CN103293041B - Fiber filtering membrane solid-liquid microextraction method and device - Google Patents
Fiber filtering membrane solid-liquid microextraction method and device Download PDFInfo
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- CN103293041B CN103293041B CN201310238642.0A CN201310238642A CN103293041B CN 103293041 B CN103293041 B CN 103293041B CN 201310238642 A CN201310238642 A CN 201310238642A CN 103293041 B CN103293041 B CN 103293041B
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Abstract
The invention discloses a fiber filtering membrane solid-liquid microextraction method and a device. The fiber filtering membrane solid-liquid microextraction method comprises the following steps that: fiber filtering membranes cut into small pieces are put into a extracting solvent, so as to be soaked and ensure that micropores are filled with solvent; the filtering membranes filled with the solvent are put into a sample solution, so that target analyte is extracted; the filtering membranes are taken out after the extraction; the target analyte on the filtering membranes is dissolved through the solvent or solution; assay determination is performed. The solid-liquid microextraction method is simple and rapid, with a low organic solvent use level and high enrichment multiple, and is applied to the extraction, separation, purification and concentration of trace target analyte in complex samples.
Description
Technical field
The present invention relates to analytical chemistry sample pre-treatments, particularly relate to the method and device that from sample solution, target analytes are extracted.
Background technology
Micro-extraction technique as a kind of centralized procurement sample, extract, concentrate in the sample-pretreating method of one, have simple, fast, environmental friendliness, the feature such as efficient.
Solid-phase microextraction is generally that certain macromolecular material synthesized or molecularly imprinted polymer are coated on specific support, utilizes the activated centre of polymeric coating layer or the special selectivity of molecularly imprinted polymer to specific template molecule or microsphere to extract the target analytes in sample, concentrate.As can be seen here, surface coating solid-phase microextraction needs synthesis or prepares coating and need special technology Coating.
The microporous barrier that microporous barrier micro-extraction is the organic polymer (as teflon, nylon or Polyvinylchloride) of synthesis, cellulose or glass fibre are made is as the barrier film of sample separation solution and receptor solution, namely sample solution is on one side of filter membrane, receptor solution is at the another side of filter membrane, target analytes in sample solution enters receptor solution by filter membrane, target analytes is purified and concentrates.Therefore, microporous membrane extraction also effectively need can separate two-phase by fixing for filter membrane, and device technique is complicated.
Liquid-phase micro-extraction mainly comprises single dropping liquid-phase microextraction, hollow fiber liquid-phase micro-extraction and dispersive liquid-liquid microextraction.(1) single dropping liquid-phase microextraction can be divided into again: directly immerse liquid-phase micro-extraction and headspace liquid-phase microextraction.Direct immersion liquid-phase micro-extraction is that organic drop is hung on syringe needle, and direct immersion in water miscible sample solution extracts target analytes.Headspace liquid-phase microextraction is that the droplet of extraction solvent is suspended on the syringe needle of microsyringe, and is placed in sample solution head space and extracts volatile analytes thing.(2) hollow fiber liquid-phase micro-extraction utilizes porous hollow fiber as extraction solvent carrier, the extraction solvent of certain volume is filled in its cinclides and/or pipe, sealing two ends or fiber is folded in half into " U " type, be placed in water miscible sample solution, under certain stirring rate, extract (3) dispersive liquid-liquid microextraction to target analytes is join in sample solution by the extractant of certain volume and spreading agent, under the effect of certain external force, extraction solvent is dispersed into fine drop and forms nebulous turbid solution, target analytes is extracted simultaneously.If use the extractant heavier than water, after nebulous turbid solution is centrifugal, containing analyzing the extraction solvent coagulation of thing in the bottom of sample phase, if use the extraction solvent heavier than water, after nebulous turbid solution is centrifugal, swim in sample top mutually containing the organic solvent analyzing thing.Collection is assembled mutually or analysis mensuration is carried out in floating gathering mutually.If the melting point of organic solvent is close to room temperature (as undecyl alcohol, lauryl alcohol), centrifuge tube can be frozen several minutes at ice bath or refrigerator and cooled, after organic solvent solidifies, collect the solids accumulation phase swimming in sample surfaces, carry out analysis to it after at room temperature melting to measure, thus also referred to as floating organic drop solidification liquid phase extraction.As can be seen here, all there is the shortcomings such as complicated operation, difficulty, reappearance be poor in above-mentioned liquid-phase micro extraction technique.
