CN109225165B - Preparation method and application of silicｃA @ P-A-betｃA-CD/NIPAM adsorption medium - Google Patents
Preparation method and application of silicｃA @ P-A-betｃA-CD/NIPAM adsorption medium Download PDFInfo
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Abstract
The invention discloses SiO2The preparation method of the @ P-A-betｃA-CD/NIPAM adsorption medium comprises the following steps: (1) synthesizing an acryloyl cyclodextrin functional monomer; (2) KH570 for SiO2Silanization is carried out to obtain silanized SiO2(ii) a (3) Synthesis of SiO2@ P-A-betｃA-CD/NIPAM adsorbent mediｃA. Meanwhile, the invention also discloses the SiO2The application of the @ P-A-betｃA-CD/NIPAM adsorption medium in solid phase micro-extraction. The SiO provided by the invention2The @ P-A-betｃA-CD/NIPAM adsorption medium can enable phenolic organic pollutants to achieve rapid adsorption and resolution on the surface of the adsorption medium, can be used for preparing ｃA solid phase micro-extraction column, can be used for detecting phenolic substances in water on line, and is good in stability and reusable.
Description
Technical Field
The invention belongs to the technical field of solid phase microextraction, and particularly relates to SiO2ｃA preparation method of ｃA @ P-A-betｃA-CD/NIPAM adsorption medium and application thereof in solid phase micro-extraction.
Background
The organic pollutants in the environmental water are various, the matrix is complex, the content is low, the change along with the environment is rapid, the influence factors are many, the related range is wide, the method is a prominent environmental problem and is a hotspot of environmental science research. Compared with the rapid development of analytical instruments, the development of the sample pretreatment technology is relatively lagged, which determines the speed and accuracy of the analysis process and also is a bottleneck restricting the application of online analytical instruments. Therefore, designing a complex sample pretreatment system with a functionalized and multi-action mode to achieve the characteristics of rapidness and good stability in online monitoring becomes a critical issue for research in the field at present.
The existing method for enriching the phenolic organic pollutants in the environmental water is mainly a solid phase extraction method, and commercial extraction columns are plastic disposable commodity columns with the diameter of about 1cm, are expensive, cannot simultaneously enrich and purify various matrixes, are long in analysis time consumption and large in error, are difficult to realize online and cannot be reused; capillary microcolumns generally need to be increased in capacity by increasing the length due to capacity problems, but this increases the system pressure and also decreases the stability of the on-line pretreatment system. On-line monitoring is poor in time resolution and large in error due to the memory effect and the slow dissociation speed of the pre-treated adsorption medium, and the used extraction column is large in volume, so that the defects of large dead volume, high column pressure and the like are overcome. Therefore, the functionalization of the adsorption medium in the sample pretreatment and the design of the pretreatment extraction column become the key problems of the online analysis system.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides silicon dioxide @ P-A-betｃA-CD/NIPAM (namely SiO)2@ P-A-betｃA-CD/NIPAM, the Chinese name: acryloyl cyclodextrin and isopropyl acrylamide grafted silicon dioxide microspheres) adsorption medium which can be used as a stationary phase for solid phase extraction, solid phase micro-extraction and the like, and can realize high-efficiency separation and enrichment of target compounds. Meanwhile, the invention also provides application of the adsorption medium in a solid-phase extraction column and an online detection method for organic pollutants in environmental water by using the extraction column.
