CN116586047B - Polymer coated fiber, preparation method and application thereof in detection of trace polycyclic aromatic hydrocarbon - Google Patents
Polymer coated fiber, preparation method and application thereof in detection of trace polycyclic aromatic hydrocarbon Download PDFInfo
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- CN116586047B CN116586047B CN202310826565.4A CN202310826565A CN116586047B CN 116586047 B CN116586047 B CN 116586047B CN 202310826565 A CN202310826565 A CN 202310826565A CN 116586047 B CN116586047 B CN 116586047B
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- cyclodextrin
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- 239000000835 fiber Substances 0.000 title claims abstract description 99
- 229920000642 polymer Polymers 0.000 title claims abstract description 93
- 238000001514 detection method Methods 0.000 title claims abstract description 40
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 154
- 238000000576 coating method Methods 0.000 claims abstract description 66
- 239000011248 coating agent Substances 0.000 claims abstract description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000003365 glass fiber Substances 0.000 claims abstract description 50
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 40
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 26
- 238000002470 solid-phase micro-extraction Methods 0.000 claims abstract description 22
- 238000001212 derivatisation Methods 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 102
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 73
- 229960004853 betadex Drugs 0.000 claims description 61
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 58
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 claims description 47
- 229940043377 alpha-cyclodextrin Drugs 0.000 claims description 46
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 claims description 46
- 229940080345 gamma-cyclodextrin Drugs 0.000 claims description 46
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 239000011259 mixed solution Substances 0.000 claims description 29
- 239000001116 FEMA 4028 Substances 0.000 claims description 26
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 25
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 20
- -1 benzyl cyclodextrin Chemical compound 0.000 claims description 18
- 239000003431 cross linking reagent Substances 0.000 claims description 18
- 239000010410 layer Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 17
- 238000001704 evaporation Methods 0.000 claims description 16
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 12
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 claims description 12
- 235000010290 biphenyl Nutrition 0.000 claims description 12
- 239000004305 biphenyl Substances 0.000 claims description 12
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 12
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 12
- 239000012312 sodium hydride Substances 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 11
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000000605 extraction Methods 0.000 claims description 8
- 238000004132 cross linking Methods 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 6
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 6
- 239000011241 protective layer Substances 0.000 claims description 6
- 238000000944 Soxhlet extraction Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- YYGRHZGRPBCGKN-UHFFFAOYSA-N ClC1=C(C=CC=C1)Cl.C1(=CC=CC=C1)C1=CC=CC=C1 Chemical compound ClC1=C(C=CC=C1)Cl.C1(=CC=CC=C1)C1=CC=CC=C1 YYGRHZGRPBCGKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 239000000356 contaminant Substances 0.000 claims description 2
- 239000007809 chemical reaction catalyst Substances 0.000 claims 1
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- 239000000463 material Substances 0.000 abstract description 13
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- 239000002957 persistent organic pollutant Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
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- 238000011084 recovery Methods 0.000 description 10
- 230000002194 synthesizing effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 238000003795 desorption Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229920006037 cross link polymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000002657 fibrous material Substances 0.000 description 3
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- GSOXNLLPTMSRCO-UHFFFAOYSA-N 1,2-dichloro-3,4-diphenylbenzene Chemical compound C=1C=CC=CC=1C1=C(Cl)C(Cl)=CC=C1C1=CC=CC=C1 GSOXNLLPTMSRCO-UHFFFAOYSA-N 0.000 description 2
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000002372 labelling Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920005594 polymer fiber Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000581 reactive spray deposition Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005574 benzylation reaction Methods 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 235000012206 bottled water Nutrition 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 238000005887 phenylation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- 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
-
- 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
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- 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
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
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- 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
- B01J20/28014—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 form
- B01J20/28023—Fibres or filaments
-
- 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
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention belongs to the technical field of organic pollutant detection, and discloses a polymer coating fiber, a preparation method and application thereof in trace polycyclic aromatic hydrocarbon detection, wherein the method comprises the following steps: s1, performing phenyl derivatization treatment on glass fibers to obtain phenyl-derivatized glass fibers; s2, preparing homogeneously synthesized benzylated cyclodextrin; s3, preparing polymer coating fibers to obtain cyclodextrin crosslinked porous polymer coating fibers. The invention adopts an in-situ polymerization method, and the prepared polymer coating fiber has unique microstructure by matching components, proportion and preparation process, has the advantages of wide linear range, good repeatability, large enrichment multiplying power, low detection limit and the like, and has the advantages of simple synthesis, good repeatability, strong adsorption capacity, easy mass production and the like; the invention is easy for batch production and low in comprehensive cost, can be used as a sample pretreatment material, and can meet the requirement of detecting the content of trace polycyclic aromatic hydrocarbon in the water sample by solid-phase microextraction in the tube.
Description
Technical Field
The invention belongs to the technical field of organic pollutant detection, and particularly relates to a polymer coating fiber, a preparation method and application thereof in detecting trace polycyclic aromatic hydrocarbon.
Background
Polycyclic Aromatic Hydrocarbons (PAHs) are persistent, nondegradable organic hydrophobic contaminants that can bring various adverse effects to humans and the environment through air, land, and water environments. The PAHs are formed by two or more fused benzene rings, are usually generated by natural reasons such as forest spontaneous combustion, volcanic eruption and the like, but are mainly generated by the intensive development of coal mine and automobile tail gas emission which does not reach standards by human in recent years, and the existence amount and new increment of the PAHs in the environment show rapid growth trend, and especially the water environment is seriously influenced by the PAHs. The international environmental protection agency has even identified PAHs as dangerous carcinogens. In order to detect the content of trace or trace PAHs in water environment, the prior art generally adopts a solid phase extraction instrument to carry out sample pretreatment and uses a high performance liquid chromatography to measure PAHs in water, the recovery rate can reach 77% -120%, the efficiency is high, but the cost of consumables such as horizons C18 solid phase extraction membrane (47 mm) used in the pretreatment procedure of the prior solid phase extraction instrument is high, the repeatability is poor, and the method is only used in the prior laboratory and is difficult to popularize in large scale.
