, embodiments of the present invention are explained in detail.Yet, persons of ordinary skill in the art may appreciate that and propose many ins and outs in order to make the reader understand the application better in embodiment of the present invention.But, even without these ins and outs and the many variations based on following embodiment and modification, also can realize each claim of the application technical scheme required for protection.
A better embodiment of the present invention relates to a kind of organic phosphorus detection method based on hollow-core fiber, and idiographic flow as shown in Figure 1, comprises following steps:
Can prepare by following steps by the hollow-core fiber that has nano particle on inwall: adopt chemical plating process at hollow-core fiber inwall metal cladding; Then the hollow-core fiber that has plated metal level is carried out to high temperature rapid thermal annealing, on the hollow-core fiber inwall, form nano particle.Electroless plating is a kind of energising that do not need, according to principle of oxidation and reduction, utilize strong reductant in containing the solution of metallic ion, metallic ion is reduced into to metal and is deposited on the method that various material surfaces form close coating, the advantage that electroless plating is the most outstanding is plating piece how complicated no matter, as long as solution can obtain the coating of even thickness in deep place, and is easy to control thickness of coating.The technological process of electroless plating is substantially similar, and the key distinction is the preparation of chemical plating fluid, has had at present much about the research of various chemical plating fluids (such as chemical gold plating liquid, chemical plating liquid), does not repeat them here.
In addition, in order to strengthen the adhesion between metal level and hollow-core fiber, before the inner metal cladding of hollow-core fiber, can be first at the plating of hollow-core fiber inwall adhesion layer, then metal cladding on adhesion layer.In actual applications, generally select the material of titanium as adhesion layer, gold or silver are as the material of metal level.
Such as exciting light can be squeezed in hollow-core fiber perpendicular to end face (as shown in Figure 2) or with the incident angle (as shown in Figure 3, incident angle is for θ) of presetting by hollow-core fiber one end.The exciting light of light source emission incides in hollow-core fiber from an end, and after the enhancing of the total reflection of exciting light by the hollow-core fiber inwall and nano particle, the other end outgoing from hollow-core fiber, enter spectroscope by optical filter, obtains Raman spectrum.When exciting light frequency and plasma vibration frequency to coincide, produce resonance effects, surface field strengthens, thereby Raman signal is enhanced.Also depend on again the variation of organic molecule component due to the Surface Enhanced Raman Scattering Spectrum of the organic molecule of the nano grain surface of hollow-core fiber inwall, therefore, can be by Raman spectrum be resolved, analyze the organophosphorus kind that the organophosphorus sample liquid injected in hollow-core fiber comprises.
The digital signal processing such as atlas analysis can be completed by PC, and specifically, Raman spectrum is converted into digital signal by ccd detector, by PC, digital signal are carried out to spectrum analysis.The different materials spectrum that takes on a different character, therefore can analyze according to the Raman spectra qualitative measured the kind of organophosphorus.That is to say, according in hollow optic fibre, inject the sample difference, the position that in Raman spectrum, Raman peaks occurs can be different, therefore, according to the variation of peak position, can qualitative analysis goes out the kind of organophosphorus.In addition, according to the intensity of characteristic peak and demarcate in advance organophosphorus concentration and Raman peaks intensity between relation, determine the concentration of organophosphorus.Specifically, demarcation in advance can be passed through the Raman spectrum of the organophosphorus sample liquid of detection concentration known, carry out atlas analysis, obtain the intensity of Raman peaks, obtain the corresponding relation between organophosphorus concentration and Raman peaks intensity, such as the concentration of organophosphorus OPs and peak intensity are linear within the specific limits, such as can be 10
-4-10
-7linear between M.
Compared with prior art, present embodiment has in the hollow-core fiber of nano particle on inwall injects the organophosphorus sample liquid, by by exciting light from hollow-core fiber one end incident, adopt the emergent light of Raman spectrum acquisition system after the other end of hollow-core fiber detects the enhancing of inwall total reflection by hollow-core fiber and nano particle, obtain Raman spectrum, Raman spectrum is carried out to spectrum analysis, according to the variation of Raman peak position, determine the kind of organophosphorus; According to Raman peaks intensity, determine the concentration of organophosphorus.Make in the detection of organophosphorus and using hollow-core fiber as surface enhanced Raman substrate, can realize the total reflection of light signal, and, light signal is propagated in hollow-core fiber, decays very little, almost can ignore, thereby better signal humidification is arranged, and it is with low cost, change sample convenient, required sample size is few.
The step of top method is divided, and just in order being described clearly, can to merge into a step while realizing or some step is split, and is decomposed into a plurality of steps, as long as comprise identical logical relation, all in the protection domain of this patent; To adding inessential modification in algorithm or in flow process or introducing inessential design, but the core design that does not change its algorithm and flow process is all in the protection domain of this patent.
Persons of ordinary skill in the art may appreciate that the respective embodiments described above are to realize specific embodiments of the invention, and in actual applications, can do various changes to it in the form and details, and without departing from the spirit and scope of the present invention.
Claims (6)
1. the organic phosphorus detection method based on hollow-core fiber, is characterized in that, comprises following steps:
S1., one hollow-core fiber is provided; Wherein, there is nano particle on described hollow-core fiber inwall;
S2. inject the organophosphorus sample liquid in described hollow-core fiber;
S3. exciting light is from described hollow-core fiber one end incident, adopts the emergent light of Raman spectrum acquisition system after the other end of described hollow-core fiber detects the enhancing of inwall total reflection by described hollow-core fiber and nano particle, the acquisition Raman spectrum; Wherein, described Raman spectrum comprises Raman shift and raman scattering intensity;
S4. described Raman spectrum is carried out to spectrum analysis, according to the variation of Raman peak position, determine the kind of organophosphorus; According to Raman peaks intensity, determine the concentration of organophosphorus.