SiO (silicon dioxide)2The preparation method of the @ P-A-betｃA-CD/NIPAM adsorption medium comprises the following steps:
(1) synthesizing an acryloyl cyclodextrin (A-beta-CD for short) functional monomer;
(2) using silane coupling agent KH570 to SiO2Silanization is carried out to obtain silanized SiO2(SiO for short)2@ KH570）；
(3) Synthesis of SiO2@ P-A- β -CD/NIPAM adsorbent mediｃA: silanized 0.3-0.8g of SiO2Dispersing in 20mL dry DMF, adding 20-30mg azobisisobutyronitrile in N2Adding 1-6mmoL of isopropyl acrylamide and 20mL of DMF solution of acryloyl cyclodextrin functional monomer with the concentration of 0.05moL/L dropwise at the temperature of 60-80 ℃ in the atmosphere, stirring for 24-48h after the addition is finished, centrifuging, washing the precipitate obtained by centrifuging for 5 times by alternately using distilled water and methanol, and removing the precipitate which is not grafted to SiO2The surface monomer and the self-polymerization product thereof are subjected to vacuum drying for 2 days at the temperature of 50 ℃, and the silicon dioxide microsphere adsorption medium (SiO for short) grafted by acryloyl cyclodextrin and isopropyl acrylamide is obtained2@P-A-β-CD/NIPAM）。
Preferably, KH570 is used for SiO in step (2)2The specific procedure for performing the silanization is as follows:
(2a) 4g of SiO2Soaking in 10% hydrochloric acid solution, activating at 110 deg.C for 12 hr, filtering, washing the obtained residue with distilled water to neutrality, and vacuum drying at 50 deg.C for 2 days to obtain activated SiO2；
(2b) 2-5g of activated SiO2Dispersed in 15-20mL dry toluene in N2Dropwise adding 20-25mL of toluene solution of KH570 with volume concentration of 14% into the mixture under the atmosphere, refluxing for condensation, stirring at 110 deg.C for 36h, centrifuging, washing the precipitate with toluene and methanol for 5 times, removing unreacted KH570 and self-polymerization product, and vacuum drying at 50 deg.C for 3 days to obtain silanized SiO2(SiO for short)2@ KH570）。
Preferably, the step of synthesizing the acryloyl cyclodextrin functional monomer in the step (1) is as follows:
(1a) adding 5mmoL beta-cyclodextrin into 20mL of dry DMF, then adding 20mmoL triethylamine, and stirring in an ice-water bath;
(1b) 20mmoL acryloyl chloride was added to 20mL dry DMF;
(1c) in N2And (2) dropwise adding the solution obtained in the step (1 b) into the solution obtained in the step (1 a) in an atmosphere, stirring and reacting for 24 hours in an ice-water bath after the addition is finished, then filtering, precipitating the filtrate in sufficient acetone, repeating for 3 times to obtain white precipitate, and performing vacuum drying at 20 ℃ for 3 days to obtain the acryloyl cyclodextrin (A-beta-CD) functional monomer.
A solid phase micro-extraction column comprises an extraction column tube, filter discs and screw caps, wherein the central positions of the upper end and the lower end of the extraction column tube are respectively and symmetrically provided with bulges, and the filter discs are arranged on the bulges; a through hole is axially formed in the center of the nut; the bulge extends into the through hole and is connected with one end of the screw cap through a thread structure, the other end of the screw cap is connected with the screw cap joint through the thread structure, the filter disc abuts against the screw cap joint, and the screw cap joint is connected with a peek tube; the extraction column tube, the bulge and the nut joint are all of hollow structures, the hollow structures of the extraction column tube, the bulge and the nut joint are communicated to form an extraction channel, and the two peek tubes are communicated through the extraction channel; the extraction column tube is filled with a temperature-sensitive adsorption medium, and the temperature-sensitive adsorption medium is SiO prepared by the method2@ P-A-betｃA-CD/NIPAM adsorbent mediｃA.
Preferably, the extraction column tube and the screw cap are both regular hexagonal prisms, and the diameters of inscribed circles of the regular hexagonal prisms are 1-2mm
Preferably, the height of the extraction cartridge is 2cm and the height of the screw cap is 2 cm.
Preferably, the extraction column tube, the screw cap and the screw cap joint are all made of stainless steel materials.
Preferably, the filter disc is made of sintered stainless steel materials, and the protrusions are made of polyimide materials.
The application of the solid phase micro-extraction column specifically comprises the following steps: the solid phase micro-extraction column is adopted to enrich the phenolic substances in the water, and the solid phase micro-extraction-high performance liquid chromatography combination instrument is used for carrying out on-line detection to detect the phenolic substances in the water.
In the invention: DMF means N, N-dimethylformamide; NIPAM refers to N-isopropylacrylamide.
The invention has the advantages that:
(1) the SiO provided by the invention2The @ P-A-betｃA-CD/NIPAM adsorption medium can enable phenolic organic pollutants to be quickly adsorbed and resolved on the surface of the adsorption medium, and can be used for online detection;
(2) the extraction column provided by the invention is good in stability, can be repeatedly used, is used for detecting phenols in water by a solid phase microextraction-high performance liquid chromatography combination instrument, and is good in accuracy.