Solid phase microextraction is a technique that integrates sampling, separation, enrichment and sample injection. The in-tube solid phase microextraction (IT-SPME) is a special form thereof, and has the advantages of less solvent, high reproducibility, easy realization of on-line automation and the like. The fiber coating is a key component in the pretreatment process of the sample, and the enrichment performance of the fiber coating determines the extraction performance of IT-SPME, including reproducibility, stability and the like.
In the prior art, cyclodextrin crosslinked polymers are fiber coating materials with excellent performance, and various cyclodextrin crosslinked polymers have been reported to be synthesized. For example, chinese patent application CN202210604573.X synthesizes hepta-amino-beta-cyclodextrin and terephthalaldehyde into a cyclodextrin porous polymer by using a coating method, and coats the cyclodextrin porous polymer on the surface of a steel wire to absorb and extract purine in water, chinese patent application CN202010119377.4 synthesizes beta-cyclodextrin cross-linked polymer by using a precipitation method for removing bisphenol organic pollutants in water, but the coating method and the precipitation method generally have the phenomena of low reproducibility and poor durability. Chinese patent application CN 202210330038. X discloses an ultra-high cross-linked beta cyclodextrin polymer synthesized by using benzylated cyclodextrin, but its performance is limited, and it can only be used for removing organic pollutants in water, but cannot be used in the field of high-precision target separation and enrichment detection. Meanwhile, the preparation process of the method is complex, the preparation cost is high, and the method is not beneficial to popularization.
Therefore, researchers are required to provide a new polycyclic aromatic hydrocarbon sample pretreatment material which is simple in synthesis, less in raw material use, rapid in pretreatment process, good in repeatability and durability, high in enrichment factor and high in detection result accuracy, and the cost is reduced, so that the pretreatment material meets the requirements of large-scale and large-scale popularization and application of trace polycyclic aromatic hydrocarbons in water samples.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a novel polymer coating fiber, a preparation method and application thereof in trace polycyclic aromatic hydrocarbon detection, and the polymer coating fiber is prepared by adopting an in-situ polymerization method, and has the advantages of simple synthesis, good repeatability, strong adsorption capacity, easiness in mass production and the like; the coating fiber prepared by the method has the advantages of unique microstructure, wide linear range, good reproducibility, large enrichment multiplying power, low detection limit and the like through matching components, proportions and preparation processes, is easy to produce in batches, has low comprehensive cost, can meet the requirement of detecting the content of trace polycyclic aromatic hydrocarbon in a water sample by solid-phase microextraction in a pipe as a sample pretreatment material, and can meet the requirements of large-scale and large-scale popularization and application.
The technical scheme provided by the invention for solving the problems is as follows:
a method for preparing a polymer coated fiber, comprising the steps of:
s1, phenyl derivatization treatment of glass fibers: removing the fiber surface protective layer from the glass fiber by using methylene dichloride, drying, immersing the glass fiber in a mixed solution of an anhydrous and anaerobic toluene solvent and trimethyloxyphenyl silane, and continuously reacting under anhydrous and anaerobic and micro-boiling conditions in the anhydrous and anaerobic mixed solution; then cleaning the glass fiber with dichloromethane and methanol respectively for one time, and vacuum drying to obtain phenyl derivative glass fiber;
s2, preparing benzyl cyclodextrin: respectively taking one of alpha, beta or gamma cyclodextrin, dissolving in anhydrous N, N-Dimethylformamide (DMF) to obtain corresponding cyclodextrin solution, putting sodium hydride into the cyclodextrin solution at 0 ℃ for fully mixing, and slowly adding benzyl bromide into the system; then restoring to room temperature, reacting under anhydrous and anaerobic conditions, adding methanol after the reaction is carried out for a set period of time, and ending the reaction of the system to obtain a system solution; pouring the system solution into a separating funnel, and extracting with a mixed solution of dichloromethane and water to obtain a lower layer liquid; finally, evaporating the lower layer liquid in a rotary way, and evaporating the solvent to obtain one of the uniformly synthesized benzylated alpha, beta or gamma cyclodextrin;
s3, preparing polymer coating fibers: taking one of benzylated alpha, beta or gamma cyclodextrin, and respectively carrying out a crosslinking polymerization reaction on phenyl derivatization glass fiber by nucleophilic substitution with a double cross-linking agent consisting of biphenyl dichlorobenzyl and 1,4 dichlorobenzyl, wherein the benzylated cyclodextrin and the double cross-linking agent in the step S2 are dissolved in an anhydrous 1, 2-dichloroethane solvent under anhydrous and anaerobic conditions; adding the phenyl-derived glass fiber and the anhydrous aluminum chloride serving as a catalyst in the step S1 into the system, and enabling the system to react for a set period of time at 80 ℃; after the reaction is carried out for a set period of time, water and methanol are used for cleaning once respectively, and then methanol is used for Soxhlet extraction; finally, vacuum drying is carried out to obtain the alpha, beta or gamma cyclodextrin crosslinked porous polymer coating fiber respectively.
The polymer coating fiber prepared by the method is cyclodextrin crosslinked porous polymer coating fiber, and specifically is one of alpha cyclodextrin crosslinked porous polymer coating fiber, beta cyclodextrin crosslinked porous polymer coating fiber or gamma cyclodextrin crosslinked porous polymer coating fiber.