Summary of the invention
The object of this invention is to provide a kind of simple, fast, consumption of organic solvent is few, the fibrous filter membrane solid-liquid micro-extracting method that enrichment times is high and device, for the extracting and developing of trace target analytes in complex sample, purifying and concentrated.
Solve the problems of the technologies described above, the present invention sets up a kind of fibrous filter membrane solid-liquid micro-extracting method, the fibrous filter membrane being cut into small pieces is put into extraction solvent soak, its micropore is made to be full of solvent, the filter membrane being full of solvent is placed in sample solution extract target analytes, after extraction terminates, filter membrane is taken out, with the target analytes on solvent or solubilize filter membrane, and carry out analysis mensuration.
As a kind of optimal way of the present invention, said method comprises step: (1) adds sample solution by sample flasket with cover; (2) put into stirrer in the vial and be placed on magnetic stirring apparatus; (3) fibrous filter membrane is cut into small pieces, cleans, naturally dry; (4) filter membrane processed is placed in extraction solvent, is full of after extraction solvent until filter membrane, take out, wipe filter membrane surface excess of solvent away; (5) this filter membrane is placed in sample solution to extract; (6), after extraction terminates, take out filter membrane, use redistilled water clean surface; (7) resolve by methyl alcohol or aqueous solution the target analytes that is concentrated on filter membrane and carry out analysis and measure.
Filter membrane selected by the present invention is for filtering organic filter membrane of 0.45 μm of organic solvent in high performance liquid chromatography.The chemical composition of this filter membrane has stronger adsorption activity, and the microcellular structure of filter membrane can hold and protect extraction solvent.Therefore, filter membrane activated centre is dissolved as to analyzing extraction solvent in the absorption of thing, filter membrane micropore to what analyze thing the platform that the invention provides an extraction and concentrated target analytes.In addition, extraction solvent forms droplet in the aperture of filter membrane, is not only uniformly dispersed, and adds the area of extraction solvent and active ingredient contacts, further increases cycles of concentration and the detection sensitivity of target analytes.
There is adsorption activity center and the tiny micropore be evenly distributed in the molecule of composition fibrous filter membrane structure.Therefore, in filter membrane/solvent-solid-liquid micro-extraction, extraction solvent can distribute or be dispersed in the interior also formation of aperture and the filter sizes solvent droplet of the same size of filter membrane uniformly.When the filter membrane being full of extraction solvent be placed in complex sample solution extract time, carry out adsorption and desorption, distribution and dissolving in the extraction solvent phase of target analytes in filter membrane surface solid phase and micropore thereof (the two jointly composition accept phase) and sample phase (confession phase).After extraction reaches balance, target analytes is concentrated to very small size (1cm effectively
2filter membrane approximately hold the extraction solvent of 5 μ L) acceptance mutually in.After extraction terminates, with specific solvent or solution, the target analytes that filter membrane accepts is mutually dissociated, and analysis mensuration is carried out to it.Extraction of the present invention accepts smaller (about 10 of phase volume and sample phase volume
-3), extraction solvent is uniformly dispersed, and specific surface area is large, accept with effective contact area of target analytes greatly, the extraction solvent in the adsorption site of filter membrane and micropore thereof can carry out synergic solvent extraction to target analytes.Therefore, the cycles of concentration of the present invention to target analytes is large, detection sensitivity is high.
As preferred mode, the bottle that the sample flasket with cover described in step (1) is 10mL, 20mL, 50 mL are with rubber lid.
As preferred mode, in step (3), selecting in high performance liquid chromatography for filtering the fibrous filter membrane of organic solvent, being cut into the small pieces that the length of side is 1cm.
As preferred mode, cleaning described in step (3), naturally drying is by filter membrane successively with acetone, methyl alcohol, acid, alkali cleaning, then after repeatedly cleaning with distilled water, naturally dries under room temperature.
