CN105548381A - Method for detecting tributyltin in marine fishes and shellfishes - Google Patents

Method for detecting tributyltin in marine fishes and shellfishes Download PDF

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CN105548381A
CN105548381A CN201510902569.1A CN201510902569A CN105548381A CN 105548381 A CN105548381 A CN 105548381A CN 201510902569 A CN201510902569 A CN 201510902569A CN 105548381 A CN105548381 A CN 105548381A
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tbt
methanol
albacore
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杨华
潘道东
朱晓艳
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Zhejiang Wanli University
Zhejiang Wanli College
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    • 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
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    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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    • 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
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    • G01N2030/022—Column chromatography characterised by the kind of separation mechanism
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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
    • G01N30/04—Preparation or injection of sample to be analysed
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Abstract

The invention provides a method for detecting tributyltin in marine fishes and shellfishes. The method comprises the following steps: taking a to-be-detected sample, adding a standard TBT solution into the to-be-detected sample, and performing ultrasonic extraction with an acetic-acid-methanol solution to obtain a to-be-adsorbed solution; preparing Fe3O4 nanoparticles, modifying the Fe3O4 nanoparticles with APTS, modifying the obtained Fe3O4@APTS particles with MAA, and coating the obtained Fe3O4@MAA particles with an MIP layer to obtain a magnetic molecularly imprinted polymer Fe3O4@MIPs; and adding the to-be-adsorbed solution into Fe3O4@MIPs for adsorption while performing magnetic stirring, performing elution with a formic-acid-methanol solution, and detecting the obtained eluate with HPLC-ICP-MS. The method has characteristics of good interference resistance and high sensitivity and speed. At the same time, according to the method, gathering of tributyltin is improved during a detection process and provides necessary requirements for detection, and adoption of the imprinted polymer is beneficial for specificity detection.

Description

The detection method of tributyl tin in a kind of albacore shellfish
Technical field
The present invention relates to the safety detection technology field of marine aquatic product, be specifically related to a kind of detection method based on tributyl tin in the albacore shellfish of magnetic molecularly imprinted technology HPLC-ICP-MS detection.
Background technology
Organo-tin compound has good reactivity and biologically active, so be widely used in industrial or agricultural every field.(1) as the antifoulant additive of naval vessels: tributyl tin, triphenyltin have special toxic action to fungi, algae etc., therefore be mainly used in the antifouling paint of ship, to prevent the biological attachment such as mussel aboard ship, and then reduce waste of fuel, ship's speed reduction etc.(2) as pesticide germifuge: triphenyl tin acetate is mainly used in the control of beet cercospora leaf spot, rice blast etc.; Triphenyl tin chloride can be used for synthesizing sterilization pesticide fentin hydroxide and sterilization pesticide fentinacetate, also can be used as sterile insect technique agent, suppresses breeding of housefly; Tricyclohexyltin and phenyltin are used to produce agricultural chemicals and pesticide.(3) as stabilizer for plastics: dibutyl tin is the catalyzer of polycarbamate plastics and the stabilizing agent of PVC, methyl tin and ethyl tin are used for Polyvinylchloride (PVC) stabilizing agent, lauric organo-tin het stabilizer is mainly used in PVC soft transparent goods, as mantle, film, plastic shoes, flexible pipe and PVC conveying belt etc., the catalyzer etc. of Polyurethane foaming product particularly can be used as.
Due to widely using of organo-tin compound, organo-tin compound poisonous is in a large number by all means in the entered environment ecosystem, thus the ecosystem is damaged, cause a series of problem of environmental pollution, thus receive the concern of various countries' scientists.Especially the water pollution in the global range caused by the anti-spiral shell coating of boats and ships containing tributyl tin (TBT), can not only exist lastingly, also by biological concentration to sea life even human health cause high risks, be considered to artificially introduce one of maximum material of marine environment toxicity up to now.Tributyl tin causes the infringement of liver, strong stimulation effect is had to mucous membrane and skin, hormone receptor in the hormone competition cell secreted with human normal, disturbance endocrine system and produce a series of ill-effect, comprise carcinogenic, damage physiological function, cause nervous system and immune system abnormality etc.And make tributyl tin enter into the fish of ocean and shellfish goes owing to polluting, cause accumulation.Therefore, set up the detection method of high sensitivity and high selectivity, rapidly and efficiently to detect micro-tributyl tin in seafood fish and shellfish extremely urgent.