The application of the polymer coating fiber in the solid-phase microextraction trace detection in the polycyclic aromatic hydrocarbon pollutant pipe in a water sample is that the polymer coating fiber is filled into a stainless steel pipe for the solid-phase microextraction detection of the polycyclic aromatic hydrocarbon content in the pipe. The polymer coating fiber has the advantages of simple preparation, good repeatability, strong adsorption capacity and the like. The polymer coating fiber is applied to in-tube solid-phase microextraction detection, and has the advantages of wide linear range, large enrichment multiplying power, low detection limit and the like.
Compared with the prior art, the polymer coating fiber, the preparation method and the application thereof in trace polycyclic aromatic hydrocarbon detection have the beneficial effects that at least:
1. the invention adopts an in-situ polymerization method to prepare polymer coating fiber, and the synthesized homogeneous cyclodextrin crosslinked porous polymer is uniformly polymerized on the three-dimensional surface of the phenylated glass fiber in-situ through the coordination of components, proportion and preparation process, and a unique microstructure is molded on the three-dimensional surface of the glass fiber, so that the prepared coating fiber has the advantages of wide linear range, good reproducibility, strong adsorption capacity, high enrichment multiplying power, low detection limit and the like based on the unique microstructure, is easy to produce in batches and has low comprehensive cost, and can meet the requirements of detecting the trace polycyclic aromatic hydrocarbon content in a water sample by solid-phase microextraction in a pipe, and the requirements of large-scale and large-scale popularization and application can be met.
2. Through practical tests, the cyclodextrin crosslinked porous polymer coated fiber prepared by the invention has low detection limit (the detection limit is as low as ng/L level), has the characteristics of wide linear range, good repeatability and satisfactory labeling recovery rate, can meet the detection requirement of trace-level polycyclic aromatic hydrocarbon in a water sample, and can obtain a high-precision detection result.
3. Through practical tests, the cyclodextrin crosslinked porous polymer fiber coating prepared by the invention is used as a pretreatment material for in-tube solid-phase microextraction detection, is accurate and rapid, can be reused at least 100 times, has no obvious change in extraction performance, has excellent stability and durability, and breaks through the limitations of the existing similar products.
Drawings
Fig. 1 is an SEM image of a fiber of a beta-cyclodextrin crosslinked porous polymer coating prepared in an embodiment of the invention, wherein fig. 1 (a) shows the surface of the beta-cyclodextrin crosslinked porous polymer coating at a magnification of 50 μm, and fig. 1 (B) shows the surface of the beta-cyclodextrin crosslinked porous polymer coating at a magnification of 10 μm;
FIG. 2 is a schematic flow chart of a process for preparing cyclodextrin crosslinked porous polymer coated fibers according to an embodiment of the invention, wherein FIG. 2 (A) shows the preparation of fibers by phenylation and FIG. 2 (B) shows the preparation of cyclodextrin crosslinked porous polymer coated fibers;
FIG. 3 is a thermogravimetric analysis of an inventive example beta cyclodextrin crosslinked porous polymer coating;
FIG. 4 is a graph showing isothermal desorption of a beta cyclodextrin crosslinked porous polymer coating according to an embodiment of the present invention;
FIG. 5 is a chromatogram of six kinds of polycyclic aromatic hydrocarbons in an actual water sample by using the beta cyclodextrin crosslinked porous polymer coating fiber of the embodiment of the invention for in-tube solid phase microextraction, wherein FIG. 5 (A) shows a chromatogram of labeled recovery of bottled water, FIG. 5 (B) shows a chromatogram of labeled recovery of Dong lake water, FIG. 5 (C) shows a chromatogram of labeled recovery of soil water, and FIG. 5 (D) shows a chromatogram of labeled recovery of tap water;
FIG. 6 is a graph of durability analysis of inventive example beta cyclodextrin crosslinked porous polymer coated fibers for in-tube solid phase microextraction.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be further described in detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
Example 1
The preparation method of the polymer coating fiber for trace polycyclic aromatic hydrocarbon detection provided by the embodiment comprises the following steps:
s1, phenyl derivatization treatment of glass fibers: removing the fiber surface protective layer from the glass fiber by using methylene dichloride, drying, immersing the glass fiber in a mixed solution of an anhydrous and anaerobic toluene solvent and trimethyloxyphenyl silane, and continuously reacting under anhydrous and anaerobic and micro-boiling conditions in the anhydrous and anaerobic mixed solution; then cleaning the glass fiber with dichloromethane and methanol respectively for one time, and vacuum drying to obtain phenyl derivative glass fiber;
s2, preparing benzyl cyclodextrin: respectively taking one of alpha, beta or gamma cyclodextrin, dissolving in anhydrous N, N-dimethylformamide DMF to obtain corresponding cyclodextrin solution, putting sodium hydride into the cyclodextrin solution at 0 ℃ for fully mixing, and slowly adding benzyl bromide into the system; then restoring to room temperature, reacting under anhydrous and anaerobic conditions, adding methanol after the reaction is carried out for a set period of time, and ending the reaction of the system to obtain a system solution; pouring the system solution into a separating funnel, and extracting with a mixed solution of dichloromethane and water to obtain a lower layer liquid; finally, evaporating the lower layer liquid in a rotary way, and evaporating the solvent to obtain one of the uniformly synthesized benzylated alpha, beta or gamma cyclodextrin;
s3, preparing polymer coating fibers: taking one of benzylated alpha, beta or gamma cyclodextrin, and respectively carrying out a crosslinking polymerization reaction on phenyl derivatization glass fiber by nucleophilic substitution with a double cross-linking agent consisting of biphenyl dichlorobenzyl and 1,4 dichlorobenzyl, wherein the benzylated cyclodextrin and the double cross-linking agent in the step S2 are dissolved in an anhydrous 1, 2-dichloroethane solvent under anhydrous and anaerobic conditions; adding the phenyl-derived glass fiber and the anhydrous aluminum chloride serving as a catalyst in the step S1 into the system, and enabling the system to react for a set period of time at 80 ℃; after the reaction is carried out for a set period of time, water and methanol are used for cleaning once respectively, and then methanol is used for Soxhlet extraction; finally, vacuum drying is carried out to obtain the alpha, beta or gamma cyclodextrin crosslinked porous polymer coating fiber respectively.