Drawings
FIG. 1 is a scanning electron micrograph.
FIG. 2 is an infrared spectrum detection spectrum.
FIG. 3 is a schematic diagram of the components of the solid phase extraction column.
FIG. 4 is a schematic diagram of a solid phase extraction column;
wherein, 11: a nut; 21: a filter disc; 31: extracting a column tube; 41: a nut fitting; 51: a protrusion; 61: a peek tube.
FIG. 5 is a schematic diagram showing a connection relationship of a six-way valve in a solid phase microextraction-high performance liquid chromatography apparatus;
wherein, 511-six way valve.
FIG. 6 chromatogram of solid phase microextraction column at high temperature (50 ℃ C.).
FIG. 7 is a chromatogram of a solid-phase microextraction column at a low temperature (25 ℃ C.).
FIG. 8 is a chromatogram of an uncalibrated water sample.
FIG. 9 is a chromatogram obtained when a water sample is labeled with 0.5 ng/mL.
FIG. 10 is a chromatogram obtained when a water sample is labeled with 5 ng/mL;
wherein, 1: p-nitrophenol (PNP); 2: beta-naphthol (beta-NP); 3: bisphenol a (bpa); 4: 2, 4-dichlorophenol (2, 4-DCP); 5: 2,4, 6-trichlorophenol (2, 4, 6-TCP).
Detailed Description
Example 1
SiO (silicon dioxide)2The preparation method of the @ P-A-betｃA-CD/NIPAM adsorption medium comprises the following steps:
(1) synthesizing an acryloyl cyclodextrin functional monomer:
(1a) adding 5mmoL beta-cyclodextrin (beta-CD) into 20mL of dry DMF (N, N-dimethylformamide), then adding 20mmoL triethylamine, and stirring in an ice-water bath;
(1b) 20mmoL acryloyl chloride was added to 20mL dry DMF;
(1c) in N2Dropwise adding the solution obtained in the step (1 b) into the solution obtained in the step (1 a) in an atmosphere, stirring and reacting for 24 hours in an ice-water bath after the addition is finished, then filtering, precipitating the filtrate in sufficient acetone, repeating for 3 times to obtain white precipitate, and performing vacuum drying at 20 ℃ for 3 days to obtain an acryloyl cyclodextrin (A-beta-CD) functional monomer;
(2) using silane coupling agent KH570 to SiO2Silanization is carried out to obtain silanized SiO2：
(2a) 4g of SiO2Soaking in 10% hydrochloric acid solution, activating at 110 deg.C for 12 hr, filtering, washing the obtained residue with distilled water to neutrality, and vacuum drying at 50 deg.C for 2 days to obtain activated SiO2；
(2b) 3.5g of activated SiO2Dispersed in 17mL of dry toluene in N2Dropwise adding 21mL of toluene solution of KH570 with volume concentration of 14% into the mixture under the atmosphere, refluxing for condensation, stirring at 110 deg.C for 36h, centrifuging, alternately washing the precipitate with toluene and methanol for 5 times, removing unreacted KH570 and self-polymerization product, and vacuum drying at 50 deg.C for 3 days to obtain silanized SiO2(SiO for short)2@ KH570）；
(3) Synthesis of SiO2@ P-A- β -CD/NIPAM adsorbent mediｃA: 0.5g of silanized SiO2Dispersed in 20mL dry DMF, 25mg azobisisobutyronitrile was added, in N2Dropwise adding 20mL of DMF solution of 4mmol of isopropyl acrylamide and 0.05moL/L acryloyl cyclodextrin functional monomer in 70 ℃ in an atmosphere, stirring for 36h after the addition is finished, centrifuging, washing the precipitate obtained by centrifuging for 5 times by using distilled water and methanol alternately to remove the precipitate which is not grafted to SiO2And self-polymerization products thereof, will precipitate at 50Vacuum drying at 2 days to obtain the silicon dioxide microsphere adsorption medium (SiO for short) grafted by acryloyl cyclodextrin and isopropyl acrylamide2@P-A-β-CD/NIPAM）。
Example 2
SiO (silicon dioxide)2The preparation method of the @ P-A-betｃA-CD/NIPAM adsorption medium comprises the following steps:
(1) synthesizing an acryloyl cyclodextrin functional monomer:
(1a) adding 5mmoL beta-cyclodextrin (beta-CD) into 20mL of dry DMF (N, N-dimethylformamide), then adding 20mmoL triethylamine, and stirring in an ice-water bath;
(1b) 20mmoL acryloyl chloride was added to 20mL dry DMF;
