CN110470758A - Sulfonylurea agriculture residual device and analysis method in a kind of on-line checking environmental water sample - Google Patents
Sulfonylurea agriculture residual device and analysis method in a kind of on-line checking environmental water sample Download PDFInfo
- Publication number
- CN110470758A CN110470758A CN201910751143.9A CN201910751143A CN110470758A CN 110470758 A CN110470758 A CN 110470758A CN 201910751143 A CN201910751143 A CN 201910751143A CN 110470758 A CN110470758 A CN 110470758A
- Authority
- CN
- China
- Prior art keywords
- sulfonylurea
- sample
- infusion pump
- water sample
- way valve
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/22—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the construction of the column
-
- 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
- G01N30/14—Preparation by elimination of some components
-
- 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
- G01N30/14—Preparation by elimination of some components
- G01N2030/146—Preparation by elimination of some components using membranes
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Sulfonylurea agriculture residual device and analysis method, is related to environmental sample chemical analysis and testing area in a kind of on-line checking environmental water sample.Utilize sulfonylurea pollutant diamagnetism characteristic and magnetic separation technique, and In-tube SPME technology and high-efficient liquid phase chromatogram technology based on integral material are combined, establish the device and analysis method residual based on sulfonylurea agriculture in magnetic enhancing solid phase microextraction-hyphenated techniques chromatography on-line checking environmental water sample.The on-line analysis to sulfonylurea object can be achieved, have many advantages, such as that operating process is simple, analysis time is short, accuracy is good, high sensitivity, can be used for the extraction of organic micro-pollutant, there is wide practical application value.
Description
Technical field
The present invention relates to environmental sample chemical analysis and testing areas, more particularly to one kind is based on the micro- extraction of solid phase in magnetic reinforced pipe
Take-hyphenated techniques chromatography on-line checking environmental water sample in the residual device and analysis method of sulfonylurea agriculture.
Background technique
Sulfonylurea herbicide (SUHs) is made of aromatic radical, urea bridge and active group three parts, has wide spectrum, height living
Property, it is highly selective the advantages that[1], it is a kind of herbicide most widely used so far.However, on a large scale and not due to people
The use of supernumerary segment, causes it to remain in environment water[2]And soil[3]In, this crops to subsequent farming, aquatic ecosystem
System and human health threaten.Studies have shown that SUHs residual will generate different journeys to crops such as corn and soybeans in the soil
The phytotoxicity of degree acts on[4], remain the existence that will seriously affect aquatile in water[5], while also will affect the quality of aquatic products.
Currently, chromatography is the main method of SUHs residue detection, but SUHs concentration in actual sample is very low, and locating
Substrate is complicated, therefore needs to carry out pre-treatment appropriate before carrying out chromatography to reduce the influence of sample substrate and improve detection
Sensitivity.Sample Pretreatment Technique currently used for SUHs analysis has SPE[6,7]、DSPE[8]And MSPE[9]Deng, but these methods without
Method and chromatographic separation technology realize on-line coupling.In-tube SPME (in-tube solid phase
Microextraction, IT-SPME) since on-line coupling can be carried out with high performance liquid chromatograph, realize enrichment, separation and inspection
The online progress surveyed, therefore have been favored by people.But IT-SPME has that loading capacity is limited, and extraction efficiency is inclined in the application
The problems such as low.The extraction efficiency of IT-SPME can be improved in magnetic enhancing technology, because under the action of an external magnetic field, diamagnetic substance becomes
To the region clustering most weak in magnetic field strength, and most of organic pollutant all has diamagnetism.
Summary of the invention
It is an object of the invention to solve the above problem in the prior art, sulphur in a kind of on-line checking environmental water sample is provided
The residual device of ureide derivative agriculture and analysis method realize on-line analysis to object, have that operating process is simple, analysis time is short
The advantages that.
In order to achieve the above objectives, the present invention adopts the following technical scheme:
The residual device of sulfonylurea agriculture in a kind of on-line checking environmental water sample, including the first infusion pump, the second infusion pump,
Three infusion pumps, microextraction column, the first six-way valve, the second six-way valve, quantitative loop, chromatographic column and chromatography detector；Described first is defeated
Liquid pump and the second infusion pump are separately connected the first six-way valve, and the first infusion pump is for conveying sample, and the second infusion pump is for conveying
Stripping liquid；The microextraction column is placed in magnetic field, and the both ends of microextraction column are connected on six-way valve；First six-way valve and
The connection of two six-way valves, the both ends of the quantitative loop are connected on the second six-way valve；The third infusion pump and chromatographic column point
The second six-way valve is not connected, and third infusion pump is used for transport flow phase, and the output of the chromatographic column connects chromatography detector；Its
In, switch absorption, parsing and the measurement for realizing sample by the valve position of the first six-way valve and the second six-way valve.
