CN114452958B - Dopant-polypyrrole composite coating material for solid-phase microextraction column and preparation method thereof - Google Patents
Dopant-polypyrrole composite coating material for solid-phase microextraction column and preparation method thereof Download PDFInfo
- Publication number
- CN114452958B CN114452958B CN202210209484.5A CN202210209484A CN114452958B CN 114452958 B CN114452958 B CN 114452958B CN 202210209484 A CN202210209484 A CN 202210209484A CN 114452958 B CN114452958 B CN 114452958B
- Authority
- CN
- China
- Prior art keywords
- coating material
- composite coating
- dopant
- phase microextraction
- polypyrrole
- 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.)
- Active
Links
Images
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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- 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
- B01D15/20—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the conditioning of the sorbent material
- B01D15/206—Packing or coating
-
- 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
- B01J20/22—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
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/405—Concentrating samples by adsorption or absorption
Abstract
The invention belongs to the technical field of environmental detection and analysis, and particularly relates to a dopant-polypyrrole composite coating material for a solid-phase microextraction column and a preparation method thereof. The composite coating material is formed by compounding a doping agent and a polypyrrole nano material, the particle size of the composite coating material is 50-280nm, and the thickness of the composite coating material is 100-700nm; the dopant includes dodecylbenzene sulfonic acid, sodium dodecylbenzene sulfonate, sodium dodecylsulfate, sodium polystyrene sulfonate, cetyltrimethylammonium bromide, and phenol saffron. The preparation method of the solid-phase microextraction coating in the polypyrrole composite pipe is simple and easy to operate, safe and reliable, easy to scale, good in chemical stability, capable of being recycled and used for many times, high in extraction efficiency on polar pesticides, and capable of realizing the adsorption capacity regulation and control on the polypyrrole composite film by regulating the concentration of the doping agent, the concentration of the pyrrole, the concentration of the oxidizing agent and the thickness of the film.
Description
Technical Field
The invention belongs to the technical field of environmental detection and analysis, and particularly relates to a dopant-polypyrrole composite coating material for a solid-phase microextraction column and a preparation method thereof.
Background
Although the traditional sample pretreatment methods for pesticide residue detection, such as liquid-liquid extraction (LLE), quECHERS and Solid Phase Extraction (SPE), have expected extraction performance, the method still has the defects of consuming a large amount of organic solvents, having complicated and time-consuming treatment procedures, such as extraction and purification procedures, poor extraction efficiency, low sensitivity, high cost and the like, so that the development of the sample pretreatment method for pesticide residue detection is particularly urgent, and the method is environment-friendly, high in extraction efficiency, high in cost benefit and convenient to operate. As a rapid replacement technology of a conventional pretreatment technology, the in-tube solid-phase microextraction (IT-SPME) has the unique advantages of environment friendliness, jian Xiao volume, simplicity and convenience in operation, capability of being combined with other analytical instruments, high sensitivity and the like, and is widely applied to detection of pesticide residues in environmental samples.
The working principle of IT-SPME is adsorption equilibrium, i.e. the concentration equilibrium between the target analyte and the adsorption phase occurs over the coating, so the coating material is a key factor determining IT-SPME performance. Porous divinylbenzene (Supel-Q), TRB-5 (95% dimethyl-5% diphenylpolysiloxane), polysiloxanes (14% cyanopropylpropylphenylmethylpolysiloxane), polyethylene glycol, and the like are the most commonly used coating materials for IT-SPME, which are expensive, and the broad spectrum of materials also makes them less selective for target analytes; the most important problem is that commercial coating materials are suitable for analysis of weakly polar and volatile compounds, interactions and retention of polar compounds are poor. In the novel coating material, polypyrrole (PPy) has great potential as an in-tube solid-phase microextraction material, and polypyrrole and derivatives thereof have multifunctional characteristics and porous surface properties, and polar groups can be introduced into polymer chains through interaction such as ion exchange, hydrogen bond interaction, hydrophobic interaction and the like, so that the extraction and separation capability of the polypyrrole adsorption material on target analytes is greatly promoted. In addition, polypyrrole is nontoxic, inexpensive, and can be rapidly prepared by simple chemical oxidation or electrochemical methods. Polypyrrole and ITs composite material have great potential as IT-SPME coating material.
