CN112934200A - Supermolecule imprinting solid-phase microextraction fiber coating, and preparation method and application thereof - Google Patents
Supermolecule imprinting solid-phase microextraction fiber coating, and preparation method and application thereof Download PDFInfo
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- CN112934200A CN112934200A CN202110154112.2A CN202110154112A CN112934200A CN 112934200 A CN112934200 A CN 112934200A CN 202110154112 A CN202110154112 A CN 202110154112A CN 112934200 A CN112934200 A CN 112934200A
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- phase microextraction
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- tetracycline
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- 238000000576 coating method Methods 0.000 title claims abstract description 102
- 239000011248 coating agent Substances 0.000 title claims abstract description 95
- 239000000835 fiber Substances 0.000 title claims abstract description 93
- 238000002470 solid-phase micro-extraction Methods 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 25
- 229940072172 tetracycline antibiotic Drugs 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000004458 analytical method Methods 0.000 claims abstract description 6
- 239000003999 initiator Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 52
- 239000011521 glass Substances 0.000 claims description 46
- 239000004098 Tetracycline Substances 0.000 claims description 43
- 229960002180 tetracycline Drugs 0.000 claims description 43
- 235000019364 tetracycline Nutrition 0.000 claims description 43
- 229930101283 tetracycline Natural products 0.000 claims description 43
- 150000003522 tetracyclines Chemical class 0.000 claims description 43
- 238000000605 extraction Methods 0.000 claims description 39
- 239000011259 mixed solution Substances 0.000 claims description 31
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 14
- 239000011780 sodium chloride Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- SVWLIIFHXFGESG-UHFFFAOYSA-N formic acid;methanol Chemical compound OC.OC=O SVWLIIFHXFGESG-UHFFFAOYSA-N 0.000 claims description 9
- ROHTVIURAJBDES-UHFFFAOYSA-N 2-n,2-n-bis(prop-2-enyl)-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N(CC=C)CC=C)=N1 ROHTVIURAJBDES-UHFFFAOYSA-N 0.000 claims description 8
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 8
- 230000003213 activating effect Effects 0.000 claims description 8
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 7
- 235000019253 formic acid Nutrition 0.000 claims description 7
- 239000012491 analyte Substances 0.000 claims description 6
- 239000003480 eluent Substances 0.000 claims description 6
- WWECJGLXBSQKRF-UHFFFAOYSA-N n,n-dimethylformamide;methanol Chemical compound OC.CN(C)C=O WWECJGLXBSQKRF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- SGKRLCUYIXIAHR-AKNGSSGZSA-N (4s,4ar,5s,5ar,6r,12ar)-4-(dimethylamino)-1,5,10,11,12a-pentahydroxy-6-methyl-3,12-dioxo-4a,5,5a,6-tetrahydro-4h-tetracene-2-carboxamide Chemical compound C1=CC=C2[C@H](C)[C@@H]([C@H](O)[C@@H]3[C@](C(O)=C(C(N)=O)C(=O)[C@H]3N(C)C)(O)C3=O)C3=C(O)C2=C1O SGKRLCUYIXIAHR-AKNGSSGZSA-N 0.000 claims description 5
- 239000004099 Chlortetracycline Substances 0.000 claims description 5
- 239000004100 Oxytetracycline Substances 0.000 claims description 5
- CYDMQBQPVICBEU-UHFFFAOYSA-N chlorotetracycline Natural products C1=CC(Cl)=C2C(O)(C)C3CC4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O CYDMQBQPVICBEU-UHFFFAOYSA-N 0.000 claims description 5
- 229960004475 chlortetracycline Drugs 0.000 claims description 5
- CYDMQBQPVICBEU-XRNKAMNCSA-N chlortetracycline Chemical compound C1=CC(Cl)=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O CYDMQBQPVICBEU-XRNKAMNCSA-N 0.000 claims description 5
- 235000019365 chlortetracycline Nutrition 0.000 claims description 5
- 229960003722 doxycycline Drugs 0.000 claims description 5
- BUTPBERGMJVRBM-UHFFFAOYSA-N methanol;methylsulfinylmethane Chemical compound OC.CS(C)=O BUTPBERGMJVRBM-UHFFFAOYSA-N 0.000 claims description 5
- 229960000625 oxytetracycline Drugs 0.000 claims description 5
- IWVCMVBTMGNXQD-PXOLEDIWSA-N oxytetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3[C@H](O)[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-PXOLEDIWSA-N 0.000 claims description 5
- 235000019366 oxytetracycline Nutrition 0.000 claims description 5
- IWVCMVBTMGNXQD-UHFFFAOYSA-N terramycin dehydrate Natural products C1=CC=C2C(O)(C)C3C(O)C4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-UHFFFAOYSA-N 0.000 claims description 5
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 3
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 3
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012984 antibiotic solution Substances 0.000 claims description 2
- 238000006392 deoxygenation reaction Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 abstract description 24
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- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 3