The invention also includes DC power supply and magnetic coil, the magnetic coil is wound in microextraction column, and the two of magnetic coil
End is separately connected DC power supply.
The chromatography detector uses HPLC-DAD.
The microextraction column is the entire capillary solid phase microextraction column of doped magnetic nanoparticle；The doped magnetic is received
The entire capillary solid phase microextraction column of rice corpuscles the preparation method is as follows: by reaction monomers intermixture, pore-foaming agent, magnetic Nano
After particle mixes, ultrasound pours into above-mentioned pre-polymer solution in tubular container at uniform pre-polymer solution, and sealing is placed on 40
~80 DEG C of polymerization reactions 6~for 24 hours, then free from admixture is rinsed into liquid with methanol, acetonitrile or ethyl alcohol and is detected；Before use,
Again with methanol, acetonitrile or ethyl alcohol are rinsed activation.
The reaction monomers intermixture and pore-foaming agent are 1:(1~4 in mass ratio), magnetic nano-particle is 0.5~10mg/
0.1g pre-polymer solution.
The reaction monomers intermixture includes function monomer, initiator and crosslinking agent.
The composition of the reaction monomers intermixture is function monomer vinyl imidazole 20%~60%, draws by mass percentage
Send out agent azodiisobutyronitrile or benzoyl peroxide 0.5%~2%, it is remaining be crosslinking agent ethylene glycol dimethacrylate.
The pore-foaming agent includes Macrogol 4000 and dimethylformamide, and the composition ratio of pore-foaming agent is dimethyl formyl
Amine is the 160 μ L/0.1g Macrogol 4000s of μ L~300；The magnetic nano-particle includes MODIFIED Fe3O4Nanoparticle.
The residual analysis method of sulfonylurea agriculture is as follows in a kind of on-line checking environmental water sample: first to sample pretreatment, water sample
It needs first to adjust sample pH value through membrane filtration to 4.0~6.0, then pass through the first infusion pump for sample input to micro- extraction before use
Take in column, object adsorbed, keep magnetic direction identical with sample flow direction at this time, magnetic field strength for 0~
100Gs；After the completion of absorption, stripping liquid is input in microextraction column using the second infusion pump, while keeping magnetic direction and sample
On the contrary, magnetic field strength is 0~100Gs, completion desorbs object for product flow direction；Stripping liquid is temporarily stored in flow path
In, it is finally brought into chromatography detector by mobile phase and is separated and detected.
The stripping liquid be the methanol containing 0%~10% formic acid, acetonitrile or ethanol solution, first infusion pump with
The sample solution of 0.1~20mL is input in microextraction column by the flow velocity of 0.01~0.2mL/min, second infusion pump with
Stripping liquid is input in microextraction column by the flow velocity of 0.01~0.3mL/min.
High-efficient liquid phase chromatogram condition includes chromatographic column, mobile phase A, Mobile phase B, elution program and Detection wavelength；Wherein, color
Spectrum column is C18 column, and mobile phase A is the aqueous solution of 0.4% phosphoric acid, and Mobile phase B is acetonitrile, gradient elution: 0~5.0min, 30%
B；5.0~10.0min, 30%~55%B；10.0~13.0min, 55%~60%B；13.0~15.0min, 60%B；15.0
~18.0min, 60%~90%B；18.0~23.0min, 90%~30%B；23.0~28.0min, 30%B；Sample volume is
10~100 μ L, flow velocity 1mL/min, Detection wavelength 230nm.
Compared with the existing technology, the beneficial effect that technical solution of the present invention obtains is:
Magnetic enhancing solid phase microextraction-hyphenated techniques chromatography is applied to the on-line analysis of SUHs in environmental water sample by the present invention,
By preparing the entire capillary solid phase microextraction column of doped magnetic nanoparticle, magnetic miniflow and the anti-magnetic of organic molecule are utilized
Property principle, apply the magnetic field of different directions and intensity in absorption and desorption process, improve to the extraction efficiency of object, simultaneously plus
Fast extraction process；By the way that the technology in conjunction with high performance liquid chromatography detection instrument, to be realized to the on-line analysis to SUHs object, letter
Change operating process, shorten analysis time, which has wide practical application value.
