CN102087216A - Novel paraquat detecting method - Google Patents
Novel paraquat detecting method Download PDFInfo
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- CN102087216A CN102087216A CN2009102412541A CN200910241254A CN102087216A CN 102087216 A CN102087216 A CN 102087216A CN 2009102412541 A CN2009102412541 A CN 2009102412541A CN 200910241254 A CN200910241254 A CN 200910241254A CN 102087216 A CN102087216 A CN 102087216A
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- paraquat
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Abstract
The invention relates to a novel paraquat detecting method. In the method, core-shell type Fe3O4/silver magnetic nanoparticles are used as an SERS (Surface-Enhanced Raman Scattering) substrate, the method is used for enriching and detecting the paraquat in water body, and an SERS spectrogram of the paraquat is obtained through a portable type Raman spectrometer. Proved by a series of experiments, the paraquat detecting method adopted by the invention is simple and convenient for operation, and rapid detection for the paraquat can be realized.
Description
One. the technical field of the invention
The environmental analysis field
Two. technical background of the present invention
Raman spectrum (RS) technology is to be the molecular structure characterization technology that the basis is set up with the Raman scattering effect, and conventional Raman spectroscopy is widely used in fields such as crystalline nature, molecular structure and analytical chemistry.And Surface enhanced raman spectroscopy (SERS) but more because its high detection sensitivity, high resolving power, water disturb little quench fluorescence, good stability and be fit to characteristics such as research interface, be widely used in interface orientation and configuration, conformation research and the structure analysis etc. of study of surfaces, the research of adsorbate interface surface state, biomacromolecule.
Since observing the SERS effect on the coarse silver electrode in pyridine adsorption the first time such as Fleischmann in 1974, the researcher has made a large amount of work in this field.The preparation of SERS substrate is one of the research focus in SERS field, and constantly towards easy to prepare, good stability, direction effort that signal is strong.Although the SERS technology has obtained using widely, prepare satisfactory nanostructured surface and remain a challenge experimentally.The sharpest edges of utilizing nanometer technology to obtain at the bottom of the SERS active group are: (1) can obtain shape and the controlled substantially rough surface of size under the nanoscale; (2) preparation can be simulated the various ordered nano-structures surface of " rough surface ", quantitative examination SERS enhanced mechanism; (3) be convenient to seek the optimum experimental condition that produces strong SERS effect.At the bottom of noble metal colloidal sol particle method is SERS active group the most frequently used in the present Surface enhanced raman spectroscopy.Adopt noble metal, prepare the SERS active substrate such as gold, silver colloidal sol, can obtain the metallic of homogeneous shape, in 10nm～100nm scope, particle size distribution range is narrower usually for diameter, and the scope of application is extensive, and can place in the air midium or long term, more stable.
Paraquat (PQ) has another name called Aerial gramoxone, Gramoxone, is organic heterocyclic class contact defoliant and herbicide, and paraquat and lucigenin, diquat dibromide belong to the purpurine compounds.More than 120 countries, 50 various crop are extensive use of paraquat in the whole world at present.As a kind of special efficacy herbicide, its effect is human approval, but the hidden danger that paraquat brings to human health also can not be ignored.1966, Britain Bullvant found 2 routine PQ accidental poisoning death incidents first, has reported the PQ poisoning subsequently all over the world in succession.PQ is poisoned to death rate generally between 25%～76%, also has the death rates of indivedual countries report up to more than 80%.Because PQ poisons and still not have special efficacy antidote, so PQ poisons and caused the concern of countries in the world, but the at present also without comparison research about the paraquat poisoning Prognostic Factors of system.As one of paraquat big producing country, in some big agricultural province of China Shandong Province etc. for example, the paraquat poisoning rate is high always, and has become one of common anxious danger illness of internal medicine.
The present invention has synthesized a kind of core-shell type Fe
3O
4/ silver-colored magnetic nanoparticle, and use it for enrichment and the detection of paraquat in the water body, utilize Portable Raman spectrometer to obtain the raman characteristic peak of PQ.Easy and simple to handle by the analytical approach that a series of the present invention of experimental results show that adopt, can realize the fast detecting of PQ.
Three. summary of the invention of the present invention
Illustrate main contents of the present invention and feature of the present invention by following description.
The present invention relates to a kind of novel paraquat detection method, this method is with core-shell type Fe
3O
4/ Ag magnetic nanoparticle is used it for the fast enriching of paraquat in the water body as the SERS substrate, by Portable Raman spectrometer, has obtained the SERS spectrogram of paraquat.
The present invention has at first synthesized Fe
3O
4Nano particle utilizes hydride modified Fe
3O
4Behind the surface, it is scattered in the liquor argenti nitratis ophthalmicus, under the effect of reducing agent hydroxylamine hydrochloride, prepares core-shell type Fe
3O
4/ Ag magnetic nanoparticle, this composite particles has Fe concurrently
3O
4Magnetic and the Raman of nano-Ag particles strengthen the property.With the Fe for preparing
3O
4/ Ag magnetic nanoparticle is distributed in the certain density PQ solution, because there are chemical action in main body functional group and the magnetic nanoparticle surface of PQ molecule, therefore it can be attracted to rapidly the outer silver-colored shell of magnetic-particle surface, after utilizing externally-applied magnetic field will be dispersed in magnetic-particle in the solution to reclaim, namely can detect the raman characteristic peak of PQ by Portable Raman spectrometer.