Disclosure of Invention
In order to solve the problems, the invention provides a dopant-polypyrrole composite coating material for a solid-phase microextraction column, wherein the composite coating material is formed by compounding a dopant and a polypyrrole material, the particle size of the composite coating material is 50-280nm, and the thickness of the composite coating material is 100-700nm;
dopants include dodecylbenzene sulfonic acid (DBSA), sodium dodecylbenzene sulfonate (SDBS), sodium Dodecyl Sulfate (SDS), sodium polystyrene sulfonate (PSS), cetyltrimethylammonium bromide (CTAB), phenol safranine.
A method for preparing a dopant-polypyrrole composite coating material on a solid phase microextraction column, comprising the following steps:
1) Pretreatment of the inner surface of the column: etching the inner surface of the support material by using 1.0mol/L hydrochloric acid solution and 1.0mol/L sodium hydroxide solution respectively, and then washing with pure water and acetone and drying;
2) Preparing a composite coating material: sequentially passing the mixed solution of the pyrrole monomer and the dopant and the oxidant solution through a capillary tube, and preparing a dopant-polypyrrole composite coating material on the inner surface of the capillary tube;
3) Repeating the operation of the step 2), then adopting methanol to flush the inner surface of the support material, and drying to obtain the solid-phase microextraction column with the dopant-polypyrrole composite coating material in the tube, wherein the composite coating material is fixed on the inner wall of the support material in a chemical bonding mode.
In the step 1), the supporting material comprises a quartz capillary column, a polytetrafluoroethylene tube or a stainless steel tube; the inner diameter is 0.1-1.0mm, and the length is 4.0-30.0cm.
In the step 2), the oxidant is ammonium persulfate.
Further, in the step 2), the molar ratio of the pyrrole monomer to the dopant ranges from 10:1 to 500:1; the molar ratio of pyrrole monomer to ammonium persulfate is in the range of 5:1 to 40:1.
Further, in the mixed solution in the step 2), the dopant and the pyrrole monomer are dissolved by isopropanol and water, wherein the volume ratio of the pyrrole monomer to the isopropanol to the water is 2:1:3, 1:1:2 or 9:10:5.
In the step 2), the concentration of pyrrole monomers ranges from 1 mol/L to 10mol/L, and the concentration of ammonium persulfate ranges from 0.1 mol/L to 0.6mol/L.
In the step 2), when the doping agent is dodecyl benzene sulfonic acid, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, cetyltrimethylammonium bromide or phenol saffron red, the concentration range is 0.005-0.5mol/L;
when the doping agent is sodium polystyrene sulfonate, the concentration range is 0.01-20.0g/L.
The repetition number in the step 3) is 4-15.
The drying mode adopts nitrogen to dry.
The solid phase microextraction column with the dopant-polypyrrole composite coating material prepared in the tube is applied to the extraction of polar pesticides, and comprises nicotine, phenylurea or antibiotics; the method specifically comprises the following steps:
and (3) nicotine: imidacloprid, acetamiprid, clothianidin, thiamethoxam, or diflubenzuron;
phenylureas: chlorazuron, isoproturon or linuron;
antibiotics: tetracycline, oxytetracycline, aureomycin, or doxycycline.
The invention has the beneficial effects that:
1. the preparation method adopts an in-situ chemical oxidation polymerization method to modify the doping agent and the polypyrrole on the inner wall of the supporting material, so that the solid-phase microextraction column in the polypyrrole composite tube is prepared, and the preparation process of the microextraction column is safe and reliable, simple in operation, short in consumption time, low in cost, easy to scale, good in chemical stability, capable of being recycled and used for multiple times, and suitable for environmental sampling, preservation and transportation.
2. In the invention, the solid-phase microextraction column in the pipe based on the polypyrrole composite material not only has larger adsorption capacity, but also has the coating which is interacted with target analytes by various chemical bonds, and has high extraction efficiency on polar pesticides; the pesticide has good adsorption capacity, such as pesticide, herbicide, antibiotic pesticide and the like, and the recovery rate reaches 70% -110%.
3. In the invention, the sample solution extracted by the doped polypyrrole composite solid-phase microextraction column can be directly injected, is suitable for analyzing actual samples in water, and can conveniently and efficiently extract and measure polar pesticides in water; and has the advantages of high recovery rate, high sensitivity, good reproducibility and good selectivity.
