CN103357391A - Ionic liquid sol-gel coating stirring rod, preparation method and applications - Google Patents
Ionic liquid sol-gel coating stirring rod, preparation method and applications Download PDFInfo
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- CN103357391A CN103357391A CN2013103296722A CN201310329672A CN103357391A CN 103357391 A CN103357391 A CN 103357391A CN 2013103296722 A CN2013103296722 A CN 2013103296722A CN 201310329672 A CN201310329672 A CN 201310329672A CN 103357391 A CN103357391 A CN 103357391A
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- 238000003756 stirring Methods 0.000 title claims abstract description 75
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 54
- 238000000576 coating method Methods 0.000 title claims abstract description 51
- 239000011248 coating agent Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 238000000605 extraction Methods 0.000 claims abstract description 43
- 239000011521 glass Substances 0.000 claims abstract description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- -1 Tetrafluoroborate Chemical compound 0.000 claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000004458 analytical method Methods 0.000 claims abstract description 12
- XLXCHZCQTCBUOX-UHFFFAOYSA-N 1-prop-2-enylimidazole Chemical compound C=CCN1C=CN=C1 XLXCHZCQTCBUOX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000002431 foraging effect Effects 0.000 claims abstract 2
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- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 11
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 11
- 230000004913 activation Effects 0.000 claims description 10
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- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims 1
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- 238000003795 desorption Methods 0.000 description 12
- ZPAKPRAICRBAOD-UHFFFAOYSA-N fenbufen Chemical compound C1=CC(C(=O)CCC(=O)O)=CC=C1C1=CC=CC=C1 ZPAKPRAICRBAOD-UHFFFAOYSA-N 0.000 description 12
- 229960001395 fenbufen Drugs 0.000 description 12
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- CMWTZPSULFXXJA-VIFPVBQESA-M naproxen(1-) Chemical compound C1=C([C@H](C)C([O-])=O)C=CC2=CC(OC)=CC=C21 CMWTZPSULFXXJA-VIFPVBQESA-M 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 238000000092 stir-bar solid-phase extraction Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- DKYWVDODHFEZIM-UHFFFAOYSA-N ketoprofen Chemical compound OC(=O)C(C)C1=CC=CC(C(=O)C=2C=CC=CC=2)=C1 DKYWVDODHFEZIM-UHFFFAOYSA-N 0.000 description 8
- 229960000991 ketoprofen Drugs 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
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- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种离子液体溶胶凝胶涂层搅拌棒及其制备方法与应用，属于分析化学样品前处理技术领域。离子液体溶胶凝胶涂层搅拌棒包括玻璃毛细管、铁芯和萃取涂层，铁芯置于两端熔封的玻璃毛细管内，萃取涂层为化学键合在玻璃毛细管表面的1-烯丙基咪唑四氟硼酸盐离子液体凝胶涂层。通过将用NaOH溶液活化的玻璃搅拌棒浸入离子液体溶胶中进行涂覆，再置于烘箱中老化得到离子液体溶胶凝胶涂层搅拌棒。本发明的离子液体溶胶凝胶涂层搅拌棒可用于极性有机物的萃取分析，具有制备简单、环境友好、萃取效率高、耐高温、耐有机溶剂和机械稳定性好等优点，能实现在环境、食品以及生物样品等样品体系中极性化合物的选择性萃取富集，有实际应用价值。
The invention discloses an ionic liquid sol-gel coated stirring rod, a preparation method and an application thereof, and belongs to the technical field of analytical chemical sample pretreatment. The ionic liquid sol-gel coating stirring rod includes a glass capillary, an iron core and an extraction coating. The iron core is placed in a glass capillary that is fused at both ends, and the extraction coating is 1-allylimidazole chemically bonded on the surface of the glass capillary. Tetrafluoroborate ionic liquid gel coating. The ionic liquid sol-gel coated stirring rod is obtained by immersing the glass stirring rod activated with NaOH solution into the ionic liquid sol for coating, and then placing it in an oven for aging. The ionic liquid sol-gel coated stirring rod of the present invention can be used for the extraction and analysis of polar organic substances, and has the advantages of simple preparation, environmental friendliness, high extraction efficiency, high temperature resistance, organic solvent resistance and good mechanical stability, etc., and can be realized in the environment The selective extraction and enrichment of polar compounds in sample systems such as , food and biological samples has practical application value.
Description
?