As preferred mode, described in step (4), extraction solvent is organic solvent, ionic liquid, complexing or sequestrant or their mixed solvent, and filter membrane is immersed in 30s in extraction solvent.
As preferred mode, described in step (5), filter membrane being placed in sample solution is use the bottle with rubber lid, the filter membrane tweezers handled well by extraction solvent are clamped and are through on the syringe needle of micro syringe, this micro syringe syringe needle is vertically inserted the rubber lid of bottle, again rubber lid is covered on bottle, compress, the position of adjustment filter membrane, makes it be immersed in sample solution to be extracted.
As preferred mode, in step (5), when filter membrane is placed in sample solution, filter membrane remains on the position of under liquid level 1/3.The position of filter membrane is too high, and the extraction solvent volatilization on filter membrane increases; Position is too low, and the rotation of stirrer may make the extraction solvent on filter membrane come off.The two all can affect the extraction efficiency of filter membrane/solvent-solid-liquid micro-extraction.
As preferred mode, be the filter membrane taken out is moved in the bottle containing 1mL redistilled water and rinsing gently, to wash away the water-solubility impurity or matrix that filter membrane surface carries by redistilled water clean surface described in step (6).
Carry out analysis mensuration described in step (7) and refer to that getting target analytes eluent carries out spectrum, chromatogram, liquid phase/mass spectrum or gas phase/mass spectrophotometry mensuration.For the character of different activities composition, the solution of different solvents or different pH, polarity, ionic strength etc. can be selected to resolve the active component be enriched on filter membrane.
The present invention is also provided for the fibrous filter membrane solid-liquid micro-extracting method of said method, comprise thermostatic mixer, stirrer, fibrous filter membrane, vial, rubber lid and micro syringe syringe needle containing extraction solvent, vial is placed on thermostatic mixer, stirrer is positioned in vial, micro syringe syringe needle inwardly passes rubber lid and on micro syringe syringe needle, fixes the fibrous filter membrane containing extraction solvent, is covered on vial by rubber lid.
The present invention establishes a kind of method of extracting and developing, purifying and concentrated target analytes from complex sample, and simple, quick, consumption of organic solvent is few, and enrichment times is high, favorable reproducibility, is adapted to the trace constituent analysis in different field complex matrices.Compared with prior art, the present invention (1) avoids surface coating Solid-phase Microextraction to be needed synthesis or prepares coating and the complex process of Coating.(2) complicated technology and device of preparing barrier film in microporous barrier micro-extraction is simplified.(3) avoid in hollow fiber liquid-phase micro-extraction and use microsyringe to inject in fiber core mutually and the process of taking out in fiber core by accepting; Overcome in dispersive liquid-liquid microextraction the difficulty being gathered in extraction solvent drop bottom sample solution (particularly full-bodied extraction solvent) and not easily taking out; Solve in floating organic drop solidification liquid phase extraction because organic solvent swims in the top highly volatile of sample phase and the problem of loss; (4) the present invention has the advantage of Solid-Phase Extraction, film micro-extraction and liquid-phase micro-extraction concurrently.
Accompanying drawing explanation
Fig. 1 is filter membrane/solvent-solid-liquid micro-extraction device
In figure, 1-thermostatic mixer, 2-stirrer, 3-sample solution, 4-contains the fibrous filter membrane of extraction solvent, 5-vial, 6-rubber lid, 7-micro syringe syringe needle.
Fig. 2 is 3 kinds of compounds derived from phenyl acrylic acid reference substance chromatograms
In figure, 1-caffeic acid, 2-forulic acid, 3-cinnamic acid; Before a-filter membrane solid-liquid phase micro-extraction, after b-filter membrane solid-liquid phase micro-extraction.
Fig. 3 is 3 kinds of compounds derived from phenyl acrylic acid reference substance chromatograms in rhizoma typhonii medicinal material
In figure, 1-caffeic acid, 2-forulic acid, 3-cinnamic acid; A-reference substance, before b-rhizoma typhonii sample filter membrane/solvent-solid-liquid micro-extraction, after c-rhizoma typhonii sample filter membrane/solvent-solid-liquid micro-extraction.