4. The invention can realize the adsorption capacity regulation and control of the polypyrrole composite film by regulating the concentration of the doping agent and the pyrrole, the concentration of the oxidizing agent and the film thickness, and has good application prospect in the aspect of adsorbing polar pesticides in environmental samples.
Drawings
FIG. 1 is a scanning electron microscope image of a DBSA-doped polypyrrole coating prepared in example 1;
FIG. 2 is a scanning electron microscope image of the SDBS doped polypyrrole coating prepared in example 2;
FIG. 3 is a scanning electron microscope image of the PSS doped polypyrrole coating prepared in example 3;
FIG. 4 is a scanning electron microscope image of the SDS-doped polypyrrole coating prepared in example 4;
FIG. 5 is a scanning electron microscope image of the CTAB-doped polypyrrole coating prepared in example 5;
fig. 6 is a scanning electron microscope image of the phenol saffron doped polypyrrole coating prepared in example 6.
Detailed Description
The invention is described in further detail below in connection with specific examples:
example 1
Preparation of solid-phase microextraction column (DBSA-PPy/IT-SPME column for short) in dodecylbenzenesulfonic acid-polypyrrole composite coating tube:
1) Pretreatment of the inner surface of the column: a quartz capillary tube with a length of 15.0cm and an inner diameter of 0.53mm was prepared, the inner surface of the quartz capillary tube was etched with 1.0mol/L hydrochloric acid solution and 1.0mol/L sodium hydroxide solution, respectively, for 1 hour, then rinsed with 2.0mL pure water and 2.0mL acetone, and finally dried with nitrogen gas.
2) Preparing a composite coating material: a polypyrrole inner surface coating was prepared by preparing a mixed solution of pyrrole monomer-isopropanol-water at a volume ratio of pyrrole monomer to isopropanol to water of 2:1:3, wherein the pyrrole monomer concentration was 5.0mol/L, then adding DBSA such that the DBSA concentration in the mixed solution was 0.23mol/L, passing 0.5mL of the mixed solution of pyrrole monomer-isopropanol-water doped with DBSA through a capillary tube with nitrogen to form a thin monomer liquid film on the inner surface of the capillary tube, and then passing 0.5mL of an oxidizing agent (ammonium persulfate concentration was 0.35 mol/L) through the capillary tube in the same manner as the monomer. When the oxidizing agent is mixed with the monomer in the capillary, a polymer is formed by the oxidation reaction, a process known as a PPy coating cycle.
3) 10 PPy coating cycles of step 2) were repeated. In the polymerization process, the color of the capillary tube is gradually changed from yellow to black, which indicates that the inner wall of the capillary tube forms a composite coating material. And finally, flushing the PPy coating capillary tube with 2.0mL of methanol, and then blowing with nitrogen for 5min to obtain the solid-phase microextraction column with the dopant-polypyrrole composite coating material in the tube.
And observing the prepared composite coating material by adopting a scanning electron microscope, wherein the particle size is 181nm and the thickness is 100-155nm as shown in figure 1.
5 kinds of nicotinic pesticides with concentration of 0.1mg/L in water are extracted by adopting a solid-phase microextraction column in a dodecylbenzenesulfonic acid-polypyrrole composite coating tube prepared in example 1.
The specific extraction process is as follows:
a) Pretreatment: the solid phase microextraction column is pushed with 1.0mL of methanol for activation, and then 1.0mL of pure water is used for balancing the mixture flowing through the solid phase microextraction column.
b) Adsorption: extracting 100 mu L of a sample to be detected, pushing the sample into a solid-phase microextraction column, taking the end section by adopting a sample injection small bottle, and completing 1 adsorption cycle; and then the sample in the sample injection vial is extracted back, and the 2 nd adsorption cycle is carried out, and the total adsorption cycle process is carried out for 5 times.
c) Eluting: each time 100 μl of methanol was pushed into the solid phase microextraction column for elution for a total of 3 times, and the eluates were collected together into another sample vial.
d) Cleaning: the solid phase microextraction column was washed with 1mL methanol.