The polymer coating fiber prepared by the method is cyclodextrin crosslinked porous polymer coating fiber, and specifically is one of alpha cyclodextrin crosslinked porous polymer coating fiber, beta cyclodextrin crosslinked porous polymer coating fiber or gamma cyclodextrin crosslinked porous polymer coating fiber.
The application of the polymer coating fiber in the solid-phase microextraction trace detection in the polycyclic aromatic hydrocarbon pollutant pipe in a water sample is that the polymer coating fiber is filled into a stainless steel pipe for the solid-phase microextraction detection of the polycyclic aromatic hydrocarbon content in the pipe.
The following description is made with respect to a number of specific examples.
Example 2
The embodiment provides a polymer coating fiber for trace polycyclic aromatic hydrocarbon detection, specifically one of α, β or γ cyclodextrin crosslinked porous polymer coating fibers, based on embodiment 1, and the preparation method comprises the following steps:
s1, phenyl derivatization treatment of glass fibers, which specifically comprises the following steps:
s11: extracting glass fiber in Soxhlet extraction device with dichloromethane overnight, and removing the glass fiber surface protective layer;
s12: the glass fiber was dried according to glass fiber and trimethyloxyphenyl silane 1:2, immersing the glass fiber in an anhydrous and anaerobic mixed solution of toluene solvent and trimethyloxyphenyl silane, and continuously reacting for two days under the conditions of anhydrous and anaerobic mixed solution and micro-boiling of the mixed solution in the anhydrous and anaerobic mixed solution; in the anhydrous and anaerobic mixed solution, the volume ratio of toluene solvent to trimethyloxyphenyl silane is 50:1, a step of;
s13: then cleaning each glass fiber with dichloromethane and methanol for one time, and vacuum drying to obtain phenyl-derived glass fibers;
s2, preparing benzyl cyclodextrin:
respectively taking one of alpha, beta or gamma cyclodextrin, dissolving in anhydrous DMF to obtain corresponding cyclodextrin solution, putting sodium hydride into the cyclodextrin solution at 0 ℃ for fully mixing, and slowly adding benzyl bromide into the system; then restoring to room temperature, reacting under anhydrous and anaerobic conditions, adding methanol after the reaction is carried out for a set period of time, and ending the reaction of the system to obtain a system solution; pouring the system solution into a separating funnel, and extracting with a mixed solution of dichloromethane and water to obtain a lower layer liquid; finally, evaporating the lower layer liquid in a rotary way, and evaporating the solvent to obtain one of the uniformly synthesized benzylated alpha, beta or gamma cyclodextrin; the method specifically comprises the following steps:
s21, respectively taking one of alpha, beta or gamma cyclodextrin, dissolving in anhydrous DMF to obtain one solution of the alpha, beta or gamma cyclodextrin, putting sodium hydride into the solution at the temperature of 0 ℃ for fully mixing, and slowly adding benzyl bromide into the system; wherein, one of the alpha, beta or gamma cyclodextrin, sodium hydride and benzyl bromide have a mass ratio of 2:0.6:2.5;
s22, recovering the reaction solution from 0 ℃ to room temperature, and reacting for 12 hours under anhydrous and anaerobic conditions;
s23, adding methanol after the reaction is carried out for 12 hours, and ending the reaction of the system to obtain a system solution;
s24, pouring the system solution into a separating funnel, and extracting for three times by using a mixed solution of dichloromethane and water to obtain a lower layer liquid; wherein, in the mixed solution of dichloromethane and water, the volume ratio of dichloromethane to water is 1:2;
s25, finally, spin-evaporating the lower layer liquid at 35 ℃ and 30 rpm to obtain one of the homogeneously synthesized benzylated alpha, beta or gamma cyclodextrin;
s3, preparing polymer coating fibers: taking one of benzylated alpha, beta or gamma cyclodextrin, and respectively carrying out a crosslinking polymerization reaction on phenyl derivatization glass fiber by nucleophilic substitution with a double cross-linking agent consisting of biphenyl dichlorobenzyl and 1,4 dichlorobenzyl, wherein the benzylated cyclodextrin and the double cross-linking agent in the step S2 are dissolved in an anhydrous 1, 2-dichloroethane solvent under anhydrous and anaerobic conditions; adding the phenyl-derived glass fiber and the anhydrous aluminum chloride serving as a catalyst in the step S1 into the system, and enabling the system to react for a set period of time at 80 ℃; after the reaction is carried out for a set period of time, water and methanol are used for cleaning once respectively, and then methanol is used for Soxhlet extraction; finally, vacuum drying is carried out to obtain alpha, beta or gamma cyclodextrin crosslinked porous polymer coating fiber respectively; specifically:
s31, taking one of the benzylated alpha, beta or gamma cyclodextrin prepared in the step S2, and dissolving the benzylated alpha, beta or gamma cyclodextrin and a double cross-linking agent prepared by biphenyl dichlorobenzyl and 1,4 dichlorobenzyl in advance in an anhydrous and anaerobic condition in an anhydrous 1, 2-dichloroethane solvent;
the double cross-linking agent in the step is a mixture of biphenyl dichlorobenzyl and 1,4 dichlorobenzyl with the mass ratio of 1:0.2-0.25;
s32, adding the phenyl-derived glass fiber prepared in the step S1 and anhydrous aluminum chloride serving as a catalyst, entering the system, enabling the system to react for 12 hours at 80 ℃, and enabling the benzyl beta cyclodextrin and biphenyl dichlorobenzyl and 1,4 dichlorobenzyl to form a double-crosslinking agent, and carrying out crosslinking polymerization on the phenyl-derived glass fiber through nucleophilic substitution;
the double cross-linking agent in the step is a mixture of biphenyl dichlorobenzyl and 1,4 dichlorobenzyl with the mass ratio of 1:0.2-0.25;
one of the benzylated alpha, beta or gamma cyclodextrin in the step, biphenyl dichlorobenzyl, 1,4 dichlorobenzyl and anhydrous aluminum chloride in the molar ratio of 20:66:22:500;
s33, after the reaction is finished for a set period of time, washing the reaction product once by water and methanol, and then extracting the reaction product by methanol Soxhlet 24 h;
and S34, finally, carrying out vacuum drying to obtain the cyclodextrin crosslinked porous polymer coated fiber.
