CN109331795A - A kind of magnetic nanometer composite material and its preparation and application - Google Patents
A kind of magnetic nanometer composite material and its preparation and application Download PDFInfo
- Publication number
- CN109331795A CN109331795A CN201811284090.6A CN201811284090A CN109331795A CN 109331795 A CN109331795 A CN 109331795A CN 201811284090 A CN201811284090 A CN 201811284090A CN 109331795 A CN109331795 A CN 109331795A
- Authority
- CN
- China
- Prior art keywords
- magnetic
- water
- carbon nanotube
- walled carbon
- added
- 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.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
- B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
Abstract
The invention belongs to trace drugs in water environment to remain safety detection technology field, it is related to a kind of magnetic nanometer composite material and its preparation and application, and in particular to a kind of magnetic multi-walled carbon nanotube of polypyrrole modifying and its preparation and the application in sulfonamides analyte detection.Invention also provides a kind of detection methods of sulfa drug residue in sensitive reliable water environment.Magnetic nanometer composite material of the present invention is prepared via a method which: (1) magnetic multi-walled carbon nanotube is prepared in alkaline solution by multi-walled carbon nanotube, Ammonium ferric sulfate dodecahyrate and six ferrous sulfate hydrate ammoniums.(2) the magnetic multi-walled carbon nanotube of polypyrrole modifying is prepared under certain condition by magnetic multi-walled carbon nanotube, pyrroles and iron chloride.The magnetic multi-walled carbon nanotube for the polypyrrole modifying being prepared can detect 8 kinds of sulfa drugs in water environment simultaneously.
Description
Technical field
The invention belongs to trace drugs in water environment to remain safety detection technology field, be related to a kind of magnetic Nano composite wood
Material and its preparation and application, and in particular to a kind of magnetic multi-walled carbon nanotube of polypyrrole modifying and its preparation and in sulfonamides
Application in analyte detection.Invention also provides a kind of detection sides of sulfa drug residue in sensitive reliable water environment
Method.
Background technique
Sulfa drugs belongs to the artificial synthesized antimicrobial that uses earliest, has a broad antifungal spectrum, and curative effect is stablized, low in cost and can mention
High animal growth rate is therefore widely used in animal husbandry, culture fishery and treatment human bacterial infections' property disease.This
A little drugs can be discharged into environment water with urine, excrement, breeding wastewater etc., be made to environment, the ecosystem and human health
At security risk.Therefore, the detection of sulfa drugs in environmental water sample is increasingly valued by people.
For such drug degradation rate compared with slow, the residence time is long, such drug for being transferred to water body by all means is residual
Chronic, at a specified future date and accumulation harm can be caused to the mankind by staying, and such as generate allergic reaction, drug resistance even carcinogenicity.Currently, multiple
Country has detected the sulfa drugs of various concentration in waste water, surface water or even drinking water.For example, studies have reported that,
The sulfamethoxazole of 0.22 μ g/L is detected in U.S.'s underground water；0.06-15 μ g/L sulfanilamide (SN) diformazan is detected in surface water
Oxygen pyrimidine and 0.08 μ g/L sulphathiazole；11-112ng/L sulfamethoxazole is detected in Spain's river valley.Although from
The concentration of sulfa drugs is with space-time difference in right water body, but has focused largely on ng/L- μ g/L level, is in trace level, and ring
Border matrix is more complicated, therefore it is essential for carrying out enrichment purification before sample detection.
Magnetic solid phase extraction is a kind of micro- solid phase extraction method using magnetic material as adsorbent.With time saving quick, nothing
The advantages that need to being centrifuged or filtering, simplifies sample pretreatment operation.Multi-walled carbon nanotube good, large specific surface area with absorption property
The features such as, it is therefore widely used in the enrichment of trace drug.Magnetic nano-particle is introduced in multi-wall carbon nano-tube pipe surface to obtain
To magnetic multi-walled carbon nanotube the quick separating with sample solution may be implemented, be common magnetic solid phase extraction adsorbent it
One.But the magnetic nano-particle of multi-wall carbon nano-tube pipe surface can be such that material surface adsorption site reduces, due to polypyrrole and certain
There are π-π, hydrogen bond or hydrophobic effects between a little analytes, can compensate the reduction of adsorption site to a certain extent, therefore,
The magnetic multi-walled carbon nanotube of polypyrrole modifying is applied as magnetic solid phase extraction adsorbent in the invention.
For left drug existing for trace in complex environment or ultra trace, single pre-treating method tends not to meet
Such as there is biggish matrix interference in the testing requirements of instrument.Accordingly, it is considered to sample pre-treatments combination technology.Magnetic solid phase extraction knot
Closing dispersive liquid-liquid microextraction (MSPE-DLLME), to have that easy to operate, the rate of recovery is high, enrichment times are high, matrix interference is small etc. excellent
Point.The present invention joins the pre-treating method and the analysis ultra performance liquid chromatography tandem mass spectrum that speed is fast and detection sensitivity is high
With realizing the accurate quick measurement to trace sulfa drug residue in complex environment water sample.