Detailed description of the invention
Fig. 1 is the apparatus structure schematic diagram that sulfonylurea agriculture is residual in on-line checking environmental water sample；
Fig. 2 is the infrared spectrogram of material in extraction column in embodiment 2；
Fig. 3 is the scanning electron microscope (SEM) photograph of material in extraction column in embodiment 2；
(a) separates spectrogram with the liquid chromatogram of rear (b) before the water sample extraction that Fig. 4 is 5 kinds of SUHs of mark-on in embodiment 4.
Specific embodiment
In order to be clearer and more clear technical problems, technical solutions and advantages to be solved, tie below
Drawings and examples are closed, the present invention is described in further details.
As shown in Figure 1, the residual device of sulfonylurea agriculture includes the first infusion in on-line checking environmental water sample of the present invention
Pump, quantifies the second infusion pump, third infusion pump, microextraction column, DC power supply, magnetic coil, the first six-way valve, the second six-way valve
Ring, chromatographic column and chromatography detector；
First infusion pump and the second infusion pump are separately connected the first six-way valve, and the first infusion pump is used to convey sample,
Second infusion pump is for conveying stripping liquid；The microextraction column is placed in magnetic field, and it is logical that the both ends of microextraction column are connected to six
On valve；First six-way valve is connect with the second six-way valve, and the both ends of the quantitative loop are connected on the second six-way valve；Described
Three infusion pumps and chromatographic column are separately connected the second six-way valve, and third infusion pump is used for transport flow phase, the output of the chromatographic column
Connect chromatography detector；Wherein, by the valve position of the first six-way valve and the second six-way valve switch realize sample absorption, parsing and
Measurement.
The magnetic coil is wound in microextraction column, and the both ends of magnetic coil are separately connected DC power supply, is conciliate in absorption
When suction, by controlling current direction, the magnetic field of the magnetic field certain orientation and intensity that generate magnetic coil, at this time in integral material
Magnetic nano-particle will be induced to generate magnetic field gradient identical with externally-applied magnetic field direction, and the extraction effect to object can be improved
Rate, while accelerating extraction process.
The chromatography detector uses HPLC-DAD.
The microextraction column is the entire capillary solid phase microextraction column of doped magnetic nanoparticle.
The residual device of sulfonylurea agriculture and analysis method are made in 1~4 pair of on-line checking environmental water sample by the following examples
It further illustrates.
Embodiment 1
1) pretreatment of sample:
Water sample adjusts sample pH value to 4.0 using the first membrane filtration through 0.22 μm is preceding needed.
2) the entire capillary solid phase microextraction column of doped magnetic nanoparticle is prepared:
Using vinyl imidazole as function monomer, ethylene glycol dimethacrylate is crosslinking agent, and azodiisobutyronitrile is to draw
Agent is sent out, Macrogol 4000 and dimethylformamide are pore-foaming agent, MODIFIED Fe3O4Nanoparticle is as magnetic nano-particle, composition
Pre-polymer solution；The composition of the reaction monomers intermixture is vinyl imidazole 20%, azodiisobutyronitrile by mass percentage
0.5%, ethylene glycol dimethacrylate 79.5%；The composition ratio of the pore-foaming agent is Macrogol 4000 50%, diformazan
Base formamide is 160 μ L/0.1g Macrogol 4000s；In mass ratio, reaction monomers intermixture: pore-foaming agent 1:1, MODIFIED Fe3O4
Nanoparticle is 0.5mg/0.1g pre-polymer solution.After weighing reactive material mixing according to the above ratio, ultrasound is at uniform pre-polymerization
Solution is closed, above-mentioned pre-polymer solution is poured into quartz capillary (internal diameter is 200 μm, length 15cm), sealing is placed on 40
DEG C polymerization reaction 6h, then free from admixture detection is rinsed into liquid with methanol.Before use, again with methanol is rinsed work
Change.
3) the entire capillary solid phase microextraction column of the doped magnetic nanoparticle prepared is mounted on as shown in Fig. 1
Device in, referring to attached drawing 1, in extraction, the first six-way valve and the second six-way valve are in the position " Load ", open direct current
Source makes to generate in the entire capillary solid phase microextraction column of doped magnetic nanoparticle and flows the consistent magnetic in direction with sample solution
, 0.1mL sample solution is input to doping magnetic with the flow velocity of 0.01mL/min using the first infusion pump by magnetic field strength 10Gs
Object is adsorbed in the entire capillary solid phase microextraction column of property nanoparticle；After the completion of absorption, the two or six is kept to lead to
Valve goes to the position " inject " still in the position " Load ", by the first six-way valve, and changing simultaneously DC power supply direction makes to adulterate magnetic
Magnetic direction in the entire capillary solid phase microextraction column of property nanoparticle inverts, and magnetic field strength 10Gs utilizes
10 μ L methanol are inputted the micro- extraction of entire capillary solid phase of doped magnetic nanoparticle with the flow velocity of 0.01mL/min by two infusion pumps
Column is taken to desorb object, stripping liquid is stored in the quantitative loop being connected on the second six-way valve；It, will after the completion of desorption
Second six-way valve goes to the position " inject ", and object is brought into HPLC-DAD by mobile phase and separated and detected.