- 241000282412 Homo Species 0.000 description 2
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- XBJFCYDKBDVADW-UHFFFAOYSA-N acetonitrile;formic acid Chemical group CC#N.OC=O XBJFCYDKBDVADW-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
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- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
-
- 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
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
-
- 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
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to the technical field of chemical analysis and detection and sample pretreatment, and particularly discloses a supermolecular imprinting solid-phase microextraction fiber coating, and a preparation method and application thereof. The invention uses tetracycline antibiotics as template molecules to react with functional monomers to prepare the supermolecular imprinting solid-phase microextraction fiber coating with multiple hydrogen bond effects; the specific adsorption capacity can be improved due to the existence of such multiple acting forces. Firstly, obtaining a complex of a template molecule based on a DAD-ADA (triple hydrogen bond association mode) triple hydrogen bond and a functional monomer through pre-assembly; polymerization is then initiated by heating in a water bath in the presence of a crosslinking agent and an initiator. And obtaining a fiber coating after the polymerization reaction is finished, and intercepting the fiber coating to a proper length to obtain the supermolecular imprinting solid-phase microextraction fiber coating with multiple hydrogen bonds. The fiber coating prepared by the invention can be applied to adsorption separation and enrichment of tetracycline antibiotics.
Description
Technical Field
The invention relates to the technical field of chemical analysis and detection and sample pretreatment, in particular to a supermolecular imprinting solid-phase microextraction fiber coating, a preparation method and application thereof.
Background
Due to the potential accumulation and mobility of pollutants, environmental pollutants in water quality samples and various complex samples can be gradually accumulated through a biological chain, and finally harm human health, and rapid trace analysis and effective removal of target analytes from low concentration are a key point of environmental toxicological research.
Tetracycline antibiotics (TCs) are multifunctional, broad-spectrum antimicrobial antibiotics that have been widely used for the treatment of various non-viral infections because they not only kill bacteria but also have excellent inhibitory and bactericidal effects against other pathogenic microorganisms. Common tetracycline antibiotics include tetracycline, oxytetracycline, chlortetracycline, doxycycline and the like. In addition to its wide application in aquaculture, tetracycline antibiotics are widely used in the treatment of human diseases and as pharmaceutical additives for preventing intestinal infections and promoting growth in animals. Unfortunately, the frequent use of tetracycline for the prevention and treatment of infections in animals results in elevated levels of antibiotic residues in the water, which residues can be transferred to humans through the food chain and pose a health hazard to humans, including tooth yellowing, allergic reactions, liver damage and even gastrointestinal disorders. Therefore, the need for ultra-sensitive detection of tetracycline antibiotic content has increased dramatically.
At present, there are many methods for measuring tetracycline antibiotic residues in complex matrix samples, but in practical studies, due to the low concentration of target residues, sample pretreatment becomes an indispensable part, and Molecular Imprinted Polymers (MIPs) are widely used due to their specific selectivity. MIPs exist as three-dimensional cavities formed by template molecules, and can form the shape and size of specific analytes or structural analogs, thereby realizing selective separation and enrichment. However, most imprinted polymer cavities for tetracycline antibiotics only have a single interaction force with a target analyte, and have the problems of low sensitivity, small linear range, poor selectivity and the like.
Therefore, how to provide a supramolecular imprinted solid-phase microextraction fiber coating and improve the selectivity and enrichment efficiency of tetracycline antibiotics is a difficult problem to be solved in the field.
Disclosure of Invention
In view of the above, the invention discloses a supramolecular imprinted solid-phase microextraction fiber coating, a preparation method and application thereof, and solves the problems that in the prior art, an imprinted polymer cavity for tetracycline antibiotics has single interaction force with a target analyte, low sensitivity, small linear range, poor selectivity and the like.