Technical field
The invention belongs to analytical chemistry Sample Pretreatment Technique field, relate to a kind of absorbent-type extraction stirring rod, be specifically related to a kind of ion liquid sol gel coat stirring rod and preparation method thereof and application.
Background technology
Stir bar sorptive extraction (SBSE) (Baltussen E., Sandra P., David F., Cramers C. Stir bar sorptive extraction (SBSE), a novel extraction technique for aqueous samples:theory and principles [J]. Journal of Microcolumn Separations, 1999,11 (10): 737-747) as a kind of novel Sample Pretreatment Technique, has microminiaturization, easy and simple to handle, with low cost, the extraction efficiency high, compare with solid phase micro-extraction technique, avoided using and stirred the competitive Adsorption that magneton causes, larger coating volume has strengthened the extracting and enriching ability to target analytes, have higher extraction efficiency, thereby be widely used in environment, in food and the biological sample analysis.Yet the development of stirring rod coating is comparatively slow, using at present more is the nonpolar coating dimethyl silicone polymer (PDMS) of or low pole compound nonpolar for benzene homologues, polycyclic aromatic hydrocarbon etc., thereby the extraction coating that preparation is fit to opposed polarity and has certain mechanical strength and a chemical stability is one of development trend of present SBSE.
Ionic liquid (ionic liquid) be that a class is comprised of organic cation and inorganic/organic anion, near the salt that is in a liquid state under the room temperature condition, have wider liquid temperature scope, good solvability, higher electrical conductivity and wider electrochemical window, the advantageous property such as heat endurance and chemical stability preferably, be called visually " solid-state " liquid (solid liquid) or " liquid " molecular sieve (liquid zeolite) of having liquid and solid property concurrently.Wherein glyoxaline ion liquid because of its to water and air all stablize, the characteristics such as filming performance is good, green safety all are widely used (Maiti A. and Rogers R. D. A correlation-based predictor for pair-association in ionic liquids. Physical Chemistry Chemical Physics. 2011,13 (26): 12138-12145 in synthetic chemistry, functional material, life science and fields such as separating detection; [3] Dupont J., de Souza R. F., et al. Ionic liquid (molten salt) phase organometallic catalysis. Chemical Reviews. 2002,102 (10): 3667-3691; [4] Blanchard L. A., Hancu D., Beckman E. J., et a1. Green processing using ionic liquids and CO2. Nature, 1999,399 (6731): 28-29).Aspect compartment analysis, ionic liquid is as extraction phase (Zhou X., Xie P. F., et al. Preparation and characterization of novel crown ether functionalized ionic liquid-based solid-phase microextraction coatings by sol-gel technology. Journal of Chromatography A. 2011,1218 (23): 3571-3580), strippant (Martin-Calero A., Ayala J. H., et al. Ionic liquids as desorption solvents and memory effect suppressors in heterocyclic aromatic amines determination by SPME-HPLC fluorescence. Analytical and Bioanalytical Chemistry. 2009,394 (4): 937-946) or (Shearrow such as intermediate medium, A. M., G. A. Harris, et al. Ionic liquid-mediated sol-gel coatings for capillary microextraction. Journal of Chromatography A. 2009,1216 (29): 5449-5458) be used for improving extraction or desorption efficiency.Because ionic liquid liquid temperature wide ranges and solvability are good, with the not anti-immersion extraction of the ion liquid abstraction coating of physics coating method preparation and solvent desorption, multiplex in headspace extraction and thermal desorption, detection limit is higher and can not reuse, and certain limitation is arranged.
Summary of the invention
Primary and foremost purpose of the present invention is to provide a kind of 1-allyl imidazole tetrafluoroborate ion liquid sol-gel coating stirring rod, this stirring rod is applicable to the extractive analysis of polar organic matter, has that preparation is simple, advantages such as environmental friendliness, extraction efficiency are high, high temperature resistant, organic solvent-resistant and good mechanical stability.
Another object of the present invention is to provide the preparation method of above-mentioned ion liquid sol gel coat stirring rod, by adopting sol-gal process, take KH-570(γ-methacryloxypropyl trimethoxy silane) ionic liquid that will contain two key groups as bridging agent is bonded in the glass stirring rod surface, to avoid the loss at extraction and desorption process intermediate ion liquid.How the method will have in the ionic liquid introducing stirring rod coating of better extracting power the polarity target analytes if having solved, both ensured higher extraction efficiency, have again preferably heat endurance and chemical stability, and good mechanical stability, reusable technical problem.