Four. description of drawings
Accompanying drawing 1 is the Fe of the present invention's preparation
3O
4The XRPD collection of illustrative plates of nano particle.Can find out the Fe for preparing by the XRPD collection of illustrative plates
3O
4Be purer crystal, the particle diameter that calculates according to the Scherrer formula is about 11nm.
Accompanying drawing 2 is the core-shell type Fe of the present invention's preparation
3O
4The transmission electron microscope photo of/Ag magnetic nanoparticle, experimental result show the core-shell type Fe for preparing
3O
4/ Ag magnetic nanoparticle size is even, and average grain diameter is less than 20nm.
Accompanying drawing 3 is the core-shell type Fe of the present invention's preparation
3O
4The EDX scintigram of/Ag magnetic nanoparticle.Can find out that by the EDX scanning result silver is wrapped in Fe more uniformly
3O
4The surface.
Accompanying drawing 4 is the structural formula of paraquat (PQ) two villaumites.
Accompanying drawing 5 is that PQ is at the core-shell type Fe of the present invention's preparation
3O
4The SERS spectrogram on/Ag magnetic nanoparticle surface.Testing result proves absolutely that PQ can initiatively be enriched to the magnetic-particle surface from the aqueous solution, and has produced good Raman enhancement effect.
Accompanying drawing 6 is the core-shell type Fe with PQ and the present invention's preparation
3O
4/ Ag magnetic nanoparticle mixed after two weeks, the SERS spectrogram that scanning obtains.This experimental result not only illustrates the core-shell type Fe that the present invention makes
3O
4/ Ag magnetic nanoparticle has good stability, and proof PQ and magnetic-particle surface conjunction is very firm.
Five. inventive embodiments
Further set forth the present invention below by embodiment.
Embodiment 1Fe
3O
4The preparation of nano particle: get 5.4g FeCl
36H
2O and 2g FeCl
34H
2O is dissolved in the 100mL deionized water, equals 10 to dropping ammonia to pH value wherein, and the sediment that generates is made Fe in 70 ℃ of dry 3h of vacuum
3O
4Nano particle; Core-shell type Fe
3O
4The preparation of/Ag magnetic nanoparticle: get the 0.25g nanometer Fe
3O
4Be scattered in the 100mL absolute ethyl alcohol, ultrasonic 30min pours in three mouthfuls of round-bottomed flasks, drips 1mLAPTMS (3-aminopropyl-trimethoxy silane) under mechanical agitation, after 6h is carried out in reaction, with the sediment that the generates Fe after 70 ℃ of dry 2h of vacuum obtain intermediate product-amido modified
3O
4Nano particle is scattered in the 100mL liquor argenti nitratis ophthalmicus (2 * 10 with the 0.05g intermediate product
-3M), ultrasonic 30min to wherein dripping 30mL hydroxylamine hydrochloride (0.06M) and the mixed solution that NaOH (0.1M) forms, makes SERS substrate-core-shell type Fe behind the reaction 30min under mechanical agitation
3O
4/ Ag magnetic nanoparticle; The enrichment of PQ and detection: with 0.05g core-shell type Fe
3O
4It is 10 that/Ag magnetic nanoparticle is scattered in 50mL concentration
-6In the PQ aqueous solution of M, after the 5min, utilize externally-applied magnetic field that magnetic-particle is reclaimed, use Portable Raman spectrometer that magnetic-particle is detected, be decided to be 15s sweep time, obtain the SERS spectrogram of PQ.
Embodiment 2Fe
3O
4The preparation of nano particle: get 2.7g FeCl
36H
2O and 1g FeCl
34H
2O is dissolved in the 100mL deionized water, equals 10 to dropping ammonia to pH value wherein, and the sediment that generates is made Fe in 70 ℃ of dry 3h of vacuum
3O
4Nano particle; Core-shell type Fe
3O
4The preparation of/Ag magnetic nanoparticle: get the 0.2g nanometer Fe
3O
4Be scattered in the 100mL absolute ethyl alcohol, ultrasonic 30min pours in three mouthfuls of round-bottomed flasks, drips 0.8mL APTMS (3-aminopropyl-trimethoxy silane) under mechanical agitation, after 6h is carried out in reaction, with the sediment that the generates Fe after 70 ℃ of dry 2h of vacuum obtain intermediate product-amido modified
3O
4Nano particle is scattered in the 100mL liquor argenti nitratis ophthalmicus (4 * 10 with the 0.05g intermediate product
-3M), ultrasonic 30min to wherein dripping 60mL hydroxylamine hydrochloride (0.06M) and the mixed solution that NaOH (0.1M) forms, makes SERS substrate-core-shell type Fe behind the reaction 45min under mechanical agitation
3O
4/ Ag magnetic nanoparticle; The enrichment of PQ and detection: with 0.05g core-shell type Fe
3O
4It is 10 that/Ag magnetic nanoparticle is scattered in 50mL concentration
-5In the PQ aqueous solution of M, after the 5min, utilize externally-applied magnetic field that magnetic-particle is reclaimed, use Portable Raman spectrometer that magnetic-particle is detected, be decided to be 10s sweep time, obtain the SERS spectrogram of PQ.
