CN106706795A - Magnetic-nano-composite-based dispersive solid-phase extraction-chromatographic detection method of malachite green (MG) and crystal violet (CV) in water sample - Google Patents

Magnetic-nano-composite-based dispersive solid-phase extraction-chromatographic detection method of malachite green (MG) and crystal violet (CV) in water sample Download PDF

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CN106706795A
CN106706795A CN201710023990.4A CN201710023990A CN106706795A CN 106706795 A CN106706795 A CN 106706795A CN 201710023990 A CN201710023990 A CN 201710023990A CN 106706795 A CN106706795 A CN 106706795A
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nano
water sample
magnetic
sample
composite
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许淑霞
张磊磊
张信凤
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Chengdu Univeristy of Technology
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Chengdu Univeristy of Technology
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
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  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)

Abstract

The invention relates to a magnetic-nano-composite-based dispersive solid-phase extraction-chromatographic detection method of malachite green (MG) and crystal violet (CV) in a water sample. MG and CV are two common triphenylmethane cationic dyes, and are effective antifungal and antiparasitic agents in aquiculture. However, when the dyes enter the human body, the metabolites have high residue level, and have carcinogenicity, teratogenesis, mutagenesis and other toxicities, thereby causing great hazards to the human body. Therefore, the development of a simple and sensitive method for detecting MG and CV is very necessary. The Fe3O4/GO (graphene oxide) nano composite simultaneously has larger specific area and paramagnetism, and can well enrich the target substances in the sample and be separated from the substrate under the action of a magnetic field. After the Fe3O4/GO nano composite is separated, a small amount of eluting agent is added for desorption, thereby achieving the goal of concentrating the sample; and HPLC (high performance liquid chromatography)-VIS is adopted to separate and detect the mixed target substance. The method has higher sensitivity; and the detection limits for MG and CV can respectively reach 0.18 and 0.19 mu g L<-1>. The method is convenient and quick, can perform solid-liquid-phase separation only by using a magnet, and avoids the operation steps of salt ion addition and centrifugation. The enrichment factor can reach 60 times or above, so the method is convenient for popularization and application.