Fig. 4 is 5 kinds of Protoberberine Alkoloids reference substance chromatograms
In figure, 1-jateorrhizine, 2-epiberberine, 3-coptisine, 4-palmatine, 5-jamaicin; Before a-fibrous filter membrane solid-liquid phase micro-extraction, after b-fibrous filter membrane solid-liquid phase micro-extraction.
Fig. 5 is 5 kinds of Protoberberine Alkoloids compound chromatograms in Rhizoma Coptidis sample
In figure, 1-jateorrhizine, 2-epiberberine, 3-coptisine, 4-palmatine, 5-jamaicin; A-reference substance, before b-coptis sample filter membrane/solvent-solid-liquid micro-extraction, after c coptis sample filter membrane/solvent-solid-liquid micro-extraction.
Embodiment
By reference to the accompanying drawings and embodiment, the embodiment of the solid-liquid micro-extracting method proposed according to the present invention and application, feature, effect are described in detail.Effective constituent in embodiment centering prodrug complex sample carries out extracting and concentrating, but is not limited only to this embodiment, and the present invention is also applicable to the separation and consentration of trace target analytes in the complex samples such as environment, food, medicine, biology.
Material and reagent organic filter film (Beijing marine origin Shi Jie Filters company limited), caffeic acid, forulic acid, cinnamic acid reference substance (purity >=98%) provide by Man Site bio tech ltd, Chengdu, experimental water is redistilled water, and it is pure that other reagent is analysis.
Instrument Agilent Technologies 1200 Series high performance liquid chromatograph.
Experimental procedure
Solid-liquid micro-extraction device is shown in Fig. 1, comprise thermostatic mixer 1, stirrer 2, fibrous filter membrane 4, vial 5, rubber lid 6 and micro syringe syringe needle 7 containing extraction solvent, vial 5 is placed on thermostatic mixer 1, stirrer 2 is positioned in vial 5, micro syringe syringe needle 7 inwardly passes rubber lid 6 and on micro syringe syringe needle 7, fixes the fibrous filter membrane 4 containing extraction solvent, and rubber lid 6 covers on vial 5.Sample solution 3 is injected in vial 5.
Experimental technique is the bottle getting 10mL, 20mL or 50 mL band rubber lid, adds a certain amount of reference substance solution or sample solution, puts into stirrer, be placed on magnetic stirring apparatus.Fibrous filter membrane is cut into small pieces, cleans, naturally dry.Fibrous filter membrane after process is soaked in extraction solvent, takes out with tweezers after membrane micropore to be filtered is full of extraction solvent, thieving paper presses filter membrane gently, to wipe the unnecessary extraction solvent of filter membrane surface away.The filter membrane tweezers handled well by extraction solvent are clamped and are through on the syringe needle of micro syringe, this micro syringe syringe needle is vertically inserted the rubber lid of bottle, then rubber lid is covered on bottle, compress, the position of adjustment filter membrane, makes it be immersed in sample solution to be extracted.Under agitation extract, after extraction terminates, take off bottle cap, clamp rinsing gently in the bottle that filter membrane edge moves into containing redistilled water, to wash away the water-solubility impurity or matrix that filter membrane surface carries with tweezers.Resolve by methyl alcohol or aqueous solution the target analytes be concentrated on filter membrane, discard filter membrane, spectrum, chromatogram, liquid phase/mass spectrum or gas phase/mass spectrophotometry is carried out to target analytes eluent and measures.
