CN114740129A - On-line detection device and analysis method for organotin morphological analysis - Google Patents
On-line detection device and analysis method for organotin morphological analysis Download PDFInfo
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- 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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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N30/26—Conditioning of the fluid carrier; Flow patterns
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- G—PHYSICS
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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
- G01N30/02—Column chromatography
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- G—PHYSICS
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- 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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- G01N2030/062—Preparation extracting sample from raw material
Abstract
An on-line detection device and an analysis method for organotin morphological analysis, which belong to the field of environmental sample pretreatment and chemical analysis detection. Firstly, preparing an integral solid phase micro-extraction column doped with MNPs, applying electric fields with different directions and strengths to the extraction column in the adsorption and desorption processes, and inducing magnetic nanoparticles in an integral adsorbent to generate magnetic field gradient. According to the magnetic micro-flow principle, the diamagnetic target tends to gather in the area with the weakest magnetic field intensity, so that the extraction efficiency of the target is improved, the enrichment of the target is accelerated, and the analysis time is shortened. By utilizing the diamagnetic characteristic and the magnetic microfluidic principle of an organic tin compound and combining an in-tube solid phase microextraction technology based on an integral material and a high performance liquid chromatography separation means, an in-tube solid phase microextraction-chromatography on-line combined system based on magnetic field assistance is established, and the on-line operation from extraction to detection and analysis of OTCs in different forms is realized. Simple operation, high automation degree, good accuracy and environmental protection.
Description
Technical Field
The invention belongs to the field of pretreatment and chemical analysis and detection of environmental samples, and particularly relates to an online detection device and an analysis method for organotin morphological analysis, which can be used for environmental water samples, marine products and other complex samples.
Background
Organotin compounds (OTCs) are metal organic compounds formed by directly combining tin and carbon elements, and are widely used as antifouling paints, herbicides, insecticides for ships and stabilizers in the plastic industry because of their thermal stability (wang 23022, huhongmei, guo yun, etc. the development of methods for detecting organotin compounds in aquatic products, the bulletin of food safety and quality, 2019,10: 7245-. The OTCs are various in types, and can be divided into mono-substituted tin, di-substituted tin, tri-substituted tin and tetra-substituted tin according to the number of organic substituent groups connected with tin, and the toxicity of the tri-substituted tin is more than that of the di-substituted tin and more than that of the mono-substituted tin. Studies have shown that the ng/L level of tributyltin (TBT) in water can lead to sexual distortion of marine gastropods (Alzieu C. environmental impact of TBT: the family experiment, Science of the Total Environment,2000,258: 99-102).
At present, the detection method of OTCs mainly includes gas chromatography-mass spectrometry (Munoz J, Baena JR, Gallego M, et al60and gas Chromatography-mass spectrometry, Journal of Chromatography A,2004,1023: 175-, noble, segmented, et al HPLC-ICP 563) and HPLC-FD (high Performance liquid chromatography-fluorescence detection, HPLC-FD) (Graupere, Lealc, Granados M, et altriphenylin segments by liquid Chromatography with fluorine detection of spiking products, Journal of Chromatography A,1999,846: 413-423). The complex containing the fluorescent chromophore can be generated by the reaction of the OTCs and the fluorescent reagent, and the complex can be detected by HPLC-FD, so that the simultaneous and rapid analysis of the OTCs in different forms can be realized. Compared with other detection methods, the HPLC-FD has the advantages of simple operation, small substrate interference, low operation cost and obvious advantages in the morphological analysis of the OTCs.
The concentration of OTCs in practical samples is low, so that sample pretreatment is usually required before detection, which reduces substrate interference and improves detection sensitivity. Currently, the sample pretreatment techniques for OTCs mainly include liquid-liquid extraction (in flowers, Jing 2815634, Wang, et al. liquid Chromatography-inductively coupled plasma mass spectrometry, used to simultaneously detect various organotins in seafood, 2008,36:1035-, massanisso P, Morabito R.Complex of wet selected extraction methods for the determination of butyl-and phenyltin compounds in music samples, TrAC Trends in Analytical Chemistry,2000,19: 97-106). An in-tube solid-phase microextraction (IT-SPME) technology is developed on the basis of solid-phase microextraction, and has the advantages of simplicity and convenience in operation, environmental friendliness, easiness in online combination with a chromatographic instrument and the like. However, the IT-SPME has the problems of limited extraction capacity and low extraction efficiency in practical application, and the magnetic field auxiliary technology can improve the extraction efficiency of the IT-SPME and accelerate the extraction process. The magnetic field auxiliary technology has the action principle that Magnetic Nano Particles (MNPs) are doped in an extraction column, an external electric field is applied to the extraction column in the extraction process to induce the magnetic nano particles in the extraction column to generate a magnetic field gradient in an extraction medium, so that a target object with diamagnetism is gathered in an area with the weakest magnetic field intensity, and efficient separation and enrichment of the target object are further realized.