The experimental results are shown in table 1:
TABLE 1 recovery of 5 Nicotine insecticides by DBSA-PPy/IT-SPME column extraction
Example 2
Preparation of solid-phase microextraction column (SDBS-PPy/IT-SPME column for short) in sodium dodecyl benzene sulfonate-polypyrrole composite coating tube:
1) Pretreatment of the inner surface of the column: a polytetrafluoroethylene tube with a length of 15.0cm and an inner diameter of 0.75mm was prepared, the inner surface of the tube was etched with 1.0mol/L hydrochloric acid solution and 1.0mol/L sodium hydroxide solution, respectively, for 1 hour, then rinsed with 2.0mL pure water and 2.0mL acetone, and finally dried with nitrogen gas.
2) Preparing a composite coating material: a mixed solution of pyrrole monomer, isopropanol and water was prepared in a volume ratio of pyrrole monomer, isopropanol and water of 2:1:3 (wherein the concentration of pyrrole monomer was 4.8 mol/L), SDBS was added so that the concentration of SDBS in the mixed solution was 0.04mol/L, 0.5mL of the mixed solution of pyrrole monomer, isopropanol and water doped with SDBS was passed through a polytetrafluoroethylene tube with the aid of nitrogen gas to form a thin monomer liquid film on the inner surface of the tube, and then 0.5mL of an oxidizing agent (ammonium persulfate concentration was 0.35 mol/L) was passed through the polytetrafluoroethylene tube in the same manner as the monomer, thereby preparing a polypyrrole inner surface coating. When the oxidizing agent is mixed with the monomer in the capillary, a polymer is formed by the oxidation reaction, a process known as a PPy coating cycle.
3) 10 PPy coating cycles of step 2) were repeated. In the polymerization process, the color of the polytetrafluoroethylene tube gradually shows black from transparent, which indicates that the inner wall of the polytetrafluoroethylene tube forms a composite coating material. Finally, 2.0mL of methanol is adopted to flush the polytetrafluoroethylene column of the composite coating material, and then nitrogen is used for blowing for 5min.
The prepared composite coating material is observed by a scanning electron microscope, and the particle size is 163-179nm and the thickness is 140-150nm as shown in figure 2.
The sodium dodecyl benzene sulfonate-polypyrrole composite coated tube prepared in example 2 is used for extracting 4 phenylurea herbicides with the concentration of 0.1mg/L in water by a solid phase microextraction column.
The specific extraction process is as follows:
a) Pretreatment: the solid phase microextraction column is pushed with 1.0mL of methanol for activation, and then 1.0mL of pure water is used for balancing the mixture flowing through the solid phase microextraction column.
b) Adsorption: extracting 100 mu L of a sample to be detected, pushing the sample into a solid-phase microextraction column, taking the end section by adopting a sample injection small bottle, and completing 1 adsorption cycle; and then the sample in the sample injection vial is extracted back, and the 2 nd adsorption cycle is carried out, and the total adsorption cycle process is carried out for 5 times.
c) Eluting: each time 100 μl of methanol was pushed into the solid phase microextraction column for elution for a total of 5 times, and the eluates were collected together into another sample vial.
d) Cleaning: the solid phase microextraction column was washed with 1.0mL methanol.
The experimental results are shown in table 2:
TABLE 2 recovery of 4 phenylurea herbicides by SDBS-PPy/IT-SPME column extraction
Example 3
Preparation of a solid-phase microextraction column (PSS-PPy/IT-SPME column for short) in a sodium polystyrene sulfonate-polypyrrole composite coating tube:
1) Pretreatment of the inner surface of the column: a polytetrafluoroethylene tube with a length of 10.0cm and an inner diameter of 0.75mm was prepared, the inner surface of the tube was etched with 1.0mol/L hydrochloric acid solution and 1.0mol/L sodium hydroxide solution, respectively, for 1 hour, then rinsed with 2.0mL pure water and 2.0mL acetone, and finally dried with nitrogen gas.
2) Preparing a composite coating material: a mixed solution of pyrrole monomer-isopropanol-water was prepared at a volume ratio of pyrrole monomer to isopropanol to water of 2:1:3 (wherein the concentration of pyrrole monomer was 3.0 mol/L), then PSS was added so that the concentration of PSS in the mixed solution was 8.3g/L, 0.5mL of the mixed solution of pyrrole monomer-isopropanol-water doped with PSS was passed through a polytetrafluoroethylene tube with the aid of nitrogen gas to form a thin monomer liquid film on the inner surface of the tube, and then 0.5mL of an oxidizing agent (ammonium persulfate concentration was 0.35 mol/L) was passed through the polytetrafluoroethylene tube in the same manner as the monomer, thereby preparing a polypyrrole inner surface coating. When the oxidizing agent is mixed with the monomer in the capillary, a polymer is formed by the oxidation reaction, a process known as a PPy coating cycle.