Summary of the invention
The purpose of the present invention is intended to overcome prior art defect, provides a kind of magnetic solid phase extraction adsorbent, and by the absorption
Agent is used for while measuring 8 kinds of sulfanilamide (SN) in water environment (river water, lake water, sewage treatment plant's disengaging saliva and animal farm waste discharge)
Class medicament residue.
The method that another object of the present invention provides while measuring 8 kinds of sulfa drug residues in water environment.
The present invention is achieved through the following technical solutions:
The present invention provides a kind of magnetic nanometer composite material, and the magnetic nanometer composite material is made by the following method
It is standby:
(1) it is made in alkaline solution by multi-walled carbon nanotube, Ammonium ferric sulfate dodecahyrate and six ferrous sulfate hydrate ammoniums
Standby magnetism multi-walled carbon nanotube.
(2) magnetism of polypyrrole modifying is prepared under certain condition by magnetic multi-walled carbon nanotube, pyrroles and iron chloride
Multi-walled carbon nanotube.
Wherein,
The mass ratio of multi-walled carbon nanotube, Ammonium ferric sulfate dodecahyrate and six ferrous sulfate hydrate ammoniums in step (1) are as follows:
1.0:2.0-8.0:0.8-3.5.
The pH of alkaline solution described in step (1) is 10-12, by the way that the alkaline matters tune such as ammonium hydroxide, sodium hydroxide are added
Section.
Magnetism multi-walled carbon nanotube described in step (2), pyrroles, iron chloride mass ratio are as follows: 1:0.35-1.5:0.5-
2.0。
Specifically,
The magnetic nanometer composite material is prepared via a method which:
Ammonium ferric sulfate dodecahyrate, six ferrous sulfate hydrate ammoniums are dissolved in water, multi-walled carbon nanotube is added to
It states in solution, under nitrogen protection, ammonium hydroxide is added and adjusts pH value of solution and is ultrasonically treated 15-20min, mixture is at 40-60 DEG C
0.5-1h is stirred to obtain magnetic multi-walled carbon nanotube；
Magnetic multi-walled carbon nanotube is dispersed in water, 5-10min is stirred, pyrroles is then added, stirs 10-30min, it
After ferric chloride solution is added dropwise, gained mixture stirs 8-12h at 20-30 DEG C to obtain the magnetic multi wall of polypyrrole modifying
Carbon nanotube.
The saturated magnetization of the magnetic multi-walled carbon nanotube of magnetic nanometer composite material polypyrrole modifying prepared by the present invention is strong
Degree is 25-35emu/g.
It is solid that the magnetic multi-walled carbon nanotube of magnetic nanometer composite material polypyrrole modifying prepared by the present invention can be used as magnetic
Mutually extraction adsorbent, the pretreatment technology using MSPE-DLLME as environmental water sample, and utilize ultra performance liquid chromatography string
Join mass spectrum as detection instrument, quantitative analysis is carried out to sulfa drugs.Especially to a variety of sulfa drugs simultaneous quantitatives point
Analysis.The problems such as existing method matrix interference is more, detection limit for height and organic reagent consumption are big are overcome, water ring can be quickly detected
Sulfacetamide, sulphadiazine, sulphathiazole, sulfapryidine, sulfamethyldiazine, sulfamethazine, sulfalene are disliked in border
The content of azoles, sulfadimethoxine, sample pretreatment is easy to operate, and matrix interference is small, and measurement result is accurate, sensitive.
The magnetic multi-walled carbon nanotube for the magnetic nanometer composite material polypyrrole modifying that the present invention synthesizes extracts as magnetic solid phase
The method for taking adsorbent and dispersive liquid-liquid microextraction being combined to be used to detect sulfa drug residue in water environment, specific steps are such as
Under:
(1) pretreatment of water sample
It collects water sample and filters；
(2) magnetic solid phase extraction is enriched with concentration process
The magnetic multi-wall carbon nano-tube tube material for preparing resulting polypyrrole modifying is added in the water sample of step (1) processing,
Oscillation, separates material by magnet, and discard supernatant liquid, and methanol is added, and is vortexed, and separation material collects supernatant nitrogen
Drying, it is spare to obtain residue；
(3) dispersive liquid-liquid microextraction purification process
Residue obtained in step (2) is dissolved with pure water, then is rapidly added the mixed solution of dichloroethanes and acetonitrile, whirlpool
Rotation, centrifugation, upper strata aqueous phase is removed, it is spare to obtain residue with being dried with nitrogen for lower layer's organic phase；
(4) 8 kinds of sulfa drugs in ultra performance liquid chromatography-mass spectrometry water environment
Ultra performance liquid chromatography separation
Chromatographic condition is as follows: chromatographic column: ACQUITY UHPLCC18Chromatographic column (2.1mm × 100mm, 1.7 μm)；Stream
Dynamic phase: A:0.1% formic acid-water, B: acetonitrile；Using gradient elution program, Gradient program are as follows: 0-4min:10-50%B；4-
4.5min:50-10%B；4.5-7min:10%B；Flow velocity: 0.2mL/min；Column temperature: 20-25 DEG C；Sample volume: 10 μ L；
Mass Spectrometer Method
Mass Spectrometer Method condition is as follows: ion source: electrospray ionisation source (source ESI)；Detection mode: positive ion mode；Scanning
Mode: more reactive ions detect (MRM)；Ion source temperature: 110 DEG C；Capillary voltage: 3.5kV；Desolvation temperature: 400
℃；Desolvention gas velocity: 450L/hr.