(1c) in N2In the atmosphere, dropwise adding the solution obtained in the step (1 b) into the solution obtained in the step (1 a), stirring and reacting for 24 hours in an ice-water bath after the addition is finished, then filtering, precipitating the filtrate in sufficient acetone, repeating for 3 times to obtain white precipitate, and performing vacuum drying at 20 ℃ for 3 days to obtain the acryloyl cyclodextrin functional monomer;
(2) using silane coupling agent KH570 to SiO2Silanization is carried out to obtain silanized SiO2：
(2a) 4g of SiO2Soaking in 10% hydrochloric acid solution, activating at 110 deg.C for 12 hr, filtering, washing the obtained residue with distilled water to neutrality, and vacuum drying at 50 deg.C for 2 days to obtain activated SiO2；
(2b) 2g of activated SiO2Dispersed in 15mL of dry toluene in N2Dropwise adding 20mL of toluene solution of KH570 with volume concentration of 14% into the mixture under the atmosphere, refluxing for condensation, stirring at 110 deg.C for 36h, centrifuging, alternately washing the precipitate with toluene and methanol for 5 times, and vacuum drying at 50 deg.C for 3 days to obtain silanized SiO2；
(3) Synthesis of SiO2@ P-A- β -CD/NIPAM adsorbent mediｃA: 0.3g of silanized SiO2Dispersed in 20mL dry DMF, 20mg azobisisobutyronitrile was added, in N2In the atmosphereAdding 20mL of DMF solution of 1mmoL of isopropyl acrylamide and 0.05moL/L of acryloyl cyclodextrin functional monomer dropwise at 60 ℃, stirring for 48h after the addition is finished, centrifuging, washing the precipitate obtained by centrifuging for 5 times by using distilled water and methanol alternately to remove the precipitate which is not grafted to SiO2The precipitate is dried in vacuum at 50 ℃ for 2 days to obtain SiO2@ P-A-betｃA-CD/NIPAM adsorbent mediｃA.
Example 3
SiO (silicon dioxide)2The preparation method of the @ P-A-betｃA-CD/NIPAM adsorption medium comprises the following steps:
(1) synthesizing an acryloyl cyclodextrin functional monomer:
(1a) adding 5mmoL beta-cyclodextrin (beta-CD) into 20mL of dry DMF (N, N-dimethylformamide), then adding 20mmoL triethylamine, and stirring in an ice-water bath;
(1b) 20mmoL acryloyl chloride was added to 20mL dry DMF;
(1c) in N2In the atmosphere, dropwise adding the solution obtained in the step (1 b) into the solution obtained in the step (1 a), stirring and reacting for 24 hours in an ice-water bath after the addition is finished, then filtering, precipitating the filtrate in sufficient acetone, repeating for 3 times to obtain white precipitate, and performing vacuum drying at 20 ℃ for 3 days to obtain the acryloyl cyclodextrin functional monomer;
(2) using silane coupling agent KH570 to SiO2Silanization is carried out to obtain silanized SiO2：
(2a) 4g of SiO2Soaking in 10% hydrochloric acid solution, activating at 110 deg.C for 12 hr, filtering, washing the obtained residue with distilled water to neutrality, and vacuum drying at 50 deg.C for 2 days to obtain activated SiO2；
(2b) 5g of activated SiO2Dispersed in 20mL of dry toluene in N2Adding 25mL of toluene solution of KH570 with volume concentration of 14% dropwise into the mixture under reflux, condensing, stirring at 110 deg.C for 36h, centrifuging, washing precipitate with toluene and methanol for 5 times, and removing unreacted KH570 and its derivativesThe polymerization product was dried under vacuum at 50 ℃ for 3 days to obtain silanized SiO2；
(3) Synthesis of SiO2@ P-A- β -CD/NIPAM adsorbent mediｃA: 0.8g of silanized SiO2Dispersed in 20mL dry DMF, 30mg azobisisobutyronitrile was added in N2Adding dropwise 6mmoL isopropyl acrylamide and 20mL of DMF solution of acryloyl cyclodextrin functional monomer with the concentration of 0.05moL/L at 80 ℃ in an atmosphere, stirring for 24h after the addition is finished, centrifuging, washing the precipitate obtained by centrifuging for 5 times by using distilled water and methanol alternately to remove the precipitate which is not grafted to SiO2The precipitate is dried in vacuum at 50 ℃ for 2 days to obtain SiO2@ P-A-betｃA-CD/NIPAM adsorbent mediｃA.