In order to achieve the above object, the present invention provides the following technical solutions:
a preparation method of a supermolecular imprinting solid-phase microextraction fiber coating comprises the following specific steps:
(1) dissolving template molecules and functional monomers in a polymerization solvent for preassembly to obtain a preassembly solution, adding a cross-linking agent and an initiator after preassembly is finished, introducing nitrogen into the mixed solution for deoxygenation, injecting the mixed solution into a glass capillary outer sleeve, inserting an active glass capillary inner liner into the glass capillary outer sleeve, and heating through a constant-temperature water bath to initiate polymerization;
(2) after the polymerization reaction is finished, removing the outer sleeve of the glass capillary tube, taking out the active glass capillary tube lining coated with the fiber coating, and then intercepting the fiber coating;
(3) and (3) eluting the template molecules of the fiber coating intercepted in the step (2) by using a methanol-formic acid aqueous solution as an eluting solvent until no template molecules remain in the eluent, thus obtaining the supermolecular imprinting solid-phase microextraction fiber coating.
Preferably, the active glass capillary lining in the step (1) is obtained by activating the glass capillary lining, wherein the activating treatment is to soak the glass capillary lining in 0.1-1mol/L NaOH solution for 2-12h, then soak the glass capillary lining in 0.1-1mol/L HCl solution for 2-5h, and then dry the glass capillary lining at 120 ℃ for 3 h.
Preferably, the template molecule in step (1) is a tetracycline antibiotic, and the tetracycline antibiotic comprises one or more of tetracycline, oxytetracycline, chlortetracycline and doxycycline; the functional monomer is one of 2, 4-diamino-6-diallyl-amino-1, 3, 5-triazine, acrylamide, methacrylic acid and 4-vinyl pyridine; the polymerization solvent is one of dimethyl sulfoxide, a dimethyl sulfoxide-methanol mixed solution, dimethylformamide and a dimethylformamide-methanol mixed solution;
the volume ratio of dimethyl sulfoxide to methanol in the dimethyl sulfoxide-methanol mixed solution is 1: 1;
the volume ratio of the dimethylformamide to the methanol in the dimethylformamide-methanol mixed solution is 1: 1.
Preferably, the cross-linking agent in the step (1) is one of ethylene glycol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate and pentaerythritol tetraacrylate; the initiator in the step (1) is azobisisobutyronitrile.
Preferably, the molar ratio of the template molecule, the functional monomer and the cross-linking agent is 1:4: 15.
Preferably, the preassembly time in the step (1) is 7-9 h; the heating time of the thermostatic waterbath is 23-25 h.
Preferably, in the step (3), the methanol-formic acid aqueous solution is formed by mixing methanol and formic acid aqueous solution, wherein the volume ratio of the methanol to the formic acid aqueous solution is 9:1, and the volume fraction of the formic acid aqueous solution is 0.1%.
Another object of the present invention is to provide a coating layer of supramolecular imprinted solid-phase microextraction fibers prepared by the above method.
The invention further aims to provide an application of the supermolecular imprinting solid-phase microextraction fiber coating prepared by the method in detection of tetracycline antibiotic content.
Preferably, the specific steps are as follows:
placing tetracycline antibiotic solution in extraction flask, adjusting pH to 2-12, NaCl content in the solution to 0-25%, and performing supramolecular imprinting to obtain solid phaseExtracting the micro-extraction fiber coating for 110-130min at normal temperature and at the rotating speed of 500-600 r/min; detecting the concentration of tetracycline in the solution by high performance liquid chromatography, and determining the concentration of tetracycline in the solution by the formula Q ═ V (C)0-C) calculating the extracted amount;
wherein: q-the amount of extracted analyte by the fiber coating, μ g;
C0-concentration of the solution before extraction, mg/L;
c-concentration of the extracted solution, mg/L;
v-volume of sample injection analysis, μ L.
According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:
(1) the invention adopts tetracycline antibiotics as template molecules, can form DAD-ADA triple hydrogen bond interaction with functional monomers, and prepares the supermolecular imprinting solid-phase microextraction fiber coating based on multiple hydrogen bonds through polymerization reaction.