Example 3
Referring to fig. 1-6, this embodiment further provides a polymer coated fiber for trace polycyclic aromatic hydrocarbon detection, specifically a β -cyclodextrin crosslinked porous polymer coated fiber, based on embodiment 2, and the preparation method thereof comprises the following steps:
s1, synthesizing a phenylate fiber, wherein the specific method is as follows:
3.37g of glass fibers were extracted in a Soxhlet apparatus with methylene chloride overnight to remove the protective layer on the surface of the fibers. The fiber is dried, immersed in a mixed solution of 100ml of anhydrous toluene solvent and 6.75g of trimethyloxyphenyl silane, and reacted for two days under the condition of no water and no oxygen and slight boiling of the solution; then cleaning the fiber with dichloromethane and methanol for one time respectively, and drying in vacuum to obtain phenyl derivatization fiber;
s2, synthesizing the benzylated beta cyclodextrin. The specific method comprises the following steps:
2.00g of beta cyclodextrin is dissolved in 40ml of anhydrous DMF, sodium hydride is put into the solution at the temperature of 0 ℃ for thorough mixing, and 2.5g of benzyl bromide is slowly added into the system; then the reaction is carried out for 12 hours after the reaction is restored to the room temperature; allowing the reaction to proceed under anhydrous and anaerobic conditions; when the reaction is completed for 12 hours, adding 5ml of methanol to finish the reaction; pouring the system solution into a separating funnel, and extracting with a mixed solution of dichloromethane and water for three times to obtain a lower layer liquid; and finally, evaporating the lower layer liquid by spin, and evaporating the solvent to obtain the benzyl beta cyclodextrin.
S3, synthesizing cyclodextrin crosslinked porous polymer coating fibers. The specific method comprises the following steps:
taking 0.265g of the benzylated beta-cyclodextrin prepared in the step S2, 0.205g of the bis-crosslinking agent diphenyl dichlorobenzene and 0.0475g of 1,4 dichlorobenzene, and dissolving the materials in an anhydrous 1, 2-dichloroethane solvent under anhydrous and anaerobic conditions; adding the phenylated fiber prepared in the step S1 and 1.04g of anhydrous aluminum chloride serving as a catalyst into the system; allowing the reaction to react at 80 ℃ for 12 hours; after the reaction, the mixture is washed once by water and methanol, and then 24 h is extracted by methanol Soxhlet; finally, vacuum drying is carried out to obtain the beta cyclodextrin crosslinked porous polymer coating fiber.
FIG. 1 is an SEM image of a fiber coated with a beta-cyclodextrin crosslinked porous polymer prepared by the above-mentioned preparation method, and it can be seen from FIG. 1A that the beta-cyclodextrin crosslinked porous polymer is uniformly polymerized on the surface of the fiber and the thickness thereof is 2.0 μm on average. As can be seen from FIG. 1B, the cyclodextrin crosslinked porous polymer coating is a laminated structure formed by stacking small particles, and a large number of gaps and spaces with different dimensions exist among the particle materials, namely, the cyclodextrin crosslinked porous polymer coating is a fibrous material with a multi-layer and multi-scale three-dimensional pore structure on the surface. The three-dimensional particle stack, porous interweaving and interconnected microstructure of the fiber material surface can enable target molecules to be adsorbed on the fiber material surface more easily, and meanwhile, the mass transfer rate and the extraction efficiency can be improved.
FIG. 2 is a flow chart of the synthesis of the cyclodextrin crosslinked porous polymer coated fiber prepared by the above method, and it can be seen from FIG. 2A that the glass fiber surface is uniformly benzyl derivatized, providing sites for the cyclodextrin. It can be seen from fig. 2B that after the cyclodextrin benzylation, a uniform in situ polymerization is carried out on the benzylated fibrous surface.
The thermogravimetric analysis adopted by the invention is a method for changing physical properties and chemical properties of a substance along with the increase of temperature or time. As can be seen from the thermogravimetric analysis of FIG. 3, the material has a weight loss rate lower than 17% after 230 ℃, so that the cyclodextrin crosslinked porous polymer coating has good thermal stability at the desorption temperature of 280 ℃ and completely meets the requirements of the in-tube solid-phase microextraction process.
FIG. 4 is a graph of isothermal desorption of cyclodextrin crosslinked porous polymer coating, and it can be seen from FIG. 4 that the specific surface area of the material is up to 240m 2 g -1 The average pore diameter was 11.37nm. The fiber surface is polymerized in situ with a plurality of porous polymer coatings that provide a plurality of attachment sites for target analytes, facilitating enhanced extraction of analytes. Furthermore, as can be seen from FIG. 4, N of beta-CD-HCP 2 The adsorption curve belongs to the type IV isotherm. The adsorption isotherm increases rapidly over a range of low pressures, indicating the presence of a large number of microporous structures in the material.