Embodiment 1 solid-liquid micro-extraction is concentrated 3 kinds of compounds derived from phenyl acrylic acid simultaneously
1. the present invention is in conjunction with high performance liquid chromatography concentrated 3 kinds of compounds derived from phenyl acrylic acid reference substances simultaneously
Get the bottle that 10mL is with rubber lid, add 1.0 mL reference substance mixed solutions (3 kinds of cinnamic acid compound control product concentration are 8 μ g/mL), 1.2g NaCl and 0.1 mol/L HCl solution 9 mL, make the pH=1 for phase solution.Put into stirrer (8 mm × 4 mm), be placed on magnetic stirring apparatus.The organic filter membrane cleaned, dry up is cut into the square small pieces of 1 cm, takes out with tweezers soak 30 s in enanthol after, thieving paper presses filter membrane gently, to wipe the unnecessary extraction solvent of filter membrane surface away.Vertically inserted by micro syringe syringe needle in the rubber lid of bottle, clamp the filter membrane that soaked in enanthol and be through on syringe needle, covered by bottle cap on bottle, make filter membrane hang in sample solution with tweezers, adjustment filter membrane makes it to be positioned at the position of under liquid level 1/3.20 min are extracted under the stirring rate of 300 rpm.After extraction terminates, take off bottle cap, clamp rinsing gently in the bottle that filter membrane edge moves into containing 1mL redistilled water, to wash away the water-solubility impurity or matrix that filter membrane surface carries with tweezers.Resolve the analysis thing on filter membrane with methyl alcohol, discard filter membrane, desorbed solution carries out efficient liquid phase chromatographic analysis.
Chromatographic condition C18 post (250 mm × 4.6 mm, 5 mm, Dikma Technologies); Determined wavelength: 285 nm; Flow velocity: 1.5mL/min; Column temperature: 35 DEG C; Sample size: 20 mL; Mobile phase: methyl alcohol-0.3% H
3pO
4solution (40: 60, V/V).
Utilize the present invention in conjunction with high performance liquid chromatography simultaneously concentrated 3 kinds of compounds derived from phenyl acrylic acid reference substance chromatograms see Fig. 2, the present invention to the enrichment times of 3 kinds of derived from phenyl acrylic acid reference substances in table 1.
The enrichment times of table 13 kinds of compounds derived from phenyl acrylic acid
| Target analytes | Caffeic acid | Forulic acid | Cinnamic acid |
| Average enrichment times | 144.1 | 42.7 | 47.9 |
| Maximum enrichment times | 469 | 62 | 71 |
2. the present invention measures cinnamic acid active component in Chinese crude drug in conjunction with high performance liquid chromatography is simultaneously concentrated
The preparation of 2.1 medicinal material rhizoma typhonii sample solutions is got rhizoma typhonii medicinal material (Sichuan) and is smashed to pieces, porphyrize, and precision takes 10.0 g in conical flask, adds 100 mL water ultrasonic extraction 60 min, weighs and supplies the weight of loss with water, shaking up, 4 DEG C of preservations, stand-by.
2.2 the present invention concentrate in conjunction with high performance liquid chromatography simultaneously, measure 3 kinds of cinnamic acid active components in rhizoma typhonii gets the bottle that 10 mL are with rubber lids, add above-mentioned rhizoma typhonii ultrasonic extraction sample solution 1.0 mL, NaCl 1.2 g and 0.1 mol/L HCl solution 9 mL, make the pH=1 for phase solution.Put into stirrer (8 mm × 4 mm), be placed on magnetic stirring apparatus.The organic filter membrane cleaned, dry up is cut into the square small pieces of 1 cm, takes out with tweezers soak 30 s in enanthol after, thieving paper presses filter membrane gently, to wipe the unnecessary extraction solvent of filter membrane surface away.Vertically inserted by micro syringe syringe needle in rubber lid, clamp the filter membrane soaked in enanthol and be through on syringe needle, then cover on bottle by bottle cap with tweezers, make filter membrane hang in sample solution, adjustment filter membrane makes it to be positioned at the position of under liquid level 1/3.20min is extracted under the stirring of 300 rpm.After extraction terminates, take off bottle cap, clamp rinsing gently in the bottle that filter membrane edge moves into containing 1 mL redistilled water, to wash away the water-solubility impurity or matrix that filter membrane surface carries with tweezers.Resolve the analysis thing on filter membrane with methyl alcohol, discard filter membrane, desorbed solution carries out efficient liquid phase chromatographic analysis.
Utilize the present invention in conjunction with high performance liquid chromatography simultaneously chromatogram that is concentrated and that measure target analytes in rhizoma typhonii medicinal material see Fig. 3.