High-efficient liquid phase chromatogram condition includes chromatographic column, mobile phase A, Mobile phase B, elution program and Detection wavelength；Wherein, color
Spectrum column is C18 column, and mobile phase A is the aqueous solution of 0.4% phosphoric acid, and Mobile phase B is acetonitrile, gradient elution: 0~5.0min, 30%
B；5.0~10.0min, 30%~55%B；10.0~13.0min, 55%~60%B；13.0~15.0min, 60%B；15.0
~18.0min, 60%~90%B；18.0~23.0min, 90%~30%B；23.0~28.0min, 30%B；Sample volume is
10 μ L, flow velocity 1mL/min, Detection wavelength 230nm.
Embodiment 2
1) pretreatment of sample:
Water sample adjusts sample pH value to 5.0 using the first membrane filtration through 0.22 μm is preceding needed.
2) the entire capillary solid phase microextraction column of doped magnetic nanoparticle is prepared:
Using vinyl imidazole as function monomer, ethylene glycol dimethacrylate is crosslinking agent, and azodiisobutyronitrile is to draw
Agent is sent out, Macrogol 4000 and dimethylformamide are pore-foaming agent, MODIFIED Fe3O4Nanoparticle is as magnetic nano-particle, composition
Pre-polymer solution；The composition of the reaction monomers intermixture is vinyl imidazole 45%, azodiisobutyronitrile by mass percentage
1%, ethylene glycol dimethacrylate 54%；The composition ratio of the pore-foaming agent is Macrogol 4000 70%, dimethyl methyl
Amide is 240 μ L/0.1g Macrogol 4000s；In mass ratio, reaction monomers intermixture: pore-foaming agent 1:2.3, MODIFIED Fe3O4It receives
Rice corpuscles is 2.5mg/0.1g pre-polymer solution.After weighing reactive material mixing according to the above ratio, ultrasound is at uniform prepolymerization
Above-mentioned pre-polymer solution injection inner surface, is contained in the quartz capillary of C-C double bond that (internal diameter is 320 μm, and length is by solution
20cm), sealing is placed on 70 DEG C of polymerization reaction 12h, then is rinsed into liquid free from admixture detection with acetonitrile.Before use,
Activation is rinsed with acetonitrile again.
Fig. 2 is the infrared spectrogram of material in extraction column, and the wave number of major absorbance peak is respectively 2954cm-1、1732cm-1、
1635cm-1、1464cm-1、1228cm-1,1149cm-1；Fig. 3 is the scanning electron microscope (SEM) photograph of material in extraction column, it can be seen that whole
There are many holes for material internal, and structure is uniform.
3) the entire capillary solid phase microextraction column of the doped magnetic nanoparticle prepared is mounted on as shown in Fig. 1
Device in, referring to attached drawing 1, in extraction, the first six-way valve and the second six-way valve are in the position " Load ", open direct current
Source makes to generate in the entire capillary solid phase microextraction column of doped magnetic nanoparticle and flows the consistent magnetic in direction with sample solution
, 5mL sample solution is input to doped magnetic with the flow velocity of 0.14mL/min using the first infusion pump by magnetic field strength 40Gs
Object is adsorbed in the entire capillary solid phase microextraction column of nanoparticle；After the completion of absorption, the second six-way valve is kept
Still in the position " Load ", the first six-way valve is gone into the position " inject ", changing simultaneously DC power supply direction makes doped magnetic
Magnetic direction in the entire capillary solid phase microextraction column of nanoparticle inverts, and magnetic field strength 30Gs utilizes second
The acetonitrile solution of 80 μ L, 2% formic acid is inputted the whole hair of doped magnetic nanoparticle with the flow velocity of 0.02mL/min by infusion pump
Tubule solid phase microextraction column desorbs object, and stripping liquid is stored in the quantitative loop being connected on the second six-way valve；
After the completion of desorption, the second six-way valve is gone into the position " inject ", object by mobile phase bring into HPLC-DAD carry out separation and
Detection.