Example 4
The present embodiment further provides a polymer coated fiber for trace polycyclic aromatic hydrocarbon detection, specifically an α -cyclodextrin crosslinked porous polymer coated fiber, based on embodiment 2 or embodiment 3, wherein step S1 of the preparation method is the same as that of embodiment 2 or embodiment 3, and the method further comprises the following steps:
s2, synthesizing the benzylated alpha cyclodextrin. The specific method comprises the following steps:
2.00g of alpha cyclodextrin is dissolved in 40ml of anhydrous DMF, sodium hydride is put into the solution at 0 ℃ for thorough mixing, and 2.5g of benzyl bromide is slowly added into the system; then the reaction is carried out for 12 hours after the reaction is restored to the room temperature; allowing the reaction to proceed under anhydrous and anaerobic conditions; when the reaction is completed for 12 hours, adding 5ml of methanol to finish the reaction; pouring the system solution into a separating funnel, and extracting with a mixed solution of dichloromethane and water for three times to obtain a lower layer liquid; finally, the lower layer liquid is distilled in a rotary way to obtain benzylated alpha cyclodextrin;
s3, synthesizing the alpha cyclodextrin crosslinked porous polymer coating fiber. The specific method comprises the following steps:
0.265g of benzylated alpha cyclodextrin prepared in the step S2, 0.205g of bis-crosslinking agent diphenyl dichlorobenzene and 0.0475g of 1,4 dichlorobenzene are dissolved in an anhydrous and anaerobic condition in an anhydrous 1, 2-dichloroethane solvent; adding the phenylated fiber prepared in the step S1, adding 1.04g of anhydrous aluminum chloride serving as a catalyst into the system, reacting at 80 ℃ for 12 hours, washing once with water and methanol after the reaction is finished, extracting 24 h by using methanol Soxhlet, and finally drying in vacuum to obtain the alpha cyclodextrin crosslinked porous polymer coated fiber.
Example 5
The present embodiment further provides a polymer coated fiber for trace polycyclic aromatic hydrocarbon detection, specifically a γ -cyclodextrin crosslinked porous polymer coated fiber, based on embodiment 2 or embodiment 3, and the step S1 of the preparation method is the same as that of embodiment 2 or embodiment 3, except that the method further comprises the following steps:
s2, synthesizing the benzylated gamma cyclodextrin. The specific method comprises the following steps:
2.00g of gamma cyclodextrin is dissolved in 40ml of anhydrous DMF, sodium hydride is put into the solution for full mixing at the temperature of 0 ℃, 2.5g of benzyl bromide is slowly added into the system, and then the reaction is carried out for 12 hours at room temperature; the reaction was allowed to proceed under anhydrous and anaerobic conditions. Adding 5ml of methanol when the reaction is completed for 12 hours to finish the reaction of the system; pouring the system solution into a separating funnel, and extracting with a mixed solution of dichloromethane and water for three times to obtain a lower layer liquid; and finally, spin-evaporating the lower liquid to obtain the benzylated gamma cyclodextrin.
S3, synthesizing the gamma cyclodextrin crosslinked porous polymer coating fiber. The specific method comprises the following steps:
0.265g of the benzylated gamma cyclodextrin prepared in the step S2, 0.205g of the bis-crosslinking agent biphenyl dichlorobenzene and 0.0475g of 1,4 dichlorobenzene are dissolved in an anhydrous and anaerobic condition in an anhydrous 1, 2-dichloroethane solvent; adding the phenylated fiber prepared in the step S1 and 1.04g of anhydrous aluminum chloride serving as a catalyst into the system; allowing the reaction to react at 80 ℃ for 12 hours; after the reaction, the mixture is washed once by water and methanol, and then 24 h is extracted by methanol Soxhlet; finally, vacuum drying is carried out to obtain the gamma cyclodextrin crosslinked porous polymer coating fiber.
Application examples
The beta-cyclodextrin crosslinked porous polymer coated fiber prepared in the embodiment 3 is applied to trace detection of solid-phase microextraction in a polycyclic aromatic hydrocarbon pollutant pipe in a water sample, and specifically, the beta-cyclodextrin crosslinked porous polymer coated fiber is filled into a stainless steel pipe, and trace polycyclic aromatic hydrocarbon content is detected by solid-phase microextraction in the pipe.
1. The beta cyclodextrin crosslinked porous polymer coated fiber prepared in the embodiment 3 of the invention adopts an in-tube solid phase microextraction and detection instrument to detect water samples containing PAHs with trace concentration in batches, and the detected water samples comprise: a is bottled distilled water, B is lake water, C is soil water and D is tap water. The linear range, the detection limit, the linear correlation coefficient (r), the enrichment multiplying power (EFs) and the recovery rate of PAHs are determined, under the optimal condition, the extraction volume is 70mL, the sampling rate is 2.5 mL/min, the methanol is not contained, the desorption time is 2.0min, the linear range and the detection limit, the linear correlation coefficient (r) and the enrichment multiplying power (EFs) are shown in the following table 1, the recovery rate of an actual water sample is detected in FIG. 5 (A is bottled distilled water, B is lake water, C is soil water and D is tap water), and the recovery rate is 80.6% -106.7%.
2. The peak area differences for all analytes of the different batches were not significant, as shown in fig. 5, with RSDs (n=3) for all analytes in the range of 0.6% -1.8%. According to the results, the online analysis method has repeatability and good test tube reproducibility. The extraction tube has good durability, and the accuracy of experimental results is ensured. As shown in FIG. 6, by comparing the peak areas of the 1 st, 50 th and 100 th tests on a single tube, the difference between these peak areas was small (RSDs. Ltoreq.6.0%) and durability was obtained, i.e., the polymer-coated fiber could be reused at least 100 times.
TABLE 1
Practical tests show that the cyclodextrin crosslinked porous polymer coating fiber prepared by the method has low detection limit (the detection limit is as low as ng/L level), has the characteristics of wide linear range, good repeatability and satisfactory labeling recovery rate, can meet the detection requirement of trace-level polycyclic aromatic hydrocarbon in a water sample, and can obtain a high-precision detection result.