(2) The supermolecule imprinting solid-phase microextraction fiber coating prepared by the invention has specific adsorption and enrichment capacity and good adsorption performance on tetracycline antibiotics. Compared with the commercial fiber coating, the coating has remarkable advantages.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a diagram showing the influence of different polymerization solvents on the extraction performance of a coating of a supramolecular imprinted solid-phase microextraction fiber;
FIG. 2 accompanying drawings are different template molecules: functional monomer: influence of the molar ratio of the cross-linking agent on the extraction performance of the coating of the supermolecular imprinting solid-phase microextraction fiber;
FIG. 3 is a graph showing the effect of different cross-linking agents on the extraction performance of a coating of a supramolecular imprinted solid-phase microextraction fiber;
FIG. 4 is a graph showing the effect of different functional monomers on the extraction performance of a coating of a supramolecular imprinted solid-phase microextraction fiber;
FIG. 5 is a graph showing the effect of a coating of supramolecular imprinted solid phase microextraction fibers on the amount of tetracycline extracted at different pH values;
FIG. 6 is a graph showing the effect of the coating of supramolecular imprinted solid phase microextraction fibers on the extraction amount of tetracycline under different NaCl mass fractions;
FIG. 7 is a chromatogram of tetracycline extracted from a supramolecular imprinted solid-phase microextraction fiber coating and two commercial fiber coatings respectively;
FIG. 8 is a drawing showing that 4 tetracycline antibiotics are adsorbed by the coating of supramolecular imprinted solid-phase microextraction fiber.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The activation treatment of the glass capillary lining comprises the steps of firstly soaking the glass capillary lining in 0.1-1mol/L NaOH solution for 2-12h, then soaking in 0.1-1mol/L HCl solution for 2-5h, and then drying at 120 ℃ for 3 h.
For the convenience of the experiment, the preparation method of the activated glass capillary liner adopted in the following examples is as follows: firstly, soaking a glass capillary lining in 0.5mol/L NaOH solution for 10h, then soaking in 0.5mol/L HCl solution for 4h, and then drying at 120 ℃ for 3 h. (particularly, the activated glass capillary lining prepared by the preparation method of the activated glass capillary lining disclosed by the invention can meet the requirements of the technical scheme of the invention)
Example 1: the preparation method of the supermolecular imprinting solid-phase microextraction fiber coating under different polymerization solvents comprises the following specific steps:
(1) activating a lining of a sintered glass capillary tube of 0.9cm for later use, and meanwhile preparing a sintered glass capillary tube of 1.8cm as an outer sleeve; dissolving 1mmol of template molecule tetracycline in 15mL of polymerization solvent, wherein the polymerization solvent is dimethyl sulfoxide, a dimethyl sulfoxide-methanol mixed solution, dimethylformamide and a dimethylformamide-methanol mixed solution respectively; then adding 4mmol of functional monomer 2, 4-diamino-6-diallyl-amino-1, 3, 5-triazine, uniformly mixing, and pre-assembling for 9h to obtain a pre-assembled solution. Adding 8mmol of trimethylolpropane triacrylate and 20mg of azobisisobutyronitrile into the pre-assembled mixed solution, ultrasonically dissolving and uniformly mixing to obtain a mixed solution; and introducing nitrogen into the mixed solution to remove oxygen, injecting the mixed solution into a glass capillary outer sleeve by using an injector, inserting a capillary inner liner, and wrapping the pores between the capillary inner liner and the outer sleeve by using a raw adhesive tape. Heating in constant temperature water bath for 23h to initiate polymerization reaction;
(2) after the polymerization reaction is finished, removing the outer sleeve of the glass capillary tube, taking out the inner lining of the glass capillary tube coated with the coating, and then cutting the length of the coating to be 1.8cm to obtain the required fiber coating;
(3) and (3) removing the template molecules in the fiber coating intercepted in the step (2) by using a methanol-formic acid aqueous solution as an elution solvent until no chromatographic peak of the template molecules is detected in the eluent, thus preparing the supermolecule imprinted solid-phase microextraction fiber coating with the specific recognition cavity.
The multi-hydrogen bond molecular imprinting and non-molecular imprinting solid-phase microextraction fiber coatings prepared in the embodiment are respectively used for extracting tetracycline, the chromatographic conditions are that a J & K Scientific LTD C18 column is adopted, the mobile phase is acetonitrile-formic acid aqueous solution which is 20:80(v/v), wherein the volume fraction of the formic acid aqueous solution is 0.1%, the column temperature is 25 ℃, the flow rate is 1.0mL/min, and the detection wavelength is 355 nm.
Extraction conditions are as follows: the extraction solvent is purified water, the volume of the extraction solution is 50mL, the concentration is 1mg/L, the extraction time is 120min, the elution solution is methanol-formic acid aqueous solution, the desorption time is 5min, the volume of the desorption solution is 200 mu L, the desorption mode is ultrasonic desorption, the high performance liquid chromatography is used for analysis, and the sample injection volume is 20 mu L.