Performance testing
1. Scanning electron microscope detection
To SiO2Scanning electron micrographs are taken before and after grafting, see FIG. 1, wherein a and a1Is SiO without any treatment2，b,b1For the SiO obtained in step (3)2@P-A-β-CD/NIPAM；
As can be seen from FIG. 1, the ratio a to a1Graphs b, b1The surface became "rough" clearly, demonstrating that SiO2The material on the surface is successfully grafted.
2. Infrared spectroscopy detection
For the SiO prepared in example 12Infrared spectrum detection of the @ P-A-betｃA-CD/NIPAM adsorption medium is carried out, and the result is shown in figure 2, wherein ｃA is SiO2B is the silanized SiO obtained in step (2)2C is SiO obtained in step (3)2Infrared spectrogram of @ P-A-betｃA-CD/NIPAM adsorption medium.
As can be seen from FIG. 2, b is 2978cm higher than a-1And 2852 cm-1The absorption peaks are C-H stretching vibration, 1725cm-1Is a C = O telescopic vibration, proving successful coupling; c is in 1542cm-1The absorption at (A) is a characteristic absorption peak of the free amino group of the amide group, 1454cm-1And 1392 cm-1The absorption peak of (A) is a characteristic absorption peak of isopropyl group, which indicates adsorptionDielectric SiO2The synthesis of @ P-A-betｃA-CD/NIPAM is successful.
Example 4
The solid phase micro-extraction column is described in detail with reference to fig. 3 and 4:
a solid phase micro-extraction column comprises an extraction column tube (31), filter discs (21) and screw caps (11), wherein the central positions of the upper end and the lower end of the extraction column tube (31) are respectively and symmetrically provided with bulges (51), and the filter discs (21) are arranged on the bulges (51); a through hole is axially formed in the center of the nut (11); the protrusion (51) extends into the through hole and is connected with one end of the screw cap (11) through a thread structure, the other end of the screw cap (11) is connected with the screw cap joint (41) through the thread structure, the filter disc (21) abuts against the screw cap joint (41), and the screw cap joint (41) is connected with a peek pipe (61); the extraction column tube (31), the bulge (51) and the nut joint (41) are all of hollow structures, the hollow structures of the extraction column tube (31), the bulge (51) and the nut joint (41) are communicated to form an extraction channel, and the two peek tubes (61) are communicated through the extraction channel; the extraction column tube (31) is internally filled with a temperature-sensitive adsorption medium, and the temperature-sensitive adsorption medium is SiO prepared in example 12@ P-A-betｃA-CD/NIPAM adsorbent mediｃA;
the extraction column tube (31) and the screw cap (11) are both regular hexagonal prisms, and the diameters of inscribed circles of the regular hexagonal prisms are 1-2 mm;
the height of the extraction column tube (31) is 2cm, and the height of the screw cap (11) is 2 cm;
the extraction column tube (31), the screw cap (11) and the screw cap joint (41) are made of stainless steel or brass;
the filter disc (21) is made of sintered stainless steel materials, and the protrusions (51) are made of polyimide materials.