Practical tests show that the cyclodextrin crosslinked porous polymer fiber coating prepared by the invention is used as a pretreatment material for in-tube solid-phase microextraction detection, is accurate and rapid, can be reused for at least 100 times, has no obvious change in extraction performance, has excellent stability and durability, and breaks through the limitations of the existing similar products.
In other application embodiments, the α -cyclodextrin crosslinked porous polymer coated fiber, the β -cyclodextrin crosslinked porous polymer coated fiber, or one of the γ -cyclodextrin crosslinked porous polymer coated fibers prepared in other embodiments is respectively put into a stainless steel tube, and the trace amount of polycyclic aromatic hydrocarbon content can be detected by solid-phase microextraction in the tube, and the technical effects described in the present invention can be achieved.
The cyclodextrin crosslinked porous polymer coating fiber prepared by the method can be repeatedly used for a plurality of times, so that the cost of detection consumable materials can be greatly reduced, and the method is favorable for large-scale and large-scale popularization and application.
In other embodiments of the present invention, the technical effects described in the present invention may be achieved by other different schemes obtained by specific selection within the ranges of steps, components, proportions, process parameters and conditions described in the present invention, so the present invention is not listed one by one.
The above description is only of the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any person skilled in the art can make many possible variations and modifications to the technical solution of the present invention or modifications to equivalent embodiments using the methods and technical contents disclosed above, without departing from the scope of the technical solution of the present invention. All equivalent changes of the components, proportions and processes according to the invention are covered in the protection scope of the invention.
Claims (11)
1. The preparation method of the polymer coating fiber for detecting the content of trace polycyclic aromatic hydrocarbon in a water sample by solid phase microextraction is characterized by comprising the following steps:
s1, phenyl derivatization treatment of glass fibers: removing the fiber surface protective layer from the glass fiber, drying, immersing in a mixed solution of toluene solvent and trimethyloxyphenyl silane, and continuously reacting; cleaning and drying to obtain phenyl-derived glass fibers;
s2, preparing benzyl cyclodextrin: respectively taking one of alpha, beta or gamma cyclodextrin, dissolving in anhydrous N, N-Dimethylformamide (DMF) to obtain a corresponding cyclodextrin solution, adding sodium hydride into the cyclodextrin solution, then slowly adding benzyl bromide, and obtaining a system solution after finishing the reaction; extracting lower liquid from the system solution, and evaporating the solvent of the lower liquid to obtain one of the homogeneously synthesized benzylated alpha, beta or gamma cyclodextrin;
s3, preparing polymer coating fibers: and (3) taking one of the benzylated alpha, beta or gamma cyclodextrin, carrying out a crosslinking polymerization reaction on the phenyl derivatization glass fiber by nucleophilic substitution on the benzylated alpha, beta or gamma cyclodextrin and a double crosslinking agent consisting of biphenyl dichlorobenzyl and 1,4 dichlorobenzyl respectively, and carrying out vacuum drying on the reaction catalyst which is anhydrous aluminum chloride to obtain the alpha, beta or gamma cyclodextrin crosslinking porous polymer coating fiber respectively.
2. The method according to claim 1, wherein the phenyl derivatization treatment of the glass fiber of step S1 is specifically: removing a fiber surface protective layer from glass fiber by using dichloromethane, drying, immersing the glass fiber in a mixed solution of an anhydrous and anaerobic toluene solvent and trimethyloxyphenyl silane, and continuously reacting under anhydrous and anaerobic and micro-boiling conditions in the anhydrous and anaerobic mixed solution; and then cleaning the glass fiber once by using dichloromethane and methanol respectively, and drying in vacuum to obtain the phenyl derivative glass fiber.
3. The preparation method according to claim 2, wherein the step S1 specifically comprises the following steps:
s11: extracting the glass fiber in an extraction device by using dichloromethane, removing a glass fiber surface protection layer, and then drying;
s12: the glass fiber was mixed with trimethyloxyphenyl silane 1:2, immersing the glass fiber in a mixed solution of anhydrous and anaerobic toluene solvent and trimethyloxyphenyl silane, and continuously reacting for two days under the conditions of anhydrous and anaerobic mixed solution and micro-boiling of the mixed solution in the anhydrous and anaerobic mixed solution; in the anhydrous and anaerobic mixed solution, the volume ratio of toluene solvent to trimethyloxyphenyl silane is 50:1, a step of;
s13: and then cleaning the glass fiber once by using dichloromethane and methanol respectively, and drying in vacuum to obtain the phenyl-derived glass fiber.
4. The preparation method according to claim 1, wherein the step S2 specifically comprises: respectively taking one of alpha, beta or gamma cyclodextrin, dissolving in anhydrous N, N-Dimethylformamide (DMF) to obtain corresponding cyclodextrin solution, putting sodium hydride into the cyclodextrin solution at 0 ℃ for fully mixing, and slowly adding benzyl bromide into the system; then restoring to room temperature, reacting under anhydrous and anaerobic conditions, adding methanol after the reaction is carried out for a set period of time, and ending the reaction of the system to obtain a system solution; pouring the system solution into a separating funnel, and extracting with a mixed solution of dichloromethane and water to obtain a lower layer liquid; and finally, evaporating the lower layer liquid by spin evaporation, and evaporating the solvent to obtain one of the homogeneously synthesized benzylated alpha, beta or gamma cyclodextrin.