2. the organic phosphorus detection method based on hollow-core fiber according to claim 1, is characterized in that, by following steps, prepared by the hollow-core fiber that has nano particle on described inwall:
Adopt chemical plating process at hollow-core fiber inwall metal cladding;
The described hollow-core fiber that has plated metal level is carried out to high temperature rapid thermal annealing, on described hollow-core fiber inwall, form nano particle.
3. the organic phosphorus detection method based on hollow-core fiber according to claim 1, is characterized in that, the diameter of described hollow-core fiber is 2 millimeters, and the diameter of described nano particle is less than or equal to 200 nanometers.
4. the organic phosphorus detection method based on hollow-core fiber according to claim 1, is characterized in that, in described step S2, comprises following steps:
An end punching at described hollow-core fiber;
Described organophosphorus sample liquid is injected in hollow-core fiber from described hole.
5. the organic phosphorus detection method based on hollow-core fiber according to claim 1, is characterized in that, in described step S3, described exciting light squeezed in described hollow-core fiber perpendicular to end face or with the incident angle of presetting by described hollow-core fiber one end.
6. the organic phosphorus detection method based on hollow-core fiber according to claim 1, is characterized in that, in described step S4, comprises following sub-step:
Described Raman spectrum is converted into digital signal by ccd detector;
By PC, described digital signal is carried out to spectrum analysis.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104535498A (en) * | 2014-12-05 | 2015-04-22 | 复旦大学 | Organophosphorus detector |
| EP2889609A3 (en) * | 2013-12-30 | 2015-08-12 | Nuctech Company Limited | Pesticide residue detection method |
| CN106404741A (en) * | 2016-10-11 | 2017-02-15 | 北京信息科技大学 | Enhanced Raman spectrum liquid detection method based on double hollow-core fibers |
| CN108613968A (en) * | 2018-08-17 | 2018-10-02 | 山东省科学院激光研究所 | One kind testing system based on hollow pipe liquid fiber Raman probe and Raman |
| CN108760718A (en) * | 2018-08-03 | 2018-11-06 | 华南师范大学 | SERS (surface enhanced Raman Scattering) probe based on hollow anti-resonance optical fiber and preparation method thereof |
| CN113552110A (en) * | 2021-07-16 | 2021-10-26 | 中国民航大学 | Raman spectrum-based dynamic early warning system and method for thermal runaway of lithium ion battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1448742A (en) * | 2003-04-24 | 2003-10-15 | 吉林大学 | Surface reinforced Lamman scattering active liquid core optical fibre, method for making and use |
| US6900890B1 (en) * | 2003-11-17 | 2005-05-31 | The Boeing Company | Fiber Raman sensor for remote chemical detection |
| CN101140234A (en) * | 2007-06-27 | 2008-03-12 | 中国科学院上海光学精密机械研究所 | Preparation method of surface reinforced Raman diffuse transmission substrate |
| JP4809067B2 (en) * | 2006-01-20 | 2011-11-02 | 独立行政法人理化学研究所 | Hollow fiber probe |
| CN202421071U (en) * | 2011-12-14 | 2012-09-05 | 中国科学院合肥物质科学研究院 | Vehicle-mounted Raman spectrum soil detector |
-
2013
- 2013-06-25 CN CN2013102569972A patent/CN103472049A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1448742A (en) * | 2003-04-24 | 2003-10-15 | 吉林大学 | Surface reinforced Lamman scattering active liquid core optical fibre, method for making and use |
| US6900890B1 (en) * | 2003-11-17 | 2005-05-31 | The Boeing Company | Fiber Raman sensor for remote chemical detection |
| JP4809067B2 (en) * | 2006-01-20 | 2011-11-02 | 独立行政法人理化学研究所 | Hollow fiber probe |
| CN101140234A (en) * | 2007-06-27 | 2008-03-12 | 中国科学院上海光学精密机械研究所 | Preparation method of surface reinforced Raman diffuse transmission substrate |
| CN202421071U (en) * | 2011-12-14 | 2012-09-05 | 中国科学院合肥物质科学研究院 | Vehicle-mounted Raman spectrum soil detector |
Non-Patent Citations (2)
| Title |
|---|
| 孙旭东等: "表面增强拉曼光谱法检测农药残留的研究进展", 《食品安全质量检测学报》 * |
| 欧阳思怡等: "表面增强拉曼光谱法在农药残留检测中的研究进展", 《食品与机械》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2889609A3 (en) * | 2013-12-30 | 2015-08-12 | Nuctech Company Limited | Pesticide residue detection method |
| CN104535498A (en) * | 2014-12-05 | 2015-04-22 | 复旦大学 | Organophosphorus detector |
| CN106404741A (en) * | 2016-10-11 | 2017-02-15 | 北京信息科技大学 | Enhanced Raman spectrum liquid detection method based on double hollow-core fibers |
| CN108760718A (en) * | 2018-08-03 | 2018-11-06 | 华南师范大学 | SERS (surface enhanced Raman Scattering) probe based on hollow anti-resonance optical fiber and preparation method thereof |
| CN108760718B (en) * | 2018-08-03 | 2023-09-19 | 华南师范大学 | SERS probe based on hollow anti-resonance optical fiber and preparation method thereof |
| CN108613968A (en) * | 2018-08-17 | 2018-10-02 | 山东省科学院激光研究所 | One kind testing system based on hollow pipe liquid fiber Raman probe and Raman |
| CN113552110A (en) * | 2021-07-16 | 2021-10-26 | 中国民航大学 | Raman spectrum-based dynamic early warning system and method for thermal runaway of lithium ion battery |
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