Embodiment 2 solid-liquid micro-extraction is concentrated 5 kinds of Protoberberine Alkoloidses simultaneously
1. filter membrane/solvent-solid-liquid micro-extraction is in conjunction with high performance liquid chromatography concentrated 5 kinds of Protoberberine Alkoloids reference substances simultaneously
Get the bottle that 10 mL are with rubber lid, add 1.0 mL reference substance mixed solutions (5 kinds of alkaloid reference substance concentration are 8 μ g/mL) and 1 × 10
-3mol/L NaOH solution 9 mL, makes the pH=11 for phase solution.Put into stirrer (8 mm × 4 mm), be placed on magnetic stirring apparatus.The organic filter membrane cleaned, dry up is cut into the square small pieces of 1 cm, takes out with tweezers soak 30 s in enanthol after, thieving paper presses filter membrane gently, to wipe the unnecessary extraction solvent of filter membrane surface away.Vertically inserted by micro syringe syringe needle in rubber lid, clamp the filter membrane that soaked in enanthol and be through on syringe needle, covered by bottle cap on bottle, make filter membrane hang in sample solution with tweezers, adjustment filter membrane makes it to be positioned at 1/3 place under liquid level.Extract 20 min under the stirring rate of 300 rpm after.After extraction terminates, take off bottle cap, clamp rinsing gently in the bottle that filter membrane edge moves into containing 1mL redistilled water, to wash away the water-solubility impurity or matrix that filter membrane surface carries with tweezers.Resolve the analysis thing on filter membrane with 0.01mol/L HCl solution, discard filter membrane, desorbed solution carries out efficient liquid phase chromatographic analysis.
Chromatographic condition C18 post (250 mm × 4.6 mm, 5 mm, Dikma Technologies); Determined wavelength: 345 nm; Flow velocity: 1.0 mL/min; Column temperature: 25 DEG C; Sample size: 20 mL; Mobile phase: acetonitrile: water (every premium on currency contains 3.4g potassium dihydrogen phosphate, 1.7g lauryl sodium sulfate)=50:50.
Utilize the present invention in conjunction with high performance liquid chromatography simultaneously concentrated mensuration 5 kinds of Protoberberine Alkoloids reference substance chromatograms see Fig. 4, the present invention to the enrichment times of 5 kinds of Protoberberine Alkoloidses in table 2.
Table 25 kinds of Protoberberine Alkoloids compound enrichment times
| Target analytes | Jateorrhizine | Epiberberine | Coptisine | Palmatine | Jamaicin |
| Average enrichment times | 0.8 | 8.0 | 12.4 | 8.3 | 10.2 |
2. solid-liquid micro-extraction measures Protoberberine Alkoloids active component in Chinese crude drug in conjunction with high performance liquid chromatography is simultaneously concentrated
The preparation of 2.1 Rhizoma Coptidis sample solutions is got Rhizoma Coptidis (Sichuan) and is pulverized, porphyrize, and precision takes 1.0288g, be placed in 100 mL volumetric flasks, precision adds methyl alcohol 90 mL and 1 mL concentrated hydrochloric acid, close plug, ultrasonic process (power 150 W, frequency 40 kHz) 50 min, let cool, by methanol constant volume, shake up, filter, get subsequent filtrate, 4 DEG C of preservations, stand-by.
2.2 the present invention concentrate in conjunction with high performance liquid chromatography simultaneously, measure 5 kinds of Protoberberine Alkoloids active components in Rhizoma Coptidis
Get the bottle that 10 mL are with rubber lid, add 1mL coptis sample solution and 1 × 10
-3mol/L NaOH solution 9 mL, makes the pH=11 for phase solution.Put into stirrer (8 mm × 4 mm), be placed on magnetic stirring apparatus.The organic filter membrane cleaned, dry up is cut into the square small pieces of 1 cm, takes out with tweezers soak 30 s in enanthol after, thieving paper presses filter membrane gently, to wipe the unnecessary extraction solvent of filter membrane surface away.Vertically inserted by micro syringe syringe needle in rubber lid, clamp the filter membrane that soaked in enanthol and be through on syringe needle, covered by bottle cap on bottle, make filter membrane hang in sample solution with tweezers, adjustment filter membrane makes it to be positioned at the position of under liquid level 1/3.20 min are extracted under the speed of 300 rpm stirs.After extraction terminates, take off bottle cap, clamp rinsing gently in the bottle that filter membrane edge moves into containing 1mL redistilled water, to wash away the water-solubility impurity or matrix that filter membrane surface carries with tweezers.Resolve the analysis thing on filter membrane with 0.01mol/L HCl solution, discard filter membrane, desorbed solution carries out efficient liquid phase chromatographic analysis (Fig. 5).