In step (1), 0.45 μm of membrane filtration of water sample；
The magnetic multi-walled carbon nanotube of polypyrrole modifying and the w/v of water in step (2) are as follows: 1:1-1:2 (mg:
ML), duration of oscillation: 5-10min, methanol volume: 6-10mL, vortex time: 3-5min；
In step (3), the dosage of acetonitrile is 1.5-2 times of dichloroethanes volume；Vortex time: 1-3min；Centrifugal rotational speed:
3000-4500rpm；Centrifugation time: 3-5min.
Specifically, the present invention can be prepared with the following method:
(1) pretreatment of water sample
Water sample is collected, and with 0.45 μm of membrane filtration.
(2) magnetic solid phase extraction is enriched with concentration process
Filtered water sample 100-200mL in step (1) is taken, the magnetic multi wall carbon of 100-200mg polypyrrole modifying is added
Nanotube vibrates 5-10min, and the separation of material and sample solution is realized under extraneous magnet auxiliary, liquid is discarded supernatant, in gained
6-10mL methanol is added in material, vortex 3-5min is separated material with eluent using magnet, collects eluent and in 30-
With being dried with nitrogen at 35 DEG C, it is spare to obtain residue；
(3) dispersive liquid-liquid microextraction purification process
It is above-mentioned residue obtained with the dissolution of 5mL pure water, it is rapidly injected 500-1000 μ L dichloroethanes and dichloroethanes volume
1.5-2 times of acetonitrile, vortex 1-3min obtain dirty solution, and 3-5min is then centrifuged under 3000-4500rpm, remove upper strata aqueous phase,
Lower layer's organic phase, with being dried with nitrogen, it is spare to obtain residue at 30-35 DEG C；
(4) 8 kinds of residual quantity of sulfonamide in ultra performance liquid chromatography-mass spectrometry water environment
(4.1) ultra performance liquid chromatography separates
Chromatographic column: ACQUITY UHPLCC18Chromatographic column (2.1mm × 100mm, 1.7 μm)；Mobile phase: A:0.1%
Formic acid-water, B: acetonitrile；Using gradient elution program, Gradient program are as follows: 0-4min:10-50%B；4-4.5min:50-10%
B；4.5-7min:10%B；Flow velocity: 0.2mL/min；Column temperature: 20-25 DEG C；Sample volume: 10 μ L；
(4.2) Mass Spectrometer Method
Mass Spectrometer Method condition is as follows: ion source: electrospray ionisation source (source ESI)；Detection mode: positive ion mode；Scanning
Mode: more reactive ions detect (MRM)；Ion source temperature: 110 DEG C；Capillary voltage: 3.5kV；Desolvation temperature: 400
℃；Desolvention gas velocity: 450L/hr.
(4.3) acetonitrile and water that the residue for obtaining step (3) is 1:9 with 200 μ L volume ratios dissolve, with 0.22 μm of filter membrane
Filtering obtains test sample, carries out sample analysis；
The calculating of (5) 8 kinds of sulfa drugs measurement results.
The present invention uses the magnetic multi-walled carbon nanotube of polypyrrole modifying as magnetic solid phase extraction adsorbent, with other magnetism
Sorbent material has better adsorption capacity to sulfa drugs compared to the material；
Magnetic solid phase extraction and dispersive liquid-liquid microextraction are combined by this method, i.e. MSPE-DLLME, have easy to operate, enrichment
The advantages such as multiple is high, matrix interference is small, detection limit is low, the detection of sulfa drug residue suitable for Complex Water Environment, before this
Processing method provides new approaches for the development and application of Sample Pretreatment Technique, while being also point of Environmental Trace medicament residue
Analysis measurement increases new method.
Detailed description of the invention
Fig. 1 is the magnetic multi-walled carbon nanotube (c) of multi-walled carbon nanotube (a), magnetic polypyrrole (b) and polypyrrole modifying
Scanning electron microscope (SEM) photograph；
Fig. 2 is the infrared of the magnetic multi-walled carbon nanotube of magnetic multi-walled carbon nanotube, magnetic polypyrrole and polypyrrole modifying
Spectrogram；
Fig. 3 is the hysteresis loop figure of the magnetic multi-walled carbon nanotube of magnetic multi-walled carbon nanotube and polypyrrole modifying；
Fig. 4 is influence of the adsorbent species to 8 kinds of sulfa drugs rate of recovery；
Fig. 5 is influence of the adsorbent amount to 8 kinds of sulfa drugs rate of recovery；
Fig. 6 is influence of the pH value of solution to 8 kinds of sulfa drugs rate of recovery；
Fig. 7 is influence of the desorption solvent type to 8 kinds of sulfa drugs rate of recovery；
Fig. 8 is influence of the desorption solvent volume to 8 kinds of sulfa drugs rate of recovery；
Fig. 9 is influence of the extractant type to 8 kinds of sulfa drugs rate of recovery；
Figure 10 is influence of the extractant volume to 8 kinds of sulfa drugs rate of recovery；
Figure 11 is influence of the dispersant to 8 kinds of sulfa drugs rate of recovery；
Figure 12 is influence of the dispersing agent volume to 8 kinds of sulfa drugs rate of recovery.