High-efficient liquid phase chromatogram condition includes chromatographic column, mobile phase A, Mobile phase B, elution program and Detection wavelength；Wherein, color
Spectrum column is C18 column, and mobile phase A is the aqueous solution of 0.4% phosphoric acid, and Mobile phase B is acetonitrile, gradient elution: 0~5.0min, 30%
B；5.0~10.0min, 30%~55%B；10.0~13.0min, 55%~60%B；13.0~15.0min, 60%B；15.0
~18.0min, 60%~90%B；18.0~23.0min, 90%~30%B；23.0~28.0min, 30%B；Sample volume is
80 μ L, flow velocity 1mL/min, Detection wavelength 230nm.
Embodiment 3
1) pretreatment of sample:
Water sample adjusts sample pH value to 6.0 using the first membrane filtration through 0.22 μm is preceding needed.
2) the entire capillary solid phase microextraction column of doped magnetic nanoparticle is prepared:
Using vinyl imidazole as function monomer, ethylene glycol dimethacrylate is crosslinking agent, and azodiisobutyronitrile is to draw
Agent is sent out, Macrogol 4000 and dimethylformamide are pore-foaming agent, MODIFIED Fe3O4Nanoparticle is as magnetic nano-particle, composition
Pre-polymer solution；The composition of the reaction monomers intermixture is vinyl imidazole 60%, azodiisobutyronitrile by mass percentage
2%, ethylene glycol dimethacrylate 38%；The composition ratio of the pore-foaming agent is Macrogol 4000 80%, dimethyl methyl
Amide is 300 μ L/0.1g Macrogol 4000s；In mass ratio, reaction monomers intermixture: pore-foaming agent 1:4, MODIFIED Fe3O4Nanometer
Particle is 10mg/0.1g pre-polymer solution.After weighing reactive material mixing according to the above ratio, ultrasound is molten at uniform prepolymerization
Liquid pours into above-mentioned pre-polymer solution in quartz capillary (internal diameter is 530 μm, length 25cm), and sealing is placed on 80 DEG C and gathers
It closes reaction for 24 hours, then is rinsed into liquid free from admixture detection to it with ethyl alcohol.Before use, being rinsed work with ethyl alcohol again
Change.
3) the entire capillary solid phase microextraction column of the doped magnetic nanoparticle prepared is mounted on as shown in Fig. 1
Device in, referring to attached drawing 1, in extraction, the first six-way valve and the second six-way valve are in the position " Load ", open direct current
Source makes to generate in the entire capillary solid phase microextraction column of doped magnetic nanoparticle and flows the consistent magnetic in direction with sample solution
, 20mL sample solution is input to doping magnetic with the flow velocity of 0.2mL/min using the first infusion pump by magnetic field strength 100Gs
Object is adsorbed in the entire capillary solid phase microextraction column of property nanoparticle；After the completion of absorption, the two or six is kept to lead to
Valve goes to the position " inject " still in the position " Load ", by the first six-way valve, and changing simultaneously DC power supply direction makes to adulterate magnetic
Magnetic direction in the entire capillary solid phase microextraction column of property nanoparticle inverts, and magnetic field strength 100Gs utilizes
The ethanol solution of 100 μ L, 10% formic acid is inputted the entirety of doped magnetic nanoparticle with the flow velocity of 0.3mL/min by two infusion pumps
Capillary pipe solid phase micro-extraction column desorbs object, and stripping liquid is stored in the quantitative loop being connected on the second six-way valve
In；After the completion of desorption, the second six-way valve is gone into the position " inject ", object is brought HPLC-DAD by mobile phase and separated
And detection.
High-efficient liquid phase chromatogram condition includes chromatographic column, mobile phase A, Mobile phase B, elution program and Detection wavelength；Wherein, color
Spectrum column is C18 column, and mobile phase A is the aqueous solution of 0.4% phosphoric acid, and Mobile phase B is acetonitrile, gradient elution: 0~5.0min, 30%
B；5.0~10.0min, 30%~55%B；10.0~13.0min, 55%~60%B；13.0~15.0min, 60%B；15.0
~18.0min, 60%~90%B；18.0~23.0min, 90%~30%B；23.0~28.0min, 30%B；Sample volume is
100 μ L, flow velocity 1mL/min, Detection wavelength 230nm.
