CN102087216B - Novel paraquat detecting method - Google Patents

Novel paraquat detecting method Download PDF

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CN102087216B
CN102087216B CN2009102412541A CN200910241254A CN102087216B CN 102087216 B CN102087216 B CN 102087216B CN 2009102412541 A CN2009102412541 A CN 2009102412541A CN 200910241254 A CN200910241254 A CN 200910241254A CN 102087216 B CN102087216 B CN 102087216B
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paraquat
sers
detection method
core
shell type
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CN102087216A (en
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杜晶晶
景传勇
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Research Center for Eco Environmental Sciences of CAS
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Research Center for Eco Environmental Sciences of CAS
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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

A kind of novel paraquat detection method
One. technical field under the present 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 SERS (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 SERS hot research fields, and constantly towards preparation convenience, 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 basically 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 SERS.Adopt noble metal, prepare the SERS active group like gold, silver colloidal sol at the bottom of, can obtain the metallics 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.Paraquat is widely used on more than 120 countries in the whole world, 50 various crop 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%, and the mortality ratio that also have indivedual countries report are up to more than 80%.Because PQ poisons and still not have special efficacy antidote, so PQ poisons that oneself causes the concern of countries in the world, but the also research about paraquat poisoning prognosis factor of system without comparison at present.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 the enrichment and the detection of paraquat in the water body, utilize the Portable Raman optical spectrum appearance to obtain the raman characteristic peak of PQ.Analytical approach through the present invention of a series of experiment proof adopts is easy and simple to handle, can realize the fast detecting of PQ.
Three. summary of the invention of the present invention
Illustrate main contents of the present invention and characteristic of the present invention through 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, through the Portable Raman optical spectrum appearance, 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 reductive agent oxammonium 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 the main body functional group and the magnetic nanoparticle surface of PQ molecule; Therefore it can be attracted to the outer silver-colored shell of magnetic-particle surface rapidly; Utilize externally-applied magnetic field will be dispersed in after magnetic-particle in the solution reclaims, promptly can detect the raman characteristic peak of PQ through the Portable Raman optical spectrum appearance.
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 mean grain size 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 PQ core-shell type Fe in the present invention's preparation 3O 4The SERS spectrogram on/Ag magnetic nanoparticle surface.Testing result proves absolutely that PQ can initiatively enrichment be surperficial to magnetic-particle from the WS, 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 is not only explained 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 combination is very firm.
Five. inventive embodiments
Further set forth the present invention below through 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, under mechanical raking, drips 1mLAPTMS (3-aminopropyl-trimethoxy silane); After 6h is carried out in reaction, with the Fe of the sediment that generates 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 the mixed solution of 30mL oxammonium hydrochloride (0.06M) with NaOH (0.1M) composition, makes SERS substrate-core-shell type Fe behind the reaction 30min under mechanical raking 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 WS of M, after the 5min, utilize externally-applied magnetic field that magnetic-particle is reclaimed, use the Portable Raman optical spectrum appearance 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, under mechanical raking, drips 0.8mL APTMS (3-aminopropyl-trimethoxy silane); After 6h is carried out in reaction, with the Fe of the sediment that generates 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 the mixed solution of 60mL oxammonium hydrochloride (0.06M) with NaOH (0.1M) composition, makes SERS substrate-core-shell type Fe behind the reaction 45min under mechanical raking 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 WS of M, after the 5min, utilize externally-applied magnetic field that magnetic-particle is reclaimed, use the Portable Raman optical spectrum appearance that magnetic-particle is detected, be decided to be 10s sweep time, obtain the SERS spectrogram of PQ.

Claims (4)

1. 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 WS (PQ) as the SERS substrate, through the Portable Raman optical spectrum appearance, has obtained the SERS spectrogram of PQ, has realized the fast detecting to this herbicide.
2. paraquat detection method as claimed in claim 1, the used SERS substrate preparation step of this detection method is following: 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 reductive agent oxammonium hydrochloride, prepares core-shell type Fe 3O 4/ Ag magnetic nanoparticle.
3. paraquat detection method as claimed in claim 1, the used paraquat enrichment mode of this detection method is following: 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 the 5min, the SERS substrate of PQ that formed surface enrichment.
4. paraquat detection method as claimed in claim 1, the paraquat analytical approach is following: through the Portable Raman optical spectrum appearance to surface enrichment the SERS substrate of PQ scan, in 15s, detect the SERS spectrogram of paraquat.
CN2009102412541A 2009-12-03 2009-12-03 Novel paraquat detecting method Expired - Fee Related CN102087216B (en)

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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
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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