CN103877863B - Suppress modified micropore tunica fibrosa and the application of inorganic ions migration in electrolemma extraction - Google Patents
Suppress modified micropore tunica fibrosa and the application of inorganic ions migration in electrolemma extraction Download PDFInfo
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- CN103877863B CN103877863B CN201210562668.6A CN201210562668A CN103877863B CN 103877863 B CN103877863 B CN 103877863B CN 201210562668 A CN201210562668 A CN 201210562668A CN 103877863 B CN103877863 B CN 103877863B
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- tunica fibrosa
- electrolemma
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Abstract
The present invention relates to a kind of modified micropore tunica fibrosa suppressing inorganic ions migration in electrolemma extraction, described method adopts dip-coating method, hydrophobic polymer is dispersed in the micropore of tunica fibrosa membranous wall, realize carrying out modification to tunica fibrosa, the tunica fibrosa of modification is used for the mesophase spherule that occlusion organic solvent extracts as electrolemma.Because the hydrophobic polymer disperseed in the skeleton of tunica fibrosa improves the hydrophobicity of film, effectively reduce extraction electric current, inhibit the migration of inorganic ions.Do not affect the interpolation of extraction organic solvent and extraction additive simultaneously, be conducive to the extraction of organic compound.Method is simple, easy to operate, effective, is applicable to very much the extraction containing organic compound in a large amount of salt complex sample.
Description
Technical field
The present invention relates to a kind of modified micropore tunica fibrosa suppressing inorganic ions migration in electrolemma extraction.Relate to a kind of tunica fibrosa of hydrophobic organic polymer modification particularly, effectively can suppress the migration that inorganic ions is subject to electric field action in mesophase spherule, simultaneously on the migration of organic ion substantially without impact, thus increase system to organic ion move selective.
Background technology
Electrolemma extraction is a kind of novel sample pre-treatments extracting process proposed by Pedersen-Bjergaard for 2006, for the micro-organic ion in enrichment complex sample or inorganic ions (JournalofChromatographyA, 1152 (2007) 220 – 225, JournalofChromatographyA, 1216 (2009) 7687).It makes under ionogenic organic matter or the effect of inorganic ions at electric field through the organic film it by adding DC electric field in the acceptance phase and providing mutually of three-phase liquid-phase extraction, thus reach the object of Rapid Extraction, and the organic film of centre often plays the effect of the selective exclusion interfering ion through specific ion.Meanwhile, similar system is industrially also had for extracting metals ion or inorganic anion.
The advantage of electrolemma extraction mainly under electric field acceleration extraction rate fast, organic film and voltage all can carry out regulating that system is had is certain selective simultaneously, are suitable for the fast enriching of micro-ionizable compound in complex matrices.But this method adds due to electric field, make the competition of inorganic ions and interference comparatively large, because inorganic ions has larger charge-mass ratio usually, thus there is larger electromigration mobility.All there is a large amount of inorganic salts in usual complex sample (as blood plasma, plant extraction liquid) in addition, the migration of a large amount of inorganic ions will increase the base electric current of system, thus produce a large amount of electrolysis bubble and heat.These phenomenons all will make extracting system unstable thus hinder normally carrying out of extraction.
If suppress the migration of inorganic ions on film, just need to increase selective to organic ion of film itself.Inorganic ions and organic ion maximum morphological differentiation is in the solution the hydrone number of its hydration, usually because the electrostatic attraction of inorganic ions is larger than organic ion, so the hydrone number of inorganic ions hydration is far longer than organic ion.And the hydrophobicity increasing film can reduce the migration of the ion of many hydrations greatly.At present, the normal hydrophobicity adopting following two kinds of methods increase film, 1) change the organic solvent of occlusion in hollow-fibre membrane into hydrophobicity strong organic solvent; 2) the strong organic solvent additive of polarity is not added.Although said method improves the hydrophobicity of film, result of practical application shows, the inhibitory action that said method moves inorganic ions is very little, also can suppress the migration of the organic ion of polarity simultaneously.Therefore, how under the prerequisite not reducing organic compound migration, suppress the migration of inorganic ions in electrolemma extraction, be still a technical barrier in this field.
Summary of the invention
The invention provides a kind of modified micropore tunica fibrosa suppressing inorganic ions migration in electrolemma extraction, by dispersing hydrophobic organic polymer in tunica fibrosa skeleton, to reach better electric current inhibitory action.The hydrophobic organic polymer adopted can be swelling but be not dissolved in extraction organic solvent used, therefore do not affect the use of conventional organic solvent and extraction additive, thus do not affect the migration of organic ion.