Specific embodiment
The present invention establishes a kind of method for accurately and reliably analyzing 8 kinds of residual quantity of sulfonamide in water environment.Firstly,
The magnetic multi-walled carbon nanotube of polypyrrole modifying is successfully prepared as magnetic solid phase extraction adsorbent, then, is extracted using magnetic solid phase
It takes and dispersive liquid-liquid microextraction technology is combined to utilize ultra performance liquid chromatography-series connection matter later to environmental water sample progress pre-treatment
Analysis measurement of the spectrum to analyte accurate quantitative analysis, applied to 8 kinds of sulfa drugs in true environment water sample.
Embodiment 1: the analysis measurement of 8 kinds of sulfa drugs in water sample
(1) synthesis of the magnetic multi-walled carbon nanotube of polypyrrole modifying
(1.1) synthesis of magnetic multi-walled carbon nanotube
It is obtained firstly, the iron ammonium sulfate of the Ammonium ferric sulfate dodecahyrate of 4.18g and 1.70g is dissolved in 200mL water
Then 1.0g multi-walled carbon nanotube is added in clear solution, under nitrogen protection, ammonium hydroxide is added makes suspension to ultrasonic 10min simultaneously
PH value be adjusted to 11.Then, gained mixture is stirred into 30min at 50 DEG C.It, will with magnet after object to be mixed is cooled to room temperature
Magnetic material, which is separated from the mixture, to be used together pure water and ethyl alcohol and elutes respectively three times, dry 10h at 60 DEG C, grinding for into
One step prepares the magnetic multi-walled carbon nanotube of polypyrrole modifying.
(1.2) synthesis of the magnetic multi-walled carbon nanotube of polypyrrole modifying
0.6g magnetism multi-walled carbon nanotube is added in the round-bottomed flask containing 250mL water (pH 9), 5min is stirred,
Then 0.4mL pyrroles is added, stirs 10min.Then, 0.56g ferric trichloride is dissolved in 50mL pure water, and be added dropwise to
In round-bottomed flask, gained mixture is by continuous mechanical stirring 10h.Magnetic material is collected with magnet, and is carried out with pure water and methanol
Washing is until filtrate is colourless.Finally by resulting materials, dry 10h, grinding are spare at 60 DEG C.
(2) water sample pre-processes
River water, lake water, sewage treatment plant's Inlet and outlet water and herding factory waste discharge are collected respectively, with 0.45 μm of filter membrane mistake
Filter.
(3) magnetic solid phase extraction-dispersive liquid-liquid microextraction (MSPE-DLLME) is enriched with concentration process
The resulting sample 100mL of step (2) is taken, the magnetic multi-walled carbon nanotube of 100mg polypyrrole modifying, oscillation is added
Then material is separated under extraneous magnet auxiliary with sample solution, liquid is discarded supernatant, above-mentioned by 5min (30 DEG C, 250rpm)
6mL methanol is added in material, vortex 3min is separated material with eluent to elute determinand, using magnet, and eluent is 30
With being dried with nitrogen at DEG C, residue is collected.It is above-mentioned residue obtained with the dissolution of 5mL pure water, it is rapidly injected 500 μ L dichloroethanes and 900 μ
L acetonitrile, vortex 1min form dirty solution.Then mixture is centrifuged 3min at 4000rpm, removes upper water, lower layer is organic
It is spare mutually to collect residue with being dried with nitrogen at 30 DEG C.
(4) Waters Acquity is utilizedTMSuperelevation liquid chromatogram and Micromass Quattro MicroTMAPI mass spectrum
The content of 8 kinds of sulfa drugs in system measurement water environment
Chromatographic column:BEH C18Chromatographic column (2.1mm × 100mm, 1.7 μm)
Mobile phase: A:0.1% formic acid-water, B: acetonitrile
Gradient elution program: 0-4min:10-50%B；4-4.5min:50-10%B；4.5-7min:10%B
Flow velocity: 0.2mL/min
Column temperature: 25 DEG C
Sample volume: 10 μ L；
Ion source: electrospray ionisation source (source ESI)
Detection mode: positive ion mode
Scanning mode: more reactive ions detect (MRM)
Ion source temperature: 110 DEG C
Capillary voltage: 3.5kV
Desolvation temperature: 400 DEG C
Desolvention gas velocity: 450L/hr.
Mass spectrometry parameters of 8 kinds of target analytes for quantitative analysis are shown in Table 1.