3) 8 PPy coating cycles of step 2) were repeated. In the polymerization process, the color of the polytetrafluoroethylene tube gradually shows black from transparent, which indicates that the inner wall of the polytetrafluoroethylene tube forms a composite coating material. Finally, 2.0mL of methanol is adopted to flush the polytetrafluoroethylene column of the composite coating material, and then nitrogen is used for blowing for 5min.
The prepared composite coating material is observed by a scanning electron microscope, and the particle size is 192-197nm and the thickness is 220-229nm as shown in figure 3.
The sodium polystyrene sulfonate-polypyrrole composite coated tube prepared in example 3 is used for extracting 4 antibiotic bactericides with the concentration of 0.1mg/L in water by a solid-phase microextraction column.
The specific extraction process is as follows:
a) Pretreatment: the solid phase microextraction column is pushed with 1.0mL of methanol for activation, and then 1mL of pure water is used for balancing the mixture flowing through the solid phase microextraction column.
b) Adsorption: extracting 100 mu L of a sample to be detected, pushing the sample into a solid-phase microextraction column, taking the end section by adopting a sample injection small bottle, and completing 1 adsorption cycle; and then the sample in the sample injection vial is extracted back, and the 2 nd adsorption cycle is carried out, and the total adsorption cycle process is carried out for 5 times.
c) Eluting: each time 100 μl of a mixed solution of toluene and methanol (v/v=1:5, 1.0% trifluoroacetic acid added) was pushed into the solid phase microextraction column for elution, 3 times total, and the eluates were collected together in another sample injection vial.
d) Cleaning: the solid phase microextraction column was washed with 1.0mL methanol.
The experimental results are shown in table 3:
TABLE 3 recovery of PSS-PPy/IT-SPME column extraction of 4 antibiotic-based bactericides
Example 4
Preparation of a solid-phase microextraction column (SDS-PPy/IT-SPME column for short) in a sodium dodecyl sulfate-polypyrrole composite coating tube:
1) Pretreatment of the inner surface of the column: a quartz capillary column with a length of 15.0cm and an inner diameter of 0.53mm was prepared, the inner surface of the column was etched with 1.0mol/L hydrochloric acid solution and 1.0mol/L sodium hydroxide solution, respectively, for 1 hour, then rinsed with 2.0mL pure water and 2.0mL acetone, and finally dried with nitrogen gas.
2) Preparing a composite coating material: a mixed solution of pyrrole monomer-isopropanol-water was prepared at a volume ratio of pyrrole monomer to isopropanol to water of 1:1:2, wherein the concentration of pyrrole monomer was 5.0mol/L, SDS was then added so that the concentration of SDS in the mixed solution was 0.23mol/L, 0.5mL of the mixed solution of pyrrole monomer-isopropanol-water doped with SDS was passed through a capillary tube with the aid of nitrogen gas to form a thin monomer liquid film on the inner surface of the capillary tube, and then 0.5mL of an oxidizing agent (ammonium persulfate concentration was 0.35 mol/L) was passed through the capillary tube in the same manner as the monomer, thereby preparing a polypyrrole inner surface coating. When the oxidizing agent is mixed with the monomer in the capillary, a polymer is formed by the oxidation reaction, a process known as a PPy coating cycle.
3) 10 PPy coating cycles of step 2) were repeated. In the polymerization process, the color of the capillary tube is gradually changed from yellow to black, which indicates that the inner wall of the quartz capillary column forms a composite coating material. Finally, 2.0mL of methanol is adopted to flush the quartz capillary tube of the composite coating material, and then nitrogen is used for blowing for 5min.
The prepared composite coating material is observed by a scanning electron microscope, and the particle size is 97-114nm and the thickness is 129-138nm as shown in figure 4.