A further object of the present invention is to provide the application of above-mentioned ion liquid sol gel coat stirring rod.
Purpose of the present invention is achieved through the following technical solutions:
A kind of ion liquid sol gel coat stirring rod comprises capillary glass tube, iron core and extraction coating, and iron core places in the capillary glass tube of two ends sealing by fusing, and the extraction coating is coated in the capillary glass tube outer surface; Described extraction coating is the ion liquid sol gel coat that is chemically bound in the capillary glass tube surface; Described ionic liquid is preferably 1-allyl imidazole tetrafluoroborate ion liquid.
Described capillary glass tube is preferably dimensioned to be long 2 cm, internal diameter 0.9-1.1 mm, wall thickness 0.10-0.15 mm, and capillary glass tube two ends sealing by fusing forms the dumbbell shape structure; Described iron core is preferably dimensioned to be 1.7 cm, diameter 0.50 mm.
The preparation method of above-mentioned ion liquid sol gel coat stirring rod comprises the steps:
(1) activation of glass stirring rod: the capillary glass tube of establishing iron core and two ends sealing by fusing in inciting somebody to action places NaOH solution to activate, and the capillary glass tube outer surface is rich in-the OH group, cleans dry for standby after the activation.
(2) preparation of ion liquid sol: with CH
2Cl
2(carrene), OH-PDMS(hydroxyl endblocked polydimethylsiloxane), the TEOS(tetraethoxysilane), KH-570(γ-methacryloxypropyl trimethoxy silane), [AIM] [BF4] (1-allyl imidazole tetrafluoroborate), PMHS(polymethyl hydrogen siloxane) and the TFA(trifluoroacetic acid) behind the mixing, ultrasonic processing makes colloidal sol.
(3) preparation of ion liquid sol gel coat stirring rod: the glass stirring rod after will activating immerses in the ion liquid sol and applies, and takes out to be placed in the baking oven and wears out, and obtains ion liquid sol gel coat stirring rod.
The concentration of the sodium hydroxide solution described in the step (1) is preferably 1 mol/L.
The time of the activation described in the step (1) is preferably more than 3 h.
Cleaning described in the step (1) is preferably and uses successively ultra-pure water, 0.1 mol/L HCl(hydrochloric acid), ultra-pure water cleans to neutral.
The preparation of the described ion liquid sol of step (2) is preferably: pipette successively 100 μ L CH
2Cl
2(carrene), 150 μ L OH-PDMS(hydroxyl endblocked polydimethylsiloxanes), 100 μ L TEOS(tetraethoxysilanes), 60 μ L KH-570(γ-methacryloxypropyl trimethoxy silane), 30 μ L [AIM] [BF4] (1-allyl imidazole tetrafluoroborate), 20 μ L PMHS(polymethyl hydrogen siloxanes) and 40 μ L 95%(v/v) the TFA(trifluoroacetic acid), ultrasonic reaction 10 min make colloidal sol behind the vortex mixing.
Aging condition described in the step (3) is preferably 60 ℃ and wore out 3 days.
After preparing ion liquid sol gel coat stirring rod, preferably use again methyl alcohol ultrasonic cleaning 20 min in the step (3).
The course of reaction of preparation ion liquid sol as shown in Figure 1.
The application of above-mentioned ion liquid sol gel coat stirring rod in the extractive analysis of polar organic matter.
The present invention has following advantage and effect:
The present invention will with ionic liquid and the KH-570 chemical bonding of two key function bases, prepare a kind of polar compound and stable ion liquid sol gel coat of coating performance of extracting.Utilize the ion liquid sol gel-coat surface pattern of sol-gal process preparation better, the mode of chemical bonding has strengthened heat endurance and the chemical stability of coating, is applicable to multiple extraction and desorption mode.Imidazole group in the coating can produce hydrophobic, hydrogen bond and π-π effect etc. with polar compound, can be implemented in the selective extraction enrichment of the complex sample system Semi-polarity compounds such as environment, food and biological sample, and actual application value is arranged.Ion liquid sol gel coat stirring rod of the present invention is applicable to the extractive analysis of polar organic matter, has that preparation is simple, advantages such as environmental friendliness, extraction efficiency are high, high temperature resistant, organic solvent-resistant and good mechanical stability.
Description of drawings
Fig. 1 is the course of reaction figure of preparation ion liquid sol.