As can be seen from fig. 1, when the polymerization solvent is a mixed solution of dimethyl sulfoxide and dimethylformamide-methanol, the response signal intensity of the prepared solid-phase microextraction fiber coating for extracting tetracycline is equivalent, and the corresponding signal ratio of the molecularly imprinted polymer fiber coating (MIP) to the non-molecularly imprinted fiber coating (NIP) is 1.95 and 1.72 respectively, so that the optimal polymerization solvent is dimethyl sulfoxide.
Example 2: the preparation method of the multiple hydrogen bond supramolecular imprinted solid-phase microextraction fiber coating in the embodiment comprises the following specific steps:
(1) activating a lining of a sintered glass capillary tube of 1.1cm for later use, and preparing a sintered glass capillary tube of 2.2cm as an outer sleeve; dissolving 1mmol of template molecule tetracycline in 15mL of dimethyl sulfoxide, adding 4mmol of functional monomer 2, 4-diamino-6-diallylamino-1, 3, 5-triazine, uniformly mixing, and pre-assembling for 7h to obtain a pre-assembled solution. Then adding 20mg of azodiisobutyronitrile into the pre-assembled mixed solution, adjusting the adding amount of trimethylolpropane triacrylate to be 8mmol, 10mmol, 15mmol and 20mmol respectively, and performing ultrasonic dissolution and uniform mixing to obtain a mixed solution; and introducing nitrogen into the mixed solution to remove oxygen, injecting the mixed solution into a glass capillary outer sleeve by using an injector, inserting a capillary inner liner, and wrapping the pores between the capillary inner liner and the outer sleeve by using a raw adhesive tape. Heating in a constant-temperature water bath for 25h to initiate polymerization reaction;
(2) after the polymerization reaction is finished, removing the outer sleeve of the glass capillary tube, taking out the inner lining of the glass capillary tube coated with the coating, and then cutting the length of the coating to be 1.8cm to obtain the required fiber coating;
(3) and (3) removing the template molecules in the fiber coating intercepted in the step (2) by using a methanol-formic acid aqueous solution as an elution solvent until no chromatographic peak of the template molecules is detected in the eluent, thus preparing the supermolecule imprinted solid-phase microextraction fiber coating with the specific recognition cavity.
The multiple hydrogen bond supramolecular imprinting and non-molecularly imprinted solid-phase microextraction fiber coatings prepared in the embodiment are adopted to respectively extract tetracycline, and the chromatographic conditions and the extraction conditions are the same as those in the embodiment 1.
The results are shown in FIG. 2 when the template molecule: functional monomer: when the molar ratio of the cross-linking agent is 1:4:15, the extraction response signal of the supermolecular imprinting solid-phase microextraction fiber coating with multiple hydrogen bonds to tetracycline is moderate, the ratio of the supermolecular imprinting solid-phase microextraction fiber coating to the non-molecularly imprinting solid-phase microextraction fiber coating is 1.67, and the optimal template molecule: functional monomer: the molar ratio of the cross-linking agent is 1:4: 15.
Example 3: the preparation method of the supermolecular imprinting solid-phase microextraction fiber coating under different cross-linking agent conditions comprises the following specific steps:
(1) activating a lining of a sintered glass capillary tube of 1.0cm for later use, and meanwhile preparing a sintered glass capillary tube of 2.0cm as an outer sleeve; dissolving 1mmol of template molecule tetracycline in 15mL of dimethyl sulfoxide, adding 4mmol of functional monomer 2, 4-diamino-6-diallylamino-1, 3, 5-triazine, uniformly mixing, and pre-assembling for 8h to obtain a pre-assembled solution. And then adding 20mg of azodiisobutyronitrile and 15mmol of cross-linking agents into the pre-assembled mixed solution, wherein the cross-linking agents are ethylene glycol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate and pentaerythritol tetraacrylate respectively. Ultrasonically dissolving and uniformly mixing to obtain a mixed solution; and introducing nitrogen into the mixed solution to remove oxygen, injecting the mixed solution into a glass capillary outer sleeve by using an injector, inserting a capillary inner liner, and wrapping the pores between the capillary inner liner and the outer sleeve by using a raw adhesive tape. Heating in constant temperature water bath for 24h to initiate polymerization reaction;
(2) after the polymerization reaction is finished, removing the outer sleeve of the glass capillary tube, taking out the inner lining of the glass capillary tube coated with the coating, and then cutting the length of the coating to be 1.8cm to obtain the required fiber coating;
(3) and (3) removing the template molecules in the fiber coating intercepted in the step (2) by using a methanol-formic acid aqueous solution as an elution solvent until no chromatographic peak of the template molecules is detected in the eluent, thus preparing the supermolecule imprinted solid-phase microextraction fiber coating with the specific recognition cavity.