Claims (4)
1. novel paraquat detection method, this method is with core-shell type Fe
3O
4/ Ag magnetic nanoparticle is used it for the enrichment of paraquat in the aqueous solution (PQ) as the SERS substrate, by Portable Raman spectrometer, has obtained the SERS spectrogram of PQ, has realized the fast detecting to this herbicide.
2. a kind of novel paraquat detection method as claimed in claim 1, the used SERS substrate preparation process of this detection method is as follows: synthesize Fe with coprecipitation
3O
4Nano particle utilizes hydride modified Fe
3O
4Behind the surface, it is scattered in the liquor argenti nitratis ophthalmicus, under the effect of reducing agent hydroxylamine hydrochloride, prepares core-shell type Fe
3O
4/ Ag magnetic nanoparticle.
3. a kind of novel paraquat detection method as claimed in claim 1, the used paraquat enrichment mode of this detection method is as follows: with the core-shell type Fe for preparing
3O
4/ Ag magnetic nanoparticle is distributed in the certain density PQ solution, with externally-applied magnetic field magnetic-particle is collected behind about 5min, the SERS substrate of PQ that formed surface enrichment.
4. as claims 1 described a kind of novel paraquat detection method, the used paraquat analytical approach of this detection method is as follows: by the Portable Raman optical spectrum instrument to surface enrichment the SERS substrate of PQ scan, can in 15s, detect the SERS spectrogram of paraquat.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103198913A (en) * | 2012-01-10 | 2013-07-10 | 中国科学院合肥物质科学研究院 | Silver-ferroferric oxide core-shell nano-particles and preparation method thereof |
| CN104597024A (en) * | 2014-12-01 | 2015-05-06 | 中检国研(北京)科技有限公司 | Raman spectrometry used for rapidly detecting paraquat in fruit and vegetable on site |
| CN104964959A (en) * | 2015-05-19 | 2015-10-07 | 中检国研(北京)科技有限公司 | Raman spectrum method used for rapid detection of basic flavine O in bean products and beverage, reagent formula, and application method |
| CN106153596A (en) * | 2015-04-13 | 2016-11-23 | 中国人民解放军军事医学科学院毒物药物研究所 | A kind of quick detection N,N'-dimethyl-.gamma..gamma.'-dipyridylium and/or the method for diquat dibromide and test kit |
| CN106770174A (en) * | 2017-01-14 | 2017-05-31 | 南京简智仪器设备有限公司 | A kind of method of utilization Raman spectrum quick detection paraquat |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1284795C (en) * | 2003-08-15 | 2006-11-15 | 上海师范大学 | Magnetic nano particle nucleic acid separator, and its preparing method and use |
| CN101373652A (en) * | 2008-07-01 | 2009-02-25 | 湖南工业大学 | Novel method for preparing Fe3O4/Ag magnetic compound nanometer particle |
| CN102081043A (en) * | 2009-11-27 | 2011-06-01 | 中国科学院生态环境研究中心 | Novel aldrin detection method |
| CN102012372B (en) * | 2010-11-10 | 2012-03-28 | 吉林大学 | Method for detecting medicinal molecules by magnetic imprinting surface enhanced Raman spectroscopy technology |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103198913A (en) * | 2012-01-10 | 2013-07-10 | 中国科学院合肥物质科学研究院 | Silver-ferroferric oxide core-shell nano-particles and preparation method thereof |
| CN103198913B (en) * | 2012-01-10 | 2016-03-02 | 中国科学院合肥物质科学研究院 | Silver-tri-iron tetroxide core shell nanoparticles and preparation method thereof |
| CN104597024A (en) * | 2014-12-01 | 2015-05-06 | 中检国研(北京)科技有限公司 | Raman spectrometry used for rapidly detecting paraquat in fruit and vegetable on site |
| CN106153596A (en) * | 2015-04-13 | 2016-11-23 | 中国人民解放军军事医学科学院毒物药物研究所 | A kind of quick detection N,N'-dimethyl-.gamma..gamma.'-dipyridylium and/or the method for diquat dibromide and test kit |
| CN106153596B (en) * | 2015-04-13 | 2020-01-14 | 中国人民解放军军事医学科学院毒物药物研究所 | Method for rapidly detecting paraquat and/or diquat |
| CN104964959A (en) * | 2015-05-19 | 2015-10-07 | 中检国研(北京)科技有限公司 | Raman spectrum method used for rapid detection of basic flavine O in bean products and beverage, reagent formula, and application method |
| CN106770174A (en) * | 2017-01-14 | 2017-05-31 | 南京简智仪器设备有限公司 | A kind of method of utilization Raman spectrum quick detection paraquat |
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