Disclosure of Invention
The invention aims to provide an on-line detection device which is simple and convenient to operate, high in accuracy and environment-friendly and can be used for analyzing the organotin form.
The second purpose of the invention is to provide an on-line analysis method for organotin morphological analysis, which can be used for organotin morphological analysis of environmental water samples, marine products and complex samples.
The invention provides an on-line detection device for organotin morphological analysis, which comprises a first flow pump, a second flow pump, a third flow pump, a fourth flow pump, a solid phase micro-extraction column, a first six-way valve, a second six-way valve, a chromatographic column, a quantitative ring, a high performance liquid chromatograph, a magnetic coil and a direct current power supply, wherein the first flow pump is connected with the first flow pump;
the first flow pump and the second flow pump are both connected with the first six-way valve and are respectively used for conveying samples and desorbing liquid; the solid phase micro-extraction column is arranged in a magnetic field, and two ends of the solid phase micro-extraction column are respectively connected to the first six-way valve; the first six-way valve is connected with the second six-way valve, and two ends of the quantitative ring are respectively connected to the second six-way valve; the third flow pump and the chromatographic column are both connected with the second six-way valve, the third flow pump is used for conveying a mobile phase, and the chromatographic column is connected with the high performance liquid chromatograph; the fourth flow pump is used for conveying a fluorescence derivatization reagent of the organic tin compound; the on-line adsorption, desorption and detection processes of the sample are realized through the valve position switching of the first six-way valve and the second six-way valve; the magnetic coil is wound on the solid-phase micro-extraction column, and two ends of the magnetic coil are respectively connected with a direct-current power supply.
The first six-way valve and the second six-way valve are connected through a PEEK pipe.
The high performance liquid chromatograph may be HPLC-FD.
The solid phase micro-extraction column can adopt a magnetic nanoparticle-doped monolithic solid phase micro-extraction column (MMEC), and the preparation method of the magnetic nanoparticle-doped monolithic solid phase micro-extraction column (MMEC) comprises the following steps: mixing the monomer mixture, a pore-forming agent and Magnetic Nanoparticles (MNPs), performing ultrasonic treatment to obtain a uniform solution, injecting the uniform solution into a tubular container, sealing, and performing polymerization reaction at 60-80 ℃ for 6-48 h; after the synthesis is finished, washing the product with methanol, ethanol or acetonitrile until no impurity is detected in the effluent; before use, the mixture is washed and activated by methanol, ethanol or acetonitrile.
The mass percentage of the monomer mixture in the prepolymerization solution is 20-50%, and the mass percentage of MNPs is 0.5-5 mg/100mg of the prepolymerization solution.
The monomer mixture comprises a functional monomer, an initiator and a cross-linking agent.
The monomer mixture comprises, by mass, 20-60% of functional monomers (1-allyl-3-methylimidazolium bis (fluoromethanesulfonyl) imide salt and 9-vinylanthracene), 0.5-4% of initiator azobisisobutyronitrile, and the balance of crosslinking agent divinylbenzene.
The pore-foaming agent comprises n-propanol and 1, 4-butanediol, and the composition ratio of the pore-foaming agent is n-propanol: 1, 4-butanediol: 1: 3-3: 1; the MNPs are modified Fe3O4Nanoparticles.