Embodiment 4
5 kinds of SUHs in farmland water, lake water and tap water are detected by embodiment 2.Fig. 4 is the water of 5 kinds of SUHs of mark-on
The liquid chromatogram of (a) and rear (b) separate spectrogram before sample extraction, it can be seen from the figure that mark-on water sample without be enriched with directly into
The object chromatographic peak peak height that sample obtains is lower, and the peak height of object is significantly increased after extraction.
Table 1 is the range of linearity, detection limit, quantitative limit and the precision data of 5 kinds of SUHs in pure water, such as the result table of table 1
Bright: 5 kinds of SUHs concentration and peak area in 0.1~200 μ g/L range of linearity have good linear relationship, and linear minimum point is
0.1 μ g/L, correlation coefficient r2> 0.99.
Table 1
Table 2
Table 2 is the measurement result and recovery of standard addition data of 5 kinds of SUHs in farmland water, lake water and tap water, such as 2 result of table
Shown, the average recovery rate range when spiked levels are 1 μ g/L, 10 μ g/L, 50 μ g/L is between 79.5%~114%, phase
To standard deviation RSD < 10.0, minimum concentrations LODs is between 0.03~0.14 μ g/L.
Claims (10)
1. the residual device of sulfonylurea agriculture in a kind of on-line checking environmental water sample, it is characterised in that: including the first infusion pump, second
Infusion pump, third infusion pump, microextraction column, the first six-way valve, the second six-way valve, quantitative loop, chromatographic column and chromatography detector；Institute
It states the first infusion pump and the second infusion pump is separately connected the first six-way valve, the first infusion pump is for conveying sample, the second infusion pump
For conveying stripping liquid；The microextraction column is placed in magnetic field, and the both ends of microextraction column are connected on six-way valve；One or six
Port valve is connect with the second six-way valve, and the both ends of the quantitative loop are connected on the second six-way valve；The third infusion pump and
Chromatographic column is separately connected the second six-way valve, and third infusion pump is used for transport flow phase, the output connection chromatography inspection of the chromatographic column
Survey instrument；Wherein, switch absorption, parsing and the measurement for realizing sample by the valve position of the first six-way valve and the second six-way valve.
2. the residual device of sulfonylurea agriculture in a kind of on-line checking environmental water sample as described in claim 1, it is characterised in that: also
Including DC power supply and magnetic coil, the magnetic coil is wound in microextraction column, and the both ends of magnetic coil are separately connected direct current
Source.
3. the residual device of sulfonylurea agriculture in a kind of on-line checking environmental water sample as described in claim 1, it is characterised in that: institute
Chromatography detector is stated using HPLC-DAD.
4. the residual device of sulfonylurea agriculture in a kind of on-line checking environmental water sample as described in claim 1, it is characterised in that: institute
State the entire capillary solid phase microextraction column that microextraction column is doped magnetic nanoparticle；The doped magnetic nanoparticle it is whole
Capillaries solid phase microextraction column the preparation method is as follows: by reaction monomers intermixture, pore-foaming agent, magnetic nano-particle mix
Afterwards, ultrasound pours into above-mentioned pre-polymer solution in tubular container at uniform pre-polymer solution, and sealing is placed on 40~80 DEG C and gathers
Conjunction reaction 6~for 24 hours, then free from admixture is rinsed into liquid with methanol, acetonitrile or ethyl alcohol and is detected；Before use, again with methanol,
Acetonitrile or ethyl alcohol are rinsed activation.
5. the residual device of sulfonylurea agriculture in a kind of on-line checking environmental water sample as claimed in claim 4, it is characterised in that: institute
State reaction monomers intermixture and pore-foaming agent is 1:(1~4 in mass ratio), magnetic nano-particle is 0.5~10mg/0.1g prepolymerization
Solution.
6. the residual device of sulfonylurea agriculture, feature exist in a kind of on-line checking environmental water sample as described in claim 4 or 5
In: the reaction monomers intermixture includes function monomer, initiator and crosslinking agent.
7. the residual device of sulfonylurea agriculture in a kind of on-line checking environmental water sample as claimed in claim 6, it is characterised in that: institute
The composition for stating reaction monomers intermixture is function monomer vinyl imidazole 20%~60%, initiator azo two by mass percentage
Isobutyronitrile or benzoyl peroxide 0.5%~2%, it is remaining be crosslinking agent ethylene glycol dimethacrylate.
8. the residual device of sulfonylurea agriculture, feature exist in a kind of on-line checking environmental water sample as described in claim 4 or 5
In: the pore-foaming agent includes Macrogol 4000 and dimethylformamide, and the composition ratio of pore-foaming agent is that dimethylformamide is
The 160 μ L/0.1g Macrogol 4000s of μ L~300；The magnetic nano-particle includes MODIFIED Fe3O4Nanoparticle.