The detection method that current laboratory is commonly used mainly contains: vapor-phase chromatography (GC), liquid phase chromatography (HPLC), Capillary Electrophoresis (CE) and coupling technique thereof.In the detection of organotin, being most widely used with vapor-phase chromatography.The conventional gas chromatography-mass spectrum that has detects (GC-MS), gas chromatographic flame photometric detection (GC-FPD), the detection of gas chromatography atomic absorption spectrum (GC-AAS), gas chromatography-microwave plasma atomic emission spectroscopy (GC-MIP-AES) etc.But these methods or length consuming time, or sensitivity is very low or threshold value is high, is unsuitable for trace organotin and measures.
Summary of the invention
Technical matters to be solved by this invention is for above prior art, the detection method of tributyl tin in a kind of albacore shellfish is provided, the magnetic molecularly imprinted technical tie-up HPLC-ICP-MS of main employing detects the tributyl tin in the fish of marine products and seashell products, this detection method has better anti-interference, highly sensitive and feature fast; Meanwhile, the enrichment that the method can improve tributyl tin in testing process provides necessary condition for detecting, and adopts microsphere to be conducive to specific detection simultaneously.
The technical solution adopted in the present invention is:
A detection method for tributyl tin in albacore shellfish, comprises the following steps:
(1) preparation of detected sample: get detected sample and be placed in centrifuge tube, add the standard TBT solution of 50-100 μ g/L, every 0.1g detected sample adds 100 μ L standard TBT solution, vibration 1-1.5h, leave standstill, then use acetate-methanol solution to carry out ultrasonic extraction as extract, centrifuging and taking precipitation re-extract 1-3 time, then merge extraction supernatant and use ultrapure water to be settled to certain volume, obtaining liquid upon adsorption;
(2) Fe 3o 4prepared by nano particle: take FeCl 36H 2o and Fe (NH 4) 2(SO 4) 26H 2o, in container, adds 0.1mol/L hydrochloric acid solution, FeCl 36H 2o ︰ Fe (NH 4) 2(SO 4) 26H 2o ︰ hydrochloric acid solution=4.7g ︰ 3.9g ︰ 200ml, logical nitrogen drives oxygen, make dissolving complete under mechanical stirring, then regulate pH value of solution >9, make system become black from yellow, be warming up to 80-85 DEG C, ageing 1-1.5h, waits and is down to room temperature, product magnet separated and collected, and be washed with distilled water to neutrality, vacuum drying;
(3) Fe 3o 4the APTS of nano particle modifies: get Fe3O4 nano particle and be dissolved in ethanol-water solution, dropwise add the amino pyrene-1 of 8-, 3,6-trisulfonic acid trisodium salt (APTS) also stirs, the amino pyrene-1 of Fe3O4 Na meter Ke Li ︰ alcohol-water Rong Ye ︰ 8-, 3,6-trisulfonic acid trisodium salt=100mg ︰ 150mL ︰ 50 μ L, potpourri at room temperature reacts 7-7.5h, and product is separated by external magnetic field, ethanol purge, vacuum drying obtains Fe 3o 4nano grain surface modifies the Fe of upper APTS 3o 4aPTS particle;
(4) Fe 3o 4the MAA of APTS particle modifies: get Fe 3o 4aPTS particle and excessive methacrylic acid (MAA) react, and then magnet is separated, and ethanol washs, and vacuum drying, obtains Fe 3o 4nano grain surface modifies the Fe of upper MAA 3o 4mAA particle;
(5) preparation of the magnetic-particle of MIP layer is coated with: by Fe 3o 4mAA particle and TBT are dissolved in acetonitrile, Fe 3o 4mAA Ke Li ︰ TBT=︰ 100mg ︰ 1mmol, stirring at room temperature 6-6.5h, then Ethylene glycol dimethacrylate (EGDMA) and azo diethyl butyronitrile (AIBN) is added, ice-bath ultrasonic 5-10min under logical nitrogen, in 50 DEG C of stirring reaction 5-5.5h, 20-20.5h is polymerized at 65 DEG C, slaking 5-5.5h at 80-85 DEG C, finally be separated, clean with methanol dichloromethane solution, then extract until not containing template molecule TBT in polymkeric substance with NaOH-methanol solution for several times as eluant, eluent, product separation, vacuum drying obtains the coated magnetic molecularly imprinted polymer Fe of MIP layer 3o 4mIPs, stand-by concentration and separation analysis,
(6) absorption of detected sample: add the magnetic molecularly imprinted polymer Fe that step (5) obtains in the liquid upon adsorption obtained of step (1) 3o 4mIPs, Ye ︰ Fe upon adsorption 3o 4mIPs=50mL ︰ 20mg, magnetic agitation is adsorbed, centrifugal, and get formic acid-methanol solution wash-out absorption TBT in the polymer, dried up by eluent Nitrogen evaporator, and use methanol-water solution constant volume, every 50mL liquid upon adsorption is settled to 1mL, filtering membrane, to be detected;
(7) HPLC-ICP-MS detects: adopt C18 silica gel chromatographic column to carry out stratographic analysis.