The invention provides an on-line analysis method for organotin morphological analysis, which comprises the following specific steps:
pretreating a sample, filtering the water sample by a filter membrane before using the water sample, and adjusting the pH value of the sample to 5.0-8.0; performing ultrasonic extraction on marine products before use, wherein an extraction solvent is acetonitrile: ultrapure water: acetic acid: 65: 12: 23(v/v/v, containing 0.15% of triethylamine), and the extraction time is 10-40 min; centrifuging at a speed of 2000-6000 r/min for 5-30 min, filtering the centrifuged supernatant by a filter membrane, diluting by 1-10 times, and adjusting the pH to 5.0-8.0; inputting a sample into a solid-phase micro-extraction column through a first flow pump, adsorbing a target object, and keeping the direction of a magnetic field to be the same as the flow direction of the sample at the moment, wherein the magnetic field intensity is 0-70 Gs; after adsorption is finished, inputting desorption liquid into a solid-phase micro-extraction column by using a second flow pump, desorbing a target object, and changing the direction of a magnetic field with the magnetic field intensity of 0-70 Gs; after the desorption is finished, the third flow pump conveys the chromatographic mobile phase to bring the eluent into a chromatographic column, the fluorescence derivative reagent loaded by the fourth flow pump and the OTCs in the eluent are mixed and reacted after the column, and finally the mixture enters a high performance liquid chromatograph for determination.
The desorption solution can adopt a methanol, ethanol or acetonitrile solution containing 0-5% (v/v) formic acid, the first flow pump inputs 0.5-10 mL of sample solution into the solid phase micro-extraction column at the flow rate of 0.02-0.20 mL/min, and the second flow pump inputs the desorption solution into the solid phase micro-extraction column at the flow rate of 0.01-0.10 mL/min.
The conditions of the post-column mixing reaction comprise a fluorescence derivatization reagent, a reagent concentration and a reagent flow rate, wherein the fluorescence derivatization reagent is morin and fisetin, the reagent concentration is 2-10 mg/L, and the reagent flow rate is 2-5 mL/min.
The chromatographic conditions of the high performance liquid chromatograph comprise a chromatographic column, a mobile phase, an elution program, an excitation wavelength and an emission wavelength, wherein the chromatographic column is a C18 column, the mobile phase is acetonitrile, ultrapure water, acetic acid, 65, 12, 23(v/v/v, containing 0.15% of triethylamine), and the elution program is isocratic elution for 7 min; the sample injection amount is 20-120 mu L, the flow rate is 1.0mL/min, the excitation wavelength is 412nm, and the emission wavelength is 498 nm.
The invention firstly prepares the integral solid phase micro-extraction column doped with MNPs, and then applies electric fields with different directions and strengths to the extraction column in the adsorption and desorption processes to induce the magnetic nano particles in the integral adsorbent to generate magnetic field gradient. According to the magnetic micro-flow principle, the diamagnetic target tends to gather in the area with the weakest magnetic field intensity, so that the extraction efficiency of the target is improved, the enrichment of the target is accelerated, and the analysis time is shortened. The invention applies the magnetic field auxiliary in-tube solid phase microextraction-chromatography coupling technology to the online morphological analysis of OTCs in environmental water samples, marine products and other complex samples for the first time. The on-line analysis and detection of different forms of OTCs from extraction to detection and analysis are realized through an IT-SPME device and HPLC-FD, and the method has the advantages of simplicity and convenience in operation, high accuracy, environmental friendliness and the like, so that the established analysis method has a wide practical application prospect.
Drawings
FIG. 1 shows the reaction equation for MMEC synthesis in the example of the present invention.
Fig. 2 is a schematic structural diagram of an online detection device according to an embodiment of the present invention.
FIG. 3 is an infrared spectrum of the material in the extraction column in example 3 of the present invention.
FIG. 4 is a scanning electron micrograph of the material in the extraction column in example 3 of the present invention.
FIG. 5 is a chromatogram for separating 3 OTCs labeled with ultrapure water in example 3 of the present invention. Wherein, a is directly injected sample, and b is injected sample after solid phase micro-extraction in the magnetic field auxiliary tube.
FIG. 6 is a chromatogram of the separation of 3 OTCs from different samples according to example 5 of the present invention. Wherein, the left picture is a seawater sample; the right panel is a prawn sample; a is blank and b is labeled.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following embodiments will be further described with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
First, preparing the MMEC:
the synthesis reaction equation of MMEC is shown in figure 1, AMT and VA are used as functional monomers, DVB is used as a cross-linking agent, AIBN is used as an initiator, n-propanol and 1, 4-butanediol are used as pore-foaming agents, and modified Fe3O4The nano particles are used as MNPs to form a prepolymerization solution; the monomer mixture (comprising a functional monomer, a cross-linking agent and an initiator) comprises 20 percent of the functional monomer, 0.5 percent of AIBN and 79.5 percent of DVB by mass percent; the functional monomers comprise AMT 20% and VA 80% in percentage by mass; the mass ratio of the n-propanol to the 1, 4-butanediol in the pore-foaming agent is 1: 3; the composition of the prepolymerization solution comprises 20 percent of the monomer mixture, 80 percent of pore-forming agent and 0.5mg/100mg of MNPs by mass percent. Weighing the reactants according to the proportion, mixing, performing ultrasonic treatment to obtain a uniform solution, and injecting into a tubeSealing the container, and then placing the container at 60 ℃ for polymerization reaction for 24 hours. After the synthesis is finished, the product is washed by acetonitrile until no impurities are detected in the effluent. Before use, the activated product is washed with acetonitrile for activation.