Suppress the modified micropore tunica fibrosa of inorganic ions migration in electrolemma extraction, it is characterized in that: be dispersed in by hydrophobic polymer molecule in the micropore of tunica fibrosa membranous wall, make a kind of tunica fibrosa of modification, the electrolemma for organic compound extracts; The axial coverage of polymer in membranous wall be film thickness 3% ~ 10% between.
Tunica fibrosa immerses in hydrophobic polymer solution and makes it be dispersed in the micropore of tunica fibrosa membranous wall by the method for hydrophobic polymer employing dip coating.
The load amount of hydrophobic polymer in microporous fiber membranes is 0.01-0.2g/cm
3pore volume.
Hydrophobic polymer is the linear amorphous polymer (molecular weight 10000-300000) dissolving in volatile organic solvent, its swellable but be not dissolved in electrolemma extraction mesophase spherule organic solvent used.
Volatile organic solvent refers to the organic solvent of boiling point 100 ° of below C, as short chain alkanes class (cyclohexane, propane etc.) short chain halogenated hydrocarbon (1,2-dichloroethanes, chloroform), ketone (acetone), aromatics (toluene, benzene, meta-xylene), one or two or more kinds in ester class (ethyl acetate etc.);
Electrolemma extraction mesophase spherule organic solvent used refers to have the full-bodied organic solvent of low volatility, as long-chain alcohols (n-octyl alcohol, n-heptanol), long-chain alkanes (normal octane, n-hexane), long-chain ester class (2-nitrobenzene monooctyl ester, ethyl hexanoate), one or more in long-chain acids (caprylic acid, pelargonic acid) etc.
When adopting n-octyl alcohol to be electrolemma extraction organic solvent, the polyvinyl chloride of molecular weight 80000 or Kynoar can be selected as polymer-modified.
Hydrophobic polymer adopts the method for dip coating to be dispersed in the micropore of tunica fibrosa membranous wall, immersing in hydrophobic polymer solution by tunica fibrosa makes it be dispersed in the micropore of tunica fibrosa membranous wall, then dry, the concentration of described hydrophobic polymer is 1%-5%(w/v, g/ml).
Suppress the modified micropore tunica fibrosa of inorganic ions migration in electrolemma extraction to be used for electrolemma extraction process, mesophase spherule extract as electrolemma with Modified Membrane occlusion organic solvent, suppress the migration of inorganic ions in mutually, and then selective to organic ion of increase system.The extraction of described electrolemma is a kind of three phase extraction, by providing phase, and mesophase spherule and accept phase composition; Thering is provided is the aqueous solution mutually, and mesophase spherule is immiscible organic solvent with water, accepts to be alkalescence or acid pH aqueous buffer solution mutually);
To there is provided mutually and between accepting mutually in addition 9-500V DC electric field to accelerate compound in alternate migration rate; Communicated in the middle of it organic mutual-assistance of tunica fibrosa cinclides occlusion its be stabilized in the micropore of tunica fibrosa be placed in provide mutually and accept mutually between carry out the transmission of material.
Tool of the present invention has the following advantages:
1, can suppress a large amount of inorganic ions in complex sample in electrolemma extraction system, move the interference caused greatly, make electrolemma extract the pre-treatment being more suitable for complex sample.
2, the modifying process of whole film is simple to operate, and can realize repeatability, does not affect the selective extraction of target organic ion.
Accompanying drawing explanation
Fig. 1 is modified fibre film schematic diagram.
In figure: 101 is tunica fibrosa, 102 is fiber membranous wall, and 103 is the micropore of fiber membranous wall, and 104 is the polyvinyl chloride polymer of dispersion;
Fig. 2 is the comparison diagram of the extraction efficiency of gibberellin and the extraction efficiency of inorganic ions;
Fig. 3 uses the current vs of the electric current in Modified Membrane extraction process and unmodified membrane extraction process to scheme;
In figure: A is unmodified process, B is modifying process.
Detailed description of the invention
1. prepared polymer solution: hydrophobic polymer is dissolved in volatile organic solvent.
2. the modification of tunica fibrosa: the tunica fibrosa of drying is immersed in the polymer solution described in step 1, take out after dipping a period of time, and dry in the shade.This step can be repeatedly.
