CN105136774A

CN105136774A - Quick analysis method for PBDEs (polybrominated diphenyl ethers)

Info

Publication number: CN105136774A
Application number: CN201510600131.8A
Authority: CN
Inventors: 景传勇; 杜晶晶
Original assignee: Research Center for Eco Environmental Sciences of CAS
Current assignee: Research Center for Eco Environmental Sciences of CAS
Priority date: 2015-09-18
Filing date: 2015-09-18
Publication date: 2015-12-09
Anticipated expiration: 2035-09-18
Also published as: CN105136774B

Abstract

The invention provides a gold solid substrate synthesized with a high-temperature method and supported by a carbon skeleton, PBDEs (polybrominated diphenyl ethers) are adsorbed on the surface of the substrate, and Raman characteristic peaks of BDE-47 (2,2',4,4'-tetrabromodiphenyl ether) are observed through a portable Raman spectrometer. A series of experiments prove that a sample preparation method and a target pollutant analysis method are simple and convenient to operate, and PBDEs in an environment substrate can be quickly detected.

Description

A kind of rapid analysis of PBDE

Technical field

The invention belongs to environmental analysis field, be specifically related to a kind of analytical approach of PBDE.

Technical background

1974, when people's Late Cambrian Pyridine Molecules such as Fleischmann are adsorbed on the Ag electrode surface of electrochemical roughening, its Raman signal intensity obtained very large enhancing.They have larger adsorption area viewed enhancing phenomenon owing to the Ag electrode surface after coarse, thus cause the number of Adsorption of Pyridine Molecules to increase.1977, VanDuyne etc. were independently repeated again above experiment with Creighton etc., and added 10 by the raman scattering spectrum that the Pyridine Molecules that theory calculate finds to be adsorbed on silver electrode surface produces than normal raman spectrum strength ⁴~ 10 ⁶doubly.This Raman signal caused by rough surface is strengthened phenomenon and is defined as Surface enhanced raman spectroscopy (SurfaceEnhancedRamanScattering, SERS) by VanDuyne etc.1997, the particle that the article that Nie etc. deliver on Science demonstrates nanometer scale can realize 10 as SERS substrate ¹⁴~ 10 ¹⁵enhancer, far exceed the effect of traditional Raman detection.Researchers further demonstrate that SERS technology can realize single molecules level and detect subsequently.As a kind of high detection sensitivity, high resolving power, to water inertia, can quench fluorescence, good stability technology, SERS has broad application prospects in environmental analysis field.

The preparation of substrate is the key realizing excellent SERS signal, is also one of the study hotspot in SERS field.Prepare the nanoscale SERS substrate meeting particular requirement and remain a challenge experimentally.Utilize nanometer technology to obtain the sharpest edges of SERS active-substrate to be: (1) can obtain the substantially controlled rough surface of shape and size under nanoscale; (2) preparation can simulate the various ordered nano-structure surfaces of " rough surface ", and quantitative examination SERS strengthens mechanism; (3) be convenient to find the optimum experimental condition producing strong SERS effect.Current noble metal gold, silver are active substrates the most frequently used in Surface enhanced raman spectroscopy, and wherein golden active substrate is applied widely, and can place for a long time in atmosphere, more stable.

PBDE (PolybrominatedDiphenylEthers, PBDEs) is the global organic contaminant of a class, and biological accumulation, persistence and bio-toxicity are the main environment features of PBDE.PBDE to human brain, liver and kidney and other organs and nervous system, internal system, the acute or chronic toxicity of reproductive system generation, can have carcinogenicity, bio-toxicity, neurotoxicity and endocrine disruption toxicity to animal used as test.Wherein tetrabromo Biphenyl Ether (2,2 ', 4,4 '-TetrabromodiphenylEther, BDE-47) is a kind of PBDEs homolog the most general, and the waste water in the world in environment, sediment, wild animal and human body all detect.At present conventional PBDEs detection method has vapor-phase chromatography, liquid phase chromatography, and the analytic approach such as application of gas chromatorgraphy/mass, and these methods instrument price used is expensive, and requires higher to sample pre-treatments.Therefore, explore easy economy, PBDEs detection method rapidly and efficiently possesses significance to environmental analysis field.

Summary of the invention

Because PBDE has strong-hydrophobicity, be difficult to combine with the SERS substrate of routine.In order to overcome the defect of prior art, present inventor has carried out further investigation repeatedly, thus completes the present invention.The present invention's high temperature method has synthesized the golden solid substrate that a kind of carbon skeleton supports, and achieves the absorption of BDE-47 at substrate surface, and be observed the raman characteristic peak of BDE-47 by Portable Raman spectrometer by C support frame.By series of experiments prove the sample preparation methods that the present invention adopts and target contaminant analytical approach easy and simple to handle, the quick detection of BDE-47 in environmental matrices can be realized.