The Mass Spectrometry Conditions of 18 kinds of sulfa drugs of table
(5) methodology validation
The calculating of matrix effect
Each water sample is acquired, is enriched with and is concentrated by above-mentioned steps (3), by above-mentioned steps (4) test sample, obtains accordingly result A: practical
The measurement result of water sample, B: a certain concentration standard solution measurement gained accordingly result, C: a certain concentration standard is added in actual water sample
Measure gained accordingly result after step (3) enrichment concentration after solution, D: actual water sample is after step (3) enrichment concentration
Gained accordingly result is measured after a certain concentration standard solution is added.Then matrix effect (ME), extraction recovery (RE) and main-process stream
Efficiency (PE) is calculated by following formula respectively:
ME (%)=(D-A)/B × 100%
RE (%)=(C-A)/(D-A) × 100%
PE (%)=ME × RE/100
Matrix effect the results are shown in Table 2, the results showed that MSPE-DLLME can effectively reduce matrix to the shadow of measurement result
It rings.
Matrix effect and main-process stream efficiency of each determinand of table 2 in different water samples
Sensitivity and standard curve
With the accurately weighed sulfacetamide of assay balance, sulphadiazine, sulphathiazole, sulfapryidine, sulfamethyldiazine, sulphur
Amine dimethyl pyrimidine, sulfamethoxazole, sulfadimethoxine reference substance dissolve reference substance with chromatographic grade acetonitrile, are diluted to and are
The standard solution of column concentration is measured by above-mentioned chromatographic condition.Using concentration as abscissa, response is that ordinate is returned
Return, obtains standard curve.Limit (IDL) and quantitative limit (IQL) are detected using signal-to-noise ratio method determining instrument.The method of different water samples is examined
It surveys limit (MDL) and method quantitative limit (MQL) is calculated by following formula respectively:
MDL=(IDL × 100)/(PE × 500)
MQL=(IQL × 100)/(PE × 500)
Matrix matching standard curve: taking 100mL environmental water sample, and mixed standard solution is added, is configured to a series of concentration
Mark-on water sample is handled according to step (3), and residue obtained 200 μ L initial liquid phases are redissolved, so that serial matrix be prepared
With standard solution.Quantitative analysis is carried out to 8 kinds of sulfa drugs in environmental water sample using matrix matching standard curve.
It the results are shown in Table 3.As seen from table, good linear relationship is presented within the scope of 10-500ng/L in 8 kinds of sulfa drugs
(related coefficient is all larger than 0.993), furthermore method quantitative limit is below 10ng/L, shows method high sensitivity.
Claims (10)
1. a kind of magnetic nanometer composite material, which is characterized in that be prepared via a method which:
(1) magnetic is prepared in alkaline solution by multi-walled carbon nanotube, Ammonium ferric sulfate dodecahyrate and six ferrous sulfate hydrate ammoniums
Property multi-walled carbon nanotube；
(2) the magnetic multi wall of magnetic solid phase extraction adsorbent polypyrrole modifying is prepared by magnetic multi-walled carbon nanotube, pyrroles, iron chloride
Carbon nanotube.
2. magnetic nanometer composite material as described in claim 1, which is characterized in that multi-walled carbon nanotube, 12 hydrated sulfuric acids
The mass ratio of iron ammonium, six ferrous sulfate hydrate ammoniums are as follows: 1.0:2.0-8.0:0.8-3.5, preferably are as follows: 1:4.2:1.7.
3. magnetic nanometer composite material as described in claim 1, which is characterized in that the pH of alkaline solution described in step (1)
For 10-12, pH is adjusted by the way that ammonium hydroxide or sodium hydroxide solution is added.
4. magnetic nanometer composite material as described in claim 1, which is characterized in that magnetic multi-walled carbon nanotube, pyrroles, chlorination
The mass ratio of iron: 1:0.3-1.5:0.5-2.0.
5. magnetic nanometer composite material as described in claim 1, which is characterized in that the preparation method is that:
(1) Ammonium ferric sulfate dodecahyrate, six ferrous sulfate hydrate ammoniums are dissolved in water, multi-walled carbon nanotube are added to above-mentioned
In solution, under nitrogen protection, ammonium hydroxide being added and adjusts pH value of solution and is ultrasonically treated, mixture stirs 0.5-1h at 40-60 DEG C,
Obtain magnetic multi-walled carbon nanotube；
(2) magnetic multi-walled carbon nanotube is dispersed in water, stirs, pyrroles is then added, stirred, iron chloride is added dropwise later
Solution, gained mixture stir 8-12h at 20-30 DEG C and obtain the magnetic multi wall carbon of magnetic solid phase extraction adsorbent polypyrrole modifying
Nanotube.
6. magnetic nanometer composite material described in claim 1-6 any one is in water environment in sulfa drug residue detection
Application.