5. The preparation method according to claim 4, wherein the step S2 specifically comprises the following steps:
s21, respectively taking one of alpha, beta or gamma cyclodextrin, dissolving in anhydrous N, N-Dimethylformamide (DMF) to obtain one solution of the alpha, beta or gamma cyclodextrin, putting sodium hydride into the solution at the temperature of 0 ℃ for fully mixing, and slowly adding benzyl bromide into the system; wherein, one of the alpha, beta or gamma cyclodextrin, sodium hydride and benzyl bromide have a mass ratio of 2:0.6:2.5;
s22, recovering to room temperature, and reacting for 12 hours under the anhydrous and anaerobic condition;
s23, adding methanol after the reaction is carried out for 12 hours, and ending the reaction of the system to obtain a system solution;
s24, pouring the system solution into a separating funnel, and extracting for three times by using a mixed solution of dichloromethane and water to obtain a lower layer liquid; wherein, in the mixed solution of dichloromethane and water, the volume ratio of dichloromethane to water is 1:2;
and S25, finally, spin-evaporating the lower liquid at 35 ℃ and 30 rpm, and evaporating the solvent to obtain one of the homogeneously synthesized benzylated alpha, beta or gamma cyclodextrin.
6. The method according to claim 1, wherein the step S3 is to prepare polymer-coated fibers, specifically, the benzylated cyclodextrin and the double cross-linking agent in the step S2 are dissolved in anhydrous 1, 2-dichloroethane solvent under anhydrous and anaerobic conditions; adding the phenyl-derived glass fiber and the anhydrous aluminum chloride serving as a catalyst in the step S1 into the system, and enabling the system to react for a set period of time at 80 ℃; after the reaction is carried out for a set period of time, water and methanol are used for cleaning once respectively, and then methanol is used for Soxhlet extraction; finally, vacuum drying is carried out to obtain the alpha, beta or gamma cyclodextrin crosslinked porous polymer coating fiber respectively.
7. The preparation method according to claim 6, wherein the step S3 specifically comprises the following steps:
s31, taking one of the benzylated alpha, beta or gamma cyclodextrin prepared in the step S2, and dissolving the benzylated alpha, beta or gamma cyclodextrin and a double cross-linking agent prepared by biphenyl dichlorobenzyl and 1,4 dichlorobenzyl in advance in an anhydrous and anaerobic condition in an anhydrous 1, 2-dichloroethane solvent;
s32, adding the phenyl-derived glass fiber prepared in the step S1 and anhydrous aluminum chloride serving as a catalyst, entering the system, enabling the system to react for 12 hours at 80 ℃, and enabling the double cross-linking agent consisting of benzyl alpha, beta or gamma cyclodextrin and biphenyl dichlorobenzyl and 1,4 dichlorobenzyl to carry out cross-linking polymerization reaction on the phenyl-derived glass fiber through nucleophilic substitution;
s33, after the reaction is finished for a set period of time, washing the reaction product with water and methanol once respectively, and then extracting the reaction product with methanol soxhlet 24 h;
s34, finally, carrying out vacuum drying to obtain cyclodextrin crosslinked porous polymer coating fibers;
the double cross-linking agent in the steps S31 and S32 is a mixture of biphenyl dichlorobenzene and 1,4 dichlorobenzene with the mass ratio of 1:0.2-0.25.
8. The method of claim 7, wherein the molar ratio of one of the benzylated α, β or γ cyclodextrins, biphenyl dichlorobenzyl, 1,4 dichlorobenzyl to anhydrous aluminum chloride in step S32 is 20:66:22:500.
9. A polymer coated fiber prepared according to the method of any one of claims 1-8, which is one of an alpha cyclodextrin crosslinked porous polymer coated fiber, a beta cyclodextrin crosslinked porous polymer coated fiber, or a gamma cyclodextrin crosslinked porous polymer coated fiber.
10. Use of the polymer-coated fiber of claim 9 for solid phase microextraction detection of trace amounts of polycyclic aromatic hydrocarbons in water samples.
11. The use according to claim 10, wherein the polymer-coated fiber is used for in-tube solid-phase microextraction detection of trace amounts of polycyclic aromatic hydrocarbon contaminants in water samples.
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| CN107158748A (en) * | 2017-05-08 | 2017-09-15 | 武汉大学 | A kind of open tubular capillary column and its application based on braiding aromatic ring polymer |
| CN111175422A (en) * | 2020-03-30 | 2020-05-19 | 南通市疾病预防控制中心 | Cyclodextrin polymer for polycyclic aromatic hydrocarbon solid phase extraction, solid phase extraction column and solid phase extraction method thereof |
| CN112646058A (en) * | 2019-10-11 | 2021-04-13 | 南京大学 | Amphiphilic porous cyclodextrin polymer |
| CN113960220A (en) * | 2021-12-15 | 2022-01-21 | 生态环境部华南环境科学研究所 | Synchronous detection method and application of polycyclic aromatic hydrocarbon and derivatives thereof in blood |
| CN114989688A (en) * | 2022-05-30 | 2022-09-02 | 广东省科学院测试分析研究所(中国广州分析测试中心) | Cyclodextrin porous polymer material solid phase micro-extraction probe and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107158748A (en) * | 2017-05-08 | 2017-09-15 | 武汉大学 | A kind of open tubular capillary column and its application based on braiding aromatic ring polymer |
| CN112646058A (en) * | 2019-10-11 | 2021-04-13 | 南京大学 | Amphiphilic porous cyclodextrin polymer |
| CN111175422A (en) * | 2020-03-30 | 2020-05-19 | 南通市疾病预防控制中心 | Cyclodextrin polymer for polycyclic aromatic hydrocarbon solid phase extraction, solid phase extraction column and solid phase extraction method thereof |
| CN113960220A (en) * | 2021-12-15 | 2022-01-21 | 生态环境部华南环境科学研究所 | Synchronous detection method and application of polycyclic aromatic hydrocarbon and derivatives thereof in blood |
| CN114989688A (en) * | 2022-05-30 | 2022-09-02 | 广东省科学院测试分析研究所(中国广州分析测试中心) | Cyclodextrin porous polymer material solid phase micro-extraction probe and preparation method and application thereof |
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