Particular content of the present invention is illustrated by description below:

(1) take 5g dusty yeast and be placed in pyroreaction still inner bag, supernatant is removed with after acetone cleaning, then in inner bag, the glutaraldehyde of 50mL3% and the gold chloride of 10mL2% is added successively, after mixing, in vacuum drying chamber, react 12h at 200 DEG C, remove supernatant and obtain golden presoma;

(2) step (1) presoma is placed in crucible, in muffle furnace, calcines 7h at 600 DEG C, the solid abrasive after calcining is become fine particle, namely obtain the golden solid substrate that carbon skeleton supports;

(3) the golden solid substrate that 5mg step (2) obtains carbon skeleton support is taken, be placed on silicon chip, the BDE-47 solution of 15 μ L is added drop-wise to substrate surface, Portable Raman spectrometer is used to carry out signals collecting, optical maser wavelength 785nm, sweep time, 5s, obtained the SERS spectrogram of BDE-47.

Accompanying drawing explanation

Below by marginal data principal character of the present invention:

Accompanying drawing 1 is the transmission electron microscope photo of the blank carbon skeleton formed after saccharomycete high temperature sintering of the present invention.

The transmission electron microscope photo of the golden solid substrate of carbon skeleton support prepared by accompanying drawing 2 for the present invention, golden uniform fold is in carbon skeleton surface as can be seen from Figure.

The X-ray energy spectrum photo of the golden solid substrate that the carbon skeleton that accompanying drawing 3 is prepared for the present invention supports, the as can be seen from Figure existence of substrate surface gold and carbon.

The XRD spectra of the golden solid substrate that the carbon skeleton that accompanying drawing 4 is prepared for the present invention supports, this spectrogram further demonstrates the formation of gold.

Accompanying drawing 5 is the SERS spectrogram of BDE-47 and the Raman spectrogram of solid BDE-47.By contrasting with the characteristic peak positions of BDE-47 Raman spectrogram, can find out that the feature peak-to-peak type of BDE-47 in SERS spectrogram and position remain unchanged substantially, this fully demonstrates the feasibility of detection method.

Accompanying drawing 6 be the SERS peak of BDE-47 by force with the curve of concentration change, this result shows that the inventive method can be used for the quantitative test of BDE-47.

Accompanying drawing 7 is the SERS spectrograms after adding BDE-47 in the water of Qinghe, and this result shows that the anti-matrix interference ability of the inventive method is comparatively strong, can be used for the analysis of PBDE in environmental matrices.

Inventive embodiments

The present invention is set forth below further by embodiment.

The preparation of embodiment 1 gold medal solid substrate: take 5g dusty yeast and be placed in reactor inner bag, removes supernatant with acetone cleaning, adds the glutaraldehyde of 50mL3% and the gold chloride of 10mL2% successively in inner bag.After mixing, in vacuum drying chamber, react 12h at 200 DEG C.Product supernatant is gone, takes off a layer solid and be placed in crucible, in muffle furnace, calcine 7h at 600 DEG C calcined product is ground to form fine particle, namely obtain the golden solid substrate that carbon skeleton supports.

The enrichment of embodiment 2BDE-47 and detection: take the golden solid substrate that 5mg carbon skeleton supports and be placed on silicon chip, the BDE-47 solution of 15 μ L is added dropwise to substrate surface, Portable Raman spectrometer is used to carry out signals collecting, optical maser wavelength 785nm, sweep time, 5s, obtained the SERS spectrogram of BDE-47.

Claims

1. a PBDE rapid analysis, it is made up of following step:

(1) take 5g dusty yeast and be placed in pyroreaction still inner bag, remove supernatant with after acetone cleaning, then in inner bag, add the glutaraldehyde of 3% and the gold chloride of 2% successively, after mixing, in vacuum drying chamber, react 12h at 200 DEG C, remove supernatant and obtain golden presoma;

(3) golden solid substrate step (2) being obtained carbon skeleton support is placed on silicon chip, uses Portable Raman spectrometer to complete PBDE BDE-47 signals collecting.

2. a kind of PBDE rapid analysis as claimed in claim 1, in step (1), glutaraldehyde consumption is 50mL, and the consumption of gold chloride is 10mL.

3. a kind of PBDE rapid analysis as claimed in claim 1, in step (3), the golden solid substrate consumption that carbon skeleton supports is 5mg.

4. a kind of PBDE rapid analysis as claimed in claim 1, PBDE detection method in step (3) is as follows: be placed on silicon chip by the golden solid substrate that 5mg carbon skeleton supports, the BDE-47 solution of 15 μ L is added drop-wise to substrate surface, Portable Raman spectrometer is used to carry out signals collecting, optical maser wavelength 785nm, sweep time 5s.