7. application as claimed in claim 6, which comprises the steps of:
(1) pretreatment of water sample
It collects water sample and filters；
(2) magnetic solid phase extraction is enriched with concentration process
Magnetic nanometer composite material is added in the water sample of step (1) processing, vibrates, discards supernatant liquid, methanol is added, is vortexed,
Separation collects supernatant with being dried with nitrogen, it is spare to obtain residue；
(3) dispersive liquid-liquid microextraction purification process
Residue obtained in step (2) is dissolved with water, then is rapidly added the mixed solution of dichloroethanes and acetonitrile, is vortexed, from
The heart removes upper strata aqueous phase, and it is spare to obtain residue with being dried with nitrogen for lower layer's organic phase；
(4) 8 kinds of sulfa drugs in ultra performance liquid chromatography-mass spectrometry water environment
Ultra performance liquid chromatography separation
Chromatographic condition is as follows: chromatographic column: ACQUITY UHPLCC18Chromatographic column (2.1mm × 100mm, 1.7 μm)；Flowing
Phase: A:0.1% formic acid-water, B: acetonitrile；Using gradient elution program；Flow velocity: 0.2mL/min；Column temperature: 20-25 DEG C；Sample volume:
10μL；
Mass Spectrometer Method
Mass Spectrometer Method condition is as follows: ion source: electrospray ionisation source (source ESI)；Detection mode: positive ion mode；Scanning mode:
More reactive ions detect (MRM)；Ion source temperature: 110 DEG C；Capillary voltage: 3.5kV；Desolvation temperature: 400 DEG C；Precipitation
Agent gas velocity: 450L/hr.
The acetonitrile and water that the residue that step (3) is obtained is 1:9 with 200 μ L volume ratios dissolve, and obtain test sample, carry out chromatography point
Analysis；
The calculating of (5) 8 kinds of sulfa drugs measurement results；
The amount ratio of dichloroethanes and acetonitrile in step (3) are as follows: 5:9；
In step (4), Gradient program is as follows:
。
8. the use as claimed in claim 7, which is characterized in that the sulfa drugs is sulfacetamide, sulphadiazine, sulphur
One of amine thiazole, sulfapryidine, sulfamethyldiazine, sulfamethazine, sulfamethoxazole, sulfadimethoxine
Or it is several.
9. the method for measuring 8 kinds of sulfa drug residues in water environment simultaneously, which comprises the steps of:
(1) pretreatment of water sample
It collects water sample and filters；
(2) magnetic solid phase extraction is enriched with concentration process
Magnetic nanometer composite material is added in the water sample of step (1) processing, vibrates, discards supernatant liquid, methanol is added, is vortexed,
Separation collects supernatant with being dried with nitrogen, it is spare to obtain residue；
(3) dispersive liquid-liquid microextraction purification process
Residue obtained in step (2) is dissolved with water, then is rapidly added the mixed solution of dichloroethanes and acetonitrile, is vortexed, from
The heart removes upper strata aqueous phase, and it is spare to obtain residue with being dried with nitrogen for lower layer's organic phase；
(4) 8 kinds of sulfa drugs in ultra performance liquid chromatography-mass spectrometry water environment
Ultra performance liquid chromatography separation
Chromatographic condition is as follows: chromatographic column: ACQUITY UHPLCC18Chromatographic column (2.1mm × 100mm, 1.7 μm)；Flowing
Phase: A:0.1% formic acid-water, B: acetonitrile；Using gradient elution program；Flow velocity: 0.2mL/min；Column temperature: 20-25 DEG C；Sample volume:
10μL；
Mass Spectrometer Method
Mass Spectrometer Method condition is as follows: ion source: electrospray ionisation source (source ESI)；Detection mode: positive ion mode；Scanning mode:
More reactive ions detect (MRM)；Ion source temperature: 110 DEG C；Capillary voltage: 3.5kV；Desolvation temperature: 400 DEG C；Precipitation
Agent gas velocity: 450L/hr.