In described step (1) acetate-methanol solution, the volume ratio of acetic acid and methyl alcohol is 1:1, and the addition of acetate-methanol solution is every 0.1g detected sample 5mL.
In described step (1), the frequency of ultrasonic extraction is 30-40KHz, and ultrasonic time is 30 seconds.
In described step (1), the constant volume of detected sample is every 0.1g detected sample 50mL.
In described step (3) ethanol-water solution, the volume ratio of ethanol and water is 14:1.
Fe in described step (4) 3o 4the reaction of APTS particle and methacrylic acid is carried out in methanol solvate, and temperature of reaction is 20-25 DEG C, and the reaction time is 24h.
In described step (5), the use amount of acetonitrile is 40mL, and the addition of Ethylene glycol dimethacrylate is 22mmol, and the addition of azo diethyl butyronitrile is 15mg.
In described step (5) methanol dichloromethane solution, the volume ratio of methyl alcohol and methylene chloride is 4:1, and in NaOH-methanol solution, the concentration of NaOH is 0.3mol/L.
In described step (6) formic acid-methanol solution, the concentration of formic acid is 0.1M, and the addition of formic acid-methanol solution is 6mL, and in methanol-water solution, the volume ratio of methyl alcohol and water is 7:3.
In described step (7), the testing conditions of stratographic analysis is: mobile phase is Jia Chun ︰ water=7 ︰ 3 (v/v), wherein contain acetic acid, 0.05% triethylamine of 3% in aqueous phase, sample size 20 μ L, formic acid-the methanol solution of flow velocity 1.2mL/min, 0.1M is as more than eluent 2h.
Because tributyl tin in the seawater light degradation, chemical degradation, biodegradation easily occurs, and content lower (ppt ~ ppb), therefore, form fractionation and preenrichment technology are absolutely necessary, and are also the main paties reducing detection limit further.This method adopts molecular engram solid phase extraction, using molecularly imprinted polymer as solid extracting agent, utilize it to the unfavorable factor such as analyze the compatibility of thing and specific recognition can overcome biology or environmental sample system is complicated, pre-service formality is numerous and diverse, reduce detectability, improve the precision and accuracy analyzed, for the concentration and analysis of trace components provides great convenience.Adopt further magnetic molecule mark, a kind of polymer microballoon simultaneously with paramagnetism and molecularly imprinted polymer characteristic that inorganic magnetic material and molecular imprinting are combined together to form simultaneously.Adsorbent is easy to be separated by externally-applied magnetic field, is therefore suitable for large area Dynamic Adsorption.Adsorbent band permanent magnetism after magnetization, is applied in separation and has some benefit following: velocity of separation is very fast, efficiency is high, can reuse; Practical operation is simple, does not need expensive instrument; Do not affect separated material, especially for needing the biomolecule keeping physiologically active.Therefore adopt the method for magnetic material molecular engram that tributyl tin is separated and enrichment, to measure in magnetic particle fast deposition in magnetic field.
In addition, highly sensitive detecting instrument is also essential, this method adopts HPLC and ICP-MS coupling as analysis approach, merge the efficient separation characteristic of HPLC and the low detection limit of ICP-MS, wide dynamic range liner scope and the plurality of advantages such as multielement isotope signals change can be followed the tracks of, the mensuration of organotin in seawater and marine product can be applied to better.