The multiple hydrogen bond molecular imprinting and non-molecular imprinting solid-phase microextraction fiber coatings prepared in the embodiment are adopted to respectively extract tetracycline, and the chromatographic conditions and the extraction conditions are the same as those in the embodiment 1.
As shown in FIG. 3, when the crosslinking agent is trimethylolpropane triacrylate, the extraction response signal of the multi-hydrogen bond supramolecular imprinted solid-phase microextraction fiber coating to tetracycline is strongest, and the optimal crosslinking agent is trimethylolpropane triacrylate.
Example 4: the preparation method of the multiple hydrogen bond supramolecular imprinted solid-phase microextraction fiber coating under different functional monomer conditions comprises the following specific steps:
(1) activating a lining of a sintered glass capillary tube of 1.1cm for later use, and preparing a sintered glass capillary tube of 2.0cm as an outer sleeve; dissolving 1mmol of template molecule tetracycline in 15mL of dimethyl sulfoxide, adding 4mmol of functional monomers, wherein the selected functional monomers are 2, 4-diamino-6-diallylamino-1, 3, 5-triazine (NDAM), Acrylamide (AM), methacrylic acid (MAA) and 4-vinylpyridine (4-VP) respectively, uniformly mixing, and pre-assembling for 8 hours to obtain a pre-assembled solution. Then adding 15mmol of trimethylolpropane triacrylate and 20mg of azobisisobutyronitrile into the pre-assembled mixed solution, ultrasonically dissolving and uniformly mixing to obtain a mixed solution; and introducing nitrogen into the mixed solution to remove oxygen, injecting the mixed solution into a glass capillary outer sleeve by using an injector, inserting a capillary inner liner, and wrapping the pores between the capillary inner liner and the outer sleeve by using a raw adhesive tape. Heating in constant temperature water bath for 24h to initiate polymerization reaction;
(2) after the polymerization reaction is finished, removing the outer sleeve of the glass capillary tube, taking out the inner lining of the glass capillary tube coated with the coating, and then cutting the length of the coating to be 1.8cm to obtain the required fiber coating;
(3) and (3) removing the template molecules in the fiber coating intercepted in the step (2) by using a methanol-formic acid aqueous solution as an elution solvent until no chromatographic peak of the template molecules is detected in the eluent, thus preparing the supermolecule imprinted solid-phase microextraction fiber coating with the specific recognition cavity.
The multiple hydrogen bond molecular imprinting and non-molecular imprinting solid-phase microextraction fiber coatings prepared in the embodiment are adopted to respectively extract tetracycline, and the chromatographic conditions and the extraction conditions are the same as those in the embodiment 1.
As shown in FIG. 4, when the functional monomer is 2, 4-diamino-6-diallylamino-1, 3, 5-triazine, the multiple hydrogen bond supramolecular imprinted solid phase microextraction fiber coating has the strongest extraction response signal to tetracycline due to the existence of a plurality of interaction sites with the template molecule tetracycline, and the optimal functional monomer is 2, 4-diamino-6-diallylamino-1, 3, 5-triazine.
Example 5: the application of the multi-hydrogen bond supermolecule imprinting solid-phase micro-extraction fiber coating in the extraction of tetracycline comprises the following specific steps:
50mL of tetracycline solution with the concentration of 1mg/L is placed in a 60mL extraction bottle, the pH value of the solution is adjusted to 2-12, the mass fraction of NaCl in the solution is 0-25%, the multi-hydrogen bond supramolecular imprinted solid-phase micro-extraction fiber coating prepared under the preferable conditions in the embodiment 4 is adopted, the rotating speed is 500-600r/min at normal temperature, and the extraction is 110-130 min. The concentration of tetracycline in the solution was measured by high performance liquid chromatography and the amount extracted was calculated by the formula (a).
Q＝V(C0-C) (a)
Q-the amount of extracted analyte by the fiber coating, μ g;
C0-concentration of the solution before extraction, mg/L;
c-concentration of the extracted solution, mg/L;
v-volume of sample injection analysis, μ L.