The acetonitrile and water that the residue that step (3) is obtained is 1:9 with 200 μ L volume ratios dissolve, and obtain test sample, carry out chromatography point
Analysis；
The calculating of (5) 8 kinds of sulfa drugs measurement results；
The amount ratio of dichloroethanes and acetonitrile in step (3) are as follows: 5:9；
In step (4), Gradient program is as follows:
。
10. method as claimed in claim 9, which is characterized in that the water environment refers to river water, river water, waste water treatment plant
Pass in and out saliva and animal farm waste discharge.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811284090.6A CN109331795A (en) | 2018-10-31 | 2018-10-31 | A kind of magnetic nanometer composite material and its preparation and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811284090.6A CN109331795A (en) | 2018-10-31 | 2018-10-31 | A kind of magnetic nanometer composite material and its preparation and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109331795A true CN109331795A (en) | 2019-02-15 |
Family
ID=65313057
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811284090.6A Pending CN109331795A (en) | 2018-10-31 | 2018-10-31 | A kind of magnetic nanometer composite material and its preparation and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109331795A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109772258A (en) * | 2019-03-13 | 2019-05-21 | 厦门大学 | A kind of preparation method of magnetism fluorinated carbon nanomaterial |
| CN110385116A (en) * | 2019-06-28 | 2019-10-29 | 沈阳信达泰康医药科技有限公司 | A kind of magnetic nanometer composite material and its preparation and application |
| CN111426767A (en) * | 2020-04-21 | 2020-07-17 | 沈阳信达泰康医药科技有限公司 | Magnetic nano composite material, preparation thereof and application thereof in food detection |
| CN112595783A (en) * | 2020-05-14 | 2021-04-02 | 山东省农业科学院农业质量标准与检测技术研究所 | Method for detecting multiple antibiotics in livestock and poultry excrement based on magnetic nanocomposite |
| CN113668245A (en) * | 2021-08-19 | 2021-11-19 | 南京市产品质量监督检验院 | Preparation method and application of polystyrene-hydroxylated multi-walled carbon nanotube-polypyrrole composite nanofiber |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102380353A (en) * | 2011-09-19 | 2012-03-21 | 江苏大学 | Method for preparing magnetic magnesium oxide surface molecular imprinting solid phase extractant |
| CN103616457A (en) * | 2013-12-12 | 2014-03-05 | 青岛理工大学 | Method of detecting flusilazole, fipronil, chlorfenapyr and fenpyroximate in environmental water sample |
| CN103724539A (en) * | 2012-10-12 | 2014-04-16 | 中国药科大学 | Preparation method of magnetic carbon nanotube surface molecular imprinting material |
| CN105241990A (en) * | 2015-09-25 | 2016-01-13 | 沈阳药科大学 | Method for determining 10 kinds of antibiotics in water environment through combination of sample pre-treatment technology and HPLC-MS |
| CN105424825A (en) * | 2015-11-03 | 2016-03-23 | 沈阳药科大学 | Method for measuring 12 types of remaining medicine in water environment through separation and enrichment |
| CN105771927A (en) * | 2016-03-13 | 2016-07-20 | 宿州学院 | Macromolecular magnetic composite material and preparation method thereof |
| CN106238007A (en) * | 2016-07-27 | 2016-12-21 | 齐鲁工业大学 | A kind of magnetic nanocomposites and its preparation method and application |
| CN106732470A (en) * | 2017-03-06 | 2017-05-31 | 济南大学 | A kind of preparation of 2 mercaptopyrimidine modified magnetic CNT porous adsorbent |
| CN107213882A (en) * | 2017-07-18 | 2017-09-29 | 苏州科技大学 | A kind of preparation method and application of magnetic polypyrrole/graphene oxide composite material |
| CN108355627A (en) * | 2018-03-13 | 2018-08-03 | 苏州科技大学 | A kind of preparation method and application of polypyrrole modified magnetic nanocomposite |
-
2018
- 2018-10-31 CN CN201811284090.6A patent/CN109331795A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102380353A (en) * | 2011-09-19 | 2012-03-21 | 江苏大学 | Method for preparing magnetic magnesium oxide surface molecular imprinting solid phase extractant |
| CN103724539A (en) * | 2012-10-12 | 2014-04-16 | 中国药科大学 | Preparation method of magnetic carbon nanotube surface molecular imprinting material |
| CN103616457A (en) * | 2013-12-12 | 2014-03-05 | 青岛理工大学 | Method of detecting flusilazole, fipronil, chlorfenapyr and fenpyroximate in environmental water sample |
| CN105241990A (en) * | 2015-09-25 | 2016-01-13 | 沈阳药科大学 | Method for determining 10 kinds of antibiotics in water environment through combination of sample pre-treatment technology and HPLC-MS |
| CN105424825A (en) * | 2015-11-03 | 2016-03-23 | 沈阳药科大学 | Method for measuring 12 types of remaining medicine in water environment through separation and enrichment |
| CN105771927A (en) * | 2016-03-13 | 2016-07-20 | 宿州学院 | Macromolecular magnetic composite material and preparation method thereof |
| CN106238007A (en) * | 2016-07-27 | 2016-12-21 | 齐鲁工业大学 | A kind of magnetic nanocomposites and its preparation method and application |
| CN106732470A (en) * | 2017-03-06 | 2017-05-31 | 济南大学 | A kind of preparation of 2 mercaptopyrimidine modified magnetic CNT porous adsorbent |
| CN107213882A (en) * | 2017-07-18 | 2017-09-29 | 苏州科技大学 | A kind of preparation method and application of magnetic polypyrrole/graphene oxide composite material |
| CN108355627A (en) * | 2018-03-13 | 2018-08-03 | 苏州科技大学 | A kind of preparation method and application of polypyrrole modified magnetic nanocomposite |
Non-Patent Citations (2)
| Title |
|---|
| 刘柱等: "磁性修饰多壁碳纳米管固相萃取快速测定牛奶中20种激素残留", 《分析试验室》 * |