The extraction process of 3 kinds of nicotinic pesticides with concentration of 0.1mg/L in water is extracted by using a solid-phase microextraction column in a sodium dodecyl sulfate-polypyrrole composite coating pipe prepared in example 4, and the extraction process is the same as in example 1. The experimental results are shown in table 4:
TABLE 4 recovery of 3 Nicotine insecticides by SDS-PPy/IT-SPME column extraction
Example 5
Preparation of solid-phase microextraction column (CTAB-PPy/IT-SPME column for short) in hexadecyl trimethyl ammonium bromide-polypyrrole composite coating tube:
1) Pretreatment of the inner surface of the column: a polytetrafluoroethylene tube with a length of 10.0cm and an inner diameter of 0.75mm was prepared, the inner surface of the tube was etched with 1.0mol/L hydrochloric acid solution and 1.0mol/L sodium hydroxide solution, respectively, for 1 hour, then rinsed with 2.0mL pure water and 2.0mL acetone, and finally dried with nitrogen gas.
2) Preparing a composite coating material: a mixed solution of pyrrole monomer, isopropanol and water was prepared in a volume ratio of pyrrole monomer, isopropanol and water of 9:10:5 (wherein the concentration of pyrrole monomer was 5.0 mol/L), CTAB was then added so that the concentration of CTAB in the mixed solution was 0.23mol/L, 0.5mL of the CTAB-doped pyrrole monomer, isopropanol and water mixed solution was passed through a polytetrafluoroethylene tube with the aid of nitrogen gas to form a thin monomer liquid film on the inner surface of the tube, and then 0.5mL of an oxidizing agent (ammonium persulfate concentration was 0.35 mol/L) was passed through the polytetrafluoroethylene tube in the same manner as the monomer, thereby preparing a polypyrrole inner surface coating. When the oxidizing agent is mixed with the monomer in the capillary, a polymer is formed by the oxidation reaction, a process known as a PPy coating cycle.
3) The 6 PPy coating cycles of step 2) were repeated. In the polymerization process, the color of the polytetrafluoroethylene tube gradually shows black from transparent, which indicates that the inner wall of the polytetrafluoroethylene column forms a composite coating material. Finally, 2.0mL of methanol is adopted to flush the polytetrafluoroethylene column of the composite coating material, and then nitrogen is used for blowing for 5min.
The prepared composite coating material is observed by a scanning electron microscope, and the particle size is 120-134nm and the thickness is 647-682nm as shown in figure 5.
The extraction process of 3 phenylurea herbicides with concentration of 0.1mg/L in water is carried out by adopting the solid-phase microextraction column in the hexadecyl trimethyl ammonium bromide-polypyrrole composite coating pipe prepared in the example 5, and the extraction process is the same as that of the example 2. The experimental results are shown in table 5:
TABLE 5 recovery of 3 phenylurea herbicides by CTAB-PPy/IT-SPME column extraction
Example 6
Preparation of solid-phase microextraction column (phenol saffron-PPy/IT-SPME column for short) in phenol saffron-polypyrrole composite coating tube:
1) Pretreatment of the inner surface of the column: a polytetrafluoroethylene tube with a length of 10.0cm and an inner diameter of 0.75mm was prepared, the inner surface of the tube was etched with 1.0mol/L hydrochloric acid solution and 1.0mol/L sodium hydroxide solution, respectively, for 1 hour, then rinsed with 2.0mL pure water and 2.0mL acetone, and finally dried with nitrogen gas.
2) Preparing a composite coating material: a mixed solution of pyrrole monomer-isopropanol-water was prepared at a volume ratio of pyrrole monomer, isopropanol and water of 2:1:3 (wherein the pyrrole monomer concentration was 3.0 mol/L), phenol saffron was then added so that the phenol saffron concentration in the mixed solution was 0.03mol/L, 0.5mL of the mixed solution of pyrrole monomer-isopropanol-water doped with phenol saffron was passed through a polytetrafluoroethylene tube with the aid of nitrogen gas to form a thin monomer liquid film on the inner surface of a capillary tube, and then 0.5mL of an oxidizing agent (ammonium persulfate concentration was 0.35 mol/L) was passed through the polytetrafluoroethylene tube in the same manner as the monomer, thereby preparing a polypyrrole inner surface coating. When the oxidizing agent is mixed with the monomer in the capillary, a polymer is formed by the oxidation reaction, a process known as a PPy coating cycle.
3) 8 PPy coating cycles of step 2) were repeated. In the polymerization process, the color of the polytetrafluoroethylene tube gradually changes from transparent to black, which indicates that the inner wall of the polytetrafluoroethylene column forms a composite coating material. Finally, 2.0mL of methanol is adopted to flush the polytetrafluoroethylene column of the composite coating material, and then nitrogen is used for blowing for 5min.