3. electrolemma extraction: with the organic solvent of modified tunica fibrosa occlusion extraction, build electrolemma extracting system.
Embodiment
Embodiment 1: be dispersed in polypropylene hollow fiber membrane with polyvinyl chloride and carry out membrane modifying for electrolemma extraction organic ion and the standard mixed liquor of inorganic ions
1) configuration of polymer solution: polyvinyl chloride (K value is 68-65)/1, the 2-dichloroethane solution of preparation quality volume (g/ml) concentration 3%.
2) hollow-fibre membrane process: polypropylene hollow fiber membrane is cut into 7cm every section, in acetone ultrasonic cleaning, and room temperature dries up.
3) modification of hollow-fibre membrane: curved by the hollow-fibre membrane of drying U-shaped and immerse the polymer solution of configuration with No. 6 needle holder, stops 8s in the solution and mentions and dry in the shade in atmosphere, and then immerse 8s in polymer solution, then mention.So three times repeatedly.
4) film occlusion organic solvent: the film of modification is immersed 5min in the organic solvent of n-octyl alcohol, organic solvent is made to be occluded in fenestra, pressed from both sides out by film and inject distilled water wherein with the organic solvent in flushing membrane chamber, the organic solvent of film outside embathes removing in distilled water.
5) configuration of sample solution: by 8 kinds of gibberellin and two kinds of inorganic ions (Cl
-and NO
3 -) be mixed in distilled water and be made into concentration and be respectively 0.01 μ g/mL solution.
6) electrolemma extraction: the electrode of electrolemma extraction is fixed by inserting rubber blanket, makes electrode distance at about 2mm.Then the occlusion handled well there is the film of organic solvent to inject and accept the phase aqueous solution (the 0.1M Boratex aqueous solution), film is curved U-shaped insertion negative pole, both positive and negative polarity is inserted together with film instrument and fills in sample centrifuge tube, add 50V DC voltage at the two poles of the earth and extract.Extraction time is 5min.
7) accept the collection of phase: after 5min, by power-off, electrode is mentioned together with film, take out film and accept phase with sample introduction needle sucking-off, inject 100L intubate, carry out LC-MS/MS analysis and ion chromatography.
8) analysis result: the comparison diagram of the extraction efficiency of gibberellin and the extraction efficiency of inorganic ions as shown in Figure 2.
Result shows, by the modification to hollow-fibre membrane, successfully enhances the extraction efficiency of organic matter gibberellin, significantly reduces inorganic ions (Cl simultaneously
-and NO
3 -) extraction efficiency.
Embodiment 2: be dispersed in polypropylene hollow fiber membrane with polystyrene and carry out membrane modifying for electrolemma extraction plant sample extract
1) configuration of polymer solution: polystyrene (the molecular weight 250000)/tetrahydrofuran solution of preparation 1%.
2) hollow-fibre membrane process: polypropylene hollow fiber membrane is cut into 7cm every section, in acetone ultrasonic cleaning, and room temperature dries up.
3) modification of hollow-fibre membrane: curved by the hollow-fibre membrane of drying U-shaped and immerse the polymer solution of configuration with No. 6 needle holder, stops 8s in the solution and mentions and dry in the shade in atmosphere, and then immerse 8s in polymer solution, then mention.So five times repeatedly.
4) film occlusion organic solvent: the film of modification is immersed 5min in the organic solvent of n-octyl alcohol, organic solvent is made to be occluded in fenestra, pressed from both sides out by film and inject distilled water wherein with the organic solvent in flushing membrane chamber, the organic solvent of film outside embathes removing in distilled water.
5) preparation of sample solution: be powder by 2g arabidopsis liquid nitrogen grinding, carry out lixiviate 1 night with 80% methanol-water solution, by powder suction filtration, get filtrate and steam at 30 degrees Celsius of backspins, by revolving, the water raffinate after steaming is centrifugal, gets supernatant and extracts.
6) electrolemma extraction: the electrode of electrolemma extraction is fixed by inserting rubber blanket, makes electrode distance at about 2mm.Then the occlusion handled well there is the film of organic solvent to inject and accept the phase aqueous solution (the 0.1M Boratex aqueous solution), film is curved U-shaped insertion negative pole, both positive and negative polarity is inserted together with film instrument and fills in sample centrifuge tube, add 50V DC voltage at the two poles of the earth and extract.Extraction time be the circuit comparison diagram of electric current in 5min. extraction process and unmodified membrane extraction process as shown in Figure 3.