Secondly, a magnetic field auxiliary tube solid phase microextraction-high performance liquid chromatograph (MA/IT-SPME-HPLC-FD) online combination device is set up, namely an online detection device for organotin morphological analysis:
the structure schematic diagram of the on-line detection device for organotin morphological analysis is shown in fig. 2, and the device comprises a first flow pump 1, a second flow pump 2, a third flow pump 3, a fourth flow pump 4, a solid phase micro-extraction column 5, a first six-way valve 6, a second six-way valve 7, a chromatographic column 8, a quantification ring 9, a high performance liquid chromatograph 10, a magnetic coil 11 and a direct current power supply 12; the first flow pump 1 and the second flow pump 2 are both connected with a first six-way valve 6, the first flow pump 1 is used for conveying desorption liquid (elution solvent), and the second flow pump 2 is used for conveying samples; the solid phase micro-extraction 5 column is arranged in a magnetic field, and two ends of the solid phase micro-extraction 5 column are respectively connected to the first six-way valve 6; the first six-way valve 6 is connected with the second six-way valve 7 through PEEK pipes, and two ends of the quantitative ring 9 are respectively connected to the second six-way valve 7; the third flow pump 3 and the chromatographic column 8 are both connected with the second six-way valve 7, the third flow pump 3 is used for conveying a mobile phase, and the chromatographic column 8 is connected with the high performance liquid chromatograph 10; the fourth flow pump 4 is used for conveying a fluorescent derivatization reagent of the organotin compound; the on-line adsorption, desorption and detection processes of the sample are realized through the valve position switching of the first six-way valve 6 and the second six-way valve 7; the magnetic coil 11 is wound on the solid phase micro-extraction column 5, and two ends of the magnetic coil 11 are respectively connected with the direct current power supply 12. The solid phase micro extraction column 5 is placed in an external electric field. The first flow pump 1, the second flow pump 2, the solid phase micro-extraction column 5 and the first six-way valve 6 form an extraction device.
The solid phase micro-extraction column 5 is externally wound with a magnetic coil which can be connected with a direct current power supply, and the magnetic coil generates a magnetic field with certain strength and direction by controlling the current magnitude and direction in the adsorption and desorption processes, so that the magnetic nano particles in the integral capillary column are induced to generate a certain magnetic field gradient, thereby improving the extraction efficiency of the OTCs and shortening the analysis time.
Thirdly, pretreatment of the sample:
before using, water sample is filtered by a filter membrane with the diameter of 0.22 mu m, and the pH value of the sample is adjusted to 5.0. Performing ultrasonic extraction before marine product is used, wherein the extraction solvent is acetonitrile: ultrapure water: acetic acid: 65: 12: 23(v/v/v, containing 0.15% triethylamine), and the extraction time is 10 min; then centrifuging at 2000r/min for 5min, filtering the supernatant with filter membrane, diluting by 2 times, and adjusting pH to 5.0.
Fourthly, applying an MA/IT-SPME-HPLC-FD on-line combined system:
referring to fig. 2, during adsorption, the first six-way Valve (Valve 1) and the second six-way Valve (Valve 2) are both in "Load" position, the direct current power supply is turned on to make the direction of the magnetic field in the MMEC consistent with the flow direction of the sample solution, the magnetic field strength is 20Gs, and simultaneously the pump 1 is turned on to input 0.5mL of the sample solution into the MMEC at the flow rate of 0.02mL/min to adsorb the OTCs; after adsorption, keeping Valve 2 at the "Load" position, turning Valve 1 to the "Inject" position, changing the direction of a direct current power supply to reverse the direction of a magnetic field in the MMEC, enabling the magnetic field strength to be 20Gs, inputting 20 mu L of acetonitrile containing 0.5% (v/v) formic acid into the MMEC by using a pump 2 at the flow rate of 0.02mL/min to desorb a target, and storing eluent in a quantitative ring connected to the Valve 2; after desorption, Valve 2 is transferred to the "Inject" position, the eluent is carried into the chromatographic column by using a chromatographic mobile phase, the fluorescence derivative reagent loaded by the mobile pump and OTCs in the eluent are mixed and reacted after the column, and finally the mixture enters a fluorescence detector for determination.