Example 5
The solid-phase microextraction column provided in example 4 is used for on-line detection by using a solid-phase microextraction-high performance liquid chromatography combination instrument to detect phenolic substances in water, and the detection method specifically comprises the following steps:
the solid phase micro-extraction-high performance liquid chromatography combined instrument comprises a solid phase micro-extraction column, a six-way valve, two pumps (respectively a No. 1 pump and a No. 2 pump), and two waste liquid bottles (respectively a No. 1 waste liquid bottle and a No. 2 waste liquid bottle); the pump No. 1 is used for controlling sample liquid feeding, the pump No. 2 is a gradient pump and is used for controlling eluent liquid feeding, the pump No. 2 can be simultaneously connected with 2-4 kinds of eluents, and the flow rate of the liquid feeding can be controlled by both the pumps; the No. 1 waste liquid bottle is used for receiving waste liquid obtained after a sample is enriched through an extraction column, and the No. 2 waste liquid bottle is used for receiving waste liquid generated after eluent is eluted and separated through an analysis column of high performance liquid chromatography;
the six-way valve is respectively connected with a pump No. 1, a pump No. 2, a waste liquid bottle No. 1, a solid phase micro-extraction column and an analytical column of high performance liquid chromatography; the No. 1 pump is positioned between the sample and the solid phase micro-extraction column, and the No. 2 pump is positioned between the eluent and the solid phase micro-extraction column; during sampling, the six-way valve is positioned at the LOAD position, the No. 1 pump is started, the sample is driven by the No. 1 pump, the sample is enriched by the solid phase micro-extraction column, and the waste liquid is left in the No. 1 waste liquid bottle; when the sample is introduced, the six-way valve is positioned at the INJECT position, and the eluent (namely the mobile phase) is driven by the No. 2 pump, passes through the solid phase micro-extraction column to desorb the sample and enters the analysis column of the high performance liquid chromatograph to be tested; when in detection, the six-way valve is positioned at the LOAD position, eluent (namely mobile phase) is driven by the No. 2 pump to separate samples in the analytical column, and waste liquid generated after detection flows into the No. 2 waste liquid bottle; wherein the schematic of the six-way valve in the LOAD and INJECT positions is shown in FIG. 5;
the specific operation is as follows:
the method comprises the following steps: adopting a solid phase microextraction-high performance liquid chromatography combined instrument, placing a six-way valve at a LOAD position at room temperature, starting a No. 1 pump, feeding a sample into a solid phase microextraction column at a flow rate of 0.3-1mL/min under the driving action of the No. 1 pump to enrich the sample containing the phenolic substances, wherein the enriched sample is 30-50 mL, and feeding the sample into a No. 1 waste liquid bottle after passing through the solid phase microextraction column; after the enrichment is finished, the No. 1 pump is turned off;
step two: placing the six-way valve at an INJECT position, starting a No. 2 pump, eluting the solid phase micro-extraction column by the eluent under the action of the No. 2 pump at the flow rate of 0.3mL/min for 1.7min, wherein the temperature of the extraction column is higher than 40 ℃, so that the phenolic substances adsorbed on the solid phase micro-extraction column are completely desorbed, and the liquid generated by elution enters an analysis column of a high performance liquid chromatograph; the eluent is a mixed solution of eluent A and eluent B according to the volume ratio of A: B =15:85, wherein the eluent A is methanol, and the eluent B is phosphate buffer with pH = 3;
step three: placing the six-way valve at the LOAD position again, performing gradient elution on the eluent under the action of a No. 2 pump, entering an analysis column of a high performance liquid chromatograph at the flow rate of 1mL/min to separate phenolic substances, and detecting the phenolic substances by a detector of the high performance liquid chromatograph; the elution is a gradient elution: the volume ratio of eluent A and eluent B is gradually changed from A: B =15:85 to 40:60 through a gradient pump within 20.3 min; wherein eluent a is methanol and eluent B is phosphate buffer with pH = 3.