Embodiment
Below in conjunction with embodiment, the present invention is further described in detail.Iting is noted that following illustrating is all exemplary, being intended to the invention provides further instruction.Except as otherwise noted, all Science and Technology terms that the present invention uses have the identical meanings usually understood with the technical field of the invention personnel.
1, the preparation of magnetic molecularly imprinted polymer
The preparation of molecular engram polymerization: the preparation of molecularly imprinted polymer (MIPs), the methacrylic acid (MAA) getting TBT and the 4mmol of 1mmol is blended in the flask of 50mL, and by potpourri at room temperature prepolymerization 5min.Then the acetonitrile of the Ethylene glycol dimethacrylate (EGDMA) of 20mmol, the azo diethyl butyronitrile (AIBN) of 15mg and 5mL is added respectively.20h is polymerized in 65 DEG C of water-baths.After polymer abrasive screening, make eluant, eluent surname extraction eluted template molecule repeatedly with 0.3M methanol hydrochloride solution, until not containing TBT in eluent, finally polymer beads vacuum drying preserved.The preparation method of contrast molecularly imprinted polymer (Non-imprintingpolymers, NIPs) is the same, does not add template molecule TBT in building-up process.
Fe 3o 4nano particle preparation method is as follows: take 4.7gFeCl 36H 2o and 3.9gFe (NH 4) 2(SO 4) 26H 2o is in 500mL there-necked flask, add 200mL0.1mol/L hydrochloric acid solution, logical nitrogen drives oxygen, dissolve completely under mechanical stirring, then use rapidly 3mol/L sodium hydrate regulator solution pH>9, system becomes black from yellow immediately, be warming up to 80 DEG C, ageing 1h, waits and is down to room temperature, product magnet separated and collected.The product collected is extremely neutral with second distillation water washing, and vacuum drying is for subsequent use.
Modified, at Fe by two steps 3o 4nano grain surface is modified upper methacrylic acid (MAA) (as function monomer): first, the Fe3O4 nano particle getting 100mg is dissolved in (v/v in 150mL ethanol water, 14:1), dropwise add the amino pyrene-1 of 8-of 50 μ L, 3,6-trisulfonic acid trisodium salt (APTS) also stirs, and potpourri at room temperature reacts 7h.Product is separated by external magnetic field, and ethanol purge 5 times, vacuum drying obtains product Fe 3o 4aPTS particle.APTS modify magnetic nanoparticle with excessive methacrylic acid at 25 DEG C, react 24h in methanol solvate after magnet be separated, ethanol washing after, vacuum drying obtains product Fe 3o 4mAA.
Preparation is coated with the magnetic-particle of MIP layer.By Fe 3o 4mAA particle (100mg) and TBT (1mmol) are dissolved in the acetonitrile of 40mL, after stirring at room temperature 6h, add EGDMA (22mmol) and AIBN (15mg), under logical nitrogen after ice-bath ultrasonic 5min, in 50 DEG C of stirring reaction 5h, 20h is polymerized, slaking 5h at 85 DEG C at 65 DEG C.Finally be separated, clean 5 times with methanol dichloromethane solution (v/v, 4:1), then use 0.3mol/L sodium hydrate methanol solution as eluant, eluent surname extraction until not containing template molecule TBT in polymkeric substance.Product separation, vacuum drying obtains the coated magnetic molecularly imprinted polymer (Fe of MIP layer 3o 4mIPs), stand-by concentration and separation analysis.Magnetic contrast molecularly imprinted polymer (Fe 3o 4nIPs) preparation method is the same, does not just add microsphere TBT.
2, HPLC-ICP-MS detects TBT
With the tuning liquid of 10 μ g/L to instrument manual tuning, the indices such as instrumental sensitivity, mass number, oxide, double charge are made to reach requirement.SUPELCODiscoveryC18 (15cmx4.6mm, 5 μm) is adopted to carry out stratographic analysis.Finally determine that testing conditions is: mobile phase: methanol-water=70:30 (v/v), containing acetic acid, 0.05% triethylamine of 3% in aqueous phase, flow velocity: 1.2mL/min, sample size: 20 μ L.Add 0.05% triethylamine as tailingsuppressing reagent.
3, Fe 3o 4the selection of MIPs synthesis condition
The selection of eluant, eluent: the Fe getting 20mg 3o 4mIPs is added to 20 μ gL -1in the TBT solution of concentration, stirring and adsorbing 10h, is adsorbed on Fe with the methanol dichloromethane eluant solution of formic acid, acetic acid, NaOH, ammoniacal liquor allotment variable concentrations 3o 4tBT in MIPs, measures elution amount.Select the good eluant, eluent of elute effect.