The high performance liquid chromatography conditions include a chromatography column, a mobile phase, an elution procedure, excitation and emission wavelengths, wherein the chromatography column is a C18 column, and the mobile phase is acetonitrile: ultrapure water, acetic acid, and 0.15% triethylamine are added, wherein the ratio of acetic acid to acetic acid is 65: 12: 23(v/v/v, and the amount of triethylamine is 0.15%), and the elution procedure is performed for 7min at equal rate; the sample volume was 20. mu.L, the flow rate was 1mL/min, the excitation wavelength of the fluorescence detector was 412nm, and the emission wavelength was 498 nm.
The post-column derivatization conditions comprise fluorescence derivatization reagents, reagent concentrations and reagent flow rates, wherein the fluorescence derivatization reagents are morin and fisetin, the reagent concentrations are 2mg/L, and the flow rates are 5 mL/min.
Example 2
First, preparing the MMEC:
AMT and VA are used as functional monomers, DVB is used as a cross-linking agent, AIBN is used as an initiator, n-propanol and 1, 4-butanediol are used as pore-forming agents to modify Fe3O4The nano particles are MNPs to form a prepolymerization solution; the monomer mixture (comprising a functional monomer, a cross-linking agent and an initiator) comprises 30% of the functional monomer, 1.0% of AIBN and 69% of DVB by mass percent; the functional monomers comprise 30 mass percent of AMT and 70 mass percent of VA; the mass ratio of the n-propanol to the 1, 4-butanediol in the pore-foaming agent is 3: 1; the composition of the prepolymerization solution comprises 30 percent of monomer mixture, 70 percent of pore-foaming agent and 5.0mg/100mg of MNPs by mass percent. Weighing the reactants according to the proportion, mixing, performing ultrasonic treatment to obtain a uniform solution, injecting the uniform solution into a tubular container, sealing, and performing polymerization reaction at 80 ℃ for 20 hours. After the synthesis is finished, the product is washed by acetonitrile until no impurities are detected in the effluent. Before use, the activated product is washed with acetonitrile for activation.
And secondly, constructing an online MA/IT-SPME-HPLC-FD combination device as in example 1.
Thirdly, pretreating a sample:
before being used, an environmental water sample is filtered by a filter membrane with the diameter of 0.22 mu m, and the pH value of the sample is adjusted to 6.0. Performing ultrasonic extraction on marine products and other complex samples before use, wherein the extraction solvent is acetonitrile, ultrapure water, acetic acid, 65: 12: 23(v/v, containing 0.15% triethylamine), and the extraction time is 40 min; then centrifuging at 6000r/min for 30min, filtering the supernatant obtained by centrifuging with a filter membrane, diluting by 10 times, and adjusting pH to 6.0.
Fourthly, applying an MA/IT-SPME-HPLC-FD on-line combined system:
referring to fig. 2, during adsorption, the first six-way Valve (Valve 1) and the second six-way Valve (Valve 2) are both in "Load" position, the dc power supply is turned on to make the direction of the magnetic field in the MMEC consistent with the flow direction of the sample solution, the magnetic field strength is 70Gs, and simultaneously the pump 1 is turned on to input 10mL of sample solution into the MMEC at the flow rate of 0.20mL/min to adsorb the OTCs; after adsorption is finished, keeping the Valve 2 at the 'Load' position, turning the Valve 2 to the 'Inject' position, changing the direction of a direct current power supply to enable the direction of a magnetic field in the MMEC to be reversed, enabling the magnetic field intensity to be 70Gs, inputting 120 mu L of acetonitrile containing 1.0% (v/v) formic acid into the MMEC by using a pump 2 at the flow rate of 0.10mL/min to desorb a target, and storing eluent in a quantitative ring connected to the Valve 2; after desorption, Valve 2 is transferred to the "Inject" position, the eluent is carried into the chromatographic column by using a chromatographic mobile phase, the fluorescence derivative reagent loaded by the mobile pump and OTCs in the eluent are mixed and reacted after the column, and finally the mixture enters a fluorescence detector for determination.