Fig. 2 is the structural representation of the ion liquid sol gel coat stirring rod of embodiment 1 preparation.
Fig. 3 is the infrared spectrogram of the ion liquid sol gel coat of embodiment 1 preparation, (a) for not containing the sol-gel coating of ionic liquid, (b) for containing the sol-gel coating of ionic liquid.
Fig. 4 is the surface topography map that the ion liquid sol gel coat stirring rod of embodiment 1 preparation characterizes with ESEM.
Fig. 5 is the thermogravimetric phenogram of the ion liquid sol gel coat of embodiment 1 preparation.
Fig. 6 is acid and alkali-resistance, the organic solvent resistance investigation figure of the ion liquid sol gel coat of embodiment 1 preparation.
Fig. 7 is investigation in the service life figure of the ion liquid sol gel coat stirring rod of embodiment 1 preparation.
Fig. 8 is the chromatogram that the ion liquid sol gel coat stirring rod of embodiment 1 preparation is applied to three kinds of non-steroid anti-inflammatory drugs (Ketoprofen, naproxen, fenbufen) in the SBSE-HPLC-UV testing environment sample; A, B, C, D are respectively East Lake water sample, Wei Ming Lake water sample, urine sample, milk sample; (a) be sample without Stir Bar Sorptive Extraction, directly enter the chromatogram of high performance liquid chromatography-ultraviolet; (b) be sample process Stir Bar Sorptive Extraction desorption procedure, its stripping liquid enters the chromatogram of high performance liquid chromatography-ultraviolet; (c) in sample, add in advance the titer (100 ppb) of target analytes to be measured (Ketoprofen, naproxen and fenbufen) for elder generation, and then through the Stir Bar Sorptive Extraction process, stripping liquid is entered the chromatogram of high performance liquid chromatography-ultraviolet.
The specific embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is done further detailed description, but embodiments of the present invention are not limited to this.
A kind of ion liquid sol gel coat stirring rod as shown in Figure 2, comprises capillary glass tube 2, iron core 1 and extraction coating 3, and iron core 1 places in the capillary glass tube 2 of two ends sealing by fusing, and extraction coating 3 is coated in the capillary glass tube outer surface.The extraction coating is the ion liquid sol gel coat that is chemically bound in the capillary glass tube surface, and ionic liquid is 1-allyl imidazole tetrafluoroborate ion liquid.
(1) preparation dumbbell shape glass stirring rod
Be that the thin wire of 0.50 mm cuts the segment of growing into 1.7 cm with diameter, smooth straight with sand papering, the capillary glass tube (being purchased from instrument plant of Huaxi Medical Univ) with internal diameter 0.9-1.1 mm, wall thickness 0.10-0.15 mm is cut into the segment that length is about 2.5 cm again.The thin wire of processing is placed capillary glass tube, and the capillary two ends are with alcolhol burner flame sealing by fusing and form protuberance, and finally obtaining length is the dumbbell shape glass stirring rod of 2 cm.
(2) activation of glass stirring rod
The dumbbell shape stirring rod for preparing is used ultra-pure water and washed with methanol successively, place again more than 1 mol/L NaOH activation, 3 h, activated rear taking-up, clean to neutral with ultra-pure water, 0.1 mol/L HCl, ultra-pure water successively again, place the baking oven dry for standby.
(3) preparation of ion liquid sol
Pipette successively 100 μ L CH
2Cl
2(carrene), 150 μ L OH-PDMS(hydroxyl endblocked polydimethylsiloxanes, M.W. 4200), 100 μ L TEOS(tetraethoxysilanes), 60 μ L KH-570(γ-methacryloxypropyl trimethoxy silane), 30 μ L [AIM] [BF4] (1-allyl imidazole tetrafluoroborate) (are purchased from the prompt chemical Co., Ltd of marine origin (Shanghai, China)), 20 μ L PMHS(polymethyl hydrogen siloxanes) and 40 μ L 95%(v/v) TFA, ultrasonic reaction 10 min make colloidal sol behind the vortex mixing.
(4) preparation of ion liquid sol gel coat stirring rod
Place 60 ℃ in baking oven to wear out 3 days with applying in the immersion of the glass stirring rod after the activation ion liquid sol, taking out, obtain ion liquid sol gel coat stirring rod.Prepared ion liquid sol gel coat stirring rod need be used first methyl alcohol ultrasonic cleaning 20 min before use, to remove the organic impurities on stirring rod surface.