Description

In a kind of dispersive solid-phase extraction based on magnetic nanocomposites-chromatogram detection water sample The method of malachite green and crystal violet
Technical field
Magnetic nanocomposites are prepared for dispersed solid phase micro-extracting method the present invention relates to one kind, while using efficient liquid The analysis method of organic pollution malachite green (MG) and crystal violet (CV), belongs to environment water sample analysis in phase chromatogram detection water sample Technical field.
Background technology
Malachite green (MG) is mainly as fish keep-alive is fresh-keeping as additive, but has into its metabolite after human body The toxicity such as high residue and carcinogenic, teratogenesis, mutagenesis, it is very big to harm.Crystal violet (CV) belongs to triphenylmenthane cationoid Type dye, except be widely used in weaving, print and dye and ink industry field in addition to, it can also be used to paper, toy and some plastics systems Product are dyeed.The a large amount of waste water color depths produced during production, use, contain to biodegradation in inhibitory action in structure Phenyl ring, it is difficult to be degraded into inorganic molecules, severe contamination environment, chemical functional group's triphenylmenthane therein has high poison, height residual Stay and " three cause " effect.Based on MG and CV to the harmfulness of environment, the research and application to MG in water body and CV is extremely important.
The method of existing detection MG and CV mainly has：AAS, mass spectrography, high performance liquid chromatography, capillary Electrophoresis etc..It is due to strong qualitative ability and sensitivity high that wherein high performance liquid chromatography application is relatively broad.However, by MG and CV contents are very low in water sample, so must be enriched with to object before detection.
Conventional enrichment method has liquid-liquid extraction method and solid phase extraction, but liquid-liquid extraction method takes more, it is necessary to make Use poisonous organic reagent.Solid phase extraction process is cumbersome, and extraction time is long, therefore one simple, effective pre-treatment side of exploitation Method extracts the MG and CV in water sample and detects that its content is necessary with HPLC.
The content of the invention
It is an object of the invention to utilize Fe3O4The excellent absorption property and Fe of GO in/GO nano composite materials3O4's Superpower paramagnetic performance, is enriched with and is separated to sample such that it is able to reach the purpose to trace samplings effective detection.The present invention Technical scheme it is as follows：
(1) Fe is prepared3O4/ GO nano-particles, and it is standby with after milli-Q water, adding ultra-pure water to form suspension.
(2) water sample to be measured is taken, with 0.45 μm of filter membrane suction filtration, water sample is pipetted in colorimetric cylinder.
(3) sequentially added in colorimetric cylinder：Fe3O4/ GO nano-complexes, MG, CV mixed standard solution or environmental water sample, The ammonium acetate buffer solution of pH 6.0, reacts a period of time at room temperature；
(4) after reacted solution carries out Solid-Liquid Separation with magnet, discard clear liquid, collect after magnetic retention with acetonitrile/ Glacial acetic acid elution, eluent through filter filter after detected on high performance liquid chromatograph, calculate MG in water sample With the content of CV.
Invention effect
Compared with prior art, the invention has the advantages that：
(1) sensitivity is high.Present invention utilizes Fe3O4/ GO magnetic nanocomposites are enriched with MG and CV, improve method Sensitivity, is capable of achieving to as little as 0.5 μ g L in solution-1The detection of MG and CV；
(2) sample-pretreating method is simple, without the operation such as centrifugation；
(3) method can be used for the detection of MG and CV in the complex samples such as environment, food, biology.
Specific embodiment
Embodiment 1
0.05mL concentration is sequentially added in colorimetric cylinder for 2.68mg mL-1Fe3O4/ GO nano-complexes, 0.02mL 10mg L-1(water sample is with 0.45 μm of membrane filtration and adjusts for MG and CV mixed standard solutions, the ammonium acetate buffering of pH 6.0 or water sample Section pH reacts 15min at room temperature to 6.0) 19.93mL.After reacted solution carries out Solid-Liquid Separation with magnet, discard clear Liquid.Magnetic retention 200 μ L acetonitriles/glacial acetic acid (V:V=4:1) after eluent ultrasound wash-out, through magnet separation, 0.45 μm of filter After filtering, take 20 μ L solution carries out absorbance measurement (Detection wavelength for 600nm at) in the enterprising row of high performance liquid chromatograph, according to Water sample and the absorbance of standard series, calculate the content of MG and CV in water sample.
Embodiment 2
0.1mL concentration is sequentially added in colorimetric cylinder for 2.68mg mL-1Fe3O4/ GO nano-complexes, 0.02mL 10mgL-1(water sample is with 0.45 μm of membrane filtration and adjusts for MG and CV mixed standard solutions, the ammonium acetate buffering of pH 5.0 or water sample Section pH reacts 15min at room temperature to 5.0) 19.88mL.After reacted solution carries out Solid-Liquid Separation with magnet, discard clear Liquid, magnetic retention 200 μ L acetonitriles/glacial acetic acid (V:V=4:1) after eluent ultrasound wash-out, through magnet separation, 0.45 μm of filter After filtering, take 20 μ L solution carries out absorbance measurement (Detection wavelength for 600nm at) in the enterprising row of high performance liquid chromatograph, according to Water sample and the absorbance of standard series, calculate the content of MG and CV in water sample.
Determination of recovery rates is carried out using 1,2 pairs of environmental water samples 1,2,3,4 of embodiment, experimental result is shown in Table 1.By institute's water acquisition Sample is not contaminated, and MG and CV contents are very low in general water body, therefore the method for employing mark-on reclaims, and the rate of recovery is in 91- Between 117%.
The mark-on reclaims result of MG and CV in the actual sample of table 1

Claims (5)