Feasibility of the detection method
For SiO in solid phase micro-extraction column2The temperature sensitivity of the @ P-A-betｃA-CD/NIPAM adsorption medium is detected and verified:
1. taking 5 standard samples, which are respectively:
1: p-nitrophenol (PNP);
2: beta-naphthol (beta-NP);
3: bisphenol a (bpa);
4: 2, 4-dichlorophenol (2, 4-DCP);
5: 2,4, 6-trichlorophenol (2, 4, 6-TCP), as an analysis object, at a concentration of 20ng/mL per standard sample;
using the detection method provided in example 5, 5 labeled samples were used instead of the detection sample in example 5, each sample was 30mL, and the column temperature in step two was measured at high temperature (50 ℃) and low temperature (25 ℃) respectively, with the following results:
the chromatogram of the solid phase micro-extraction column at high temperature (50 ℃) and low temperature (25 ℃) shows that the detection results are respectively shown in fig. 6 and fig. 7, and as can be seen from fig. 6, the peak emergence time of 5 standard products in the chromatogram at high temperature (50 ℃) is respectively 6.55min, 12.45min, 14.40min, 15.72min and 19.87 min; the retention time of 5 standard substances in the low temperature chromatogram in FIG. 7 is 6.63min, 12.53min, no peak, 15.77min, and 19.89min, and the retention time is low temperatureThe retention time of each component is lagged, the peak area is smaller than that at high temperature, and BPA does not generate a peak, which is mainly caused by the supermolecule and hydrogen bond action of poly isopropyl acrylamide (NIPAM) chain and BPA, and shows that the SiO in the adsorption medium is adsorbed2The @ P-A-betｃA-CD/NIPAM has temperature sensitivity and can rapidly desorb phenolic pollutants of guest molecules under the high-temperature condition.
The temperature sensitive adsorption medium has environmental stimulation responsiveness, and when the enriched organic pollutants are sufficiently eluted, the organic matters are completely eluted out when the solid-phase micro-extraction column is at a high temperature; at low temperatures, the organic material cannot be completely eluted. The temperature responsiveness is caused by the existence of hydrophilic groups and hydrophobic groups in the temperature-sensitive adsorption medium, when gradient elution is carried out, the groups can form hydrogen bonds and van der Waals acting force with organic molecules, and the adsorption medium has supermolecule action and inclusion action on organic matters. When the temperature of the solid phase micro-extraction column is less than 30 ℃, molecular chains in the adsorption medium exist in a freely extending conformation in the mobile phase, and the hydrophilic groups and organic pollutant molecules form intermolecular hydrogen bonds, so that the molecular chains cannot be completely eluted within a certain time; when the temperature of the solid phase micro-extraction column is higher than 40 ℃, the molecular chain shrinks into a spherical structure, hydrogen bonds formed by hydrophilic groups and organic pollutant molecules are broken, and hydrophobic groups play a leading role, so that the organic pollutant molecules are completely eluted from the solid phase micro-extraction column in the time. It is therefore selected to adsorb phenolic contaminants at room temperature and desorb at elevated temperatures.
Thirdly, the accuracy and precision of the detection method
Standard curve: preparing 5 standard samples with a series of concentrations, wherein the 5 standard samples are the same as the 5 standard samples in the feasibility of the detection method, the enrichment is carried out for 30min at the flow rate of 1.0 ng/mL, the ordinate Y is the peak area, and the abscissa X is the concentration; taking the peak area to concentration as a standard curve, obtaining the standard curves of 5 standard samples as follows: y is1=55.05X1-0.49；Y2=497.88X2-37.84；Y3=76.25X3+5.67；Y4=50.29X4-8.59；Y5=52.31X5+3.89. Linear range of respectivelyComprises the following steps: sample No. 1 PNP: 1-500 ng/mL; the other 4 kinds are 0.2-500 ng/mL.
And (3) researching the recovery rate by adopting a standard adding method, taking the same water sample as a sample matrix, adding 2 phenol standard samples with different concentrations, enriching the water sample under the same conditions of the phenol standard samples and the 5 standard samples, wherein the concentrations of the standard samples are respectively 0.50 ng/mL and 5.0 ng/mL, performing parallel determination for 3 times, and substituting the obtained peak area into a standard curve to obtain the detection concentration, and then calculating the recovery rate and the precision of the detection concentration. The chromatograms are shown in fig. 8, fig. 9 and fig. 10, respectively, and the results are shown in table 1 for calculating the recovery rate and precision.
TABLE 1 calculation results of recovery and precision (%)
As shown in Table 1, the recovery rate was 87.7 to 106.7%, and the precision was 0.194 to 4.55%.