The ion liquid sol gel coat stirring rod for preparing is carried out infrared detection, scanning electron microscope analysis and thermogravimetric analysis, and the result is as follows:
Fig. 3 is the infrared spectrogram of ion liquid sol gel coat, has compared (a) among the figure and has not added the sol-gel coating of ionic liquid and the infrared peak that (b) adds the sol-gel coating of ionic liquid.As can be seen from the figure, 2970 cm
-1Be the characteristic absorption peak of carbon-carbon double bond (C=C), added the rear two key peaks of ionic liquid reaction and almost disappeared 2360 cm
-1Be the characteristic absorption peak of ionic liquid boron fluorine bond (B-F) key, 666 cm
-1Be the characteristic absorption peak of ionic liquid imidazole ring, can think that thus ionic liquid 1-allyl imidazole tetrafluoroborate participates in solgel reaction by the mode of two key bondings really.
Fig. 4 is the surface topography map that ion liquid sol gel coat stirring rod characterizes with ESEM.Ionic liquid participates in solgel reaction, and not only can be used as fiber material has good extracting and enriching to target analytes, also has simultaneously the surface topography of the improved effect sol-gel coating of molecular self-assembling.The ionic liquid coating stirring rod smooth surface that can find out preparation from scanning electron microscope (SEM) photograph is even, and film forming is better, and coating surface can be seen the membrane pore structure of homogeneous, and the aperture is about 3-5 μ m.
Fig. 5 is the thermogravimetric phenogram of ion liquid sol gel coat.From thermogravimetric analysis figure, can see, the ionic liquid coating had slight mass change before 200 ℃, this mainly is to be decomposed by the reaction raw materials that has neither part nor lot in solgel reaction in the coating to cause, extraction functional coating stable in properties before 360 ℃, afterwards temperature rising coating has obvious weightlessness, weightless interval is 360-609 ℃, and Quality Down mainly is to be caused by the decomposition that extracts sol-gel coating in this section process, and irreversible change has occured material.This shows that prepared material can bear 360 ℃ with interior variations in temperature, better heat stability is applicable to the thermal desorption operation.
The extraction desorption process of ion liquid sol gel coat stirring rod is as follows: ion liquid sol gel coat stirring rod is placed 10 mL sample solutions, under 800 rpm rotating speeds, stir extraction 30 min, after finishing, extraction takes out stirring rod, the solution of drying the stirring rod surface with filter paper is residual, transfers them to ultrasonic desorb 15 min in the desorption tube that 100 μ L methyl alcohol are housed.Follow-up high performance liquid chromatography-the ultraviolet (HPLC-UV) that stripping liquid is used for behind 0.22 μ m membrane filtration detects and analyzes; Stirring rod after the desorb places ultrasonic 5 min of methyl alcohol, and is reusable after the regeneration.
Because ion liquid sol gel coat stirring rod is the extraction of direct immersion, and uses the organic solvent desorb, thereby prepared ion liquid abstraction coating has been carried out the investigation of acid and alkali-resistance, organic solvent resistance.The ion liquid sol gel coat stirring rod that embodiment 1 is prepared is immersed in respectively in 1 mol/L HCl, 0.1 mol/L HCl, 1 mol/L NaOH, 0.1 mol/L NaOH, methyl alcohol and the acetonitrile, takes out behind 24 h, and ultra-pure water cleans; To process according to the method described above the sample solution that placing respectively of ion liquid sol gel coat stirring rod contain 400 μ g/L Ketoprofens (KEP), naproxen (NAP), fenbufen (FBF) and extract desorb, relatively its extraction efficiency changes, the result as shown in Figure 6, the ability that can find out the ionic liquid coating stirring rod tolerance alkali of preparation and organic solvent is suitable, the ability of tolerance acid slightly a little less than, have preferably chemical stability.
Method according to the extraction desorb of above-mentioned ion liquid sol gel coat stirring rod, the ion liquid sol gel coat stirring rod that embodiment 1 prepares is reused 50 times, by the extraction efficiency of Ketoprofen (KEP), naproxen (NAP), fenbufen (FBF) is investigated its service life.The result as shown in Figure 7, as can be seen from the figure, after the ion liquid sol gel coat stirring rod extraction desorb 50 times to the extraction efficiency of Ketoprofen (KEP), naproxen (NAP), fenbufen (FBF) without significant change, and reuse in the process stirring rod coating without the wearing and tearing obscission, as seen the ionic liquid coating has preferably mechanical performance and stable effect of extracting, can use at least 50 times.