Result shows that modified hollow-fibre membrane significantly can suppress electric current for electrolemma extraction, and then suppresses the migration of inorganic ions.
Claims (7)
1. suppress the modified micropore tunica fibrosa of inorganic ions migration in electrolemma extraction, it is characterized in that: be dispersed in by hydrophobic polymer molecule in the micropore of tunica fibrosa membranous wall, make a kind of tunica fibrosa of modification, the electrolemma for organic compound extracts; The axial coverage of polymer in membranous wall be film thickness 3% ~ 10% between;
Described hydrophobic polymer is the linear amorphous polymer dissolving in volatile organic solvent, molecular weight 10000-300000, its swellable but be not dissolved in electrolemma extraction mesophase spherule organic solvent used.
2. the modified micropore tunica fibrosa of inorganic ions migration in suppression electrolemma extraction according to claim 1, is characterized in that: tunica fibrosa immerses in hydrophobic polymer solution and makes it be dispersed in the micropore of tunica fibrosa membranous wall by the method for hydrophobic polymer employing dip coating.
3. the modified micropore tunica fibrosa of inorganic ions migration in suppression electrolemma extraction according to claim 1, is characterized in that:
The load amount of described hydrophobic polymer in microporous fiber membranes is 0.01-0.2g/cm
3pore volume.
4. the modified micropore tunica fibrosa of inorganic ions migration in suppression electrolemma extraction according to claim 1, is characterized in that:
When adopting n-octyl alcohol to be electrolemma extraction organic solvent, select the polyvinyl chloride of molecular weight 80000 or Kynoar as polymer-modified.
5. the modified micropore tunica fibrosa of inorganic ions migration in a suppression electrolemma extraction according to claim 1, it is characterized in that: hydrophobic polymer adopts the method for dip coating to be dispersed in the micropore of tunica fibrosa membranous wall, immersing in hydrophobic polymer solution by tunica fibrosa makes it be dispersed in the micropore of tunica fibrosa membranous wall, then dry, the concentration of described hydrophobic polymer is 1%-5% (w/v, g/ml).
6. the application of the modified micropore tunica fibrosa of inorganic ions migration in suppressing electrolemma to extract described in a claim 1, it is characterized in that: for electrolemma extraction process, with the mesophase spherule that Modified Membrane occlusion organic solvent extracts as electrolemma, suppress the migration of inorganic ions in mutually, and then increase selective to organic ion of system.
7. application according to claim 6, is characterized in that: electrolemma extraction is a kind of three phase extraction, by providing phase, and mesophase spherule and accept phase composition; Thering is provided is the aqueous solution mutually, and mesophase spherule is immiscible organic solvent with water, accepts to be alkalescence or acid pH aqueous buffer solution mutually;
To there is provided mutually and between accepting mutually in addition 9-500V DC electric field to accelerate compound in alternate migration rate; Communicated in the middle of it organic mutual-assistance of tunica fibrosa cinclides occlusion its be stabilized in the micropore of tunica fibrosa be placed in provide mutually and accept mutually between carry out the transmission of material.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1704152A (en) * | 2004-06-04 | 2005-12-07 | 杨虎 | Preparation of hydrophilic polyvinylidene fluoride microporous membrane |
| CN102068922A (en) * | 2010-12-16 | 2011-05-25 | 天津膜天膜科技股份有限公司 | Preparation method of polyvinylidene fluoride composite reinforced liquid separation film |
| CN102489173A (en) * | 2011-11-18 | 2012-06-13 | 天津膜天膜科技股份有限公司 | Preparation method of heterogeneous composite hollow fiber film |
| US20120186979A1 (en) * | 2010-12-06 | 2012-07-26 | Greibrokk & Trones Septech As | Device for electro membrane extraction |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1704152A (en) * | 2004-06-04 | 2005-12-07 | 杨虎 | Preparation of hydrophilic polyvinylidene fluoride microporous membrane |
| US20120186979A1 (en) * | 2010-12-06 | 2012-07-26 | Greibrokk & Trones Septech As | Device for electro membrane extraction |
| CN102068922A (en) * | 2010-12-16 | 2011-05-25 | 天津膜天膜科技股份有限公司 | Preparation method of polyvinylidene fluoride composite reinforced liquid separation film |
| CN102489173A (en) * | 2011-11-18 | 2012-06-13 | 天津膜天膜科技股份有限公司 | Preparation method of heterogeneous composite hollow fiber film |
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