| 王芳等: "聚吡咯修饰磁性纳米材料超高效液相色谱-串联质谱法测定环境水体中11 种喹诺酮类药物残留", 《中国卫生检验杂志》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109772258A (en) * | 2019-03-13 | 2019-05-21 | 厦门大学 | A kind of preparation method of magnetism fluorinated carbon nanomaterial |
| CN110385116A (en) * | 2019-06-28 | 2019-10-29 | 沈阳信达泰康医药科技有限公司 | A kind of magnetic nanometer composite material and its preparation and application |
| CN111426767A (en) * | 2020-04-21 | 2020-07-17 | 沈阳信达泰康医药科技有限公司 | Magnetic nano composite material, preparation thereof and application thereof in food detection |
| CN111426767B (en) * | 2020-04-21 | 2022-07-12 | 沈阳信达泰康医药科技有限公司 | Magnetic nano composite material, preparation thereof and application thereof in food detection |
| CN112595783A (en) * | 2020-05-14 | 2021-04-02 | 山东省农业科学院农业质量标准与检测技术研究所 | Method for detecting multiple antibiotics in livestock and poultry excrement based on magnetic nanocomposite |
| CN113668245A (en) * | 2021-08-19 | 2021-11-19 | 南京市产品质量监督检验院 | Preparation method and application of polystyrene-hydroxylated multi-walled carbon nanotube-polypyrrole composite nanofiber |
| CN113668245B (en) * | 2021-08-19 | 2023-02-24 | 南京市产品质量监督检验院 | Preparation method and application of polystyrene-hydroxylated multi-walled carbon nanotube-polypyrrole composite nanofiber |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109331795A (en) | A kind of magnetic nanometer composite material and its preparation and application | |
| Huang et al. | Solid-phase microextraction: An appealing alternative for the determination of endogenous substances-A review | |
| Hu et al. | Facile synthesis of magnetic sulfonated covalent organic framework composites for simultaneous dispersive solid-phase extraction and determination of β-agonists and fluoroquinolones in food samples | |
| Gao et al. | Development and application of vortex-assisted membrane extraction based on metal–organic framework mixed-matrix membrane for the analysis of estrogens in human urine | |
| Zhao et al. | Determination of perfluorinated compounds in wastewater and river water samples by mixed hemimicelle-based solid-phase extraction before liquid chromatography–electrospray tandem mass spectrometry detection | |
| CN105424825B (en) | A kind of method that separation and concentration determines 12 kinds of left drugs in water environment | |
| CN107907614A (en) | A kind of molecular engram solid phase extraction high performance liquid chromatography tandem mass spectrum assay method of bisphenol compound | |
| CN108732273B (en) | Method for analyzing trace sulfonamide antibiotics in food and drinking water | |
| Bagheri et al. | Microextraction of antidepressant drugs into syringes packed with a nanocomposite consisting of polydopamine, silver nanoparticles and polypyrrole | |
| Zhai et al. | Chip-based molecularly imprinted monolithic capillary array columns coated GO/SiO2 for selective extraction and sensitive determination of rhodamine B in chili powder | |
| CN113842901B (en) | Sea urchin-shaped MOFs@COFs core-shell structure material and preparation method and application thereof | |
| Yuan et al. | Fe3O4/graphene molecularly imprinted composite for selective separation of catecholamine neurotransmitters and their analysis in rat brain tissues | |
| Lv et al. | Occurrence and distribution of pharmaceuticals in raw, finished, and drinking water from seven large river basins in China | |
| Liu et al. | The determination of pesticides in tea samples followed by magnetic multiwalled carbon nanotube-based magnetic solid-phase extraction and ultra-high performance liquid chromatography-tandem mass spectrometry | |
| Hedeshi et al. | Silane–based modified papers and their extractive phase roles in a microfluidic platform | |
| Yuan et al. | Polypyrrole-modified magnetic multi-walled carbon nanotube-based magnetic solid-phase extraction combined with dispersive liquid–liquid microextraction followed by UHPLC-MS/MS for the analysis of sulfonamides in environmental water samples | |
| Gong et al. | Amino-functionalized metal–organic frameworks for efficient solid-phase microextraction of perfluoroalkyl acids in environmental water | |
| CN101334386B (en) | Determination method for plant medicine blood plasma amygdalin for strengthening the body resistance | |
| Dong et al. | Magnetic solid-phase extraction based on magnetic amino modified multiwalled carbon nanotubes for the fast determination of seven pesticide residues in water samples | |
| Zhou et al. | Synthesis of metal-organic framework-5@ chitosan material for the analysis of microcystins and nodularin based on ultra-performance liquid chromatography-tandem mass spectrometry | |
| CN107389835A (en) | The sample-pretreating method of anticoccidial medicament residue in a kind of HPLC MS/MS methods detection animal derived food | |
| Wang et al. | Green sample clean-up based on magnetic multiwalled carbon nanotubes for the determination of lamivudine by high performance liquid chromatography | |
| Li et al. | Selective extraction and enrichment of glycoproteins based on boronate affinity SPME and determination by CIEF-WCID | |
| Qi et al. | Off-line hyphenation of molecularly imprinted magnetic nanoparticle-based extraction with large volume sample stacking capillary electrophoresis for high-sensitivity detection of trace chloro-phenols | |
| CN108794687A (en) | A kind of molecular engram material and its application in water environment in nonsteroidal anti-inflammatory drug detection |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190215 |
|
| RJ01 | Rejection of invention patent application after publication |