The ion liquid sol gel coat stirring rod of embodiment 1 preparation is applied to Stir Bar Sorptive Extraction-high performance liquid chromatography-ultraviolet detects three kinds of non-steroid anti-inflammatory drugs (Ketoprofen, naproxen and fenbufen) in (SBSE-HPLC-UV) Analysis of Complex sample, obtain best extraction desorb and separate testing conditions through a series of condition optimizings.Best extraction desorption condition is: sample solution pH is that the mass concentration of 3, NaCl is 15%, and extraction temperature is 20 ℃, and stir speed (S.S.) is 800 rpm, and extraction time is 30 min; Strippant is that volume ratio is the methyl alcohol of 7:3: 10 mM NaOH solution, ultrasonic desorb 15 min.Best HPLC-UV separates testing conditions: Agilent 1100 high performance liquid chromatography (Agilent Technologies, Waldbronn, Germany), dispose that online degasser, quaternary mixing pump, 100 μ L quantitatively encircle, Variable wavelength UV detector, chromatographic column is RP-18 post (4.6 mm * 250 mm, particle diameter 5 μ m, Merck KgaA, Germany); Take methyl alcohol: 10 mmol/L phosphate buffer solutions (volume ratio is as 63:37, and pH 3) are chromatogram flow phase, room temperature isocratic elution, flow velocity 1 mL/min; Ultraviolet detects wavelength 210 nm; Sampling volume 30 μ L.Then target analytes in analysis environments, biology and the food samples under optimum experimental condition, concrete sample and the preprocessing process of selecting is as follows:
(1) environmental water sample: East Lake Water, Wuhan and campus lake water are respectively the superficial waters that (Wuhan, China) and Wuhan University's Wei Ming Lake (Wuhan, China) gather in East Lake.Water sample is through 0.45 μ m membrane filtration, and to regulate salinity with NaCl be that to regulate pH be 3.0 for mass concentration 15%, 1 mol/L HCl.
(2) urine sample: urine sample is provided by the laboratory Healthy People, needs to use first 0.45 μ m membrane filtration before the detection, then presses the 1:1 dilution proportion with ultra-pure water, regulates simultaneously salinity and be 15%, pH is 3.0.
(3) milk sample: fresh plain chocolate is purchased from local supermarket (Wuhan, China).Preparation pipettes 4.0 mL milk in 50 mL quantity tubes, adds target analytes NSAIDs mark liquid, and vortex 2 min mixings with the ultra-pure water dilution, are regulated NaCl and be 15%, pH is 3.0, is settled to 40 mL scales.Wait complex matrices with 0.45 μ m membrane filtration with protein isolate and fat behind ultrasonic extraction 30 min.
The chromatogram of three kinds of non-steroid anti-inflammatory drugs (Ketoprofen, naproxen and fenbufen) as shown in Figure 8 in Stir Bar Sorptive Extraction-high performance liquid chromatography-ultraviolet detection (SBSE-HPLC-UV) analysis environments sample: A, B, C, D are respectively East Lake water sample, Wei Ming Lake water sample, urine sample, milk sample; Among the figure (a) be sample without Stir Bar Sorptive Extraction, directly enter the chromatogram of high performance liquid chromatography-ultraviolet; (b) is sample process Stir Bar Sorptive Extraction desorption procedure among the figure, and its stripping liquid enters the chromatogram of high performance liquid chromatography-ultraviolet; (c) is for adding in advance first the titer (100 μ g/L) of target analytes to be measured (Ketoprofen, naproxen and fenbufen) among the figure in sample, and then through the Stir Bar Sorptive Extraction process, stripping liquid is entered the chromatogram of high performance liquid chromatography-ultraviolet.From comparison diagram as can be known; All do not detect three kinds of target analytes in four kinds of samples, and this method has preferably anti-matrix interference performance to urine sample and the milk sample of matrix relative complex, can realize the purpose of extracting and enriching target analysis (Ketoprofen, naproxen and fenbufen), good using value is arranged.
Above-described embodiment is the better embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under Spirit Essence of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
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| CN115920725A (en) * | 2022-11-09 | 2023-04-07 | 武汉大学 | 3D printed Lay-Fomm60 coating stirring rod and preparation method and application thereof |
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