The high performance liquid chromatography conditions comprise a chromatographic column, a mobile phase, an elution program, an excitation wavelength and an emission wavelength, wherein the chromatographic column is a C18 column, the mobile phase is acetonitrile: ultrapure water: acetic acid: 65: 12: 23(v/v/v, containing 0.15% triethylamine), and the elution program is isocratic elution for 7 min; the sample volume was 120. mu.L, the flow rate was 1mL/min, the excitation wavelength of the fluorescence detector was 412nm, and the emission wavelength was 498 nm.
The post-column derivatization conditions comprise fluorescence derivatization reagents, reagent concentrations and flow rates, wherein the fluorescence derivatization reagents are morin and fisetin, the reagent concentrations are 2.5mg/L, and the flow rates are 4 mL/min.
Example 3
First, preparing MMEC:
AMT and VA are used as functional monomers, DVB is used as a cross-linking agent, AIBN is used as an initiator, n-propanol and 1, 4-butanediol are used as pore-forming agents to modify Fe3O4The nano particles are MNPs to form a prepolymerization solution; the monomer mixture (comprising a functional monomer, a cross-linking agent and an initiator) comprises 40% of the functional monomer, 1.0% of azodiisobutyronitrile and 59% of divinylbenzene by mass percent; the functional monomers comprise 67 mass percent of AMT and 33 mass percent of VA; the mass ratio of the n-propanol to the 1, 4-butanediol in the pore-foaming agent is 1: 1; the composition of the prepolymerization solution comprises 30 percent of monomer mixture, 70 percent of pore-foaming agent and 2.5mg/100mg of MNPs in percentage by mass. Weighing the reactants according to the proportion, mixing, performing ultrasonic treatment to obtain uniform solution, and injecting into a tubular shapeThe container is sealed and then is placed at 70 ℃ for polymerization reaction for 12 h. After the synthesis is finished, the product is washed by acetonitrile until no impurities are detected in the effluent. Before use, the activated product is washed with acetonitrile for activation.
Secondly, an online MA/IT-SPME-HPLC-FD apparatus was constructed according to example 1.
Thirdly, pretreating a sample:
before being used, an environmental water sample is filtered by a filter membrane with the diameter of 0.22 mu m, and the pH value of the sample is adjusted to 7.0. Before use, marine products and other complex samples are subjected to ultrasonic extraction, wherein an extraction solvent is acetonitrile, ultrapure water, acetic acid, 65, 12, 23(v/v, containing 0.15% of triethylamine), and the extraction time is 20 min; then centrifuging for 15min at the speed of 4000r/min, filtering the supernatant obtained by centrifuging through a filter membrane, diluting by 3 times, and adjusting the pH value to 7.0.
Fourthly, applying an MA/IT-SPME-HPLC-FD on-line combined system:
referring to fig. 2, during adsorption, the first six-way Valve (Valve 1) and the second six-way Valve (Valve 2) are both in "Load" position, the direct current power supply is turned on to make the direction of the magnetic field in the MMEC consistent with the flow direction of the sample solution, the magnetic field strength is 20Gs, and simultaneously the pump 1 is turned on to input 4mL of sample solution into the MMEC at the flow rate of 0.10mL/min to adsorb the OTCs; after adsorption, keeping Valve 2 at the "Load" position, turning Valve 1 to the "Inject" position, changing the direction of a direct current power supply to reverse the direction of a magnetic field in the MMEC, enabling the magnetic field strength to be 40Gs, inputting 90 mu L of acetonitrile containing 1.5% (v/v) formic acid into the MMEC by using a pump 2 at the flow rate of 0.04mL/min to desorb a target, and storing eluent in a quantitative ring connected to the Valve 2; after desorption, Valve 2 is switched to the "Inject" position, the eluent is carried into the chromatographic column by using a chromatographic mobile phase, the fluorescence derivative reagent loaded by the mobile pump and OTCs in the eluent are mixed and reacted after the column, and finally the mixture enters a fluorescence detector for determination.
The high performance liquid chromatography conditions comprise a chromatographic column, a mobile phase, an elution program and excitation and emission wavelengths, wherein the chromatographic column is a C18 column, the mobile phase is acetonitrile, ultrapure water, acetic acid, 65, 12, 23(v/v/v, containing 0.15% triethylamine), and the elution program is isocratic elution for 7 min; the sample volume was 90. mu.L, the flow rate was 1mL/min, the excitation wavelength of the fluorescence detector was 412nm, and the emission wavelength was 498 nm.