(1) Effect of pH on Tetracycline extractables
The method comprises the following steps: 50mL of tetracycline solution with the concentration of 1mg/L is placed in a 60mL extraction flask, the pH values of the solutions are adjusted to be 2,4, 6, 7, 8, 10 and 12 respectively, the multiple hydrogen bond supramolecular imprinted solid-phase microextraction fiber coating prepared under the optimized conditions in the example 4 is adopted, and the rotation speed is 500r/min at normal temperature and the extraction time is 110 min. And detecting the concentration of the tetracycline in the solution by high performance liquid chromatography, and calculating the extraction amount of the tetracycline. The results are shown in FIG. 5.
As can be seen from fig. 5, with the increase of the pH value, the extraction amount of the multi-hydrogen bond supramolecular imprinted solid-phase microextraction fiber coating to tetracycline increases first and then reaches equilibrium, and after the pH value is 7, the extraction amount to tetracycline reaches an extreme value and then reaches equilibrium.
(2) Effect of NaCl Mass fraction on Tetracycline extract
The method comprises the following steps: 50mL of tetracycline solution with the concentration of 1mg/L is placed in a 60mL extraction flask, the mass fractions of NaCl in the solution are adjusted to be 0, 5%, 10%, 15%, 20% and 25%, respectively, and the multiple hydrogen bond supramolecular imprinted solid-phase microextraction fiber coating prepared under the preferable conditions in example 4 is adopted, wherein the pH value of the solution is 7 at normal temperature, the rotation speed is 500r/min, and the extraction is carried out for 130 min. And detecting the concentration of the tetracycline in the solution by high performance liquid chromatography, and calculating the extraction amount of the tetracycline. The results are shown in FIG. 6.
As can be seen from fig. 6, as the mass fraction of NaCl increases, the extraction amount of tetracycline by the multi-hydrogen bond supramolecular imprinted solid-phase microextraction fiber coating increases, and when the mass fraction of NaCl is 25%, the NaCl solution tends to be saturated, and at this time, the extraction amount of tetracycline is the largest, and preferably the mass fraction of NaCl is 25%.
(3) Compared with the adsorption performance of the commercial fiber coating
Placing 50mL of tetracycline solution with the concentration of 1mg/L into a 60mL extraction flask, and respectively using the prepared supermolecular imprinting solid-phase microextraction fiber coating and the prepared commercialized fiber coating, and using two commercialized coatings of Polyacrylate (PA) and polydimethylsiloxane/divinylbenzene (PDMS/DVB); in the extraction experiment, at normal temperature, the pH value of the solution is 7, the NaCl mass fraction of the solution is 25%, the rotating speed is 500r/min, and the extraction is carried out for 120 min. The tetracycline adsorbed by the fiber coating was detected by high performance liquid chromatography. The results are shown in FIG. 7.
As can be seen from FIG. 7, neither of the two commercial fiber coatings used can enrich tetracycline from aqueous media, which means that the multiple hydrogen bond supramolecular imprinted solid-phase microextraction fiber coating prepared by the invention has excellent specific adsorption and enrichment capacity for tetracycline antibiotics.
Example 6: the method for extracting 4 tetracycline antibiotics from the multi-hydrogen bond supermolecule imprinting solid-phase micro-extraction fiber coating comprises the following steps:
the influence of the pH value and the NaCl mass fraction on the amounts of oxytetracycline, chlortetracycline and doxycycline extracted were determined as described in example 5, and a conclusion consistent with that of reference 5 was drawn.
50mL of tetracycline, oxytetracycline, chlortetracycline and doxycycline solutions with the concentration of 1mg/L are respectively placed in 60mL extraction bottles, and the multiple hydrogen bond supermolecule imprinted solid-phase microextraction fiber coating prepared under the preferable conditions in example 4 and the corresponding non-molecularly imprinted solid-phase microextraction fiber coating are adopted, wherein the pH value of the solution is 7 at normal temperature, the mass fraction of NaCl in the solution is 25%, the rotating speed is 600r/min, and the extraction is carried out for 120 min. The concentration of each analyte in the solution was measured by high performance liquid chromatography and the amount of extraction was calculated. The results are shown in FIG. 8.