9. using the device that sulfonylurea agriculture is residual in a kind of on-line checking environmental water sample according to any one of claims 1 to 8
Analysis method, it is characterised in that: first to sample pretreatment, water sample using preceding need first to adjust through membrane filtration sample pH value to 4.0~
6.0, then by the first infusion pump by sample input into microextraction column, object is adsorbed, at this time keep magnetic field side
To identical as sample flow direction, magnetic field strength is 0~100 Gs；It is using the second infusion pump that stripping liquid is defeated after the completion of absorption
Enter into microextraction column, while keeping magnetic direction contrary with sample flow, magnetic field strength is 0~100 Gs, completion pair
Object is desorbed；Stripping liquid is temporarily stored in flow path, is finally brought into chromatography detector and is divided by mobile phase
From and detection.
10. analysis method as claimed in claim 9, it is characterised in that: the stripping liquid is the first containing 0%~10% formic acid
Alcohol, acetonitrile or ethanol solution, first infusion pump is with the flow velocity of 0.01~0.2mL/min by the sample solution of 0.1~20mL
It is input in microextraction column, stripping liquid is input in microextraction column by second infusion pump with the flow velocity of 0.01~0.3mL/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910751143.9A CN110470758B (en) | 2019-08-14 | 2019-08-14 | Device and analysis method for on-line detection of sulfonylurea pesticide residues in environmental water sample |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910751143.9A CN110470758B (en) | 2019-08-14 | 2019-08-14 | Device and analysis method for on-line detection of sulfonylurea pesticide residues in environmental water sample |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110470758A true CN110470758A (en) | 2019-11-19 |
| CN110470758B CN110470758B (en) | 2020-09-08 |
Family
ID=68511709
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910751143.9A Expired - Fee Related CN110470758B (en) | 2019-08-14 | 2019-08-14 | Device and analysis method for on-line detection of sulfonylurea pesticide residues in environmental water sample |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110470758B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113960196A (en) * | 2021-10-11 | 2022-01-21 | 太湖流域水文水资源监测中心（太湖流域水环境监测中心） | Method for on-line determination of sulfonylurea herbicide in water |
| CN114740129A (en) * | 2022-04-08 | 2022-07-12 | 厦门大学 | On-line detection device and analysis method for organotin morphological analysis |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1583804A (en) * | 2004-06-10 | 2005-02-23 | 中国农业大学 | Use and preparation of molecular track polymer of sulfonyl urea herbicide |
| CN101716495A (en) * | 2009-12-17 | 2010-06-02 | 南开大学 | Sulfonylurea weedicide molecularly imprinted polymer microballoon and preparation method thereof |
| CN102253139A (en) * | 2011-06-14 | 2011-11-23 | 吉林大学 | Method for detecting tonyred concentration in environment water sample |
| WO2013011171A1 (en) * | 2011-07-18 | 2013-01-24 | Universitat De Valéncia | Device and method for magnetic in-tube solid-phase microextraction |
| CN104001347A (en) * | 2014-05-13 | 2014-08-27 | 齐鲁工业大学 | Preparation method of hydrophilic broad-spectrum solid-phase extraction column |
| CN105301265A (en) * | 2015-10-10 | 2016-02-03 | 山西师范大学 | Automatic online magnetic solid-phase micro-extraction-desorption-detection apparatus and method thereof |
| CN107383277A (en) * | 2017-07-28 | 2017-11-24 | 厦门大学 | Preparation using poly ion liquid as the sulfonylurea molecular engram material of function monomer |
| CN109323914A (en) * | 2018-10-26 | 2019-02-12 | 宁波大学 | A kind of method of magnetic field-intensification solid phase microextraction effect |
-
2019
- 2019-08-14 CN CN201910751143.9A patent/CN110470758B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1583804A (en) * | 2004-06-10 | 2005-02-23 | 中国农业大学 | Use and preparation of molecular track polymer of sulfonyl urea herbicide |
| CN101716495A (en) * | 2009-12-17 | 2010-06-02 | 南开大学 | Sulfonylurea weedicide molecularly imprinted polymer microballoon and preparation method thereof |
| CN102253139A (en) * | 2011-06-14 | 2011-11-23 | 吉林大学 | Method for detecting tonyred concentration in environment water sample |
| WO2013011171A1 (en) * | 2011-07-18 | 2013-01-24 | Universitat De Valéncia | Device and method for magnetic in-tube solid-phase microextraction |
| CN104001347A (en) * | 2014-05-13 | 2014-08-27 | 齐鲁工业大学 | Preparation method of hydrophilic broad-spectrum solid-phase extraction column |