1. it is a kind of to be based on Fe3O4The magnetic dispersive solid-phase extraction of/GO nano-particles is used to detect water sample Malachite Green and crystal violet Method, it is characterised in that including following steps：
(1) Fe is prepared3O4/ GO nano-particles：This method prepares Fe using chemical precipitation method3O4/ GO, that is, weigh 50mg GO in In 50mL ultra-pure waters, ultrasound is transferred in the there-necked flask of 250mL to the colloid for forming stabilization, leads to nitrogen deoxygenation, then in magnetic Power stirring is lower to add 25mL 0.02mol L-1FeSO4·7H2O, 50mL 0.01mol L-1FeCl3·6H2O and excess Ammoniacal liquor, condensing reflux 50 minutes at 85 DEG C in the nitrogen atmosphere.
(2) after the completion of reacting, resulting materials are repeatedly washed with ultra-pure water, is removed excessive raw material thing, and by nanometer material Pulp suspension pH is adjusted to neutrality, is eventually adding 50mL ultra-pure waters, forms it into suspension standby.
(3) water sample to be measured is taken, with 0.45 μm of membrane filtration, 50mL water samples to be measured is accurately pipetted in 50mL colorimetric cylinders, by suction filtration Good water sample glacial acetic acid and ammoniacal liquor is adjusted to pH 6.0；
(4) Fe of 0.134mg is added in colorimetric cylinder3O4/ GO nano-complexes, the water sample of the above-mentioned pH 6.0 of 20mL, in room temperature Lower absorption 15min；
(5) after the solution after adsorbing carries out Solid-Liquid Separation with magnet, clear liquid is discarded, magnetic retention is collected with 0.5mL centrifuge tubes；
(6) a small amount of eluent acetonitrile/glacial acetic acid (V is added in centrifuge tube:V=4:1), ultrasound, separation, 0.45 μm of filter mistake Filter, then carries out quantitative determination with highly effective liquid phase chromatographic system.
2. the method as described in claim 1, it is characterised in that the compound of synthesis necessary requirement, it is characterized in that having preferable Absorption property and stronger paramagnetism.
3. the method as described in claim 1, it is characterised in that Fe3O4The amount of/GO nano-complexes is 0.027-1.34mg.
4. the method as described in claim 1, it is characterised in that absorption pH is 2-7, and adsorption time is 2-30min.
5. the method as described in claim 1, it is characterised in that the suitable eluent of selection, and acetonitrile and second in selected eluent The volume ratio of acid is 95:5-70:30.
CN201710023990.4A 2017-01-13 2017-01-13 Magnetic-nano-composite-based dispersive solid-phase extraction-chromatographic detection method of malachite green (MG) and crystal violet (CV) in water sample Pending CN106706795A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108593799A (en) * 2018-04-27 2018-09-28 甘肃省食品检验研究院 A kind of method of the preparation and analysis water-like Malachite Green and crystal violet and metabolite of magnetism eutectic solvent
CN110187040A (en) * 2019-06-26 2019-08-30 渤海大学 A kind of sample-pretreating method detected simultaneously for freshwater aquiculture water body Malachite green residues liquid chromatogram-visible light and fluorescence

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CN103353495A (en) * 2011-11-15 2013-10-16 南昌大学 Method for enriching leucomalachite green and leucogentian violet in aquatic products
CN104096542A (en) * 2014-06-23 2014-10-15 广西师范大学 Novel magnetic Fe / C@ MOF composite absorbent and preparation method thereof
RU2015103341A (en) * 2015-02-02 2016-08-20 Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Томский политехнический университет" Method for solid-phase extraction of malachite green dye

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CN103353495A (en) * 2011-11-15 2013-10-16 南昌大学 Method for enriching leucomalachite green and leucogentian violet in aquatic products
CN104096542A (en) * 2014-06-23 2014-10-15 广西师范大学 Novel magnetic Fe / C@ MOF composite absorbent and preparation method thereof
RU2015103341A (en) * 2015-02-02 2016-08-20 Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Томский политехнический университет" Method for solid-phase extraction of malachite green dye

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108593799A (en) * 2018-04-27 2018-09-28 甘肃省食品检验研究院 A kind of method of the preparation and analysis water-like Malachite Green and crystal violet and metabolite of magnetism eutectic solvent
CN110187040A (en) * 2019-06-26 2019-08-30 渤海大学 A kind of sample-pretreating method detected simultaneously for freshwater aquiculture water body Malachite green residues liquid chromatogram-visible light and fluorescence
CN110187040B (en) * 2019-06-26 2021-08-17 渤海大学 Sample pretreatment method for simultaneously detecting malachite green residue in freshwater aquaculture water body by liquid chromatography-visible light and fluorescence

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Application publication date: 20170524