The selection of elution time: the Fe getting 5 parts of 20mg 3o 4mIPs is added to 20 μ gL respectively -1in the TBT solution of concentration, stirring and adsorbing 10h, with the good eluant, eluent of above-mentioned elute effect, measures Fe under different elution time 3o 4the elution amount of TBT in MIPs.Select the good elution time of elute effect.
(1) selection of eluant, eluent
Fe is adsorbed on the methanol dichloromethane eluant solution of formic acid, acetic acid, NaOH, ammoniacal liquor allotment variable concentrations 3o 4tBT in MIPs, measures elution amount.Result is as table 12.
The soda acid eluent of table 1 variable concentrations is to Fe 3o 4the eluting rate of MIPs wash-out TBT
As shown in Table 1: suitable Acidity of Aikalinity condition can make TBT more easily elute, but Acidity of Aikalinity excessive concentration also can cause eluting rate to reduce.And acid solution elute effect is better than alkaline solution elute effect, weakly acidic solution is better than the elute effect of strongly acidic solution, therefore selects concentration to be 0.1M (molL -1) formic acid methanol solution as eluant, eluent.
(2) selection of elution time
Fe 3o 4mIPs adsorbs 20 μ gL -1tBT10 hour after, be 0.1M (molL by concentration -1) formic acid methanol solution wash-out, result is as table 13.
The different elution time of table 2 is to the eluting rate of polymkeric substance wash-out TBT
As shown in Table 2: different elution times can affect Fe 3o 4the elution amount of TBT in MIPs, elution time is short, then elution amount is little, and reason fully may not contact with TBT for eluent; Elution time increases, and eluent fully contacts with TBT, and elution amount increases.After 2h, elution amount no longer includes significant change, and Fe is described 3o 4tBT in MIPs elutes substantially, therefore selects 2h to be elution time.
4, the preparation of sample
Getting freezing marine products tissue (mussel, mud blood clam, large yellow croaker) each 3 parts of each 0.1g is positioned in the centrifuge tube of 10mL, and wherein two parts of interpolation concentration are respectively 50,100 μ gL -1standard TBT solution 100 μ L, the TBT being 5,10ng (adds scalar and is respectively 50ngg -1, 100ngg -1).Tissue vibration after mark-on 1 hour, and spend the night.By 5mL volume ratio be the acetic acid methanol solution of 1:1 as the TBT30 second (frequency is about 35KHz) in extract ultrasonic extraction marine product tissue, centrifugal (rotating speed 4000rpm, time 3min).Retain supernatant, repeat single extraction experiment.Supernatant (10mL) after extracting 2 parts merges, and dilutes with the ultrapure water of 50mL.Add the conventional molecular imprinted polymer of 20mg respectively, magnetic agitation is adsorbed, centrifugal, get the formic acid methanol solution wash-out absorption TBT in the polymer of the 0.1M of 6mL, being dried up by eluent Nitrogen evaporator, is the methanol aqueous solution constant volume of 70:30 by the volume ratio of 1mL, crosses organic membrane filtration of 0.45 μm, for subsequent use, treat the analysis of HPLC-ICP-MS sample introduction.
5, the range of linearity and detection limit
Measure under the condition of work optimized, measure the concentration of TBT with HPLC-ICP-MS, with concentration X (the μ gL of absorption peak area Y to TBT -1) make linear regression equation.Be signal to noise ratio (S/N ratio) with S/N=3, the minimum detectability of each marine products under calculating this assay method.Result shows: TBT in the marine product tissue fluid, at 5ngg -1to 1000ngg -1in concentration range, concentration and peak area are good linear relationship.Related coefficient (R 2) between 0.9995 to 0.9999, relative standard deviation is no more than 5%; In mussel tissue fluid, mud blood clam tissue fluid and large yellow croaker tissue fluid, detection limit is respectively 1.0ngg -1, 3.0ngg -1with 4.0 μ gL -1.