The post-column derivatization conditions comprise fluorescence derivatization reagents, reagent concentrations and flow rates, wherein the fluorescence derivatization reagents are morin and fisetin, the reagent concentrations are 3mg/L, and the flow rates are 3 mL/min.
The infrared spectrum of the material in the extraction column of example 3 is shown in FIG. 3, in which the wave numbers of the main absorption peaks are 3018cm each-1、2922cm-1、1603cm-1、1508cm-1、1447cm-1、1165cm-1、903cm-1、797cm-1、559cm-1. The scanning electron microscope image of the materials in the extraction column is shown in figure 4, and the separation chromatogram of the ultrapure water and 3 kinds of OTCs is shown in figure 5. Wherein, a is directly injected sample, and b is injected sample after solid phase micro-extraction in the magnetic field auxiliary tube. The addition standard concentrations of diphenyltin, tributyltin and triphenyltin were 10, 200 and 20. mu.g/L, respectively.
Example 4
Standard working curves of 3 OTCs are established by respectively using ultrapure water and clams as substrates according to the conditions of example 3, and the linear range, detection limit, quantification limit and precision data of the 3 OTCs are shown in Table 1. The concentration of 3 OTCs has good linear relation with peak area in a certain linear range, and the correlation coefficient R2＞0.99。
TABLE 1
a: the low standard concentration of diphenyl tin, tributyl tin and triphenyl tin in water samples and marine products is 0.5, 10 and 1.0 mu g/L and 25, 250 and 25 mu g/kg respectively;
b: the high standard concentrations of diphenyl tin, tributyltin and triphenyl tin in water samples and marine products are respectively 10, 200 and 100 mu g/L and 2500, 5000 and 5000 mu g/kg.
Example 5
The detection of 3 OTCs in river water, sea water, reservoir water, Penaeus vannamei and oyster shell was carried out according to the conditions of example 3, and Table 2 shows the results of the determination of 3 OTCs in environmental water sample and marine products and the recovery data of spiking. The average recovery rate of the three standard adding concentrations ranges from 80.3% to 116%, the relative standard deviation RSD of the daytime precision is less than 10%, and the detected concentration of the target substance ranges from 0.48 mu g/L to 26 mu g/L and from 5.0 mu g/kg to 203 mu g/kg respectively.
TABLE 2
ND: not detected out
The chromatogram for separating the 3 OTCs in different samples in example 5 is shown in FIG. 6. Wherein, the left picture is a seawater sample; the right panel is a prawn sample; a is blank and b is labeled. The standard adding concentrations of diphenyltin, tributyltin and triphenyltin in seawater are respectively 2.0, 50 and 10 mu g/L; the spiked concentrations in the Penaeus vannamei samples were 500, 10000 and 500. mu.g/kg, respectively.
The above-described embodiments are merely preferred embodiments of the present invention, and should not be construed as limiting the scope of the invention. All equivalent changes and modifications made within the scope of the present invention should be covered by the present invention.
Claims (10)
1. An on-line detection device for organotin morphological analysis is characterized by comprising a first flow pump, a second flow pump, a third flow pump, a fourth flow pump, a solid phase micro-extraction column, a first six-way valve, a second six-way valve, a chromatographic column, a quantitative ring, a high performance liquid chromatograph, a magnetic coil and a direct current power supply;
the first flow pump and the second flow pump are both connected with the first six-way valve and are respectively used for conveying samples and desorbing liquid; the solid phase micro-extraction column is arranged in a magnetic field, and two ends of the solid phase micro-extraction column are respectively connected to the first six-way valve; the first six-way valve is connected with the second six-way valve, and two ends of the quantitative ring are respectively connected to the second six-way valve; the third flow pump and the chromatographic column are both connected with the second six-way valve, the third flow pump is used for conveying a mobile phase, and the chromatographic column is connected with the high performance liquid chromatograph; the fourth flow pump is used for conveying a fluorescence derivatization reagent of the organic tin compound; the on-line adsorption, desorption and detection processes of the sample are realized through the valve position switching of the first six-way valve and the second six-way valve; the magnetic coil is wound on the solid-phase micro-extraction column, and two ends of the magnetic coil are respectively connected with a direct-current power supply.
2. The on-line measuring device for organotin morphology analysis as recited in claim 1, wherein said first six-way valve and said second six-way valve are connected by a PEEK tube.
3. The on-line detection device for organotin morphology analysis as recited in claim 1, wherein said HPLC-FD is used as the HPLC.