And observing the prepared composite coating material by adopting a scanning electron microscope, wherein the particle size is 192-215nm, and the thickness is 209-211nm as shown in figure 6.
The extraction process of 3 phenylurea herbicides with concentration of 0.1mg/L in water by using the solid-phase microextraction column in the phenol saffron-polypyrrole composite coated tube prepared in example 6 is the same as that of example 2. The experimental results are shown in Table 6:
TABLE 6 recovery of phenol saffron red-PPy/IT-SPME column extraction of 3 phenylurea herbicides
Claims (9)
1. The method for preparing the dopant-polypyrrole composite coating material on the solid-phase microextraction column is characterized in that the composite coating material is formed by compounding a dopant and a polypyrrole nano material, the particle size of the composite coating material is 50-280nm, and the thickness of the composite coating material is 100-700nm;
the doping agent is phenol saffron;
the method comprises the following steps:
1) Pretreatment of the inner surface of the column: etching the inner surface of the support material by using 1.0mol/L hydrochloric acid solution and 1.0mol/L sodium hydroxide solution respectively, and then washing with pure water and acetone and drying;
2) Preparing a composite coating material: sequentially passing the mixed solution of the pyrrole monomer and the dopant and the oxidant solution through a capillary tube, and preparing a dopant-polypyrrole composite coating material on the inner surface of the capillary tube; the concentration of the doping agent ranges from 0.005 mol/L to 0.5mol/L; the molar ratio of pyrrole monomer to dopant ranges from 10:1 to 500:1;
3) Repeating the operation of the step 2), and then adopting methanol to flush the inner surface of the support material and drying to obtain the solid-phase microextraction column with the dopant-polypyrrole composite coating material in the tube.
2. The method for preparing a dopant-polypyrrole composite coating material on a solid phase microextraction column according to claim 1, wherein in the step 1), the support material comprises a quartz capillary column, a polytetrafluoroethylene tube or a stainless steel tube; the inner diameter is in the range of 0.1-1.0mm and the length is in the range of 4.0-30.0cm.
3. The method for preparing a dopant-polypyrrole composite coating material on a solid phase microextraction column according to claim 1, wherein in the step 2), the oxidant is ammonium persulfate.
4. A method for preparing a dopant-polypyrrole composite coating material on a solid phase microextraction column according to claim 3, wherein in step 2), the molar ratio of pyrrole monomer to ammonium persulfate is in the range of 5:1 to 40:1.
5. The method for preparing a dopant-polypyrrole composite coating material on a solid phase microextraction column according to claim 1, wherein in the step 2), the dopant and the pyrrole monomer are dissolved by isopropanol and water, wherein the volume ratio of the pyrrole monomer to the isopropanol to the water is 2:1:3, 1:1:2 or 9:10:5.
6. The method for preparing a dopant-polypyrrole composite coating material on a solid phase microextraction column according to claim 4 or 5, wherein in the step 2), the concentration of pyrrole monomer ranges from 1 to 10mol/L, and the concentration of ammonium persulfate ranges from 0.1 to 0.6mol/L.
7. The method for preparing a dopant-polypyrrole composite coating material on a solid phase microextraction column according to claim 1, wherein the number of repetitions in the step 3) is 4 to 15.
8. The method for preparing the dopant-polypyrrole composite coating material on the solid phase microextraction column according to claim 1, wherein the drying mode adopts nitrogen gas for drying.