6, sample analysis
Method process marine products sample empirically in method, concentration and separation sample introduction.Under the experiment condition of above-mentioned the best, measure the concentration of the TBT in the sample after concentrating with HPLC-ICP-MS, calculation sample recovery of standard addition, result is as table 3.Sample recovery rate scope is at 79.74-95.72%, and relative standard deviation is at 1.3%-4.7%.Show the method measurement result accurately and reliably, there is good accuracy and precision, can be used for the mensuration of TBT in marine product.
Table 3 recovery of standard addition and relative standard deviation (n=4)
With magnetic molecularly imprinted polymer as adsorbent, the TBT in sample organized by enrichment marine product, and carries out detection analysis with HPLC-ICP-MS, and result is as follows:
(1) TBT is in the marine product tissue fluid, at 5ngg -1to 1000ngg -1in concentration range, concentration and peak area are good linear relationship.Related coefficient (R 2) between 0.9995 to 0.9999, relative standard deviation is no more than 5%; In mussel tissue fluid, mud blood clam tissue fluid and large yellow croaker tissue fluid, detection limit is respectively 1.0ngg -1, 3.0ngg -1with 4.0 μ gL -1.The method is applicable to the mensuration of the TBT of complicated marine products sample.
(2) with HPLC-ICP-MS to 100 μ gL -1tBT solution METHOD FOR CONTINUOUS DETERMINATION 6 times, the relative standard deviation recording result is 1.3%, and this instrument analytical method has good repeatability.
(3) under optimal conditions, through actual sample analysis, sample recovery rate scope is at 79.74-95.72%, and relative standard deviation is at 1.3%-4.7%.Show the method measurement result accurately and reliably, can be used for the mensuration of TBT in marine product.
To sum up, magnetic molecularly imprinted polymer is that adsorber operation is easier as adsorbent than conventional molecular imprinted polymer, and the range of linearity is wider, and detectability is lower, can be applied to the mensuration of organotin in seawater and marine product better.
The material that the embodiment of the present invention relates to, reagent and experimental facilities, if no special instructions, be the commercially available prod meeting marine aquatic product safety detection technology field.
The above, be only the preferred embodiments of the present invention, should be understood that; for those skilled in the art; under the prerequisite not departing from core technology of the present invention, can also make improvements and modifications, these improvements and modifications also should belong to scope of patent protection of the present invention.Any change in the implication suitable with claims of the present invention and scope, all should think to be included in the scope of claims.

Claims (10)

1. the detection method of tributyl tin in albacore shellfish, is characterized in that comprising the following steps:
(1) preparation of detected sample: get detected sample and be placed in centrifuge tube, add the standard TBT solution of 50-100 μ g/L, every 0.1g detected sample adds 100 μ L standard TBT solution, vibration 1-1.5h, leave standstill, then use acetate-methanol solution to carry out ultrasonic extraction as extract, centrifuging and taking precipitation re-extract 1-3 time, then merge extraction supernatant and use ultrapure water to be settled to certain volume, obtaining liquid upon adsorption;
(2) Fe 3o 4prepared by nano particle: take FeCl 36H 2o and Fe (NH 4) 2(SO 4) 26H 2o, in container, adds 0.1mol/L hydrochloric acid solution, FeCl 36H 2o ︰ Fe (NH 4) 2(SO 4) 26H 2o ︰ hydrochloric acid solution=4.7g ︰ 3.9g ︰ 200ml, logical nitrogen drives oxygen, make dissolving complete under mechanical stirring, then regulate pH value of solution >9, make system become black from yellow, be warming up to 80-85 DEG C, ageing 1-1.5h, waits and is down to room temperature, product magnet separated and collected, and be washed with distilled water to neutrality, vacuum drying;
(3) Fe 3o 4the APTS of nano particle modifies: get Fe3O4 nano particle and be dissolved in ethanol-water solution, dropwise add the amino pyrene-1 of 8-, 3,6-trisulfonic acid trisodium salt also stirs, the amino pyrene-1 of Fe3O4 Na meter Ke Li ︰ alcohol-water Rong Ye ︰ 8-, 3,6-trisulfonic acid trisodium salt=100mg ︰ 150mL ︰ 50 μ L, potpourri at room temperature reacts 7-7.5h, and product is separated by external magnetic field, ethanol purge, vacuum drying obtains Fe 3o 4aPTS particle;