Claims (9)
1. a fibrous filter membrane solid-liquid micro-extracting method, it is characterized in that: selecting in high performance liquid chromatography for filtering the aperture of organic solvent is 0.45 μm of fibrous filter membrane, be cut into the small pieces that the length of side is 1 cm, the fibrous filter membrane being cut into small pieces is put into extraction solvent soak, its micropore is made to be full of extraction solvent, the filter membrane being full of extraction solvent is placed in sample solution extract target analytes, after extraction terminates, filter membrane is taken out, with the target analytes on solvent or solubilize filter membrane, and carry out analysis mensuration.
2. method according to claim 1, is characterized in that: comprise step: (1) adds sample solution by sample flasket with cover; (2) put into stirrer in the vial and be placed on magnetic stirring apparatus; (3) fibrous filter membrane is cut into small pieces, cleans, naturally dry; (4) filter membrane processed is placed in extraction solvent, is full of after extraction solvent until filter membrane, take out, wipe filter membrane surface excess of solvent away; (5) this filter membrane is placed in sample solution to extract; (6), after extraction terminates, take out filter membrane, use redistilled water clean surface; (7) resolve by methyl alcohol or aqueous solution the target analytes that is concentrated on filter membrane and carry out analysis and measure.
3. method according to claim 2, is characterized in that: the bottle that the sample flasket with cover described in step (1) is 10 mL, 20 mL, 50 mL are with rubber lid.
4. method according to claim 2, is characterized in that: cleaning described in step (3), naturally drying is by filter membrane successively with acetone, methyl alcohol, acid, alkali cleaning, then after repeatedly cleaning with distilled water, naturally dries under room temperature.
5. method according to claim 2, is characterized in that: extraction solvent described in step (4) is organic solvent, ionic liquid, complexing or sequestrant or their mixed solvent, and filter membrane is immersed in 30 s in extraction solvent.
6. method according to claim 2, it is characterized in that: described in step (5), filter membrane being placed in sample solution is use the bottle with rubber lid, micro syringe syringe needle is vertically inserted the rubber lid of bottle, the filter membrane tweezers handled well by extraction solvent are clamped and are through on the syringe needle of micro syringe, again rubber lid is covered on bottle, compress, the position of adjustment filter membrane, makes it be immersed in sample solution to be extracted.
7. method according to claim 6, is characterized in that: in step (5), when filter membrane is placed in sample solution, and filter membrane remains on the position of under liquid level 1/3.
8. method according to claim 2, it is characterized in that: be the filter membrane taken out is moved in the bottle containing 1 mL redistilled water and rinsing gently, to wash away the water-solubility impurity or matrix that filter membrane surface carries by redistilled water clean surface described in step (6).
9. for the fibrous filter membrane solid-liquid micro-extraction device of claim 1-8 either method, it is characterized in that: comprise thermostatic mixer (1), stirrer (2), fibrous filter membrane (4) containing extraction solvent, vial (5), rubber lid (6) and micro syringe syringe needle (7), vial (5) is placed on thermostatic mixer (1), stirrer (2) is positioned in vial (5), micro syringe syringe needle (7) is inwardly through rubber lid (6) and at the upper fixing fibrous filter membrane (4) containing extraction solvent of micro syringe syringe needle (7), rubber lid (6) covers on vial (5), described fibrous filter membrane (4) is that to select in high performance liquid chromatography for filtering the aperture of organic solvent be 0.45 μm of fibrous filter membrane, be cut into the small pieces that the length of side is 1 cm.
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| CN1598565A (en) * | 2004-07-21 | 2005-03-23 | 南开大学 | Method for investigating benzene series in water by liquid-phase microextract |
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