9. A solid phase microextraction column with a dopant-polypyrrole composite coating material prepared in a pipe obtained by the method of any one of claims 1-8, which is applied to extraction of phenylurea polar pesticides.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210209484.5A CN114452958B (en) | 2022-03-03 | 2022-03-03 | Dopant-polypyrrole composite coating material for solid-phase microextraction column and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210209484.5A CN114452958B (en) | 2022-03-03 | 2022-03-03 | Dopant-polypyrrole composite coating material for solid-phase microextraction column and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114452958A CN114452958A (en) | 2022-05-10 |
| CN114452958B true CN114452958B (en) | 2023-07-04 |
Family
ID=81416036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210209484.5A Active CN114452958B (en) | 2022-03-03 | 2022-03-03 | Dopant-polypyrrole composite coating material for solid-phase microextraction column and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114452958B (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1298771C (en) * | 2005-07-12 | 2007-02-07 | 天津大学 | Chemical method for preparing film of poly pyrrole in high conductivity on surface of insulating material |
| CN101637717A (en) * | 2009-08-28 | 2010-02-03 | 南京大学 | Fluorine-doped polyaniline solid-phase microextraction head as well as preparation method and application thereof |
| CN101875006B (en) * | 2010-04-30 | 2012-07-25 | 中国科学院长春应用化学研究所 | Solid-phase microextraction material composition and electrode material composition |
| CA3070616A1 (en) * | 2017-07-25 | 2019-01-31 | University Of South Australia | Improvements in solid phase micro-extraction substrate coatings |
| CN110108822A (en) * | 2019-05-14 | 2019-08-09 | 苏州贞成分析仪器有限公司 | Aflatoxin sample extraction detection method and its purification pipette tips in a kind of edible vegetable oil |
-
2022
- 2022-03-03 CN CN202210209484.5A patent/CN114452958B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN114452958A (en) | 2022-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wu et al. | Analysis of polar pesticides in water and wine samples by automated in-tube solid-phase microextraction coupled with high-performance liquid chromatography–mass spectrometry | |
| Duan et al. | Recent developments in solid-phase microextraction for on-site sampling and sample preparation | |
| Wu et al. | Solid phase microextraction of inorganic anions based on polypyrrole film | |
| Yang et al. | Rapid and on-site analysis of amphetamine-type illicit drugs in whole blood and raw urine by slug-flow microextraction coupled with paper spray mass spectrometry | |
| Djozan et al. | Solid-phase microextraction of aliphatic alcohols based on polyaniline coated fibers | |
| CN109374711B (en) | MXene nanosheet modification-based all-solid-state ion selective electrode and preparation method thereof | |
| Asiabi et al. | Development of electrochemically controlled packed-in-tube solid phase microextraction method for sensitive analysis of acidic drugs in biological samples | |
| Prasad et al. | Ion imprinted polymer based ion-selective electrode for the trace determination of dysprosium (III) ions | |
| Spijker et al. | Protein adsorption on gradient surfaces on polyethylene prepared in a shielded gas plasma | |
| Jin et al. | A novel method to prepare monolithic molecular imprinted polymer fiber for solid‐phase microextraction by microwave irradiation | |
| Chen et al. | Development of a highly robust solid phase microextraction fiber based on crosslinked methyl methacrylate–polyhedral oligomeric silsesquioxane hybrid polymeric coating | |
| Louarn et al. | Characterization of a membrane inlet interfaced with a compact chemical ionization FT-ICR for real-time and quantitative VOC analysis in water | |
| CN107192755B (en) | A kind of preparation method of ultrathin membrane and the organic field effect tube sensor based on it | |
| CN114452958B (en) | Dopant-polypyrrole composite coating material for solid-phase microextraction column and preparation method thereof | |
| CN110568056B (en) | In-situ mass spectrometry quantification method for small molecular substances on solid surface | |
| LU102485A1 (en) | Method for rapid extraction and analysis of 10 polycyclic aromatic hydrocarbons in water | |
| CN111534299A (en) | GOQDs @ PDA-ir-MIP molecularly imprinted fluorescence sensor and preparation method and application thereof | |
| EP2214010B1 (en) | High throughput autosampler | |
| Mehdinia et al. | Preparation and evaluation of solid-phase microextraction fiber based on nano-structured copolymer of aniline and m-amino benzoic acid coating for the analysis of fatty acids in zooplanktons | |
| Yu et al. | Preparation of sol–gel polyethylene glycol–polydimethylsiloxane–poly (vinyl alcohol)-coated sorptive bar for the determination of organic sulfur compounds in water | |
| CN111122673B (en) | Carbon nano-dot passivated organic-inorganic perovskite cholesterol detection sensor and preparation method thereof | |
| Bagheri et al. | Polypyrrole nanowires network for convenient and highly efficient microextraction in packed syringe | |
| Amiri et al. | Polypyrrole/carbon nanotube coated stainless steel mesh as a novel sorbent | |
| CN108997898B (en) | Cis-jasmone molecularly imprinted polymer coating and preparation method and application thereof | |
| CN111672474A (en) | Magnetic nitrogen-doped carbon oxide nanotube material and preparation 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 |