As can be seen from FIG. 8, the supramolecular imprinted solid-phase microextraction fiber coating prepared by the invention has selective recognition performance on tetracycline antibiotics.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
Claims (10)
1. A preparation method of a supermolecular imprinting solid-phase microextraction fiber coating is characterized by comprising the following specific steps:
(1) dissolving template molecules and functional monomers in a polymerization solvent for preassembly to obtain a preassembly solution, adding a cross-linking agent and an initiator after preassembly is finished, introducing nitrogen into the mixed solution for deoxygenation, injecting the mixed solution into a glass capillary outer sleeve, inserting an active glass capillary inner liner into the glass capillary outer sleeve, and heating through a constant-temperature water bath to initiate polymerization;
(2) after the polymerization reaction is finished, removing the outer sleeve of the glass capillary tube, taking out the active glass capillary tube lining coated with the fiber coating, and then intercepting the fiber coating;
(3) and (3) eluting the template molecules of the fiber coating intercepted in the step (2) by using a methanol-formic acid aqueous solution as an eluting solvent until no template molecules remain in the eluent, thus obtaining the supermolecular imprinting solid-phase microextraction fiber coating.
2. The method for preparing the coating of the supramolecular imprinted solid-phase microextraction fiber according to claim 1, wherein the method comprises the following steps: the active glass capillary lining in the step (1) is obtained by activating the glass capillary lining, wherein the activating treatment is to soak the glass capillary lining in 0.1-1mol/L NaOH solution for 2-12h, then soak the glass capillary lining in 0.1-1mol/L HCl solution for 2-5h, and then dry the glass capillary lining at 120 ℃ for 3 h.
3. The method for preparing the coating of the supramolecular imprinted solid-phase microextraction fiber according to claim 1, wherein the method comprises the following steps: the template molecule in the step (1) is tetracycline antibiotics, and the tetracycline antibiotics comprise one or more of tetracycline, oxytetracycline, chlortetracycline and doxycycline;
the functional monomer is one of 2, 4-diamino-6-diallyl-amino-1, 3, 5-triazine, acrylamide, methacrylic acid and 4-vinyl pyridine;
the polymerization solvent is one of dimethyl sulfoxide, a dimethyl sulfoxide-methanol mixed solution, dimethylformamide and a dimethylformamide-methanol mixed solution;
the volume ratio of dimethyl sulfoxide to methanol in the dimethyl sulfoxide-methanol mixed solution is 1: 1;
the volume ratio of the dimethylformamide to the methanol in the dimethylformamide-methanol mixed solution is 1: 1.
4. The method for preparing the coating of the supramolecular imprinted solid-phase microextraction fiber according to claim 1, wherein the method comprises the following steps: the cross-linking agent in the step (1) is one of ethylene glycol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate and pentaerythritol tetraacrylate; the initiator in the step (1) is azobisisobutyronitrile.
5. The method for preparing the coating of the supramolecular imprinted solid-phase microextraction fiber according to claim 1, wherein the molar ratio of the template molecule, the functional monomer and the crosslinking agent is 1:4: 15.
6. The method for preparing the coating of the supramolecular imprinted solid-phase microextraction fiber according to claim 1, wherein the method comprises the following steps: the preassembly time in the step (1) is 7-9 h; the heating time of the thermostatic waterbath is 23-25 h.
7. The method for preparing the coating of the supramolecular imprinted solid-phase microextraction fiber according to claim 1, wherein the method comprises the following steps: the methanol-formic acid aqueous solution in the step (3) is formed by mixing methanol and a formic acid aqueous solution, wherein the volume ratio of the methanol to the formic acid aqueous solution is 9:1, and the volume fraction of the formic acid aqueous solution is 0.1%.
8. The coating of supramolecular imprinted solid-phase microextraction fiber prepared by the preparation method of claim 1.
9. The application of the supramolecular imprinted solid-phase microextraction fiber coating prepared by the preparation method of claim 1 in detecting the content of tetracycline antibiotics.
10. The application of the coating of the supramolecular imprinted solid-phase microextraction fiber according to claim 9 is characterized by comprising the following specific steps:
placing the tetracycline antibiotic solution in an extraction bottle, adjusting the pH value of the solution to 2-12, adjusting the mass fraction of NaCl in the solution to 0-25%, and then adopting a supermolecule imprinting solid phase micro-extraction fiber coating at the normal temperature and the rotating speed of 500-n, extracting for 110-130 min; detecting the concentration of tetracycline in the solution by high performance liquid chromatography, and determining the concentration of tetracycline in the solution by the formula Q ═ V (C)0-C) calculating the extracted amount;
wherein: q-the amount of extracted analyte by the fiber coating, μ g;
C0-concentration of the solution before extraction, mg/L;
c-concentration of the extracted solution, mg/L;
v-volume of sample injection analysis, μ L.
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