| CN105301265A (en) * | 2015-10-10 | 2016-02-03 | 山西师范大学 | Automatic online magnetic solid-phase micro-extraction-desorption-detection apparatus and method thereof |
| CN107383277A (en) * | 2017-07-28 | 2017-11-24 | 厦门大学 | Preparation using poly ion liquid as the sulfonylurea molecular engram material of function monomer |
| CN109323914A (en) * | 2018-10-26 | 2019-02-12 | 宁波大学 | A kind of method of magnetic field-intensification solid phase microextraction effect |
Non-Patent Citations (8)
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113960196A (en) * | 2021-10-11 | 2022-01-21 | 太湖流域水文水资源监测中心（太湖流域水环境监测中心） | Method for on-line determination of sulfonylurea herbicide in water |
| CN114740129A (en) * | 2022-04-08 | 2022-07-12 | 厦门大学 | On-line detection device and analysis method for organotin morphological analysis |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110470758B (en) | 2020-09-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100509103C (en) | Method for producing solid-phase microextraction capillaries | |
| Du et al. | An in situ immobilized pipette tip solid phase microextraction method based on molecularly imprinted polymer monolith for the selective determination of difenoconazole in tap water and grape juice | |
| CN110470758A (en) | Sulfonylurea agriculture residual device and analysis method in a kind of on-line checking environmental water sample | |
| CN103454360B (en) | Ultrafiltration and UPLC-MS/MS (ultra-high performance liquid chromatography tandem mass spectrometry) method for measuring concentration of free docetaxel in human plasma | |
| Fan et al. | In-tube solid-phase microextraction with poly (methacrylic acid-ethylene glycol dimethacrylate) monolithic capillary for direct high-performance liquid chromatographic determination of ketamine in urine samples | |
| CN103505907B (en) | A kind of online solid phase micro-extraction method of flow injection and device thereof | |
| Du et al. | Pipette tip-based molecularly imprinted monolith for selective micro-solid-phase extraction of methomyl in environmental water | |
| CN103645257A (en) | Detection method for papaya decoction piece | |
| CN103149308A (en) | Pretreatment method for detecting BPA (bisphenol A) in environment samples | |
| Liu et al. | Continuous flow liquid membrane extraction: a novel automatic trace-enrichment technique based on continuous flow liquid–liquid extraction combined with supported liquid membrane | |
| CN102288696A (en) | Method for measuring blood concentration of paraquat | |
| CN106918667B (en) | Pressurized micro-extraction equipment, pressurized micro-extraction method and application thereof | |
| CN109541058A (en) | A kind of method of biogenic amine in detection pueraria lobata | |
| CN104761748A (en) | Preparation method and use of double-template molecular imprinting solid phase extraction membrane | |
| CN104910339A (en) | Magnetic molecular imprinting polyion liquid for detecting ractopamine as well as preparation method and application of magnetic molecular imprinting polyion liquid | |
| CN103599755B (en) | Phenolethanolamine A molecular engram film and preparation method thereof and application | |
| CN101334386A (en) | Determination method for plant medicine blood plasma amygdalin for strengthening the body resistance | |
| Abbaszadehbezi et al. | Application of pipette-tip solid-phase extraction technique for fast determination of levofloxacin from wastewater sample using cobalt metal-organic framework | |
| Cheng et al. | A microfluidic system for introduction of nanolitre sample in inductively coupled plasma mass spectrometry using electrokinetic flow combined with hydrodynamic flow | |
| CN106290603B (en) | A kind of method and application detecting inorganic anion in plant, organic acid and three kinds of phytochemicals simultaneously using Vavle switching method | |
| Zhao et al. | Facile DNA adsorption enabling ammonium-based hydrophilic affinity monolithic column for high-performance online selective microextraction of ochratoxin A | |
| CN105891387B (en) | A kind of enrichment method for being used to detect hydrophilic amino acid | |
| Wei et al. | In‐situ preparation of porous monolithic polymer inside hollow fiber as a micro‐solid phase extraction device for glucocorticoids in cosmetics | |
| CN103940918A (en) | A method of simultaneously detecting the content of artesunate and the content of dihydroartemisinin in animal blood plasma | |
| CN108614033B (en) | Mobile mobile phase control system with double gradient adjusting function and processing method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200908 Termination date: 20210814 |