4. The on-line detection device for organotin morphological analysis as claimed in claim 1 wherein said solid phase microextraction column can be an integral solid phase microextraction column doped with magnetic nanoparticles, said integral solid phase microextraction column doped with magnetic nanoparticles being prepared by the following steps: mixing the monomer mixture, the pore-foaming agent and the magnetic nanoparticles, performing ultrasonic treatment to obtain a uniform solution, injecting the uniform solution into a tubular container, sealing the tubular container, and performing polymerization reaction at the temperature of between 60 and 80 ℃ for 6 to 48 hours; after the synthesis is finished, the mixture is washed by methanol, ethanol or acetonitrile until no impurity is detected in the effluent; before use, the mixture is washed and activated by methanol, ethanol or acetonitrile.
5. The on-line detection device for organotin morphology analysis according to claim 4, wherein the mass percentage of the monomer mixture in the pre-polymerization solution is 20-50%, and the magnetic nanoparticles are 0.5-5 mg/100mg of the pre-polymerization solution;
the monomer mixture comprises 20 to 60 percent of functional monomer, 0.5 to 4 percent of initiator and the balance of cross-linking agent;
the functional monomer adopts 1-allyl-3-methylimidazole bis (fluoromethanesulfonyl) imide salt and 9-vinyl anthracene; the initiator adopts azobisisobutyronitrile; the crosslinking agent is divinylbenzene.
6. The on-line detection device for organotin morphological analysis as claimed in claim 4, wherein the porogen comprises n-propanol and 1, 4-butanediol, and the composition ratio of the porogen is n-propanol: 1, 4-butanediol: 1: 3-3: 1; the magnetic nano particles are modified Fe3O4Nanoparticles.
7. An on-line analysis method for organotin morphology analysis is characterized by comprising the following specific steps:
pretreating a sample, filtering the water sample by a filter membrane before using the water sample, and adjusting the pH value of the sample to 5.0-8.0; before the marine product is used, performing ultrasonic extraction, wherein the extraction solvent comprises acetonitrile, ultrapure water, acetic acid, 65: 12: 23 and 0.15% of triethylamine according to the volume ratio, and the extraction time is 10-40 min; centrifuging at a speed of 2000-6000 r/min for 5-30 min, filtering the centrifuged supernatant by a filter membrane, diluting by 1-10 times, and adjusting the pH to 5.0-8.0; inputting a sample into a solid-phase micro-extraction column through a first flow pump, adsorbing a target object, and keeping the direction of a magnetic field to be the same as the flow direction of the sample at the moment, wherein the magnetic field intensity is 0-70 Gs; after adsorption is finished, inputting desorption liquid into a solid-phase micro-extraction column by using a second flow pump, desorbing a target object, and changing the direction of a magnetic field with the magnetic field intensity of 0-70 Gs; after the desorption is finished, the third flow pump conveys the chromatographic mobile phase to bring the eluent into a chromatographic column, the fluorescence derivative reagent loaded by the fourth flow pump and the OTCs in the eluent are mixed and reacted after the column, and finally the mixture enters a high performance liquid chromatograph for determination.
8. The on-line analysis method for organotin morphology analysis according to claim 7, wherein the stripping solution is methanol, ethanol or acetonitrile solution containing 0-5 vol% formic acid, the first flow pump inputs 0.5-10 mL of sample solution into the solid phase micro-extraction column at a flow rate of 0.02-0.20 mL/min, and the second flow pump inputs stripping solution into the solid phase micro-extraction column at a flow rate of 0.01-0.10 mL/min.
9. The on-line analysis method for organotin morphology analysis according to claim 7 wherein the conditions of the post-column mixing reaction include fluorescence derivatization reagents, reagent concentration and reagent flow rate, wherein the fluorescence derivatization reagents are morin and fisetin, the reagent concentration is 2-10 mg/L, and the reagent flow rate is 2-5 mL/min.
10. The on-line analysis method for organotin morphological analysis as claimed in claim 7 wherein the chromatographic conditions of said HPLC include chromatographic column, mobile phase, elution procedure, excitation wavelength and emission wavelength, said chromatographic column is C18 column, mobile phase is acetonitrile/ultrapure water/acetic acid (v/v/v, containing 0.15% triethylamine), elution procedure is isocratic elution for 7 min; the sample injection amount is 20-120 mu L, the flow rate is 1.0mL/min, the excitation wavelength is 412nm, and the emission wavelength is 498 nm.
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