Claims (8)
1. A solid phase micro-extraction column is characterized in that: the device comprises an extraction column tube 31, filter elements 21 and a screw cap 11, wherein the central positions of the upper end and the lower end of the extraction column tube 31 are respectively and symmetrically provided with a bulge 51, and the bulge 51 is provided with the filter elements 21; a through hole is axially formed in the center of the nut 11; the bulge 51 extends into the through hole to be connected with one end of the screw cap 11 through a thread structure, the other end of the screw cap 11 is connected with the screw cap joint 41 through the thread structure, the filter disc 21 abuts against the screw cap joint 41, and the screw cap joint 41 is connected with a peek pipe 61; the extraction column tube 31, the bulge 51 and the nut joint 41 are all of hollow structures, the hollow structures of the extraction column tube 31, the bulge 51 and the nut joint 41 are communicated to form an extraction channel, and the two peek tubes 61 are communicated through the extraction channel;
the extraction column tube 31 is filled with a temperature-sensitive adsorption medium, and the temperature-sensitive adsorption medium is SiO2The @ P-A-betｃA-CD/NIPAM adsorption medium is prepared by the following method:
(1) synthesizing an acryloyl cyclodextrin functional monomer;
（2）KH570 for SiO2Silanization is carried out to obtain silanized SiO2；
(3) Synthesis of SiO2@ P-A- β -CD/NIPAM adsorbent mediｃA: silanized 0.3-0.8g of SiO2Dispersing in 20mL dry DMF, adding 20-30mg azobisisobutyronitrile in N2Dropwise adding 20mL of DMF solution of 1-6mmol of isopropyl acrylamide and 0.05mol/L acryloyl cyclodextrin functional monomer at 60-80 ℃ in an atmosphere, stirring for 24-48h after the addition is finished, centrifuging, alternately washing the precipitate obtained by centrifuging for 5 times by using distilled water and methanol, and drying the precipitate at 50 ℃ in vacuum for 2 days to obtain SiO2@ P-A-betｃA-CD/NIPAM adsorbent mediｃA.
2. The solid phase microextraction column according to claim 1, characterized in that: KH570 is adopted for SiO in the step (2)2The specific procedure for performing the silanization is as follows:
(2a) 4g of SiO2Soaking in 10% hydrochloric acid solution, activating at 110 deg.C for 12 hr, filtering, washing the obtained residue with distilled water to neutrality, and vacuum drying at 50 deg.C for 2 days to obtain activated SiO2；
(2b) 2-5g of activated SiO2Dispersed in 15-20mL dry toluene in N2Dropwise adding 20-25mL of toluene solution of KH570 with volume concentration of 14% into the mixture under the atmosphere, refluxing for condensation, stirring at 110 deg.C for 36h, centrifuging, alternately washing the precipitate with toluene and methanol for 5 times, and vacuum drying at 50 deg.C for 3 days to obtain silanized SiO2。
3. The solid phase microextraction column according to claim 1, characterized in that: the step of synthesizing the acryloyl cyclodextrin functional monomer in the step (1) is as follows:
(1a) adding 5mmol of beta-cyclodextrin into 20mL of dry DMF, then adding 20mmol of triethylamine, and stirring in an ice water bath;
(1b) 20mmol acryloyl chloride was added to 20mL dry DMF;
(1c) in N2And (2) dropwise adding the solution obtained in the step (1 b) into the solution obtained in the step (1 a) in an atmosphere, stirring and reacting for 24 hours in an ice-water bath after the addition is finished, then filtering, precipitating the filtrate in sufficient acetone, repeating for 3 times to obtain a white precipitate, and performing vacuum drying at 20 ℃ for 3 days to obtain the acryloyl cyclodextrin functional monomer.
4. The solid phase microextraction column according to claim 1, characterized in that: the extraction column tube 31 and the screw cap 11 are both regular hexagonal prisms, and the diameters of inscribed circles of the regular hexagonal prisms are 1-2 mm.
5. The solid phase microextraction column according to claim 4, wherein: the height of the extraction column 31 is 2cm, and the height of the screw cap 11 is 2 cm.
6. The solid phase microextraction column according to claim 1, characterized in that: the extraction column tube 31, the screw cap 11 and the screw cap joint 41 are all made of stainless steel materials.
7. The solid phase microextraction column according to claim 1, characterized in that: the filter disc 21 is made of sintered stainless steel material, and the protrusions 51 are made of polyimide material.
8. Use of the solid phase microextraction column according to claim 1, characterized in that: and enriching a detection sample by using the solid phase microextraction column, and detecting phenols in water on line by using a solid phase microextraction-high performance liquid chromatography combined instrument.
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