(4) Fe 3o 4the MAA of APTS particle modifies: get Fe 3o 4aPTS particle and excessive metering system acid reaction, then magnet is separated, and ethanol washs, and vacuum drying, obtains Fe 3o 4mAA particle;
(5) preparation of the magnetic-particle of MIP layer is coated with: by Fe 3o 4mAA particle and TBT are dissolved in acetonitrile, Fe 3o 4mAA Ke Li ︰ TBT=︰ 100mg ︰ 1mmol, stirring at room temperature 6-6.5h, then Ethylene glycol dimethacrylate and azo diethyl butyronitrile is added, ice-bath ultrasonic 5-10min under logical nitrogen, in 50 DEG C of stirring reaction 5-5.5h, 20-20.5h is polymerized at 65 DEG C, slaking 5-5.5h at 80-85 DEG C, finally be separated, clean with methanol dichloromethane solution, then extract for several times until not containing template molecule TBT in polymkeric substance, product separation, vacuum drying obtains the coated magnetic molecularly imprinted polymer Fe of MIP layer as eluant, eluent with NaOH-methanol solution 3o 4mIPs, stand-by concentration and separation analysis;
(6) absorption of detected sample: add the magnetic molecularly imprinted polymer Fe that step (5) obtains in the liquid upon adsorption obtained of step (1) 3o 4mIPs, Ye ︰ Fe upon adsorption 3o 4mIPs=50mL ︰ 20mg, magnetic agitation is adsorbed, centrifugal, and get formic acid-methanol solution wash-out absorption TBT in the polymer, dried up by eluent Nitrogen evaporator, and use methanol-water solution constant volume, every 50mL liquid upon adsorption is settled to 1mL, filtering membrane, to be detected;
(7) HPLC-ICP-MS detects: adopt C18 silica gel chromatographic column to carry out stratographic analysis.
2. the detection method of tributyl tin in a kind of albacore shellfish according to claim 1, it is characterized in that: in described step (1) acetate-methanol solution, the volume ratio of acetic acid and methyl alcohol is 1:1, the addition of acetate-methanol solution is every 0.1g detected sample 5mL.
3. the detection method of tributyl tin in a kind of albacore shellfish according to claim 1, is characterized in that: in described step (1), the frequency of ultrasonic extraction is 30-40KHz, and ultrasonic time is 30 seconds.
4. the detection method of tributyl tin in a kind of albacore shellfish according to claim 1, is characterized in that: in described step (1), the constant volume of detected sample is every 0.1g detected sample 50mL.
5. the detection method of tributyl tin in a kind of albacore shellfish according to claim 1, is characterized in that: in described step (3) ethanol-water solution, the volume ratio of ethanol and water is 14:1.
6. the detection method of tributyl tin in a kind of albacore shellfish according to claim 1, is characterized in that: Fe in described step (4) 3o 4the reaction of APTS particle and methacrylic acid is carried out in methanol solvate, and temperature of reaction is 20-25 DEG C, and the reaction time is 24h.
7. the detection method of tributyl tin in a kind of albacore shellfish according to claim 1, it is characterized in that: in described step (5), the use amount of acetonitrile is 40mL, the addition of Ethylene glycol dimethacrylate is 22mmol, and the addition of azo diethyl butyronitrile is 15mg.
8. the detection method of tributyl tin in a kind of albacore shellfish according to claim 1, it is characterized in that: in described step (5) methanol dichloromethane solution, the volume ratio of methyl alcohol and methylene chloride is 4:1, in NaOH-methanol solution, the concentration of NaOH is 0.3mol/L.
9. the detection method of tributyl tin in a kind of albacore shellfish according to claim 1, it is characterized in that: in described step (6) formic acid-methanol solution, the concentration of formic acid is 0.1M, the addition of formic acid-methanol solution is 6mL, and in methanol-water solution, the volume ratio of methyl alcohol and water is 7:3.
10. the detection method of tributyl tin in a kind of albacore shellfish according to claim 1, it is characterized in that: in described step (7), the testing conditions of stratographic analysis is: mobile phase is Jia Chun ︰ water=7 ︰ 3, wherein contain acetic acid, 0.05% triethylamine of 3% in aqueous phase, sample size 20 μ L, formic acid-the methanol solution of flow velocity 1.2mL/min, 0.1M is as more than eluent 2h.
CN201510902569.1A 2015-12-09 2015-12-09 Method for detecting tributyltin in marine fishes and shellfishes Pending CN105548381A (en)

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